Double-pulse laser ablation inductively coupled plasma mass spectrometry

This paper describes the use of double-pulse laser ablation to improve ICP-MS internal (temporal relative standard deviation, %TRSD) and external (%RSD) precision. The first laser pulse is used to ablate a large quantity of mass from the sample surface. The second pulse is applied with a variable time delay after the first pulse to break the ablated mass into a finer aerosol, which is more readily transported to and digested in the ICP-MS. A factor of two improvement in %TRSD and factor of five in %RSD are demonstrated.     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

Low pressure laser ablation coupled to inductively coupled plasma mass spectrometry

The particle size distribution in laser ablation inductively coupled plasma mass spectrometry is known to be a critical parameter for complete vaporization of particles. Any strategy to reduce the particle size distribution of laser generated aerosols has the potential to increase the ion signal intensity and to reduce fractionation effects. Due to the fact that vapor generation, nucleation, condensation, and agglomeration take place within an extremely short period of time, ablation under atmospheric pressure might not allow influencing these processes while under reduced pressure condition the cooling of the aerosol and therefore the condensation is expected to be slower. In this study, a low pressure laser ablation cell for the generation of laser aerosols was coupled to an ICP-MS. In contrast to the previously developed trapped ablation mode, the newly designed cell allows the adjustment of the pressure in the ablation cell between 20 and 1400 mbar prior to the ablation.Ablation experiments carried out using this configuration showed a dependence of the aerosol properties (size distribution and particle structure) on the ablation cell pressure. The intensity ratio U/Th measured as a figure of merit for complete vaporization within the ICP indicated a change in the aerosol structure at approximately 500 mbar toward smaller particle size. A significant difference between low pressure and at ambient pressure ablated aerosol was observed. The intensity ratios (U/Th) of the ablated sample moves closer to the bulk composition at lower pressures at the expense of sensitivity. Therefore the decrease in the ICP-MS signal intensity in the low pressure cell can be attributed to vapor deposition within the ablation cell walls.Moreover, scanning electron microscope images of aerosols collected on filters after the low pressure ablation cell suggest the possibility of a slower cooling velocity of the aerosol, which was observed in the condensed material on the surface of ejected spherical particles. The expansion of the laser aerosol was also investigated using polished brass substrates in the expansion path-way for particle collection.     

Elemental fractionation in laser ablation inductively coupled plasma mass spectrometry

The major challenge to the use of laser ablation sample introduction, combined with inductively coupled plasma mass spectrometry, is the problem of calibration. In the geological analysis of minerals, calibration is complicated by the extraordinarily wide variety of sample matrices which may be encountered. While there is a lack of mineral standards with well characterized concentrations near 1 g/g, the NIST glass reference materials (SRM 610–617) have been demonstrated to be very useful for the analysis of a wide variety of lithophile elements in silicate samples. An internal reference element, for which the concentration is known in the sample, has been widely used to make corrections for the multiplicative effects of volume (or weight) of the sample ablated, instrument drift, and matrix effects. This procedure works extremely well where elements being determined and the internal reference element being used share similar ablation behaviours; i.e., they do not fractionate progressively during the ablation and transport process. In this study, it is demonstrated that, in terms of ablation behaviour, elements fall into several distinct clusters and that the elements within these clusters correlate well with each other during a period of ablation. Thus, elements within a cluster can be determined using an internal reference element from within the same cluster. While a combination of periodic varying properties typifies the clusters, the geochemical classification of elements into lithophile (silicate loving), and chalcophile (sulphide loving) appears to offer the best characterization of the major groups.     

