Experimental study on equilibrium deviations in atmospheric pressure argon/helium surface wave discharges

Atmospheric pressure surface wave discharges generated with Ar–He mixtures with He concentrations up to 99% were studied using spectroscopic techniques. The variation of electron density and linear power density with He concentration and along the plasma column is discussed together with the excitation temperatures derived from the Boltzmann plot of the excited states of Ar I and the values of the b(p) parameters to derive the thermodynamic equilibrium state of the discharge. Important deviations with respect to Local Thermodynamic Equilibrium were observed for He concentrations over 50% as the discharge shifts from a recombining to an ionizing behaviour. Furthermore, the discharge kinetic variations behind these changes are discussed.     

Evaluation of hydrogen line emission and argon plasma electron concentrations resulting from the gaseous sample injection involved in hydride generation-ICP-atomic emission spectrometric analysis

The simultaneous injection of volatile hydride species and hydrogen gas, originating in reagent decomposition, was monitored during the operation of a continuous hydride generation manifold employed for the determination of trace arsenic by HG-ICP-AES. Line and background intensities as well as the FWHM of the hydrogen Hgamma and Hdelta lines were measured, and electron number densities (ne) estimated from Stark broadening of the line profiles. Results were compared with those obtained by conventional pneumatic injection of aqueous solutions. Overlapping with atomic nitrogen lines at 410 nm and 411 nm tends to distort the Hdelta line profile for the hydrogen-seeded plasma, rendering unreliable results. The N I lines seem to be quenched by the presence of water aerosol. More consistent results were obtained with the Hgamma line. When no solutions are pumped through the hydride generation manifold ("dry" plasma), the measured ne value was (1.57 +/- 0.22) x 10(15)cm(-3). Conversely, when the reducing reagent flow was replaced by pure water (corresponding to the injection of water vapor in equilibrium that is swept by the argon carrier gas passing through the phase separator), the electron concentration is 25% higher. In that case the ne value agrees between the experimental error with that obtained for a plasma in which a water aerosol is introduced at a flow rate of 1 mL/min. An enhancement of 52% relative is observed in ne when the system is operated under optimized conditions for arsine generation, employing sodium tetrahydroborate in acidic medium as reducing agent (i.e. hydrogen seeded plasma). It was also observed that the continuum emission near 410 nm for the hydrogen containing plasma correlates with the measured electron number density, suggesting that the background enhancement under hydride generation conditions may respond to the ion-electron recombination mechanism.     

Evaluation of hydrogen line emission and argon plasma electron concentrations resulting from the gaseous sample injection involved in hydride generation-ICP-atomic emission spectrometric analysis

The simultaneous injection of volatile hydride species and hydrogen gas, originating in reagent decomposition, was monitored during the operation of a continuous hydride generation manifold employed for the determination of trace arsenic by HG-ICP-AES. Line and background intensities as well as the FWHM of the hydrogen Hγ and Hδ lines were measured, and electron number densities (n_e) estimated from Stark broadening of the line profiles. Results were compared with those obtained by conventional pneumatic injection of aqueous solutions. Overlapping with atomic nitrogen lines at 410 nm and 411 nm tends to distort the Hδ line profile for the hydrogen-seeded plasma, rendering unreliable results. The N I lines seem to be quenched by the presence of water aerosol. More consistent results were obtained with the Hγ line. When no solutions are pumped through the hydride generation manifold (“dry” plasma), the measured n_e value was (1.57 ± 0.22) × 10¹⁵ cm^–3. Conversely, when the reducing reagent flow was replaced by pure water (corresponding to the injection of water vapor in equilibrium that is swept by the argon carrier gas passing through the phase separator), the electron concentration is 25% higher. In that case the n_e value agrees between the experimental error with that obtained for a plasma in which a water aerosol is introduced at a flow rate of 1 mL/min. An enhancement of 52% relative is observed in n_e when the system is operated under optimized conditions for arsine generation, employing sodium tetrahydroborate in acidic medium as reducing agent (i.e. hydrogen seeded plasma). It was also observed that the continuum emission near 410 nm for the hydrogen containing plasma correlates with the measured electron number density, suggesting that the background enhancement under hydride generation conditions may respond to the ion-electron recombination mechanism.     

