Simulation study of digital waveform-driven quadrupole mass filter operated in higher stability regions for high-resolution inductively coupled plasma mass spectrometry.

RATIONALE: The use of a frequency-scanned digital quadrupole mass filter (QMF) with varying duty cycles shows promise for application as a high-resolution mass analyzer design for inductively coupled plasma mass spectrometry (ICP-MS). High resolution in ICP-MS is important to overcome isobaric polyatomic interferences. Here, we explore the possibility and the characteristics of using a digital quadrupole operating in higher stability regions for ICP-MS. METHODS: We perform computational simulations in SIMION of a digital QMF that is operated by scanning the frequency of the digital waveform at a fixed driving voltage and various duty cycles. For ions in the atomic mass range (7-238 m/z), we investigate the expected resolution, transmission, fringe field effects, and ion trajectories. We compare different characteristics between sine and digital waveform QMF. RESULTS: Within the capability of current digital waveform generation technology, a digital QMF can produce variable mass resolution, from several hundred to more than 10 000. This mass resolution covers the low, medium, and high resolutions that are typical for sector-field ICP-MS. Additionally, simulations suggest that transmission of the QMF remains high at high resolution. For example, with 87.50/12.50 duty cycle (zone 4,1), resolution at 10% peak width is 10 420 for m/z 80. The transmission through the quadrupole, which is constant for all isoenergetic ions, is ~2.5%, and most ion loss is due to the defocusing effects of the fringe field. Compared to sinusoidal QMFs, ions need many fewer cycles in the digital QMF to obtain high resolution. CONCLUSION: The results demonstrate that the use of a frequency-scanned, duty-cycle-modulated digital QMF as the mass analyzer for ICP-MS has the potential to produce high resolution while maintaining considerable transmission, thus overcoming most spectral interferences in elemental MS.

Comparative study of the vibrating capillary nebulizer (VCN) and commercially available interfaces for on-line coupling of capillary electrophoresis with ICP-MS.

Capillary electrophoresis (CE) is a powerful and sensitive tool for speciation analysis when combined with inductively coupled plasma mass spectrometry (ICP-MS); however, the performance of this technique can be limited by the nature of pneumatic nebulizers. This study compares two commercially available pneumatic nebulizers to a newly introduced vibrating capillary nebulizer (VCN) for on-line coupling of CE with ICP-MS. The VCN is a low-cost, non-pneumatic nebulizer that is based on the design of capillary vibrating sharp-edge spray ionization. As a piezoelectrically driven nebulization source, the VCN creates an aerosol independent of gas flows and does not produce a low-pressure region at the nebulizer orifice. To compare the systems, we performed replicate analyses of sulfate in river water with each nebulizer and the same CE and ICP-MS instruments and determined the figures of merit of each setup. With the CE-VCN-ICP-MS setup, we achieved around 2-4 times lower sensitivity compared to the commercial setups. However, the VCN-based setup provided lower noise levels and better linear correlation from the analysis of calibration standards, which resulted in indistinguishable LOD and LOQ values from the in-house-built VCN-based and commercial setups for CE-ICP-MS analysis. The VCN is found to have the highest baseline stability with a standard deviation of 3500 cts s-1, corresponding to an RSD of 2.7%. High reproducibility is found with the VCN with a peak area RSD of 4.1% between 3 replicate measurements.

Experimental Investigation of a Digital Quadrupole Inductively Coupled Plasma Mass Spectrometer for Elemental Analysis.