Analyte response in laser ablation inductively coupled plasma mass spectrometry

The dependence of analyte sensitivity and vaporization efficiency on the operating parameters of an inductively coupled plasma mass spectrometer (ICPMS) was investigated for a wide range of elements in aerosols, produced by laser ablation of silicate glass. The ion signals were recorded for different carrier gas flow rates at different plasma power for two different laser ablation systems and carrier gases. Differences in atomization efficiency and analyte sensitivity are significant for the two gases and the particle size distribution of the aerosol. Vaporization of the aerosol is enhanced when helium is used, which is attributed to a better energy-transfer from the plasma to the central channel of the ICP and a higher diffusion rate of the vaporized material. This minimizes elemental fractionation caused by sequential evaporation and reduces diffusion losses in the ICP. The sensitivity change with carrier gas flow variation is dependent on m/z of the analyte ion and the chemical properties of the element. Elements with high vaporization temperatures reach a maximum at lower gas flow rates than easily vaporized elements. The sensitivity change is furthermore dependent on m/z of the analyte ion, due to the mass dependence of the ion kinetic energies. The mass response curve of the ICPMS is thus not only a result of space charge effects in the ion optics but is also affected by radial diffusion of analyte ions and the mismatch between their kinetic energy after expansion in the vacuum interface and the ion optic settings.     

Elemental fractionation in laser ablation inductively coupled plasma mass spectrometry

The major challenge to the use of laser ablation sample introduction, combined with inductively coupled plasma mass spectrometry, is the problem of calibration. In the geological analysis of minerals, calibration is complicated by the extraordinarily wide variety of sample matrices which may be encountered. While there is a lack of mineral standards with well characterized concentrations near 1 microg/g, the NIST glass reference materials (SRM 610-617) have been demonstrated to be very useful for the analysis of a wide variety of lithophile elements in silicate samples. An internal reference element, for which the concentration is known in the sample, has been widely used to make corrections for the multiplicative effects of volume (or weight) of the sample ablated, instrument drift, and matrix effects. This procedure works extremely well where elements being determined and the internal reference element being used share similar ablation behaviours; i.e., they do not fractionate progressively during the ablation and transport process. In this study, it is demonstrated that, in terms of ablation behaviour, elements fall into several distinct clusters and that the elements within these clusters correlate well with each other during a period of ablation. Thus, elements within a cluster can be determined using an internal reference element from within the same cluster. While a combination of periodic varying properties typifies the clusters, the geochemical classification of elements into lithophile (silicate loving), and chalcophile (sulphide loving) appears to offer the best characterization of the major groups.     

Imaging mass spectrometry in biological tissues by laser ablation inductively coupled plasma mass spectrometry

Of all the inorganic mass spectrometric techniques, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) plays a key role as a powerful and sensitive microanalytical technique enabling multi- element trace analysis and isotope ratio measurements at trace and ultratrace level. LA-ICP-MS was used to produce images of detailed regionally-specific element distribution in 20 microm thin sections of different parts of the human brain. The quantitative determination of copper, zinc, lead and uranium distribution in thin slices of human brain samples was performed using matrix-matched laboratory standards via external calibration procedures. Imaging mass spectrometry provides new information on the spatially inhomogeneous element distribution in thin sections of human tissues, for example, of different brain regions (the insular region) or brain tumor tissues. The detection limits obtained for Cu, Zn, Pb and U were in the ng g(-1) range. Possible strategies of LA-ICP-MS in brain research and life sciences include the elemental imaging of thin slices of brain tissue or applications in proteome analysis by combination with matrix-assisted laser desorption/ionization MS to study phospho- and metal- containing proteins will be discussed.     

Design analysis of a laser ablation cell for inductively coupled plasma mass spectrometry by numerical simulation

A laser ablation setup including outer chamber, sample tube, sample holder and transport tubing was modelled and optimized using advanced computational fluid dynamics techniques. The different components of the setup were coupled and the whole device was modelled at once. The mass transport efficiency and transit times of near infrared femtosecond (fs) laser generated brass aerosols in pure argon and helium–argon mixtures were calculated at experimentally optimized conditions and a transient signal was constructed. The use of helium or argon did not influence the mass transport efficiency, but the signal structure changed. The signal fine structure was retrieved and experimentally validated. Bimodal peak structures were observed that seemed to originate from turbulent effects in the tubing connecting a Y-connector and the injector.     