Determination of inorganic contaminants in glue by inductively coupled argon plasma optical emission spectrometry

A closed vessel method using a microwave oven was developed for the determination of As, B, Ba, Bi, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Se, Sn and Sb by Inductively Coupled Argon Plasma Optical Emission Spectrometry (ICP OES). The method was applied to samples of polyvinyl acetate-based glue in water emulsions. Parameters such as wavelength, nebulization pressure and RF power were optimized and the residual acidity after the digestion process was determined. The addition of internal standards was evaluated and the accuracy of the proposed method was verified with addition and recovery experiments and also with certified reference materials, achieving good results. Using a nebulization flow rate of 0.73 L min⁻¹and a RF power of 1200 W it was possible to obtain adequate values for limit of detection and limit of quantification as well as recovery values in the range of 80-106%, for all the analytes. The analysis of coloured glue samples (white, black, blue, yellow, red and green), widely used by children, showed no contamination by the elements studied.     

Robotic preparation of metal samples for analysis by plasma emission spectrometry

Summary A method utilizing a laboratory robotic system to automate sample preparation for the chemical analysis of metals was developed. Anticipated elemental concentration values for samples are entered into the robotic system, and the system determines the needed sample weights and calibration solution concentrations. The robot then weighs, dissolves, and dilutes the samples and prepares calibration solutions prior to multi-elemental analyses by inductively-coupled plasma — atomic-emission spectrometry. Zinc-base alloy standard reference materials were used to evaluate this method. For a batch of ten samples, operator times compared with a similar manual method were reduced by about 5-fold. Precision and accuracy data for samples prepared by robotic and manual methods were equivalent.

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Automatische Probenvorbereitung für die Analyse durch Plasma-Emissions-Spektrometrie mit Hilfe eines Laborroboters

     

Determination of platinum metals and gold by optical emission spectrometry with a radiofrequency inductively-coupled argon plasma source

Optimum operating conditions in a 2-kW inductively-coupled argon plasma source for the detection of the elements platinum, palladium, rhodium, ruthenium, iridium, osmium and gold have been established. Detection limits obtained for aqueous solutions introduced into the plasma by pneumatic nebulization range from 1.5 ppb (Rh) to 34 ppb (Ir). No interelement effects caused by chemical interference have been observed between the elements investigated or from a number of base metals; several spectral interferences were observed with the spectrometer employed. The effect of the presence of mineral acids on the nebulization of sample solutions is reported.     

Direct solid atomic emission spectrometric analysis of metal samples by an argon microwave plasma torch coupled to spark ablation

Spark ablation has been combined to microwave plasma torch atomic emission spectrometry for the direct analysis of compact metallic samples. The material is ablated by a medium voltage spark (450 V, 370 Hz) in a point-to-plane configuration and swept into a 100-W, 2.45-GHz argon microwave discharge. The microwave plasma is observed end-on and the radiation analysed with a polychromator. The detection limits for Fe, Ni, Pb and Sn in brass, Cr, Cu, Ni, Mn, Mo, Si and V in steel and Cu, Fe, Mg, Mn, Si and Zn in aluminium with the microwave plasma torch in the case of measurements with a polychromator are in the μg/g range and by a factor of up to 20 higher than those obtained with spark ablation coupled to inductively coupled plasma atomic emission spectrometry using a high resolution sequential spectrometer. The stability of the emission signal depends on the element studied and relative standard deviations usually are between 0.5 and 3.5%. In the case of low-alloy steels, the linearity and the precision of the calibration could be improved by internal standardisation. Several elements (Cr, Cu, Ni, Si and V) could be determined in a steel sample (BAS SS 410/1) with high accuracy and precision.     

On the internal standardization in optical emission spectrometry of microplasmas produced by laser ablation of solid samples

Summary The problem of internal standardization in optical emission spectrometry of a laser produced analytical microplasma has been investigated. Excellent analytical results almost independent on the plasma temperature and the state of evaporation of the ablated sample material have been found for iron and chromium using Fe/Cr binary samples. However, for elements with very different vapour pressures, internal standardization can only be carried out if the atomization process in the plasma is completed. This is demonstrated with brass samples, where the fractional evaporation of zinc and copper heavily influences the emission data in the first period of the laser produced plasma.

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Über die interne Standardisierung in der optischen Emissionsspektrometrie von Mikroplasmen, erzeugt durch Laserabtrag fester Proben

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

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.

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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.

