Workshop on
Harsh-Environment
Mass Spectrometry

"Novel Mass Spectrometric Approaches to the In situ Chemical Analysis of Galactic and Cometary Dust Particles"
Jack Beauchamp, Daniel E. Austin, Thomas J. Ahrens (California Institute of Technology)

Analysis of the chemical composition of cosmic dust particles offers a challenge for mass spectrometry. Particles of interest range from high velocity galactic mineral grains to cometary debris comprising frozen volatiles. A variety of different approaches have been taken in the past to analyze such particles in the space environment. Considering the performance and limitations of earlier instruments, we have designed and tested a novel compact impact-ionization time-of-flight mass spectrometer for analysis of cosmic dust, suitable for use on deep space missions. The instrument, Dustbuster, incorporates a large target area with a reflectron, simultaneously optimizing mass resolution, particle detection, and ion collection. Dust particles hit a 65-cm^2 target plate and are partially ionized by the impact. The resulting ions, with broad energy and angular distributions, are accelerated through a modified reflectron, focusing ions of specific m/z in space and time to produce high-resolution mass spectra. The cylindrically symmetric instrument is 10 cm in diameter and 20 cm in length, considerably smaller than previous in situ dust analyzers, and can be easily scaled as needed for specific mission requirements. Laser desorption ionization of metal and mineral samples embedded in the impact plate has been used to simulate particle impacts for evaluation of instrument performance. Mass resolution in these experiments ranged from 60-180, permitting resolution of isotopes. Instrument performance has been further verified using high-velocity (2-12 km/s) particles produced by a 2 MV Van de Graaff accelerator. We are now conducting additional impact experiments using micron-sized ice particles to simulate cometary debris. This work was supported by a grant from NASA's Planetary Instrument Definition and Development Program (PIDDP). [Reference: Austin, D. E.; Ahrens, T. J.; and Beauchamp, J. L. (2002) Rev. Sci. Instrum., 73(1), 185-189.]
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"Mass Spectrometers in Deep Space Missions"
Paul Mahaffy, Hasso Niemann, Dan Harpold (NASA/ Goddard Space Flight Center)

Mass spectrometers have been included in the payloads of several deep space missions over the past three decades. Our laboratory has designed and developed mass spectrometers for the Galileo Probe into the atmosphere of Jupiter, the Pioneer Venus Orbiter, the Cassini Orbiter Mission to Saturn, the Cassini/Huygens Probe Mission to Saturn's moon Titan, the Nozomi Mission to Mars, and most recently the CONTOUR comet nucleus flyby mission. Each mission has required attention to miniaturization, autonomous sampling, and consideration of the special hazards and measurement requirements of the target environment. Development ongoing in our laboratory includes further miniaturization, improved performance in the areas of sensitivity and precision for the important isotope measurements, and adaptation for the unusual environments to be encoutered in locations such as the surface or subsurface of Europa or Mars. Various aspects of both the technical implementation of these delivered and planned experiments and the science drivers will be described.
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"Quadrupole Ion Trap Mass Spectrometry for Space Shuttle Ground Support"
Andrew Ottens, W. Harrison (University of Florida); Timothy Griffin (Dynacs Inc.);
William Helms (NASA/ Kennedy Space Center)

