EXPRESS: Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development.

The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review.

Characterization and Optimization of a Spectral Window for Direct Gaseous Uranium Hexafluoride Enrichment Assay Using Laser-Induced Breakdown Spectroscopy.

Through a systematic scanning of 235U and 238U emission lines between 280 nm and 745 nm, the optimal emission line for direct gaseous uranium hexafluoride (UF6) enrichment assay using laser-induced breakdown spectroscopy (LIBS) was found. Screening for spectral features that are potentially useful for U isotopic analysis was gauged from the magnitude of the 235U-238U isotopic shift and the signal-to-background ratio of the emission line through a parameter termed ΔSBR 235U-238U. The ΔSBR spectrum shows peaks at wavelength positions where there are strong lines with significant 235U-238U shifts. The screening identified 13 spectral-window candidates, which were down selected based on their overall accuracy in predicting the 235U enrichment of three UF6 samples of natural (0.720 atom% 235U) and low-enriched (4.675 atom% and 9.157 atom% 235U) grades. The U(I) 646.498 nm emission line, with a determined 235U-238U isotopic shift of -17.7 pm, was found to be the optimal spectral window for direct UF6 enrichment assay. The root mean square error for enrichment assays on the three natural and low-enriched UF6 samples, with each sample measured in six replicates, was 0.31% in absolute 235U content. Each measurement comprised LIBS signals accumulated from 3000 laser shots. The analytical bias and precision were better than 0.5% and 0.3%, respectively, in absolute [235U/(235U + 238U)] ratios. Specific for the two low-enriched UF6 samples, the relative standard deviations from six replicated measurements were around 2%.

Calcium fluoride as a dominating matrix for quantitative analysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS): A feasibility study.

Calcium fluoride formed by the reaction between ammonium bifluoride and calcium chloride was investigated as a dominating matrix for quantitative analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Transformation from a solid sample to the calcium fluoride-based matrix permitted quantitative analysis based on calibration standards made from elemental standards. A low abundance stable calcium isotope, i.e. 44Ca+, was monitored as the internal standard for quantitative analysis by LA-ICP-MS. Correlation coefficient factors for multiple elements were obtained with values over 0.999. The results for multiple elements in a certified reference material of soil (NIST SRM 2710a) agreed with the certified values in the range of expanded uncertainty, indicating the present method was valid for quantitation of elements in solid samples.

Coal Discrimination Analysis Using Tandem Laser-Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

The contribution and impact of combined laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) and laser-induced breakdown spectroscopy (LIBS) were evaluated for the discrimination analysis of different coal samples. This tandem approach allows simultaneous determination of major and minor elements (C, H, Si, Ca, Al, Mg, etc.) and trace elements (V, Ba, Pb, U, etc.) in the coal. The research focused on coal-classification strategies based on principle component analysis (PCA) combined with K-means clustering, partial least-squares discrimination analysis (PLS-DA), and support vector machine (SVM) for analytical performance. Correlation analyses performed from TOF mass and LIBS emission spectra from the coal samples showed that most major, minor, and trace element emissions had negative correlation with the volatile content. Suitable variables for the classification models were determined from these data. The individual TOF data, LIBS data, and combined data of TOF and LIBS as the inputs for different models were analyzed and compared. In all cases, the results obtained with the combined TOF and LIBS data were found to be superior to those obtained with the individual TOF or LIBS data. The nonlinear SVM model combined with TOF and LIBS data provided the best coal-classification performance, with a classification accuracy of up to 98%.

Elemental Mapping of Lithium Diffusion in Doped Plant Leaves Using Laser-Induced Breakdown Spectroscopy (LIBS).

Mapping of element distributions and diffusion processes in plant tissue has great significance for understanding the systematic uptake, transport, and accumulation of nutrients and harmful elements in plants, and for studying the interaction between plants and the environment. In this work, we used laser-induced breakdown spectroscopy (LIBS) to study the elemental accumulation of Li and its diffusion in plant leaves. The spatially resolved information that LIBS offers, combined with its high sensitivity to light elements make this technology highly advantageous for the analysis of Li. Laser-induced breakdown spectroscopy mapping of Li-doped leaf samples is used to directly visualize the diffusion of Li in the plant leaf and study its distribution as a function of LiCl solution exposure time. Our findings demonstrate that diffusion of Li in plant leaves occurs though their veins (i.e., bundles of vascular tissue) and that Li concentration decreases as we move away from the LiCl exposure site. These results underline the importance of veins in transportation of toxic elements in plants, and mapping of their distribution can be instrumental in the development of possible remediation approaches for managing Li toxicity.

