Solid sample introduction by laser ablation for inductively coupled plasma source mass spectrometry
TL;DR: In this article, the results of a preliminary study of the mass spectrometry of solid samples using a ruby laser to ablate the sample into an inductively coupled plasma (ICP) source mass analyzer were described.
Abstract: The results are described of a preliminary study of the mass spectrometry of solid samples using a ruby laser to ablate the sample into an inductively coupled plasma (ICP) source mass spectrometer. Standard rock samples were used, pelletted with a binder into the form of a disc. Some 200 ablation pits could be accommodated on each sample. Laser pulse energies of 0.3–1 J were used in the fixed Q mode and the ablated material transferred from the ablation cell into the plasma torch by means of the plasma injector gas flow. The mass spectrometer was used in the fixed ion mode using mean ion current detection to evaluate the reproducibility of successive pulses on major constituents and in the scanning mode at the rate of 10 scans s–1 to produce spectra using mean current detection for major elements and pulse counting detection for traces. Problems were experienced with saturation of the detection system in both the mean current and pulse counting modes owing to the transient nature of the sample pulse from the laser, when attempting to quantify major elements, but except where a major peak was saturated, reasonably uniform sensitivity for most elements across the mass range from 7 to 238 m/z was obtained. Isotope ratio measurements were made on lead at 29 µg g–1 and detection limits for the elements examined appear to be 10 ng g–1 or less.
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TL;DR: In this article, the authors summarized the occurrence of rare earth elements in the Earth's crust, their mineralogy, different types of deposits both on land and oceans from the standpoint of the new data with more examples from the Indian subcontinent.
Abstract: Rare earth elements (REE) include the lanthanide series elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) plus Sc and Y. Currently these metals have become very critical to several modern technologies ranging from cell phones and televisions to LED light bulbs and wind turbines. This article summarizes the occurrence of these metals in the Earth's crust, their mineralogy, different types of deposits both on land and oceans from the standpoint of the new data with more examples from the Indian subcontinent. In addition to their utility to understand the formation of the major Earth reservoirs, multi-faceted updates on the applications of REE in agriculture and medicine including new emerging ones are presented. Environmental hazards including human health issues due to REE mining and large-scale dumping of e-waste containing significant concentrations of REE are summarized. New strategies for the future supply of REE including recent developments in the extraction of REE from coal fired ash and recycling from e-waste are presented. Recent developments in individual REE separation technologies in both metallurgical and recycling operations have been highlighted. An outline of the analytical methods for their precise and accurate determinations required in all these studies, such as, X-ray fluorescence spectrometry (XRF), laser induced breakdown spectroscopy (LIBS), instrumental neutron activation analysis (INAA), inductively coupled plasma optical emission spectrometry (ICP-OES), glow discharge mass spectrometry (GD-MS), inductively coupled plasma mass spectrometry (including ICP-MS, ICP-TOF-MS, HR-ICP-MS with laser ablation as well as solution nebulization) and other instrumental techniques, in different types of materials are presented.
709 citations
British Geological Survey1, University of Bergen2, University of Arizona3, Geological Survey of Canada4, University of Kansas5, University of Copenhagen6, Macquarie University7, Geoscience Australia8, Texas Tech University9, University College London10, College of Charleston11, Princeton University12
TL;DR: The LA-ICP-MS U-(Th-)Pb geochronology international community has defined new standards for the determination of U-(th)-Pb ages as discussed by the authors.
Abstract: The LA-ICP-MS U-(Th-)Pb geochronology international community has defined new standards for the determination of U-(Th-)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID-TIMS) after removing corrections for common lead and the effects of excess 230Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA-ICP-MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data-reporting standards are defined to help improve the peer-review process. With these improvements, LA-ICP-MS U-(Th-)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.
526 citations
Cites background from "Solid sample introduction by laser ..."
...Laserablation-ICP-MS technology has progressed rapidly in the thirty years since its inception (Gray 1985) and with improvements in mass spectrometer sensitivity, the technique is now capable of detecting attogram masses of analyte....