From the beginning of the Space Shuttle program, mass spectrometers have been employed as cryogenic fuel monitoring instruments. As part of ground support equipment (GSE), these systems sample and analyze the atmosphere within the Space Shuttle during launch preparations. Launch controllers are provided with a graphic representation of hydrogen, helium, oxygen and argon concentrations within the nitrogen purged aft (rear) of the Orbiter and are able to detect and quantitate the magnitude of a cryogen fuel leak. These systems have performed well through the years, having detected numerous leaks; however, NASA is investigating new technology as part of a continual effort to improve the safety of manned space flight. Transfer lines up to 400 feet long are currently used to transport sampled gas from the Space Shuttle to the mass spectrometer systems. Because the transport tubing is excessive long, a sample can take as long as 45 seconds to reach the analyzer. One of the most critical points of launch is the starting of the cryogenic fueled Main Engines, occurring six seconds prior to liftoff. A leak developed during this time will not be detected due to the time lag between sampling and analyzing the environment within the Space Shuttle. To remedy this, NASA is pursuing miniature rugged mass spectrometer technology to be mounted up close to the Space Shuttle. This will not only reduce the time lag between sampling and analyzing, but will also provide greater detail of the environment within the Space Shuttle. This is accomplished through the use of numerous mass spectrometers, compared with the limit of two currently used. As part of this effort, a quadrupole ion trap mass spectrometer (QITMS) has been designed to perform trace analysis of hydrogen, helium, oxygen and argon within a nitrogen background. The QITMS is a well-known tool for organic, environmental, and biological analysis, yet this is the first QITMS designed to monitor and quantitate permanent gases as small as hydrogen and helium. Commercial QITMS hardware and software has been modifyed as necessary to analyze these species. The resulting quantitative performance of the QITMS will be reviewed. Although the current prototype is considered compact rather than miniature, the potential for miniaturization of a second-generation QITMS will be discussed, along with additional topics pertaining to the operation of a QITMS instrument for this application.
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"Test of the a Miniature Double-Focusing Mass Spectrometer for the Variable Specific Magnetoplasma Rocket (VASIMR) at the Advanced Space Propulsion Laboratory (ASPL)"
Jorge Diaz (Universidad de Costa Rica); Franklin Chang-Diaz (Director, ASPL and Astronaut, NASA/Johnson Space Center); Jared P. Squire, Verlin Jacobson, Greg McCaskill, Andres E. Mora Vargas (ASPL- NASA/Johnson Space Center); Henry Rohrs, Rajiv Chhatwal (Mass Sensors, Inc.)

The test of a miniature double focusing mass spectrometer with just 8mm of radius was performed at the Advance Space Propulsion Laboratory (ASPL) from Johnson Space Center (NASA). The experiments were conducted to provide residual gas analysis capabilities and single ion monitoring to the VX-10 vacuum chamber where NASA's new plasma propulsion system: the Variable Specific Impulse Magnetoplasma Rocket (VASIMR) is being developed. The miniature mass spectrometer tested is an alpha version of the Integrated Leak Detector System (ILD 50) developed by Mass Sensors Inc. and is a smaller version of the original CDFMS prototype (r = 20mm) developed at the University of Minnesota . The unit demonstrated its usefulness for both residual gas analysis and single ion monitoring, achieving almost its theoretical resolving power of 40 @FWHM and designed mass range of 50 Da. The mass spectrometer was able to continue operational even when the short pulses of plasma were being generated.
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"Regolith Evolved Gas Analyzer (REGA): An Instrument to Characterize the Martial Soil Mineralogy and Atmospheric Composition"
John H. Hoffman (University of Texas at Dallas)

The Regolith Evolved Gas Analyzer (REGA), a high temperature furnace, soil handling/metering system and mass spectrometer instrument, for measuring and determining the reactivity and mineralogical composition of soil samples was develop for a future Mars lander mission. REGA would provide key mineralogical and reactivity data that is needed to understand the soil chemistry, to identify locations of possible ancient life on Mars, and to determine potential hazards to human explorers and equipment. REGA is capable of conducting measurements directly on soil samples which include: mass spectrum analysis of evolved gases from heated martian soil samples from Mars ambient temperature to 900?C, and identification of liberated chemicals, e.g. oxygen, sulfur, chlorine, and fluorine. REGA is also capable of long term chemical and isotopic composition monitoring of the martian atmosphere. The REGA instrument consists of four primary components: a flight proven mass spectrometer, a high temperature furnace, a microprocessor, and a soil handling system. Soil samples are gathered by an external arm containing a scoop or drill. A sample is place in the inlet orifice where the fines are sifted into a metering volume and subsequently dropped into a crucible placed under the metering volume. A movable arm then places the crucible in the furnace. The furnace is closed sealing the inner volume containing the crucible from the martian atmosphere. A heating cycle is initiated. As the soil sample is heated through a programmed pattern, the gases evolved at each temperature are passed through a transfer tube to the mass spectrometer for analysis and identification. The REGA Mass Spectrometer (MS) is a double focussing magnetic-sector mass spectrometer. Major components of the instrument are a transfer tube from the furnace or the atmospheric gas inlet, an inlet valve and microleak, an ion source, an electrostatic analyzer, a magnetic analyzer and two ceramic electron multipliers, one each for the high and low mass ranges. Gases to be analyzed pass into the ion source though the microleak. The ionizing electron beam is produced by thermal emission from one of two small tungsten filament; the second filament is for redundancy. The filament and associated electronics each require 1 watt of power. Alternative cold electron sources are being investigated. The ion source is controlled by a microprocessor. Two emission currents (20ľA and 200ľA) and four electron energies (from 20eV to 75eV) can be selected. This capability extends the mass spectrometer's dynamic range by a factor of 10. It also provides extra information on the molecular constituents and atomic species, by varying their cracking patterns and charge states. For example, CO2 spectrum has very high mass peaks at (besides the parent peak at 44 Da) 28 Da (CO), 22 Da (doubly charged CO2), 16 Da(O) and 12 Da (O). Using 22 eV electrons, all dissociated peaks are below 1 % of the parent. This extended dynamic range and additional information on molecular constituents will facilitate and greatly simplify analysis of the mass spectrum data. The REGA system parameters along with data from sample test runs will be presented.
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"The NEPTUNE Project: An Interactive Earth-Ocean Observatory at the Scale of a Tectonic Plate"
John Delaney (School of Oceanography, University of Washington)