Characteristics of plasma plume in ultrafast laser ablation with a weakly ionized air channel.

We report the influence of femtosecond (fs) laser weakly ionized air channel on characteristics of plasma induced from fs-laser ablation of solid Zr metal target. A novel method to create high temperature, low electron density plasma with intense elemental emission and weak bremsstrahlung emission was demonstrated. Weakly ionized air channel was generated as a result of a non-linear phenomenon. Two-dimensional time-resolved optical-emission images of plasma plumes were taken for plume dynamics analysis. Dynamic physical properties of filament channels were simulated. In particular, we investigated the influence of weakly ionized air channel on the evolution of solid plasma plume. Plasma plume splitting was observed whilst longer weakly ionized air channel formed above the ablation spot. The domination mechanism for splitting is attributed to the long-lived underdense channel created by fs-laser induced weakly ionization of air. The evolutions of atomic/molecular emission intensity, peak broadening, and plasma temperature were analyzed, and the results show that the part of plasma entering weakly ionized air channel features higher initial temperature, lower electron density and faster decay.

Solid matrix transformation and tracer addition using molten ammonium bifluoride salt as a sample preparation method for laser ablation inductively coupled plasma mass spectrometry.

Solid sampling and analysis methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are challenged by matrix effects and calibration difficulties. Matrix-matched standards for external calibration are seldom available and it is difficult to distribute spikes evenly into a solid matrix as internal standards. While isotopic ratios of the same element can be measured to high precision, matrix-dependent effects in the sampling and analysis process frustrate accurate quantification and elemental ratio determinations. Here we introduce a potentially general solid matrix transformation approach entailing chemical reactions in molten ammonium bifluoride (ABF) salt that enables the introduction of spikes as tracers or internal standards. Proof of principle experiments show that the decomposition of uranium ore in sealed PFA fluoropolymer vials at 230 °C yields, after cooling, new solids suitable for direct solid sampling by LA. When spikes are included in the molten salt reaction, subsequent LA-ICP-MS sampling at several spots indicate that the spikes are evenly distributed, and that U-235 tracer dramatically improves reproducibility in U-238 analysis. Precisions improved from 17% relative standard deviation for U-238 signals to 0.1% for the ratio of sample U-238 to spiked U-235, a factor of over two orders of magnitude. These results introduce the concept of solid matrix transformation (SMT) using ABF, and provide proof of principle for a new method of incorporating internal standards into a solid for LA-ICP-MS. This new approach, SMT-LA-ICP-MS, provides opportunities to improve calibration and quantification in solids based analysis. Looking forward, tracer addition to transformed solids opens up LA-based methods to analytical methodologies such as standard addition, isotope dilution, preparation of matrix-matched solid standards, external calibration, and monitoring instrument drift against external calibration standards.

Laser Ablation Molecular Isotopic Spectrometry for Molecules Formation Chemistry in Femtosecond-Laser Ablated Plasmas.

Recently, laser ablated molecular isotopic spectrometry (LAMIS) has expanded its capability to explore molecules formation mechanism in laser-induced plasma in addition to isotope analysis. LAMIS is a powerful tool for tracking the origination of atoms that is involved in formation of investigated molecules by labeling atoms with their isotopic substitution. The evolutionary formation pathways of organic molecules, especially of C2 dimers and CN radicals, were frequently reported. However, very little is known about the formation pathways for metallic radicals and heterodimers in laser ablated plasma. This research focuses on elucidating the formation pathways of AlO radicals in femtosecond laser ablated plasma from 18O-labeled Al2O3 pellet. Plasmas expanding with strong forward bias in the direction normal to the sample surface were generated in the wake of a weakly ionized channel created by a femtosecond laser. The formation mechanism of AlO and influence of air were investigated with multiple plasma diagnostic methods such as monochromatic fast gating imaging, spatiotemporal resolved optical emission spectroscopy, and LAMIS. An advanced LAMIS fitting procedure was used to deduce the spatiotemporal distributions of Al18O and Al16O number densities and also their ratios. We found that the Al16O/Al18O number density ratio is higher for plasma portion closer to the sample surface, which suggests that chemical reactions between the plasma plume and ambient air are more intense at the tail of the plasma. The results also reveals that direct association of free Al and O atoms is the main mechanism for the formation of AlO at the early stage of the plasma. To the contrast, chemical reactions between plasma materials and ambient oxygen molecules and the isotope exchange effect are the dominant mechanisms of the formation of AlO and evolution of Al16O/Al18O number density ratio at the late stage of the plasma.

