R. Timothy Short

A Review of the Emerging Field of Underwater Mass Spectrometry

Mass spectrometers are versatile sensor systems, owing to their high sensitivity and ability to simultaneously measure multiple chemical species. Over the last two decades, traditional laboratory-based membrane inlet mass spectrometers have been adapted for underwater use. Underwater mass spectrometry has drastically improved our capability to monitor a broad suite of gaseous compounds (e.g., dissolved atmospheric gases, light hydrocarbons, and volatile organic compounds) in the aquatic environment. Here we provide an overview of the progress made in the field of underwater mass spectrometry since its inception in the 1990s to the present. In particular, we discuss the approaches undertaken by various research groups in developing in situ mass spectrometers. We also provide examples to illustrate how underwater mass spectrometers have been used in the field. Finally, we present future trends in the field of in situ mass spectrometry. Most of these efforts are aimed at improving the quality and spatial and temporal scales of chemical measurements in the ocean. By providing up-to-date information on underwater mass spectrometry, this review offers guidance for researchers interested in adapting this technology as well as goals for future progress in the field.

Evaluation of reagentless pH modification for in situ ocean analysis: determination of dissolved inorganic carbon using mass spectrometry

RATIONALE In situ analytical techniques that require the storage and delivery of reagents (e.g., acidic or basic solutions) have inherent durability limitations. The reagentless electrolytic technique for pH modification presented here was developed primarily to ease and to extend the longevity of dissolved inorganic carbon (DIC) determinations in seawater, but can also be used for other analytical methods. DIC, a primary carbon dioxide (CO(2)) system variable along with alkalinity, controls seawater pH, carbonate saturation state, and CO(2) fugacity. Determinations of these parameters are central to an understanding of ocean acidification and global climate change. METHODS Electrodes fabricated with electroactive materials, including manganese(III) oxide (Mn(2)O(3)) and palladium (Pd), were examined for potential use in electrolytic acidification. In-line acidification techniques were evaluated using a bench-top membrane introduction mass spectrometry (MIMS) setup to determine the DIC content of artificial seawater. Linear least-squares (LLSQ) calibrations for DIC concentration determinations over a range between 1650 and 2400 µmol kg(-1) were obtained, using both the novel electrolytic and conventional acid addition techniques. RESULTS At sample rates of 4.5 mL min(-1), electrodes clad with Mn(2)O(3) and Pd were able to change seawater pH from 7.6 to 2.8 with a power consumption of less than 3 W. Although calibration curves were influenced by sampling rates at a flow of 4.5 mL min(-1), the 1σ measurement precision for DIC was of the order of ±20 µmol kg(-1). CONCLUSIONS Calibrations obtained with the novel reagentless technique and the in-line addition of strong acid showed similar capabilities for DIC quantification. However, calculations of power savings for the reagentless technique relative to the mechanical delivery of stored acid demonstrated substantial advantages of the electrolytic technique for long-term deployments (>1 year).

The Effect of the Earth’s and Stray Magnetic Fields on Mobile Mass Spectrometer Systems

AbstractDevelopment of small, field-portable mass spectrometers has enabled a rapid growth of in-field measurements on mobile platforms. In such in-field measurements, unexpected signal variability has been observed by the authors in portable ion traps with internal electron ionization. The orientation of magnetic fields (such as the Earth’s) relative to the ionization electron beam trajectory can significantly alter the electron flux into a quadrupole ion trap, resulting in significant changes in the instrumental sensitivity. Instrument simulations and experiments were performed relative to the earth’s magnetic field to assess the importance of (1) nonpoint-source electron sources, (2) vertical versus horizontal electron beam orientation, and (3) secondary magnetic fields created by the instrument itself. Electron lens focus effects were explored by additional simulations, and were paralleled by experiments performed with a mass spectrometer mounted on a rotating platform. Additionally, magnetically permeable metals were used to shield (1) the entire instrument from the Earth’s magnetic field, and (2) the electron beam from both the Earth’s and instrument’s magnetic fields. Both simulation and experimental results suggest the predominant influence on directionally dependent signal variability is the result of the summation of two magnetic vectors. As such, the most effective method for reducing this effect is the shielding of the electron beam from both magnetic vectors, thus improving electron beam alignment and removing any directional dependency. The improved ionizing electron beam alignment also allows for significant improvements in overall instrument sensitivity. Graphical Abstractᅟ

Semi-fuel cell studies for powering underwater devices: integrated design for maximized net power output

Use of sensor systems in water bodies has applications that range from environmental and oceanographic research to port and homeland security. Power sources are often the limiting component for further reduction of sensor system size and weight. We present recent investigations of metal-anode water-activated galvanic cells, specifically water-activated Alcells using inorganic alkali peroxides and solid organic oxidizers (heterocyclic halamines), in a semi-fuel cell configuration (i.e., with cathode species generated in situ and flow-through cells). The oxidizers utilized are inexpensive solid materials that are generally (1) safer to handle than liquid solutions or gases, (2) have inherently higher current and energy capacity (as they are not dissolved), and, (3) if appropriately packaged, will not degrade over time. The specific energy (S.E.) of Al-alkali peroxide was found to be 230 Wh/kg (460 Wh/kg, considering only active materials) in a seven-gram cell. Interestingly, when the cell size was increased (making more area of the catalytic cathode electrode available), the results from a single addition of water in an Al-organic oxidizer cell (weighing ~18 grams) showed an S.E. of about 200 Wh/kg. This scalability characteristic suggests that values in excess of 400 Wh/kg could be obtained in a semi-fuel-cell-like system. In this paper, we also present design considerations that take into account the energy requirements of the pumping devices and show that the proposed oxidizers, and the possible control of the chemical equilibrium of these cathodes in solution, may help reduce this power requirement and hence enhance the overall energetic balance.