The NEPTUNE project will deploy a submarine cabled network on the Juan de Fuca tectonic plate off the U.S. and Canadian west coasts. Using fiber-optic/power cable and junction boxes, this plate-scale ocean observatory will establish a linked array of undersea observatories by providing significant amounts of power and an Internet communications link to sensors and sensor networks on, above, and below the sea floor. NEPTUNE's goal is to enable real-time, long-term, plate-scale studies in the ocean and earth sciences. The network may also serve as a unique test bed for sensor and robotic systems designed to explore other oceans in the solar system. NEPTUNE will focus on a broad range of scientific inquiries ranging from research involving microbial productivity from the oceanic crust related to deformation and volcanic eruptions in a plate tectonic framework, to abroad array of earthquake and tsunami-related issues, to tracking fish migration, to observing sediment transport, to monitoring carbon fluxes related to air-sea exchange and primary productivity in the upper ocean, including earthquake generated outgassing of subduction complexes. Hard-wired to the Internet, NEPTUNE will enable a new generation of ocean and earth science to be conducted for decades from instrument arrays immersed in the dynamic environments within and beneath our oceans. It will also bring real-time data and imagery into the laboratories, classrooms and living rooms connected to the Internet. For the first time, the public will be able to electronically watch over the shoulders of oceanographers and geoscientists as they explore the time domain within the ocean basins of our planet.
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"Underwater Mass Spectrometers: Some Critical Engineering Issues"
Harold F. Hemond, Richard Camilli (Massachusetts Institute of Technology)

The designer of an underwater mass spectrometer faces a set of engineering trade-offs that involve power consumption, vacuum system capacity, analyte flow, time response, mass range, resolution, precision, detection limits, and depth capability. In this paper we first discuss a set of engineering approaches and models that have been found helpful in the design of the NEREUS system, and are believed to be generally applicable to other underwater instruments. Secondly, we focus on the design of sample inlet systems, and on means of limiting the power consumption of a mass >spectrometer that must operate for extended periods on battery power. As one example, detailed design of the highly-efficient emission regulator used on NEREUS and applicable to many instruments using EI ionization will be presented.
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"Underwater Mass Spectrometers for Detection of VOCs and Dissolved Gases"
Gottfried Kibelka, Tim Short, David Fries (Center for Ocean Technology, University of South Florida)

We have developed and deployed mass spectrometry systems that are capable of autonomous underwater operation for chemical analysis. Our primary focus is to analyze coastal marine waters for natural and anthropogenic organic compounds and gases. The high spatial and temporal resolutions of the underwater mass spectrometer (MS) systems has been used to monitor and map chemical distributions in harsh environments. The underwater mass spectrometers are housed in separate pressure vessels that are connected in series for deployment The front vessel serves as the sampling system and contains a peristaltic pump and a 4 port valve. Sample water and charcoal cleaned sample water are alternately pumped into the hollow fiber membrane in the central vessel by switching the valve. The central pressure vessel contains the MS itself, a membrane probe, the turbo molecular/drag pump and a Card PC. The back vessel contains two dry diaphragm pumps in series that serve as backing pumps for the turbo molecular/drag pump. This approach allows us to evacuate the diaphragm-pump pressure vessel at the beginning of each operation, which extends the endurance of continuous operation to longer than a week. Battery powered deployment duration is currently limited to two hours for the ion trap and four hours for the quadrupole MS. All parts can be activated and controlled via Ethernet from an external computer. For gaseous compounds and very volatile organic compounds, an Inficon Transpector quadrupole residual gas analyzer is used. In various experiments, the analyzer was used to monitor dissolved gasses in shallow marine thermal vents and to monitor volatile organic compounds in wastewater influent, water plant and rivers. For trace compounds and pollutants, a Varian Saturn 2000 ion trap analyzer is used to attain higher sensitivity and the optional advantages of MS/ MS systems. The underwater ion trap system has been used to detect plumes of volatile organic compounds in Tampa Bay water. For differing tasks, both underwater MS systems have been used in moored, towed, tethered and autonomous underwater vehicle configurations.
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"Mass SURFER Field Mass Spectrometer System for Deep Ocean and Planetary Lander Applications"
Gary McMurtry [School of Ocean and Earth Science and Technology (SOEST), University of Hawaii, and Pacific Environmental Technologies], Steven J. Smith (Jet Propulsion Laboratory)