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TL;DR: This review describes recent research to understand and utilize laser ablation for direct solid sampling, with emphasis on sample introduction to an inductively coupled plasma (ICP).
523 citations
TL;DR: In this paper, an ArF excimer laser system with imaging optics for controlled UV ablation and simultaneous petrographic viewing was designed specifically for representative sampling and quantitative multi-element analysis of microscopic fluid, melt and mineral inclusions beneath the sample surface.
520 citations
TL;DR: The aim of this review is to provide an overview of the most recent achievements in trace metal imaging while at the same time also offering a historical perspective of this rapidly evolving research field.
Abstract: Approximately a third of the human proteome contains metal cations, either in form of cofactors with catalytic functions, or as structural support elements.1,2 To guarantee a proper maintenance of this metal ion pool, both at the cellular and whole organism levels, nature has evolved a highly sophisticated machinery comprised of a complex interplay between DNA, proteins, and biomolecules.3 Over the past decades, a steadily growing number of diseases have been identified, which are characterized by metal imbalance in cells and tissues. Among the most prominent examples rank Alzheimer’s disease and Parkinson’s disease, two neurodegenerative disorders that involve abnormal accumulation of transition metals in brain tissue.4 While some progress has been made at understanding the molecular basis of these disorders, many important questions remain unanswered. For example, little is known about the cellular structures that are involved in transiently storing metal ions prior to their incorporation into metalloproteins or the fate of metal ions upon protein degradation. An important first step towards unraveling the regulatory mechanisms involved in trace metal transport, storage, and distribution represents the identification and quantification of the metals, ideally in context of their native physiological environment in tissues, cells, or even at the level of individual organelles and subcellular compartments.
Since the inception of the first histochemical methods for the microscopic demonstration of transition metals in tissues more than 140 years ago,5 many highly sensitive microanalytical techniques and instruments have been developed for the in situ analysis of trace metals. The aim of this review is to provide an overview of the most recent achievements in trace metal imaging while at the same time also offering a historical perspective of this rapidly evolving research field. Although this survey has been structured according to the various analytical techniques, particular emphasis is given to the biological background for a better understanding of the context and importance of each discussed study.
An overview of the most important microanalytical techniques currently available for the in situ detection of trace metals in cells and tissues is compiled in Table 1. Depending on the task, each technique may offer specific advantages and, of course, also disadvantages. Currently, synchrotron- and focused ion-beam microprobes presumably offer the best combination of sensitivity and spatial resolution; however, the ionizing high-energy excitation beam is not compatible with studying live organisms. Conversely, techniques that have been specifically developed for physiological imaging in clinical medicine, notably magnetic resonance imaging and positron emission tomography, inherently offer only a low spatial resolution and are merely suitable for obtaining information at the organ or tissue level. Although fluorescence microscopy based methods provide very high sensitivity down to the single molecule level while being at the same time compatible with live cell and tissue studies, scattering and limited penetration depth renders these techniques unsuitable for imaging opaque specimens. There are also important differences regarding the type of quantitative information that can be gained by each of these analytical techniques. For example, the histochemical detection with chromogenic and fluorogenic dyes relies on a competitive exchange of the metal ion within its native environment, most likely coordinated to endogenous ligands. Depending on the exchange kinetics and thermodynamic affinity of the histochemical indicator, only a fraction of the total metal ion contents in a cell or tissue can be probed. Nevertheless, this kinetically labile pool is particularly of interest in context of understanding the uptake, distribution, and regulation of trace elements at the cellular level, and in this regard, these methods offer unique opportunities to dynamically image metal ion fluxes in live cells with high sensitivity and spatial resolution. At the same time, organelles and proteins of interest can be readily labeled with genetically encoded green fluorescent protein tags,12 thus providing direct insights into dynamic processes within a larger cellular and biochemical context. In contrast, similar correlative information is difficult to gain with the fully quantitative micro beam methods, which require xenobiotic elemental tags for identifying subcellular structures. Autoradiographic tracer experiments offer much improved resolution over PET; however, the technique is only applicable to fixed or frozen tissues and cells. Furthermore, tracer studies cannot provide direct information regarding the endogenous metal composition of cells or tissues, and are therefore primarily limited to metal uptake, distribution, and release studies. Finally, mass spectrometric analyses are surface-based methods that destroy the sample while measuring its elemental composition. Clearly, only the combination of several analytical techniques and specific biochemical studies may lead to a fully comprehensive analysis of a biological system.