Analysis of Plant Leaves Using Laser Ablation Inductively Coupled Plasma Optical Emission Spectrometry: Use of Carbon to Compensate for Matrix Effects.

Direct solid sampling by laser ablation into an inductively coupled plasma synchronous vertical dual view optical emission spectroscope (LA-SVDV-ICP-OES) was used for the elemental analysis of nutrient elements Ca, B, Mn, Mg, K, and Zn and essential (non-metallic) elements P and S in plant materials. The samples were mixed with paraffin as a binder, an approach that provides better cohesion of the particles in the pellets in addition to supplying carbon to serve as an internal standard (atomic line C I 193.027 nm) as a way to compensate for matrix effects, and/or variations in the ablation process. Precision was in the range of 1-8% relative standard deviation (RSD) with limit of detection in the range of 0.4-1 mg/kg-1 and 25-640 mg/kg-1 for metallic and non-metallic elements, respectively.

Laser-Ablation Sampling for Accurate Analysis of Sulfur in Edible Salts.

We evaluated the performance of laser ablation analysis techniques such as laser-induced breakdown spectroscopy (LIBS), laser ablation inductively coupled optical emission spectrometry (LA-ICP-OES), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), in comparison with that of ICP-OES using aqueous solutions for the quantification of sulfur (S) in edible salts from different geographical origins. We found that the laser ablation based sampling techniques were not influenced by loss of S, which was observed in ICP-OES with aqueous solutions for a certain salt upon their dissolution in aqueous solutions, originating from the formation of volatile species and precipitates upon their dilution in water. Although detection of S using direct laser sampling with LA-ICP-MS has well-known isobaric and polyatomic interferences, LIBS and LA-ICP-OES showed good accuracy in the detection of S for all salts. LIBS also provided the ability to identify the dominant chemical form in which S is present in salts. Correlation between S and oxygen, observed in LIBS spectra, provided chemical information about the presence of S2- or [Formula: see text], which are associated with the origin and quality of edible salts.

A study on the in vitro percutaneous absorption of silver nanoparticles in combination with aluminum chloride, methyl paraben or di-n-butyl phthalate.

Some reports indicate that the silver released from dermally applied products containing silver nanoparticles (AgNP) (e.g. wound dressings or cosmetics) can penetrate the skin, particularly if damaged. AgNP were also shown to have cytotoxic and genotoxic activity. In the present study percutaneous absorption of AgNP of two different nominal sizes (Ag15nm or Ag45nm by STEM) and surface modification, i.e. citrate or PEG stabilized nanoparticles, in combination with cosmetic ingredients, i.e. aluminum chloride (AlCl3), methyl paraben (MPB), or di-n-butyl phthalate (DBPH) was assessed using in vitro model based on dermatomed pig skin. The inductively coupled plasma mass spectrometry (ICP-MS) measurements after 24h in receptor fluid indicated low, but detectable silver absorption and no statistically significant differences in the penetration between the 4 types of AgNP studied at 47, 470 or 750µg/ml. Similarly, no significant differences were observed for silver penetration when the AgNP were used in combinations with AlCl3 (500µM), MPB (1250µM) or DBPH (35µM). The measured highest amount of Ag that penetrated was 0.45ng/cm2 (0.365-0.974ng/cm2) for PEG stabilized Ag15nm+MPB.

Femtosecond laser ablation molecular isotopic spectrometry for zirconium isotope analysis.