We are currently developing two low-power, miniature mass spectrometer-based field-sampling systems-- a "standard" and CE (capillary electrophoresis)-enhanced version-- called Mass SURFER (Mass Spectrometer Using Rotating Fields for Exploratory Research). The units incorporate the Rotating Field Mass Spectrometer (RFMS) developed at JPL. The current marine prototypes are housed within a 6.5-in. OD pressure vessel, 5.5 feet long that are capable of 2000+ m depth deployments. For planetary applications, we can greatly reduce the size and weight of these vessels. The system components comprise an aquatic-based sensor head, vacuum system, pressure case and associated electronics. Natural fluids, including seawater and brines, with their load of dissolved gases can be directly injected into a submersible vacuum chamber via a nano-electrospray interface (ESI). The ESI is an on-line capillary nozzle capable of high-sensitivity mass spectrometry at nanoliter per minute flow rates. Mass SURFER vacuum levels need only be at the milli-torr level for a quality measurement, and the complete system draws <10 watts when active. The RFMS mass resolution of 1 part in 1000 is comparable with the best of other small mass spectrometers. Its extremely large analytical mass range (from 1 to >100,000 amu) coupled with "soft" ionization techniques make it capable of analyzing practically anything from H2 and He gas to large dissolved organic compounds such as proteins, peptides and DNA. The Mass SURFER's high sensitivity and low power requirements allow remote, automated, in situ monitoring of dissolved gases, solutes and microbial populations via protein profiling. Future plans, which include analysis of aqueous volatiles and large dissolved organic compounds in deep-ocean hydrothermal vents and cold seeps, as well as NASA projects on the Moon, Mars, and the Jovian moons, especially targeting Europa, will be presented. This work is funded by the Defense Advanced Research Projects Agency (DARPA) via the State of Hawaii's National Defense Center of Excellence for Research in Ocean Sciences (CEROS).
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"Multisensor Data Integration and Adaptive Sampling Strategies for an Autonomous Underwater Mass Spectrometer"
Richard Camilli, Harold F. Hemond (Massachusetts Institute of Technology)

Marine environments can present the challenges of vast spatial extent and highly dynamic environmental states. These factors, combined with the limited communication bandwidth usually available to a maneuvering underwater platform will often necessitate that autonomous decision and control processes be employed when studying these partially observable systems. We examine the concept of using real-time chemical data from an underwater mass spectrometer operating onboard an autonomous underwater vehicle (AUV), in concert with data from other sensors commonly used on these robots, for the purpose of pattern recognition and for providing effective adaptive sampling. This strategy is implicitly useful for a host of applications including concurrent and feature-based mapping, improving acoustic and magnetic sensor data interpretation, direction of chemotactic searches, and adaptive control of mass spectrometer scanning. A pattern recognition system within a layered control architecture is described for use with the NEREUS underwater mass spectrometer and the Odyssey autonomous underwater vehicle.
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"Mapping and Monitoring Complex Chemical Components in Ambient Air using Fast GC/MS and Multivariate Data Analysis"
Henk Meuzelaar, Neil S. Arnold (University of Utah)