Table 1
Spatially resolved microanalytical techniques for in situ imaging of trace metals in biology.6–11
2. Histochemical Techniques
Histology is the branch of biology dealing with the study of microscopic anatomy of cells and tissues of plants and animals. Histological studies are typically carried out on thin sections of tissue or with cultured cells. To visualize and identify particular structures, a broad spectrum of histological stains and indicators are available. Among the most widely used dyes are hematoxylin and eosin, which stain nuclei blue and the cytoplasm pink, respectively.13 The history of detecting biological trace metal by histological methods dates back more than 140 years. Although these techniques have been today mostly replaced by the much more sensitive modern analytical methods described in this review article, histochemical approaches for visualizing metals mark the very beginning in the exploration of the inorganic physiology of transition metals. Given this special place in history, we deemed it necessary to briefly review some of the early achievements in this field.
2.1. Chromogenic Detection with Chelators and Ligands
Ever since the inception of Perls Prussian blue method for staining of non-heme iron, numerous indicators have been developed for the in situ visualization of trace metals in biological tissues and cells.13 Due to their limited sensitivity; however, most of these techniques were only suitable for the diagnosis of pathological conditions, typically associated with excess metal accumulations, thus preventing their application for routine staining of normal tissue. Furthermore, because the dyes are engaged in a competitive exchange equilibrium with endogenous ligands, histological stains are not suitable for the analytical determination of the total metal contents in tissues and thus limited to the visualization of the histologically reactive fraction of loosely bound labile metal ions.
2.1.1. Histochemistry of Iron
The histochemical demonstration of labile iron reported by Perls in 1867 is among the earliest accounts describing the in situ visualization of a trace metal in biological tissues.5 The method was originally described by Grohe, who observed the formation of a blue coloration when he treated cadaver tissues with potassium ferrocyanide in acidic solution.14 Due to its low cost and simplicity, the technique is still used today for the histological visualization of non-heme iron. Some variations focused on optimizing the concentrations and proportions of the reagents,15–17 among which Lison’s protocol17 appears to be most popular today. An intensification of Perls’ staining can be obtained by exploiting the use of ferric ferrocyanide in catalyzing the oxidation of diaminobenzidine (DAB) to polymeric benzidine black by hydrogen peroxide.18
An alternative method employs the reaction of ferricyanide with Fe(II) resulting in Turnbull blue.19 Since almost all of the Fe in tissues is in the ferric form, the staining procedure requires the in situ conversion of Fe(III) to Fe(II) with ammonium sulfide.15 Due to often incomplete reduction, the method never gained much attention. More recently, an application of Turnbull blue, named the ‘perfusion Turnbull method’ has been developed, where in vivo perfusion of acidic ferricyanide is followed by DAB intensification.20 The direct in vivo perfusion avoids artifacts associated with tissue fixation, including the loss of loosely bound iron and oxidation of Fe(II) to Fe(III). Similarly, Perls method was modified by employing in vivo perfusion with acidic ferrocyanide. Both methods are capable of identifying organs and tissues containing histochemically reactive iron over a broad pH range, including the low endosomal pH.21,22
The history of iron histochemistry would be incomplete without mentioning Quincke’s method, which employed ammonium sulfide for the precipitation of tissue iron as its sulfide.23 A detailed account on the various techniques, including a comprehensive historical overview of non-heme iron chemistry, has been recently published.24
506 citations