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Koppenaal, David W.

Publications and source records attributed to Koppenaal, David W..

Coupling of the Liquid Sampling–Atmospheric Pressure Glow Discharge to Orbitrap Mass Analyzers for Uranium Isotope Ratio Analysis: Evolution of the Methodology and Implications to the Field

Just over a decade ago, a truly outside-of-the-box approach to isotope ratio mass spectrometry (IRMS) was undertaken between research groups at Clemson University and the Pacific Northwest National Laboratory. The original motivation dealt with projections as to whether or not microplasmas could be developed into practical elemental ionization sources, perhaps for transportable analysis applications. In particular, the use of the liquid sampling–atmospheric pressure glow discharge (LS-APGD) was pursued. Its interfacing to an ultra-high resolution Orbitrap platform, proved not only facile, but opened up a wealth of potential applications. Here, we lay out a historical, tutorial description of the interfacing and the evolution of the methodology regarding IRMS of uranium. Practical challenges and opportunities are described, which hopefully provide guidance to further applications in high resolution IRMS. It is hoped that, while detailed and lengthy, the didactic nature of the presentation provides experimental insights and tips, and also serves as an homage to our very good friend, Professor Gary M. Hieftje, whose scientific inspiration and comradery have been immeasurably important in our own careers.

Koppenaal, David W.↗

Multi-electrode/multi-modal atmospheric pressure glow discharge plasma ionization device

Apparatus include an atmospheric pressure glow discharge (APGD) analyte electrode defining an analyte discharge axis into an APGD volume, and a plurality of APGD counter electrodes having respective electrical discharge ends directed to the APGD volume, wherein the APGD analyte electrode and the APGD counter electrodes are configured to produce an APGD plasma in the APGD volume with a voltage difference between the APGD analyte electrode and one or more of the AGPD counter electrodes. An electrode can be integrated into an ion inlet. Apparatus can be configured to perform auto-ignition and/or provide multi-modal operation through selectively powering electrodes. Electrode holder devices are disclosed. Related methods are disclosed.

Koppenaal, David W.↗

Resolving Severe Elemental Isobaric Interferences with a Combined Atomic and Molecular Ionization Source - Orbitrap Mass Spectrometry Approach: The 87Sr and 87Rb Geochronology Pair

Many fields of basic and applied sciences, including geochronology, astronomy, metabolism, nutrition and forensics rely on the ability of mass spectrometry to make isotope ratio measurements with a high degree of certainty. The inability to resolve difficult isobaric interferences still plagues certain measurements of this type. A combined atomic and molecular (CAM) ionization source has been interfaced to a high-field Orbitrap mass spectrometer in an effort to alleviate severe atomic, isobaric interferences. Specifically, this work examines the geochronological-significant 87Sr and 87Rb isotope pair. The mass difference between 87Sr and 87Rb is ~0.3 mDa, requiring a minimum resolving power (R = m/?m) of ~290,000, a value ~30X higher than available with conventional (sector-field) elemental mass spectrometers. Under ultra-high resolution conditions, Sr isotope ratio accuracy and precision were evaluated using NIST Sr SRM 987, yielding precision values of <0.1% relative standard deviation (RSD) for the major isotopes and a calculated LOD of 2 pg mL-1, equivalent to 120 fg Sr for a 60 µL injection. In addition to manipulating the signal transient length, which controls the Orbitrap resolving power, the total number of ions in the electrostatic trap and the relative ion populations (i.e. the 87Sr/87Rb concentration ratio), were found to be influential towards resolving the isobaric species. Ultimately, the 87Sr and 87Rb isotopes were baseline resolved with a calculated mass resolution of >1.7 M. At equal 87Sr and 87Rb intensities, the 87Sr/86Sr was measured as 0.71294 (an error of 0.37%) with a precision of 0.097 %RSD, clearly reflecting the alleviation of the isobaric interference.

Hoegg, Edward D.↗

Metabolomic Profiling of Wild-type and Mutant Soybean Root Nodules Using Laser-ablation Electrospray Ionization Mass Spectrometry Reveals Altered Metabolism

The establishment of the nitrogen-fixing symbiosis between soybean and Bradyrhizobium japonicum is complex. In order to document the changes in plant metabolism due to the symbiosis, we utilized laser ablation electrospray ionization mass spectrometry (LAESI-MS) for in situ metabolic profiling of wild-type nodules, nodules infected with a B. japonicum nifH mutant unable to fix nitrogen, nodules doubly infected by both strains, and nodules formed on plants mutated in the stearoyl-acyl carrier protein desaturase (sacpd-c) gene, which were previously shown to have altered nodule ultrastructure. Results showed that the relative abundance of fatty acids, purines, and lipids was significantly changed in response to the symbiosis. The nifH mutant nodules had elevated levels of jasmonic acid (JA), correlating with signs of nitrogen deprivation. Nodules resulting from the mixed inoculant displayed similar, overlapping metabolic distributions within the sectors of effective (fix+) and ineffective (nifH mutant, fix-) endosymbionts. These data are inconsistent with the notion that plant sanctioning is cell autonomous. Nodules lacking sacpd-c displayed an elevation of soyasaponins and organic acids in the central necrotic regions. This study demonstrates the utility of LAESI-MS for high-throughput screening of plant phenotypes. Overall, nodules disrupted in the symbiosis were elevated in metabolites related to plant defense.

Agtuca, Beverly J.↗