Laser ablation molecular isotopic spectrometry (LAMIS) for rapid isotopic analysis of zirconium at atmospheric pressure was studied with a femtosecond-laser system operated under high repetition rate (1 kHz) and low pulse energy (160 µJ). The temporal evolution of zirconium neutral-atomic and ionic lines, as well as zirconium oxide molecular bands, were studied. Six molecular bands, belonging to the d(3)Δ-a(3)Δ (i.e., the α system) and E(1)Σ(+)-X(1)Σ(+) transitions, were observed with appreciable isotopic shifts. The assignments of the isotopic bandheads were first based on theoretical predictions of the band origins and the associated isotopic shifts of various dipole-allowed ZrO electronic transitions, followed by an experimental confirmation with a (94)Zr-enriched ZrO2 sample. In this work, the α(0,1) band from the d(3)Δ3-a(3)Δ3 subsystem was utilized for Zr isotope analysis based on a compromise between the magnitude of isotopic shifts in emission wavelengths, emission strengths, signal-to-background ratios, and spectral interferences. The analysis was performed in a standardless calibration approach; the isotopic information was extracted from the experimentally measured molecular spectra through theoretical spectral fitting. The results demonstrate the feasibility to obtain isotopic information for a spectrally complicated element like zirconium, without the need to use isotopically labeled calibration standards. The availability of comprehensive molecular constants will further improve the analytical accuracy of this standardless calibration approach.

Liquid sampling-atmospheric pressure glow discharge as a secondary excitation source for laser ablation-generated aerosols: parametric dependence and robustness to particle loading.

Liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma is being developed as a secondary vaporization-excitation source for the optical emission analysis of laser ablation (LA)-generated particle populations. The practicalities of this coupling are evaluated by determining the influence of source parameters on the emission response and the plasma's robustness upon LA introduction of easily ionized elements (EIEs). The influence of discharge current (45-70 mA), LA carrier gas flow rate (0.1-0.8 L min(-1)), and electrode separation distance (0.5-3.5 mm) was studied by measuring Cu emission lines after ablation of a brass sample. Best emission responses were observed for high-discharge currents, low He carrier gas flow rates, and relatively small (<1.5 mm) electrode gaps. Plasma robustness and spectroscopic matrix effects were studied by monitoring Mg(II) : Mg(I) intensity ratios and N2-derived plasma rotational temperatures after the ablation of Sr- and Ca-containing pellets. Plasma robustness investigations showed that the plasma is not appreciably affected by the particle loadings, with the microplasma being slightly more ionizing in the case of Ca introduction. In neither case did the concentration of the concomitant element change the robustness values, implying a high level of robustness. Introduction of the LA particles results in slight increases in the rotational temperatures (∼10% relative), with Ca-containing particles having a greater effect than Sr-containing particles. The observed variation of 9% in the plasma rotational temperature is in the same order of magnitude as the short-term reproducibility determined by the proposed LA-LS-APGD system. The determined rotational temperatures ranged from 1047 to 1212 K upon introducing various amounts of Ca and Sr. The relative immunity to LA particle-induced matrix effects is attributed to the relatively long residence times and high power densities (>10 W mm(-3)) of the LS-APGD microplasma.

Line selection and parameter optimization for trace analysis of uranium in glass matrices by laser-induced breakdown spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) has been evaluated for the determination of uranium in real-world samples such as uraninite. NIST Standard Reference Materials were used to evaluate the spectral interferences on detection of uranium. The study addresses the detection limit of LIBS for several uranium lines and their relationship to non-uranium lines, with emphasis on spectral interferences. The data are discussed in the context of optimizing the choice of emission lines for both qualitative and quantitative analyses from a complex spectrum of uranium in the presence of other elements. Temporally resolved spectral emission intensities, line width, and line shifts were characterized to demonstrate the parameter influence on these measurements. The measured uranium line width demonstrates that LIBS acquired with moderately high spectral resolution (e.g., by a 1.25 m spectrometer with a 2400 grooves/mm grating) can be utilized for isotope shift measurements in air at atmospheric pressure with single to tens of parts per million (ppm) level detection limits, as long as an appropriate transition is chosen for analysis.

Laser ablation in analytical chemistry.

In 2002, we wrote an Analytical Chemistry feature article describing the Physics of Laser Ablation in Microchemical Analysis. In line with the theme of the 2002 article, this manuscript discusses current issues in fundamental research, applications based on detecting photons at the ablation site (LIBS and LAMIS) and by collecting particles for excitation in a secondary source (ICP), and directions for the technology.

Carbon isotope separation and molecular formation in laser-induced plasmas by laser ablation molecular isotopic spectrometry.