Considering the fact that the precise composition of many ambient environmental (air, water, soil) or industrial-process related samples represents a snapshot of the interaction of multiple chemical and physical reactions and transport phenomena, not unlike those encountered in a wide variety of molecular separation techniques, the ability of spatially and/or temporally distributed sample series to add new analytical dimensions should not come as a great surprise. From a multivariate analysis point of view one can simply look at the mass spectra or gas chromatograms of complex mixtures as the more or less linear sums of spectra or chromatograms representing individual mixture components. As long as one has a large enough set (i.e. the number of spectra or chromatograms should exceed the number of individually varying compounds or compound suites) of spectra or chromatograms in which the relative contributions of the target compounds or compound suites vary substantially it then will often be possible to numerically extract the profiles of the individual mixture components and determine their relative concentrations [Windig et al.; Chemometrics and intelligent Systems, 1, 151-165, 1987]. Although the procedure is simplified and quantitative analysis is more readily possible if the spectra or chromatograms of the individual mixture components are known, this is by no means an immutable requirement. This argument applies irrespective of whether one happens to be dealing with series of mass spectra representing two or more incompletely separated chromatographic peaks or with series of spectra (or chromatograms) representing fluctuating mixture concentrations in the field. Besides the relative ease with which temporally- or spatially-resolved measurement dimensions can be added when using fast, repetitive and/or distributed analysis modes, a particularly attractive characteristic of spatially and temporally distributed chemical and physical measurements in the field is that they often represent processes and trends with which the operator is already quite familiar, e.g. natural pollutant dispersion processes or industrial process trends. This helps make the novel information provided by these ancient analytical dimensions intuitively meaningful and transparent to an operator with limited training in analytical chemistry. Finally, it is well recognized that the inherently poor transmission of optical, microwave and radio signals in U/W environments severely limits the use of the kind of stand-off spectroscopic techniques for rapid area mapping which have been so spectacularly successful in astronomy and space science. Consequently, the new generation of fast, miniaturized, multidimensional point detectors (including a wide range of MS-based techniques), promises to provide a powerful alternative, whether deployed as fixed-grid distributed sensor systems or on fast roving (robotic and/or remotely controlled) platforms.
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"Field-Portable, Fast GC/TOFMS"
Jack Syage, Brian Nies, Rick Harkewicz (Syagen Technology, Inc.)

This talk reports on a fast gas chromatograph, time-of-flight mass spectrometer (GC/TOFMS) for man-portable field use. The complete system is designed to meet performance, size, weight, power, cost, and ruggedness requirements for a laboratory in the field. The core technology is also adaptable to specific applications including real-time point detection for hazardous chemical releases (e.g., chemical weapons), for biological agent signature identification, and for mobile monitoring platforms (e.g., air, ship, truck). In this talk we present recent progress in integrating a low-power, high-speed GC and show the capability for accurately recording fast GC transients for targeted compound detection using a photoionization (PI) source coupled to a quadrupole ion trap, time-of-flight (QitTof) instrument. The system specifications are 40 lb weight, 2 cu ft. size, and 150 W of power consumption. The instrument records mass spectra at nominally 60 Hz (USA) making it suitable for fast GC. The GC is temperature programmable and can cycle typical samples in 120 to 240 s. Preliminary GC measurements gave baseline resolution with peak widths of about 1 s and detection limits of about 20-100 ppb and 10-50 pg. We also present results on a pyrolysis/GC front end showing distinct signature peaks for biological bacteria and spore detection. This work is being supported by the U.S. Army for chemical/biological defense.
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"Portable Double-Focus Mass Spectrograph with Multymembrane Inlet"
Olga Viktorova, Viktor Kogan, Sergey Manninen (A. F. Ioffe Physical Technical Institute, St. Petersburg, Russia)

Portable Mass Spectrometer is designed for direct permanent autonomous in situ analysis of mixture's composition in real time scale. Small size and weight, low consumption of the instrument and high sensitivity to organic compounds allow to utilize it for environmental investigation or technological control outside the laboratory. Simple design and small permanent magnets that require no power at all make static Mass Spectrometer attractive for miniaturization. Mass Spectrography Mode gives the best results due to possibility of monitoring of several compounds simultaneously. Software package of numerical simulation allowed to calculate the ion-optic scheme of the original Double-Focus Mass Spectrograph with curved magnet outline. This scheme supplies high dispersion and small sector angle of the magnet for the heavier masses. A number of volatile and semivolatile organic compounds have a high permeability through the silicone membrane in comparison with the nature matrix (air, water) permeability. Based on this property the multymembrane inlet was created. It allows to increase the sensitivity of Mass Spectrometer for organic impurities in air million times more. Multimembrane inlet system involving consecutively disposed membranes (N>2) enriches sample with compounds effectively in MS selective analysis. Double-Focus Mass Spectrograph with Multymembrane Inlet is a real prototype of the portable instrument.
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"Addressing Forensic Field Analytical Chemistry Issues"
Brian A. Eckenrode, Valerie Cavett (Forensic Science Research Unit, Federal Bureau of Investigation); Philip A. Smith, Gregory Kimm, Gary Hook (Uniformed Services University of the Health Sciences, Department of Preventive Medicine and Biometrics); Erin Sherry (The George Washington University, Department of Forensic Sciences)

