The analysis of archaeological glass by inductively coupled plasma optical emission spectroscopy

Summary An analytical procedure is described for the analysis of archaeological glass by inductively coupled plasma optical emission spectroscopy (ICP-OES). Glass samples were analysed in solution after fusion with lithium metaborate at 1100°C. The analyses were performed in the sequential multielemental mode of operation, with the determination of 15 elements in four analytical runs; only elements with not too large concentration difference were analysed in a single run. The following elements were accounted for: Si, Na, Ca, Al, Fe, Mg, Mn, Ti, Sr, Ba, Cr, Ni, Cu, Co, Pb.     

Elemental analysis of hair using PIXE-tomography and INAA

3D quantitative elemental maps of a section of a strand of hair were produced using a combination of PIXE-Tomography and simultaneous On/Off Axis STIM-Tomography at the University of Surrey Ion Beam Centre. The distributions of S, K, Cl, Ca, Fe and Zn were determined using the PIXE-T reconstruction package DISRA. The results were compared with conventional bulk PIXE analysis of tomographic data as determined using Dan32. The overall concentrations determined by PIXE were compared with elemental concentrations held in the University of Surrey Hair Database. All the entries currently in the database were produced using INAA. The merits and possible contributions of tomographic PIXE analysis to analysis of hair are discussed. The conclusions drawn from the PIXE-Tomography analysis can be used to argue for more stringent procedures for hair analysis at the University of Surrey.     

Multisignal calibration in optical emission spectroscopy

Summary The possibility of using more than one line for calibration in optical emission spectroscopy has been investigated. By means of principal component regression, sensitivity can be increased and part of noise can be removed. Thus, lower limits of detection can be obtained. The extent of improvement of sensitivity is considered theoretically and investigated by simulation. In the ideal case the sensitivity of the principal component regression for more than one line is calculated from the square root of the sum of squares of the sensitivities of the single lines. Practical applications in arcoptical emission spectroscopy and ICP-OES show that the theoretically expected improvements can almost be reached. The reduction in noise depends on the nature and source of noise.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

High throughput method for multielemental analysis of horse hair by oaTOF-ICP-MS

An approach for high throughput reliable multielemental analysis of trace elements in a large number of horse hair samples was designed. Suitability of time-of-flight mass spectrometer (oaTOF-ICP-MS) for fast determination of unlimited numbers of isotopes in the low volume samples was demonstrated. Due to quasi-simultaneous capability of the oaTOF-ICP-MS the large number of highly valuated data with unaffected isotopic ratio in a very short time could be obtained. The choice of horse hair was obvious because of easy reachability and clear conception about horse nutritional habits and stabling. Such large data set with preserved isotopic ratios is ideal for statistical evaluation which could reveal some interesting interconnection between elemental composition of horse hair and the way of stabling, feeding, etc. Statistical treatment of the data is not a part of this study and will be presented later. We collected one hundred horse hair samples from horse stables through Czech Republic. Samples were washed by optimized washing process to eliminate exogenic contamination prior to digestion and following analysis. A determination of 36 elements (As, Au, B, Be, Cd, Ce, Co, Cr, Dy, Er, Eu, Ga, Gd, Ge, Ho, La, Li, Lu, Nd, Ni, Pb, Pd, Pr, Pt, Rb, Sb, Sc, Sm, Ta, Tb, Te, Tm, U, V, Y, Yb) in horse hair by oaTOF-ICP-MS was optimized. A throughput of 100 samples with unlimited numbers of isotopes per 6 h was achieved. Proposed very fast multielemental method preserves isotopic ratios, and therefore, is undoubtedly highly suitable for statistical studies. Detection limits of the proposed method ranged from 0.13 μg kg^?1 (Eu, Gd, Tm) to 27.9 μg kg^?1 (Au), except for Ni (48.5 μg kg^?1) that is probably affected by contamination raised from nickel cones.     

Elemental chemical analysis of submerged targets by double-pulse laser-induced breakdown spectroscopy

Double-pulse laser-induced plasma spectroscopy (DP-LIPS) is applied to submerged targets to investigate its feasibility for elemental analysis. The role of experimental parameters, such as inter-pulse delay and detection time, has been discussed in terms of the dynamics of the laser-induced bubble produced by the first pulse and its confinement effect on the plasma produced by the second laser pulse. The analytical performance of this technique applied to targets in a water environment are discussed. The elemental analysis of submerged copper alloys by DP-LIPS has been compared with conventional (single-pulse) LIBS in air. Theoretical investigation of the plasma dynamics in water bubbles and open air has been performed.     