Detection efficiencies in nano- and femtosecond laser ablation inductively coupled plasma mass spectrometry

Detection efficiencies of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), defined as the ratio of ions reaching the detector and atoms released by LA were measured. For this purpose, LA of silicate glasses, zircon, and pure silicon was performed using nanosecond (ns) as well as femtosecond (fs) LA. For instance, ns-LA of silicate glass using helium as in-cell carrier gas resulted in detection efficiencies between approximately 1E-7 for low and 3E-5 for high mass range elements which were, in addition, almost independent on the laser wavelength and pulse duration chosen. In contrast, the application of argon as carrier gas was found to suppress the detection efficiencies systematically by a factor of up to 5 mainly due to a less efficient aerosol-to-ion conversion and ion transmission inside the ICP-MS.     

New methodical and instrumental developments in laser ablation inductively coupled plasma mass spectrometry

Many tasks in bulk analysis, micro analysis and depth profile analysis can be solved advantageously by laser ablation inductively coupled plasma mass spectrometry (Laser ICP-MS) in particular, when both the chemical and elemental distributions in the sample are to be determined. However, the analyst has to take into account that the analytical precision and accuracy of the Laser ICP-MS is influenced decisively by signal standardization, the homogeneity of the samples as well as calibration standards and the mass-spectrometric measuring mode, which is usually sequential when performed with scanning mass spectrometers such as quadrupol- or sector-based instruments. Using the ablated mass as standard, an excellent level of the analytical precision and accuracy (relative standard deviation R.S.D.<0.5%) has been obtained for homogeneous sample materials such as alloys. For inhomogeneous samples, such as pressed pellets, a statistical test is described, which is based upon the auto-correlation function to characterize the sample inhomogeneity. The application of the test allows us to calculate the representative mass for the quantitative analysis at previously defined analytical precision. In the instrumental part of the paper a new type of an ICP—time-of-flight (TOF) mass spectrometer—is described, constructed and built up in our laboratory. For fast signal counting an application-specific integrated circuit (ASIC) was developed, which permits a time resolution of 1 ns. The analytical performance of the TOF when used in combination with an ICP is demonstrated in terms of resolution, ion extraction rate, detection limits and dynamic range. The determination of ³⁹K⁺ and ⁴⁰Ca⁺ at trace level can be realized in a cool plasma condition (high central gas flow) only with a small interference by ⁴⁰Ar⁺. Detection limits of 23 elements were measured with typical values in the lower nanograms per liter range. The ion extraction rates, measured for a sample mass of 1 ng in terms of counts per second divided by the relative isotope abundance, are one order of magnitude higher than those obtained with a quadrupol-based instrument.     

Laser-generated aerosols in laser ablation for inductively coupled plasma spectrometry

This paper is a summary of the current knowledge of laser-generated aerosols under atmospheric conditions. It is restricted to typical laser sampling conditions as they are used in LA-ICP spectrometry. Published experimental evidence and proposed models are reviewed and critical summarized. The collected works show that a certain agreement exists that independently of the sample two size fractions with different chemical composition are found. The mechanism generating the different particle fractions are currently not clear. Possible sources of particle generation are described and critically reviewed. Fundamentally three distinguishable modes (gas, liquid, solid) can be described that can appear: gas-to-particle conversion, hydrodynamic sputtering, mechanical spallation/exfoliation. More recently explosive boiling as a mechanism of liquid expulsion has been discussed as a further possible source under certain conditions. Particle conditioning during transport is discussed as a source for agglomeration. The correlation between size distribution and laser parameters is discussed.     

An auto-focus system for reproducible focusing in laser ablation inductively coupled plasma mass spectrometry

A method of controlling the focus position of the ablating laser was evaluated. This system consists of a displacement measuring unit based on the triangulation displacement measurement principle. A simple preliminary experimental setup with a light source (LED, light emitting diode) and a displacement-sensor (PSD, position sensing detector) with optics and a electronic circuit, resulted in a reproducibility of a given lateral position of ±5 μm. A fine-tuning of the components, as well as the use of a laser diode as a light source will certainly improve this value.     