     

Some analytical characteristics of a three electrode d.c. argon plasma source for optical emission spectrometry

An investigation of a commercially available three electrode d.c. plasma source burning in an inverted Y configuration was carried out. It is shown that (i) for atoms the position of maximum line intensity in the plasma is determined by the norm temperature of the spectral line, (ii) the source is stable over long periods of time, (iii) high concentrations of alkali metals in the sample can disturb the plasma resulting in an enhancement of both atomic and ionic spectral lines, (iv) detection limits are generally less than one order of magnitude higher than those obtained with an inductively coupled plasma (ICP), and (v) precision of analysis is better than 2% expressed as relative standard deviation.     

Evaluation and application of argon and helium microstrip plasma for the determination of mercury by the cold vapor technique and optical emission spectrometry

The suitability of a 2.45-GHz atmospheric pressure, low-power microwave microstrip plasma (MSP) operated with Ar and He for the determination of Hg by continuous-flow cold vapor (CV) generation, using SnCl₂/HCl as the reducing agent, and optical emission spectrometry (OES) using a small CCD spectrometer was studied. The areas of stability for a discharge in the Ar and in the He MSP enclosed in a cylindrical channel in a quartz wafer were investigated. The excitation temperatures as measured for discharge gas atoms (Ar I, He I), and the electron number densities at 35–40 W and 15–400 mL min⁻¹ were found to be at the order of 3,200–5,500 K and 0.8 × 10¹⁴–1.6 × 10¹⁴ cm⁻³, respectively. The relative intensity of the Hg I 253.6-nm line and the signal-to-background ratio as a function of the forward power (35–40 W) as well as of the flow rate of the working gas (15–400 mL min⁻¹) were evaluated and discussed. For the selected measurement conditions, the Ar MSP was established to have the lower detection limit for Hg (0.6 ng mL⁻¹) compared with the He MSP. The linearity range is up to 300 ng mL⁻¹ and the precision is on the order of 1–3%. With the optimized CV Ar MSP-OES method a determination of Hg in spiked domestic and natural waters at concentration levels of 20–100 μg L⁻¹ and an accuracy of 1–4% could be performed. In an NIST domestic sludge standard reference material, Hg (3.64 μg g⁻¹) could be determined with a relative standard deviation of 4% and an agreement better than 4%.     

Matrix interactions in an inductively coupled argon plasma optimised for simultaneous multi-element analysis by atomic emission spectrometry

Matrix interactions in an inductively coupled argon plasma, optimised in the normal analytical zone (NAZ) for simultaneous multi-element analyses, have been studied using a factorial designed experiment to measure observed concentration changes of 16 analytes in the presence of K, Ca, NaSiO₃, polymaleic acid (PMA) and diethylenetriaminepentaacetic acid (DTPA). The main effects of the matrix compounds on the analyte wavelengths investigated all resulted in a suppression of the observed concentration means and follow the order PMA ⪢ Ca > K > NaSiO₃ and DTPA. The large PMA effect was mainly due to changes in transport efficiency, whereas the effects of Ca, K, NaSiO₃ and DTPA originate in the plasma. Calcium depressed the ion emission lines more than the neutral atom lines. A similar but much less marked effect was observed for K and NaSiO₃.     

The determination of traces of ammonium-nitrogen in aqueous solution by optical emission spectrometry with a high-frequency inductively coupled argon plasma source

A method for the determination of low levels of ammonium ion in solution by optical emission spectrometry with an inductively coupled argon plasma source operated at 27 MHz is presented. The ammonium ion is oxidized with sodium hypobromite in alkaline medium, the evolved nitrogen is passed into the argon plasma, and the NH emission intensity produced in the plasma at 336.0 nm is monitored. A practical detection limit of 0.1 μg N ml^-1 for 5-ml aqueous sample solutions has been obtained. The method has been applied to the determination of the exchangeable ammonium content of soil samples.     

Experimental study of the creation of a surface-wave-sustained argon plasma column at atmospheric pressure

The creation and stabilization processes of an argon surface-wave-sustained discharge at atmospheric pressure have been studied by means of a power interruption technique. The analysis of the temporal behavior of the radial electric field intensity outside the plasma has permitted us to study the advance of the ionization front along the plasma column. However, the temporal evolution of the intensity of some atomic emission lines has also been analyzed during the creation process of the discharge. Some relevant results of this study are presented and discussed in terms of the ionization front and the stabilization of the electric field as well as the temporal evolution of excited level populations of the species.     