Laser ablation molecular isotopic spectrometry (LAMIS) recently was reported for rapid isotopic analysis by measuring molecular emission from laser-induced plasmas at atmospheric pressure. This research utilized the LAMIS approach to study C2 molecular formation from laser ablation of carbon isotopic samples in a neon gas environment at 0.1 MPa. The isotopic shift for the Swan system of the C2 Δν = 1 band was chosen for carbon isotope analysis. Temporal and spatial resolved measurements of (12)C2, (12)C(13)C, and (13)C2 show that C2 forms from recombination reactions in the plasma. A theoretical simulation was used to determine the temperature from the molecular bands and to extract the isotopic ratio of (12)C/(13)C derived from (12)C2, (12)C(13)C, and (13)C2. Our data show that the ratio of (12)C/(13)C varies with time after the laser pulse and with distance above the sample. (12)C/(13)C deviates from the nominal ratio (2:1) at early times and closest to the sample surface. These measurements provide understanding of the chemical processes in the laser plasma and analytical improvement using LAMIS.

Analysis and classification of heterogeneous kidney stones using laser-induced breakdown spectroscopy (LIBS).

Kidney stones were analyzed using laser-induced breakdown spectroscopy (LIBS), utilizing a high resolution multi-channel charge-coupled device (CCD) spectrometer and a nanosecond-pulse Nd : YAG laser. The kidney stones were also characterized using X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques for comparative analysis. It was found that the ratio of hydrogen (H) to carbon (C) was an important indicator of organic compounds such as uric acid. Advantages of LIBS, especially with regards to amount of sample required and sample preparation as well as the ability to carry out elemental analysis and classification of kidney stones simultaneously, over other analytical techniques such as XRD and XRF are discussed. The common minor elements detected in the kidney stones include P, S, Si, Ti, and Zn. Principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) of broadband LIBS spectra were employed for classifying different types of kidney stones. The results are beneficial in understanding kidney stone formation processes, which can lead to preventive therapeutic strategies and treatment methods for urological patients.

Laser-nanostructure interactions for ion production.

Interactions between pulsed laser radiation and nanostructured materials, with dimensions ranging from 1 nm to 500 nm, can result in enhanced desorption and ionization of organic and biomolecular adsorbates. When the critical dimensions of the nanostructures fall below the characteristic lengths for the involved transport processes, novel regimes of ion production are observed. Systems with dimensions commensurate with the wavelength of the laser radiation are the basis of photonic ion sources with unique properties, including polarization dependent ion yields and fragmentation. The main characteristics of these systems are often governed by altered modes of transport, e.g., ballistic vs. diffusive, energy confinement, plasmon resonances, and local field enhancements. Some structures offer control over the internal energy and the active fragmentation channels for the produced ions. Emerging applications of photonic ion sources in mass spectrometry benefit from ultrahigh sensitivity, a wide dynamic range for detection and quantitation, and a broad coverage of adsorbates ranging from small organic molecules to biopolymers, as well as to highly complex samples like single cells.

Analysis of the absorption layer of CIGS solar cell by laser-induced breakdown spectroscopy.

Laser induced breakdown spectroscopy (LIBS) was applied for the elemental analysis of the thin copper indium gallium diselenide (CuIn(1-x)Ga(x)Se(2) [CIGS]) absorption layer deposited on Mo-coated soda-lime glass by the co-evaporation technique. The optimal laser and detection parameters for LIBS measurement of the CIGS absorption layer (1.23 µm) were investigated. The calibration results of Ga/In ratio with respect to the concentration ratios measured by x-ray fluorescence and inductively coupled plasma optical emission spectroscopy showed good linearity.

Optical far- and near-field femtosecond laser ablation of Si for nanoscale chemical analysis.

Extending spatial resolution in laser-based chemical analysis to the nanoscale becomes increasingly important as nanoscience and nanotechnology develop. Implementation of femtosecond laser pulses arises as a basic strategy for increasing resolution since it is associated with spatially localized material damage. In this work we study femtosecond laser far- and near-field processing of silicon (Si) at two distinct wavelengths (400 and 800 nm), for nanoscale chemical analysis. By tightly focusing femtosecond laser beams in the far-field, we were able to produce sub-micrometer craters. In order to further reduce the crater size, similar experiments were performed in the near-field through sub-wavelength apertures, resulting in the formation of sub-30-nm craters. Laser-induced breakdown spectroscopy (LIBS) was used for chemical analysis with a goal to identify the minimum crater size from which spectral emission could be measured. Emission from sub-micrometer craters (full width at half maximum) was possible, which are among the smallest ever reported for femtosecond LIBS.