Modelling the temporal intensity distribution of laser ablation inductively coupled plasma mass spectrometry in single shot mode

A transport model is proposed that describes the temporal intensity distribution observed in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in single-shot mode using quantitative signal equations. Calculations aim on the deduction of the dispersion function describing the time-dependent part of the signal equation.

The dispersion function depends on transport time in the centre of the transport tube, as related to carrier gas flow rate and tube volume and on the relation between carrier gas flow rate and ablation chamber volume. The equations describing the signal shape standardize signals from different systems and allow quantitative optimization of the ablation chamber, the transport tube and the detector.

Application of the model to ICP-MS shows that only a part of the area filled by the transported vaporization product and thus only a part of the transported vaporization product can be observed at the detector. The model is able to quantify both fractions.

As was calculated, the observed fraction of analyte is always higher than the observed fraction of the sample containing cross section and depends on the chosen transport parameters characterising the dispersion function. Thus, the determination of the signal integrals in the usual way can lead to systematic errors if the parameters influencing the dispersion function are variable.

Therefore, a different method of analysis based on signal equations is proposed and demonstrated. By this method of data treatment, all important system parameters influencing the dispersion function could be calculated and matched with theoretical ones. Furthermore, a complete integral of the transient signal including its statistical variation can be generated from a limited number of measurement points. For example, this can be applied to signals detected incompletely because of detector saturation and enables the use of high-abundance elements as internal standards.

Furthermore, the method can be used to monitor system performance, to identify the flow regime inside the ablation chamber, to take into account the sample volume for quantitative analysis and finally, to detect anomalous signal distributions that would lead to systematic errors. The prospects and limitations of the model are discussed for LA-ICP-MS in single shot mode.     

Analysis of liquid samples using dried-droplet laser ablation inductively coupled plasma mass spectrometry

In this study we developed a dried-droplet method for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method provides accurate and precise results when building calibration curves and determining elements of interest in real liquid samples. After placing just 1 μL of a liquid standard solution or a real sample onto the filter surface and then converting the solution into a very small, thin dry spot, the sample could be applied as an analytical subject for LA. To demonstrate the feasibility of this proposed method, we used LA-ICP-MS and conventional ICP-MS to determine the levels of 13 elements (Li, V, Mn, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb) in five water samples. The correlation coefficients obtained from the various calibration curves ranged from 0.9920 (²⁰⁵Tl) to 0.9998 (⁵¹V), sufficient to allow the determination of a wide range of elements in the samples. We also investigated the effects of Methylene Blue (MB) and the NaCl concentration on the elemental analyses. MB could be used as an indicator during the ablation process; its presence in the samples only negligibly influenced the intensities of the signals of most of the tested elements. Notably, high NaCl contents led to signal suppression for some of the elements. In comparison with the established sample introduction by nebulization, our developed technique abrogates the need for time-consuming sample preparation and reduces the possibility of sample contamination.     

Lead determination in whole blood by laser ablation coupled with inductively coupled plasma mass spectrometry

This work describes a simple procedure for blood lead level determination. The proposed method requires little sample pretreatment and subsequent direct analysis of a dried blood spot on a filter membrane using laser ablation coupled with inductively coupled plasma mass spectrometry (LA-ICP-MS). In general, LA-ICP-MS studies are somewhat limited by the lack of matrix-matched standards for calibration purposes. Here we describe aqueous standard calibration and matrix-matched calibration methods. This method was validated by analysis of the reference materials. With the matrix-matched calibration method, the recovery ranged from 97.8% to 112.8%, while the aqueous standard calibration method ranged 90.4% to 122.4%. The lower detection limit was estimated as 0.1 ng mL⁻¹. The determination precision, expressed as the relative standard deviation (RSD), was not worse than 10% for all results. A sample throughput of approximately 5 min per sample made it possible to rapidly screen a large number of samples.     

