Signal Stability Improvement Research Articles

The signal quality improvement of laser-induced breakdown spectroscopy due to the microwave plasma torch modulation

BackgroundLaser-induced breakdown spectroscopy (LIBS) is a versatile analytical technique for element determination in solids, liquids, and gases. However, LIBS suffers from low detection sensitivity and high relative standard deviation (RSD), restricting its large-scale applications. the process of a physical sampling can, in some cases, compromise the mechanical strength of the component under examination. It should be considered that too large laser energy is bound to cause damage to samples which cannot be tolerated in the process of safe production in the nuclear industry. It is necessary to find a method to obtain high elemental signal intensity in low energy laser. ResultsHere, we present a novel approach by integrating microwave plasma torch (MPT) with LIBS, referred to as MPT-LIBS, which effectively addresses the limitations associated with traditional LIBS. The MPT-LIBS technique is evaluated using Cu samples with a low laser pulse energy of 0.55 mJ. A remarkable enhancement factor of over 70 for Cu I 521.82 nm line is demonstrated, while that of Cu I 324.75 nm and 327.40 nm lines exceeding two orders of magnitude. Furthermore, the RSDs of all Cu spectral lines are reduced, especially for Cu I 521.82 nm, which is decreased from 11.48 % to 1.36 %. This indicates a significant improvement in signal stability. Characterization of the tested samples using con-focal microscopy reveals that the ablation area of MPT-LIBS is only 1.36 times of that of LIBS. The limit of detection of Cu I 324.75 nm line is reduced from 52.8 ppk to 319 ppm. Significance and noveltyThis study not only offers valuable guidance for improving signal stability and the limit of detection in LIBS, but also demonstrates minimal sample damage due to its low ablation amount. Consequently, the proposed methodology has the potential to significantly advance LIBS technology, expanding its applicability in industrial applications.

Improvement of Signal Stability by a Cyclone-type Particle Separator for Ceramic Analysis using Laser Ablation ICP-MS

Improvement of Signal Stability by a Cyclone-type Particle Separator for Ceramic Analysis using Laser Ablation ICP-MS

High stability breakdown of noble gases with femtosecond laser pulses

In the past, laser-induced breakdown spectroscopy (LIBS) signals have been reported to have a stability independent of the pulse length in solids. In this Letter, we perform the first stability study of femtosecond LIBS in gases (to our best knowledge) and show a significant improvement in signal stability over those achieved with longer pulses. Our study shows that ultrashort-pulse LIBS has an intrinsically higher stability in gas compared to nanosecond-pulse LIBS because of a deterministic ionization process at work in the femtosecond pulse. Relative standard deviations below 1% are demonstrated and are likely only limited by our laser output fluctuations. This enhanced emission stability may open up possibilities for a range of applications, from monitoring rapid gas dynamics to high-quality broadband light sources.

Analytical performance of a venturi-assisted array of micromachined ultrasonic electrosprays coupled to ion trap mass spectrometry for the analysis of peptides and proteins.

The analytical characterization of a novel ion source for mass spectrometry named array of micromachined ultrasonic electrosprays (AMUSE) is presented here. This is a fundamentally different type of ion generation device, consisting of three major components: (1) a piezoelectric transducer that creates ultrasonic waves at one of the resonant frequencies of the sample-filled device, (2) an array of pyramidally shaped nozzles micromachined on a silicon wafer, and (3) a spacer which prevents contact between the array and transducer ensuring the transfer of acoustic energy to the sample. A high-pressure gradient generated at the apexes of the nozzle pyramids forces the periodic ejection of multiple droplet streams from the device. With this device, the processes of droplet formation and droplet charging are separated; hence, the limitations of conventional electrospray-type ion sources, including the need for high charging potentials and the addition of organic solvent to decrease surface tension, can be avoided. In this work, a Venturi device is coupled with AMUSE in order to increase desolvation, droplet focusing, and signal stability. Results show that ionization of model peptides and small tuning molecules is possible with dc charging potentials of 100 Vdc or less. Ionization in rf-only mode (without dc biasing) was also possible. It was observed that, when combined with AMUSE, the Venturi device provides a 10-fold gain in signal-to-noise ratio for 90% aqueous sample solutions. Further reduction in the diameter of the orifices of the micromachined arrays led to an additional signal gain of at least 3 orders of magnitude, a 2-10-fold gain in the signal-to-noise ratio and an improvement in signal stability from 47% to 8.5% RSD. The effectiveness of this device for the soft ionization of model proteins in aqueous media, such as cytochrome c, was also examined, yielding spectra with an average charge state of 8.8 when analyzed with a 100 Vdc charging potential. Ionization of model proteins was also possible in rf-only mode.

Application of LA–ICP–MS in polar ice core studies

The direct determination of element signatures in polar ice core samples from Greenland by laser ablation with subsequent inductively coupled plasma mass spectrometry analysis has been investigated. A cryogenic sample chamber enables the element determination in ice directly from the solid (frozen) state. A procedure was developed to analyse up to 38 elements (traces: Mg, Al, Fe, Zn, Cd, Pb and rare earth elements; minor constituents: Na) in ice samples from Greenland with a previously unachievable spatial resolution of 4 mm along the core axis. This resolution is helpful to detect seasonal variations of element concentration in thin annual layers of deep ice. We report operating conditions and analytical performance of the experimental set up, the improvement of signal stability by (17)OH internal standardisation and application of a desolvation unit. Calibration of the system was performed with frozen multielement standard solutions along a special preparation procedure. Detection limits for the tracers Na, Mg (sea salt), Al (mineral dust) and Zn (anthropogenic source) are 0.1-1 microg kg(-1). Best detection limits in the range of 0.001-0.01 microg kg(-1 )were reached for Co, Pb and all rare earth elements. To validate the method, frozen standard reference materials were measured. The recovery is about +/-10%. Greenland ice core samples from different ages were analysed with the new technique. The results obtained by laser ablation were compared with values from solution analysis, available published data and the particle content. Most elements have shown good correlation with the particle content in the Greenland samples; however, differences could be seen between the values obtained by laser ablation and solution bulk analysis after a tri-acid digestion. The influence of particles is discussed. The high spatially resolved 2D mapping of element concentrations shows strong inhomogeneities along the core axis most probably due to seasonal variations of element deposition.