Quantitative analysis by resonant laser ablation with optical emission detection: Resonant laser-induced breakdown spectroscopy

Resonant laser ablation (RLA) is a solid sampling technique that makes use of radiation trapping, and desorption induced by electronic transitions (DIET), to produce enhanced numbers of analyte atoms in the laser-induced plasma (LIP). This is achieved by tuning the laser ablation wavelength to a gas-phase resonant transition of the analyte. In this paper, RLA was coupled with detection of optical emission in the LIP to perform resonant laser-induced breakdown spectroscopic (RLIBS) experiments with a miniature, portable spectrometer. The experiments were designed to continue an examination of the proposed mechanism of RLA, and to perform an initial assessment of the applicability of RLIBS for quantitative analysis. The study indicated that for a multi-component sample, such as steel, the signal of the wavelength-targeted atom was enhanced the most compared to other constituents, and this supported the hypothesis that the DIET phenomenon is involved. Also, RLIBS experiments indicated that ablation yields of other components were enhanced by resonant ablation of the major component, which supported the contribution of radiation trapping to the RLA phenomenon. A linear, positive slope of the RLA induced atom yield as a function of concentration suggested that the RLA mechanism allows for quantitative analysis of solid samples. Calibration graphs were created for tungsten in spectrographic steels using RLIBS. A limit of detection of 4% was calculated for tungsten in steel.     

Rotational temperature of nitrogen glow discharge obtained by optical emission spectroscopy

Measurements of rotational temperature as low as several hundred Kelvin have been measured using optical emission spectroscopy (OES) in nitrogen direct current (DC) glow discharge. The strongest band of the first negative system of nitrogen was chosen to deduce the rotational temperature at four different positions in nitrogen DC glow discharge, the back of cathode; cathode sheath; positive column; and anode glow. In positive column the rotational temperature increased apparently with the increasing discharge voltage from 500 to 1000 V when the pressure was 10 Pa. But with pressure of 20 Pa the rotational temperature in positive column increased slightly with the increase of discharge voltage. On the contrary, the rotational temperature in cathode sheath took reverse tendencies when the discharge voltage varies from 500 to 1000 V. As regard the anode glow, the rotational temperature at 10 Pa decreased with the increase of discharge voltage, but that at pressure of 20 Pa increased. We attribute the different tendencies of the rotational temperature to the different discharge statues at different pressures. When the discharge voltage varies from 500 to 1100 V, the discharge with pressure of 10 Pa is normal glow and that with 20 Pa is abnormal glow.     

Elemental analysis of steel scrap metals and minerals by laser-induced breakdown spectroscopy

The atomic emission of laser-induced plasma on steel samples has been studied for quantitative elemental analysis. The plasma has been created with 8 ns wide pulses using the second-harmonic from a Q-switched Nd:YAG laser, in air at atmospheric pressure. The plasma emission is detected with temporal resolution, using an Echelle spectrometer of wide spectral range (300–900 nm) combined with an intensified charge coupled device camera. A plasma temperature of 7800 ± 400 K is determined using the Boltzmann plot method, from spectra obtained under optimized experimental conditions.As an example of an industrial application the concentration of copper in scrap metals is studied, which is an important factor to determine the quality of the samples to recycle. Cu concentrations down to 200 ppm can be detected. Another application of the laser-induced plasma spectroscopy method is the measurement of the nickel and copper concentrations in an iron-containing sample of reduced magma from the 1870s expedition to western Greenland by Adolf Erik Nordenskiöld. Different spectral lines of nickel are used for calibration, and their results are compared.     

Elemental composition analysis of silicon carbonitride thin films by energy dispersive spectroscopy

Specific features of elemental composition analysis of silicon carbonitride thin films by energy dispersive spectroscopy (EDS) are considered. The films were preliminarily examined by IR spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron (SEM) and atomic force microscopy (AFM), and X-ray diffraction analysis using synchrotron radiation (SR-XRD) to acquire data on their chemical and phase composition, crystalline structure and surface morphology. The effect of film thickness, substrate material and electron beam energy on the results of energy dispersive analysis was investigated.     

Trace element analysis of waters by X-ray emission spectroscopy

X-ray emission spectroscopy is a rapid, simple and accurate method for multielement trace analysis of water. This is accomplished by trace elements precipitation with a nonspecific chelating agent APDC (ammonium-1-pyrollidine dithiocarbamate) and filtration through a Millipore filter. In that way the uniform targets suitable for X-ray analysis were made and elements in concentrations as low as few ppb could be determined. APDC chelation over broad pH ranges for different elements in seawater is discussed. The best pH range for simultaneous determination of these elements is found. Results of analysis of seawater samples taken near the island Krk in the Adriatic sea are presented.     