Depth profile studies of ZrTiN coatings by laser ablation inductively coupled plasma mass spectrometry

The feasibility of depth profiling was studied by using a 193-nm ArF* excimer laser ablation system (GeoLas, MicroLas, Goettingen, Germany) with a lens array-based beam homogenizer in combination with an ICP-QMS Agilent 7500. Two ablation cells (20 and 1.5 cm³) were compared at the laser repetition rate of 1 Hz, laser beam energy of 135 mJ and the carrier gas flow rate 1.5 L min^–1 He + 0.78 L min^–1 Ar. The ablation cell dimensions are important parameters for signal tailing; however, very small cell volumes (e.g. 1.5 cm³) may cause memory effects, which can be probably explained by dominant inertial losses of aerosol on cell walls with its delayed mobilization. The 20-cm³ ablation cell seems to be appropriate for depth profiling by continuous single-hole drilling. The study of the influence of the pit diameter magnitude on the waning and emerging signals under small crater depth/diameter aspect ratios, which range between 0.75 and 0.0375 for the 3-m-thick coatings and pit diameters 4–80 m, revealed that the steady-state signals of pure coating and pure substrate (out of interface) were obtained at crater diameters between 20 and 40 m. Depth resolution defined by means of slopes of tangents in the layer interface region depend on the pit diameter and has an optimum value between 20 and 40 m and gives 0.6 m for the 20-m pit. In-depth variation of concentration of coating constituent (Ti) was proved to be almost identical with two different laser/ICP systems.Viktor Kanický performed this work while on leave at ETH Zurich     

Nuclear forensic analysis with laser ablation inductively coupled plasma mass spectrometry in CMX-6

Journal of Radioanalytical and Nuclear Chemistry - The 6th Collaborative Materials Exercise, CMX-6, was organized by the Nuclear Forensic International Technical Working Group in 2018 and 2019. Two...     

Investigation on elemental and isotopic fractionation during 196 nm femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry

Despite the large number of successful applications of laser ablation, elemental and isotopic fractionation coupled to inductively coupled plasma mass spectrometry (ICP-MS) remain as the main limitations for many applications of this technique in the fields of analytical chemistry and Earth Sciences. A substantial effort has been made to control such fractionations, which are well-established features of nanosecond laser ablation systems. Technological advancements made over the past decade now allow the ablation of solids by femtosecond laser pulses in the deep ultraviolet (UV) region at wavelengths less than 200 nm. Here the use of femtosecond laser ablation and its effects on elemental and isotopic fractionation is investigated. The Pb/U system is used to illustrate elemental fractionation and stable Fe isotopes are used to illustrate isotopic fractionation. No elemental fractionation is observed beyond the precision of the multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements. Without a matrix match between standard and sample, elemental fractionation is absent even when using different laser ablation protocols for standardization and samples (spot versus raster). Furthermore, we found that laser ablation-induced isotope ratio drifts, commonly observed during nanosecond laser ablation, are undetectable during ultraviolet femtosecond laser ablation. So far the precision obtained for Fe isotope ratio determinations is 0.1‰ (2 standard deviation) for the ⁵⁶Fe/⁵⁴Fe ratio. This is close to that obtainable by solution multiple-collector inductively coupled plasma mass spectrometry. The accuracy of the results appears to be independent of the matrix used for standardization. The resulting smaller particle sizes reduce fractionation processes. Femtosecond laser ablation carries the potential to solve some of the difficulties encountered during the two prior decades since the introduction of laser ablation.     

Rapid multielemental analysis of Chinese reference soils by laser ablation inductively coupled plasma-source mass spectrometry

Summary Laser ablation inductively coupled plasma-source mass spectrometry has been used to determine thirty elements (Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, As, Rb, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Dy, Ho, Yb, Hf, Ta, W, Th, U) in seven Chinese reference soils. The Surrey prototype spectrometer was employed with sample ablation by a free-running ruby laser. Concentrations in the soils (GSS-2 to GSS-8) were calculated from elemental responses and sensitivities derived from another soil in the series, namely GSS-1. Comparisons with previous neutron activation analyses are made. Rapid semiquantitative analyses are proved feasible. About eighty percent of the LA-ICP-MS determined concentrations were within a factor of two of the concentrations measured by INAA, and many were considerably closer than this. Precisions were typically in the range 2–10% RSD, but some were considerably poorer for elements present at trace levels.