Combination of neutron activation analysis and argon plasma emission spectrocopy in the elemental analysis of biological materials

Trace elements and major constituents are analyzed in solid biological material and body fluids in order to compare the range of application of instrumental neutron activation analysis and plasma emission spectroscopic techniques. It is demonstrated that both methods should be regarded as complementary analytical techniques. In separate or sequential combination of both techniques the elemental coverage in the analysis of biological material is extended.     

Surface modifications of PET in argon atmospheric pressure plasma: Gas flow rate effect

The correlation between plasma optical properties and the treated polyethylene terephthalate (PET) surface characteristics have been studied at various Ar flow rate. The rotational T_rot and vibrational T_vib temperatures of APPJ were determined from SPS emission band. The pristine and plasma-treated PET surfaces were characterized by several techniques including X-ray photoelectrons spectroscopy (XPS), Raman spectroscopy, contact angle (CA), and atomic force microscope (AFM). The CA decreased rapidly in the flow rate range 1–3 L/min and weakly dependent as flow rate > 3 L/min. XPS results showed that C 1s % of plasma-treated PET surfaces decreases and has a minimum for samples treated at 3–4 L/min, while O 1s has a maximum at the same flow rate range. The carbon C 1s peak of pristine and plasma treated PET samples resolved into five subcomponents: C–C, C–O, C=O, O–C=O, and π–π bonds with variable percentage ratio accordance to the plasma gas flow rate. Raman data revealed a partial loss in the crystallinity of the treated PET samples and also confirm the incremental of C–O band at Ar flow rate of 3 L/min. AFM images showed that the surface roughness of treated PET films increases as Ar flow rate increases.     

Studies of a radio frequency inductively coupled argon plasma for optical emission spectrometry—III. Interference effects under compromise conditions for simultaneous multi-element analysis

This work concerns interference effects in a 0.7-kW, 50-MHz inductively coupled plasma (ICP) provided with an ultrasonic nebulizer (USN) and desolvation apparatus (DA). The observations were made under (ICP) conditions adopted previously as “compromise conditions for simultaneous multi-element analysis.” Various matrices and analytes were considered.An arrangement of two identical USN's with separate DA's was used to distinguish between interferences due to processes in the plasma (“plasma effects”) and the nebulizer—desolvation apparatus (“nebulizer—desolvation effects”). The latter were identified as “desolvation effects” and attributed to a variation in the loss of analyte in the DA. This desolvation effect, whose magnitude varies between ±10%, is related to the difference in volatility between matrix and analyte. The experiments revealed plasma effects that cannot be reconciled with the common pictures of ionization interference and are not due to incomplete volatilization or dissociation either. Possible explanations are considered. The overall interference level in the ICP studied is discussed and practical conclusions regarding the use of desolvation, “pure” aqueous solutions as standards, and spectroscopic buffers are drawn.     

Single-shot Thomson scattering on argon plasmas created by the Microwave Plasma Torch; evidence for a new plasma class

To determine the fine-structure size of plasmas created by a Microwave Plasma Torch (MPT), single-shot Thomson scattering (TS) measurements were performed. The aim was to find a solution for the long-standing discrepancy between experiments and Global Plasma Models (GPMs). Since these GPMs are based on the assumption that (ambipolar) diffusion is the main loss process for charged particles, the diffusion length and thus the fine-structure size should be known with high precision before an appropriate theory-experiment comparison can be carried out. In order to avoid the effect of blurring, which is created during the accumulation of multi-shot TS signals and which obscures the fine-structures, single-shot measurements are indispensable to determine the diffusion length.     

A spatial study of electron density and analyte emission in a d.c. argon plasma

Spatially resolved electron density measurements have been performed on a three-electrode d.c. plasma using a linear photodiode array based spectrometer. The electron density values measured are between 1× 10¹⁵ and 1 × 10¹⁶ cm^?3 depending on spatial position. The spatial distribution of Ca I (422.7 nm) and Ca II (393.4 nm) emission has also been measured and the Ca II-Ca I emission intensity ratio evaluated. Using the n_e values measured, an analagous LTE ratio has been calculated and this has been compared to the experimental values. Measured ratios are found to be from 28 to 100 times less than LTE ratios. Some possible sources leading to these infrathermal ratios are discussed.