Multielement analysis of environmental samples by total-reflection X-ray fluorescence spectrometry, neutron activation analysis and inductively coupled plasma optical emission spectroscopy

Summary In environmental research and protection trace elements have to be determined over a wide range of atomic number, down to very low concentrations, and in quite different matrices. This challenge requires the availability of complementary analytical methods characterized by a high detection power and few sources of systematic errors. Besides, the capacity of multielement detection is often desired since it facilitates the tackling of many problems in which numerous trace elements are of direct concern. Total reflection X-ray fluorescence, neutron activation analysis and inductively coupled plasma optical emission spectroscopy, in principle, fulfill these requirements quite well. However, each method has its domain, and the application to certain sample species may be less promising. Under this aspect, the paper summarizes some recent developments and investigations, including intercomparisons as far as possible. Various matrices are considered: rainwater and airborne particulates, soil samples, river sediments and suspended particulate matter, river water filtrates, ovean water, and organic matrices. Capabilities and limitations are discussed. Sample preparation techniques are described if they are new or essential for achieving the results given.

---

Multielementanalyse von Umweltproben mit Totalreflexions-Röntgenfluorescenzspektrometrie, Neutronenaktivierungsanalyse und ICP-Emissionsspektroskopie

Zusammenfassung Umweltforschung und Umweltschutz erfordern die Bestimmung von Spurenelementen über einen weiten Bereich der Ordnungszahl, z. T. bis in den extremen Spurenbereich und in ganz unterschiedlichen Matrices. Die Erfüllung dieser Aufgabe setzt die Verfügbarkeit einander ergänzender analytischer Verfahren voraus, die durch eine hohe Nachweisstärke und geringe systematische Fehler gekennzeichnet sein müssen. Hinzu kommt, daß vielfach Multielement-Eigenschaften wünschenswert sind, da bei manchen Fragestellungen zahlreiche Elemente von Interesse sind. Die Totalreflexions-Röntgenfluorescenzanalyse, die Neutronenaktivierungsanalyse und die optische Emissionsspektroskopie mit induktiv angeregter Plasmafackel erfüllen grundsätzlich diese Forderungen in hohem Maße. Jedoch besitzt jede Methode ihre besonderen Stärken, und Anwendungen auf bestimmte Probenarten können weniger erfolgreich sein. Der vorliegende Beitrag faßt unter diesem Aspekt einige neuere Entwicklungen und Untersuchungen zusammen, wobei nach Möglichkeit Vergleiche der verschiedenen Verfahren angestellt werden. Dabei werden die folgenden Matrices behandelt: Niederschlag und luftgetragene Partikel, Bodenproben, Flußsedimente und Schwebstoffe, Flußwasserfiltrate, Ozeanwasser und einige organische Matrices. Die Einsatzmöglichkeiten und die Leistungsgrenzen werden diskutiert. Die Probenvorbereitungstechniken werden beschrieben, sofern sie neu sind oder eine wesentliche Voraussetzung für die Erzielung der angegebenen Ergebnisse darstellen.

     

Atmospheric-pressure microplasma in dielectrophoresis-driven bubbles for optical emission spectroscopy

The manipulation of bubbles and the ignition of microplasma within a 200 nL bubble at atmospheric pressure and in an inert silicone oil environment were achieved. Driven by dielectrophoresis (DEP), bubble generation, transportation, mixing, splitting, and expelling were demonstrated. This process facilitated the preparation of various bubbles with tuneable gas compositions. Different gas bubbles, including air, argon (Ar), helium (He), and Ar/He mixtures, were manipulated and ignited to the plasma state by dielectric barrier discharge (DBD) within a 50 μm-high gap between parallel plates. Moving and splitting the atmospheric-pressure microplasma in different gas bubbles were achieved by DEP. The excited light of the microplasma was recorded by an optical spectrometer for the optical emission spectroscopy (OES) analyses. The characteristic peaks of air, Ar, and He were observed in the DEP-driven microplasma. With the capability to manipulate bubbles and microplasma, this platform could be used for gas analyses in the future.     

Diagnostics of a thermal plasma jet by optical emission spectroscopy and enthalpy probe measurements

An accurate determination of electron density, temperature, and velocity distributions is of primary interest for the characterization of steady-state thermal plasma spray jets. Our diagnostic capabilities based on optical emission spectroscopy include measurements of absolute emission coefficients and Stark broadening. In addition, enthalpy probe diagnostics has also been used for temperature and velocity measurements. Observation of large discrepancies between temperatures derived from absolute emission coefficients, Stark broadening, and from enthalpy probe measurements indicate that severe deviations from LTE (local thermal equilibrium) exist in various regimes of plasma spray jets. Nonequilibrum characterization of such turbulent thermal plasma jets suggests that diffusion of high-energy electrons into the fringes of plasma jets and deviations from chemical equilibrium due to high velocities in the core of plasma jets and entrainment of cold gas, are the main reasons for these discrepancies. The establishment of a reliable data base, taking these nonequilibrium effects into account, is a prerequisite for meaningful modeling of real plasma jets.     