We describe the development and initial characterization of a digital waveform scanning quadrupole mass filter (digital QMF) used for inductively coupled plasma mass spectrometry (ICP-MS). Unlike a conventional voltage scanning QMF, in the digital QMF, the frequency of the digital waveform is scanned to filter ions with different m/z through the quadrupole, and m/z is proportional to 1/f2. In digital QMF, the duty cycle of the digital waveform driving the quadrupole is modified such that stability regions of interest are accessible for mass analysis with no DC voltage applied. Here, we evaluate the performance of our digital ICP-QMS instrument at several duty cycles and corresponding stability zones: from zone 1 to zone 3,2. We demonstrate that, regardless of the stability zone used, frequency vs m/z calibration matches theory. For lower-order stability zones, the mass range of the analyzer is limited by the high-frequency waveform required; however, at zone 3,2, we demonstrate a mass range from at least 40 to 232 Th, which covers most of the elemental mass range. Similar to the conventional QMF, higher stability regions of the digital QMF can yield a higher resolution. We obtained the best resolution for our current instrument at zone 3,2 with a 62.50/37.50 duty cycle. The resolution at full-width at 10% peak height (R10%) was 1200 and 1100 for 115In+ and 232Th+, respectively. Lower pole bias yielded a R10% of 1400 for 40Ar+. Resolution and sensitivity comparisons indicate that higher q values and higher duty cycles lead to enhanced resolution, but lower sensitivity. Our results validate the operation of digital quadrupole ICP-MS and suggest that, with continuous improvement of electronics and instrumentation, a high resolution digital waveform scanning ICP-QMS for elemental analysis is possible.

Measurement bias in spICP-TOFMS: insights from Monte Carlo simulations.

Single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS) is used to measure the mass amounts of elements in individual nano and submicron particles. In spICP-TOFMS, element signals can only be recorded as "particles" if they are above the critical value, which is the threshold used to distinguish between particle-derived and background signals. If elements in particles are present in amounts close to or below the critical value, then these elements cannot be quantitatively measured, and the shape of the measured mass distributions will not be accurate. In addition, recorded spICP-TOFMS signal distributions are impacted by measurement uncertainty due to counting statistics inherent to the mass analyzer. Counting noise is most pronounced for elements detected with low signal levels and can lead to systematic biases in the observed element masses and mass ratios from a particle event. In turn, spICP-TOFMS data can lead to incorrect conclusions about element composition and/or size of recorded particles. To better understand how biases and noise can alter the interpretation of data, we employ Monte Carlo simulations to model spICP-TOFMS signals as a function of measurement parameters, such as particle size distribution (PSD), multi-element composition, absolute sensitivities (TofCts g-1), and measurement noise from ion-counting (Poisson) statistics. Monte Carlo simulations allow for the systematic comparison of known (simulated) element mass distributions to experimental (measured) data. To demonstrate the accuracy of our model in predicting spICP-TOFMS signal structure, we highlight the match between data from in-lab measurements and simulations for the detection of CeO2, ferrocerium mischmetal, and bastnaesite particles. Through Monte Carlo simulations, we explore how analyte PSDs and other measurement parameters can lead to the determination of biased particle sizes, particle numbers, element ratios, and multi-element compositions.

Prompt diagnosis of ST-elevation myocardial infarction with papillary muscle rupture by point-of-care ultrasound in the emergency department

A previously healthy 61-year-old man presented to the emergency department with chest pain and dyspnoea for 6 hours. Examination revealed distress with an apical pansystolic murmur. Initial electrocardiogram showed sinus tachycardia and ST elevation in leads II, III, and aVF compatible with an inferior ST-elevation myocardial infarction. Point-of-care echocardiography in the emergency department showed a flail anterior mitral leaflet and severe mitral regurgitation, leading to a provisional diagnosis of papillary muscle rupture. Emergency cardiac catheterization showed 100%, 80%, and 70% occlusion of the middle right coronary, left anterior descending, and left circumflex arteries, respectively. An emergency triple vessel coronary artery bypass grafting and mitral valve replacement was performed. Posteromedial papillary muscle rupture resulting in mitral regurgitation was confirmed intraoperatively. The patient recovered uneventfully. In the absence of primary percutaneous coronary intervention, thrombolysis decisions should be made with extreme caution if mechanical complications of ST-elevation myocardial infarction are suspected.