The FBI's laboratory division hazardous materials response unit and other operational units within the FBI require rapid and reliable chemical analyses in the field to improve their overall response strategy and effectiveness. Gas chromatography (GC) coupled with mass spectrometry (MS) is a mature and proven analytical technique that provides court defensible data. Raman spectroscopy is advancing quite rapidly in the amount of information that can be gleaned in a non-intrusive fashion and the commercial instrumentation is becoming much smaller. Ion mobility spectrometry (IMS) is another technique that is proven for its sensitivity. Hand-held polymeric-based sensors are being used more and more as initial screening tools for investigators. Visualizing chemical species via alternative light sources and hyperspectral imaging is on the forefront of investigative research. Each of these techniques can be field deployed; however, the use of these systems in the field, including exercising the available sample inlet methods, requires further development. We will present data from a new GC design that is small, lightweight, and has low power requirements for eventual GC/MS field systems. We have explored the use of field Raman systems and will present our results from these evaluations. Also, we have experimented with the use of solid phase microextraction (SPME) interfaced to an IMS for the analysis of headspace organic mixtures including chemical warfare agents. The practice of "temperature programming" is routinely done by changing the temperature of the oven containing a GC capillary column and heating the circulating air within it. This novel GC design does not require a convective approach to column heating. This new low thermal mass (LTM) column heating design has a high thermal efficiency toroidal wrap that can be programmed at high speed while maintaining low power consumption. We will present data on the use of this column in a conventional GC oven versus that with the LTM GC on a mixture used as a performance test for chemical warfare treaty verifications. Mass spectrometric parameters such as sampling time, scan rate, and library matching capability will be evaluated for several different, mostly high, ramping rates. The development of a field-portable battery-operated Raman system enables the application of this non-intrusive technology to analytical measurement situations requiring reliable identification of potentially hazardous materials in the field. Evaluation of these instrument prototypes will provide feedback necessary for these instruments to develop into systems useful for on-site characterization of materials relevant to public or personnel safety and security issues. Trace detection of smuggled money has been difficult and current methods rely on the use of canines. With the large number of entry points and the problems with canines such as exhaustion and maintenance, an improved methodology for screening incoming cargo is required. This research is designed to identify the VOCs and Semi-VOCs for targeted detection and identification in a rugged, field-portable system that is simple, sensitive, specific, and rapid. SPME will be used as a sampling front-end for chemical warfare-related compounds followed by IMS and/or GC-MS detection.
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"Detection of Microorganisms with MS: Field-Portable Instrumentation and Innovative Methodology"
Franco Basile, Angelo Madonna, Kent J. Voorhees [Colorado School of Mines (CSM)]; Stephen Lammert (Oak Ridge National Laboratory); Brian Musselman, Vladimir Doroshenko [Science & Engineering Services, Inc. (SESI)].

Abstract: The detection of biological warfare agents on the field is a challenging problem. Our research efforts in the last 17 years have contributed to the development of the Chemical Biological Mass Spectrometer (CBMS) for the US Army. The CBMS detector is a field-portable MS system based on a quadrupole ion-trap mass analyzer and a sample pre-processing unit. The entire unit is about 5.8 cubic feet, weights 170 lb, operates at 24 Vdc at less than 500 W. The sample pre-processing unit consists of a high efficiency impactor (optimized for 2-10 mm particles) and a thermal reaction chamber. Collected microorganisms from bioaerosols are enriched in this chamber and thermally hydrolyzed and methylated to produce specific biomarker molecules, a process that takes place in under 10 seconds. Subsequent mass analysis of these molecules produces biomarker fingerprints that are characteristic to that microorganism. A more detailed description of the sample pre-processing step as well as the ion trap MS hardware will be presented for the latest version of the CBMS block II system. In addition, new directions and approaches in biodetection with MALDI-MS will be presented. Briefly, affinity separation techniques are coupled with MALDI-MS analysis for the detection of bacteria in complex environmental/biological mixtures. Examples will be shown where these new methodologies are coupled with an atmospheric-pressure MALDI-MS instrument in order to simplify future hardware designs for field-portable systems.
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"Design of a Novel Miniature MALDI-TOF Mass Spectrometer for High Throughput Medical Screening"
Ben Gardner, Robert English, Robert Cotter (Johns Hopkins University School of Medicine)