Trace element analysis by particle and photon-induced X-ray emission spectroscopy

The analytical use of particle- and photon-induced X-ray emission spectroscopy has become an important tool in trace element analysis, especially when only small amounts of sample material are available. The physical basis, experimental procedure and typical examples are reviewed.     

Elemental trace determinations in aluminium by enrichment onto activated carbon combined with direct current arc optical emission spectrography

Summary A combined procedure including enrichment by adsorption onto activated carbon and direct current (dc) arc emission spectrography has been investigated for elemental determination. In order to obtain reproducible volatilization of the analyte in the dc arc, the activated carbon was mixed with graphite powder and the arc operated in an argon atmosphere. The procedure has been used to determine some trace impurities in high-purity aluminium metal. The analytical error in the concentration range of 10^–3–10^–5% was less than 10% and the relative standard deviation was below 12%.

---

Emissionspektroskopische Bestimmung von Spurenelementen in Aluminium mit Gleichstrom-Lichtbogen nach ihrer vorherigen Anreicherung an Aktivkohle

     

The DC arc as radiation source for optical emission spectroscopy

Summary During recent years the number of scientific papers treating arc excitation sources has rapidly decreased. But there is still a continuing interest in the research of the fundamental properties and application of arc sources. Different scientific contributions treating arc discharge and novel variations of d. c. arc sources used as radiation sources for optical emission spectroscopy are reviewed: theoretical investigations of the arc and its fundamental properties, improvement and development of arc radiation sources, influence of added substances, controlled atmosphere, matrix effects, as well as the analytical applications of the arc.

---

Gleichstrombogen-Strahlungsquelle für die optische Emissionsspektroskopie

Zusammenfassung Die Anzahl wissenschaftlicher Arbeiten, die sich mit Bogenanregungsquellen befassen, hat in letzter Zeit stark abgenommen. Dennoch besteht aber ein ständiges Interesse für Untersuchungen der Grundeigenschaften und der Anwendung dieser Anregungsquellen. Verschiedene wissenschaftliche Beiträge, die sich mit Bogenentladung befassen und neue Typen von Gleichstrombogenquellen, die als Strahlungsquellen für die optische Emissionsspektroskopie angewandt werden, sind zusammenfassend dargestellt: theoretische Untersuchungen des Lichtbogens und seiner Grundeigenschaften, Verbesserung und Entwicklung von Bogenstrahlungsquellen, Einfluß von Zusätzen, kontrollierte Atmosphäre, Matrixeffekte sowie auch die analytische Anwendung des Bogens.

     

Standard dilution analysis of beverages by microwave-induced plasma optical emission spectrometry

In this work, standard dilution analysis (SDA) is combined with microwave-induced plasma optical emission spectrometry (MIP OES) to determine seven elements in coffee, green tea, energy drink, beer, whiskey and cachaça (Brazilian hard liquor). No sample preparation other than simple dilution in HNO₃ 1% v v⁻¹ is required. Due to relatively low plasma temperatures, matrix effects may compromise accuracies in MIP OES analyzes of complex samples. The method of standard additions (SA) offers enhanced accuracies, but is time-consuming and labor intensive. SDA offers a simpler, faster approach, with improved accuracies for complex matrices. In this work, SDA's efficiency is evaluated by spike experiments, and the results are compared to the traditional methods of external calibration (EC), internal standard (IS), and standard additions (SA). SDA is comparable to the traditional calibration methods, and it provides superior accuracies for applications involving ethanol-containing beverage samples. The SDA-MIP OES procedure is effective. Using only two calibration solutions, it may be easily automated for accurate and high sample throughput routine applications.     

Experimental characterization of metallic titanium-laser induced plasma by time and space resolved optical emission spectroscopy

Time and space resolved optical emission spectroscopy has been successfully employed to investigate the evolution of the plasma produced by the interaction of UV laser beam with a metallic target of titanium at two different pressures (10⁻⁵ and 3.4×10⁻² torr) and at distances up to 3 mm from the target. By time of flight measurements and Boltzmann plots both the dynamic and the kinetic aspects have been discussed. The quasi-equilibrium state of the laser-induced plasma has been established on the basis of the failure of Saha balance equation. The effect of three-body recombination on atomic titanium temporal distribution has been explained. Temporal evolution of electron number density, as determined by Stark effect, has been used for the estimation of the three-body recombination rate constant.     

Elemental analysis of alloys by XRF

XRF was used for routine analysis of different kinds of alloys, such as archeological findings, materials used in dentistry, and Al alloyed with Ga used in industry. The results of these analyses are described in this paper.     

A heated-electrode discharge lamp for trace analysis by atomic emission spectroscopy

Graphite electrodes heated by d.c- power alone, or a combination of d.c- and r.f. power, are investigated for generating atomic emission from cadmium with specially designed discharge lamps. Best results are achieved if the plasma produced by both power sources can be concentrated within a cylindrical electrode.