Here we describe the first combination of a Distance-of-Flight Mass Spectrometry (DOFMS) instrument and an inductively coupled plasma (ICP) ion source. DOFMS is a velocity-based MS technique in which ions of a range of mass-to-charge (m/z) values are detected simultaneously along the length of a spatially selective detector. As a relative of time-of-flight (TOF) MS, DOFMS leverages benefits from both TOFMS and spatially dispersive MS. The simultaneous detection of groups of m/z values improves dynamic range by spreading ion signal across many detector elements and reduces correlated noise by signal ratioing. To ascertain the performance characteristics of the ICP-DOFMS instrument, we have employed a microchannel-plate/ phosphor detection assembly with a scientific CCD to capture images of the phosphor plate. With this simple (and commercially available) detection scheme, elemental detection limits from 2-30 ng L À1 and a linear dynamic range of 5 orders of magnitude (10-10 6 ng L À1 ) have been demonstrated.Additionally, a competitive isotope-ratio precision of 0.1% RSD has been achieved with only a 6 s signal integration period. In addition to first figures of merit, this paper outlines technical considerations for the design of the ICP-DOFMS.
In this study, we demonstrate the performance of a new mass spectrometry concept called zoom time-of-flight mass spectrometry (zoom-TOFMS). In our zoom-TOFMS instrument, we combine two complementary types of TOFMS: conventional, constant-energy acceleration (CEA) TOFMS and constant-momentum acceleration (CMA) TOFMS to provide complete mass-spectral coverage as well as enhanced resolution and duty factor for a narrow, targeted mass region, respectively. Alternation between CEA- and CMA-TOFMS requires only that electrostatic instrument settings (i.e., reflectron and ion optics) and ion acceleration conditions be changed. The prototype zoom-TOFMS instrument has orthogonal-acceleration geometry, a total field-free distance of 43 cm, and a direct-current glow-discharge ionization source. Experimental results demonstrate that the CMA-TOFMS "zoom" mode offers resolution enhancement of 1.6 times over single-stage acceleration CEA-TOFMS. For the atomic mass range studied here, the maximum resolving power at full-width half-maximum observed for CEA-TOFMS was 1,610 and for CMA-TOFMS the maximum was 2,550. No difference in signal-to-noise (S/N) ratio was observed between the operating modes of zoom-TOFMS when both were operated at equivalent repetition rates. For a 10-kHz repetition rate, S/N values for CEA-TOFMS varied from 45 to 990 and from 67 to 10,000 for CMA-TOFMS. This resolution improvement is the result of a linear TOF-to-mass scale and the energy-focusing capability of CMA-TOFMS. Use of CMA also allows ions outside a given m/z range to be rejected by simple ion-energy barriers to provide a substantial improvement in duty factor.
Laser-ablation (LA) sample introduction is combined with a new simultaneous multi-element determining, velocity-based ICPMS approach called distance-of-flight mass spectrometry (DOFMS).
Resolution in time-of-flight mass spectrometry (TOFMS) is ordinarily limited by the initial energy and space distributions within an instrument's acceleration region and by the length of the field-free flight zone. With gaseous ion sources, these distributions lead to systematic flight-time errors that cannot be simultaneously corrected with conventional static-field ion-focusing devices (i.e., an ion mirror). It is known that initial energy and space distributions produce non-linearly correlated errors in both ion velocity and exit time from the acceleration region. Here we reinvestigate an old acceleration technique, constant-momentum acceleration (CMA), to decouple the effects of initial energy and space distributions. In CMA, only initial ion energies (and not their positions) affect the velocity ions gain. Therefore, with CMA, the spatial distribution within the acceleration region can be manipulated without creating ion-velocity error. The velocity differences caused by a spread in initial ion energy can be corrected with an ion mirror. We discuss here the use of CMA and independent focusing of energy and space distributions for both distance-of-flight mass spectrometry (DOFMS) and TOFMS. Performance characteristics of our CMA-DOFMS and CMA-TOFMS instrument, fitted with a glow-discharge ionization source, are described. In CMA-DOFMS, resolving powers (FWHM) of greater than 1000 are achieved for atomic ions with a flight length of 285 mm. In CMA-TOFMS, only ions over a narrow range of m/z values can be energy-focused; however, the technique offers improved resolution for these focused ions, with resolving powers of greater than 2000 for a separation distance of 350 mm.
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