Our laboratory has been developing a series of mid-resolution miniature MALDI-TOF mass spectrometers for the detection of biomarker signatures. Applications benefiting from these devices include high throughput biological screening assays and real-time biological weapons detection. As we continue to decrease the overall size of our designs, several fundamental parameters become increasingly important to achieving suitable resolving power. Examination of these fundamental parameters has led us to a novel design having potentially greater performance than is possible with conventional linear TOF instruments. In this presentation we will discuss the fundamental improvements required for enhanced performance and our current progress in implementing this new design.
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"Fieldable MALDI-TOF Bioaerosol Analysis System"
Wayne A. Bryden (Johns Hopkins University Applied Physics Laboratory)

The mass spectrometer is known as the most powerful laboratory analytical tool for analysis of a broad spectrum of chemical and biological materials. The applicability of mass spectrometers to field detection problems has been quite limited given the large size, heavy weight, and prohibitive power requirements of the instrumentation. DARPA has funded a program at JHU-APL with the objective of integrating new and emerging mass spectrometer technologies into a highly sensitive, broadband detection system suitable for use in a field setting The matrix assisted laser desorption/ionization (MALDI) technique has revolutionized biological mass spectrometry. Using this technique in the laboratory, large molecules (particularly proteins) can be employed as signatures biological materials. These signatures have been used with the proper algorithms to identify microorganisms. The DARPA funded system is being developed to carry this technology into the field in a package with low logistics burden and capable of being operated by lightly trained personnel. The system has demonstrated rapid classification and identification of a variety of bioaerosol components including bacteria (both spores and vegetative cells), viruses and toxins. The biodetection system include an optimized time-of-flight mass analyzer; an automatic collection system for transport of concentrated airborne particle samples into the mass analyzer; an automated analytical methodology; and automated signal processing, decision aids and data displays. This system is applicable to the rapid (<5minute) detection of airborne microorganisms in a mixed environment.
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"Miniature Mass Spectrometers and Front-End Interfaces"
Ara Chutjian, Murray Darrach, Otto Orient (Jet Propulsion Laboratory/California Institute of Technology); Paul Holland (Thorleaf Research, Inc.)

Mass spectrometers (MSs) are workhorse instruments on practically every robotic mission to planetary objects in our solar system. As long-duration human flight to other planets is planned, one also needs to monitor a cabin atmosphere over a period of several years against the toxic buildup of gases. Miniaturized MSs and front ends (gas chromatographs, liquid interfaces, drills, etc.) are needed in these harsh environments. Robustness and reliability are required, and mass, power, and volume are at a premium (especially for missions to the outer planets, including Pluto). We will present work carried out in the JPL Atomic and Molecular Collisions Group and at Thorleaf Research on (1) miniaturization of a quadrupole mass-spectrometer array (QMSA), which has been aboard the International Space Station since 2/01 to monitor possible leaks of cabin air, ammonia, and hydrazines in low-earth orbit; (2) a miniature hyperboloidal Paul ion trap; (3) a miniature front-end gas chomatograph and preconcentrator for use in complex gas mixtures, and modular to the mass spectrometers in (1) and (2). Properties of the systems will be discussed, such as resolution (0.03-0.8 amu, FWHM), sensitivity (10^12 to 10^14 counts/torr-s) flow rates, and pumping. The limits to resolution and sensitivity, and the utility of building even smaller MS systems, will be discussed. This work was carried out at the Jet Propulsion Laboratory/California Institute of Technology, and was supported under contract with the National Aeronautics and Space Administration.
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"Evaluation of Small Mass Spectrometer Systems as Candidates for the Development of Miniature Mass Spectrometer Systems"
Richard Arkin, Timothy Griffin (Dynacs Inc.); Andrew Ottens (The University of Florida); Jorge Diaz (Universidad de Costa Rica); Duke Follestein, Fredrick Adams, William Helms (NASA/ Kennedy Space Center)

There is an ever increasing need for smaller mass spectrometer (MS) systems. Smaller MS systems are generally more easily transported, less expensive, operated in more diverse environments, and allow real-time analysis. Such systems have many potential applications such as environmental analysis, process monitoring, and hazardous chemical detection. At Kennedy Space Center there is a need for small, point-sensor MS systems for a variety of tasks. Such tasks include the monitoring of hazardous gases around the Space Shuttle prior to launch, the detection of toxic vapors, such as hypergols, and process control of a fuel production plant on Mars. Several types of small MS systems are evaluated and discussed, including linear quadrupole, quadrupole ion trap, time of flight and magnetic sector. The performance of each system in terms of accuracy, precision, limits of detection, response time, recovery time, scan rate, volume and weight is ascessed. A performance scale is setup for each test category in order to rank the systems and an overall rank is given to each system.
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"Miniature cylindrical ion trap mass spectrometry"
Jeremy Moxom, William Whitten, Peter Reilly, Michael Ramsey (Oak Ridge National Laboratory)

The development of miniature ion trap mass spectrometers is being driven by many new applications, such as, autonomous underwater vehicles, planetary probes, monitoring air quality in spacecraft and field portable mass spectrometers for the detection of BW/CW agents. Miniaturization of the trap electrodes to sub-millimeter sizes significantly reduces the working voltages and pumping requirements, resulting in a substantial reduction in size and power consumption compared to a conventional instrument, without a significant degradation in overall performance. The cylindrical traps used in the present work are also more easily constructed and are more compatible with micro fabrication techniques than conventional hyperbolic traps. The higher order field components present in such devices can also result in improved performance. The stability diagrams of cylindrical traps with r0 = 0.5 mm have been studied when an axial modulation is applied to the end caps of the trap. Ion ejection from normally stable trajectories was observed when the ion secular frequency was approximately that of a nonlinear resonance of the trap. The resonances are attributed to electrical as well as geometrical considerations. Under these conditions, both the peak height and the mass resolution of the resulting mass spectrum are found to increase.
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"A LIGA Fabricated Two-Dimensional Quadrupole Array for High Resolution Mass Spectroscopy"
Nosang V. Myung, Otto Orient, Kirill Shcheglov, Beverley Eyre, Dean Wiberg (Jet Propulsion Laboratory)

Microfabrication of high precision two-dimensional quadrupole array (3 X 3) is currently in progress at JPL using the LIGA processing. The target detection range for the miniaturized mass spectrometer is 1 to 300 atomic mass units (AMU) with a resolution of 0.5 AMU Mass spectrometer is one of most frequently flown instruments for planetary aeronomy studies. Development of small and portable high precision in-situ instrument are greatly needed for human environmental monitoring, geochronology, and atomspheric characterization, which is also coincide with NASA's goal of having "faster, better, cheaper" space mission. LIGA processing is combination of x-ray lithography using synchrotron radiation, electroforming (electrodeposition), and plastic molding to fabricate a high precision device. It contains two distinct electrodeposition steps. One is the electrodeposition of gold onto a mask substrate to serve as the x-ray absorber during synchrotron exposure and the other is the deposition of actual device. By controlling electrodeposition parameters and solution compositions, homogeneous, low-stressed, and dense gold mask (20 to 50 micron) was electrodeposited from gold sulfite baths to silicon substrate (100-200 micron) to provide an adequate contrast ratio. 3 mm tall polymethyl methacrylate (PMMA) was precisely patterned and developed by controlling the filter thickness, energy dosage and time. Then copper was electrodeposited to PMMA mold from acid sulfate bath. Metrology studies were also conducted to determine the dimensional precision of the quadrupoles.
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"Concept for a Miniaturized Confocal Plane Mass Spectrometer using Micromachined Detector Array"
Adi Scheidemann (Intelligent Ion, Inc.); Mahadeva Sinha (Jet Propulsion Laboratory); Bruce Darling (University of Washington)

The concept of a miniaturized Mattauch-Herzog mass spectrometer will be described; scaling laws governing miniaturizing magnetic sector mass spectrometer will be addresses and the pros-cons of the Mattauch-Herzog concept versus quads and ToF will be discussed. A DRIE based Faraday cup detector array will be compared to and an electro optical ion detector.
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