Measurement of boron isotopic ratio with non-gated molecular spectroscopy of femtosecond laser-produced plasma

Laser-induced breakdown spectroscopy can be augmented by concurrent spectroscopic measurements of molecules and molecular ions resulting from recombination of laser-ablated plasmas with the ablated sample and surrounding environment. Molecular emissions can exhibit significantly greater isotopic shifts than atomic emissions, making this approach attractive for isotopic characterization of nuclear materials. We describe a measurement of boron isotopic ratios in four boron-containing samples utilizing the emission from boron monoxide radicals formed in the expanding laser-induced ablation plume. Femtosecond laser excitation is used and the emission in the 532–540 nm region of interest is studied, where a linear superposition of characteristic spectra for two boron isotopes has been applied for reconstruction of the boron isotopic ratio. It is also demonstrated that the use of non-gated measurements of emission spectra suffices for accurate isotopic characterization using this method. The application of multivariate regression to deconvolve the isotopic ratio from the measured emission spectra is discussed in detail, including the limitations and subtleties of this approach.     

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.     

Observations on the determination of osmium by inductively-coupled plasma atomic emission spectroscopy

Osmium tetroxide gives rise to very characteristic atomic emission properties. In acidic samples it gives much higher sensitivity than that given by the lower oxidation states (IV, III, II). However, in alkaline medium (pH 10.5) its atomic emission sharply decreases, and the sensitivity is the same as that for the other oxidation states. It has been shown that there is a direct relation between these characteristics of OsO(4) solutions and pH. With increasing pH the intensity of its atomic emission decreases, the electrode potential of its solutions drops sharply and the molecular absorption of radiation at 193 nm undergoes a hyperchromic and bathochromic shift. The volatility of OsO(4) has also been studied, and found to be minimum at around pH 9.5. This favours its determination at this pH.     

Optimization of the operating conditions using factorial designs for determination of uranium by inductively coupled plasma optical emission spectrometry

A critical evaluation of the determination of uranium by inductively coupled plasma optical emission spectrometry was performed using factorial designs (2³) involving the factors: acid concentration, radio frequency power and nebulizer gas flow rate. All of the experiments in this study were made for five emission lines, in the presence of nitric and hydrochloric acid. The results demonstrated that, between nitric and hydrochloric acid, the determinations in the presence of nitric acid were most sensitive. The factorial design showed that the nebulizer gas flow rate was the most significant among the factors studied for the five emission lines. Calcium in concentrations of 10 mg L⁻¹ was observed to cause suppression of the emission intensity for some lines. Iron (at least up to 10 mg L⁻¹) did not interfere in the emission intensity of uranium across the five lines studied. Another experiment evaluated simultaneously the effect of 13 other elements, and the results demonstrated that these elements did not affect the emission intensity of uranium for the lines chosen. The optimized method, using the line at 385.957 nm, allows the determination of uranium with limit of quantification of 31 μg L⁻¹ and precision expressed as RSD lower than 2.2% for uranium concentrations of either 500 or 1000 μg L⁻¹. The accuracy was confirmed by analysis of two laboratory reference materials. The developed method was applied to the determination of uranium in an industrial effluent collected from uranium-producing mine in Caetite City, Brazil. The sample was analyzed by inductively coupled plasma mass spectrometry ICP-MS, and the observed recovery was satisfactory.     

Analysis of two colliding laser-produced plasmas by emission spectroscopy and fast photography

In this work two colliding laser-induced plasmas (LIP) on Cu and C were studied by means of time resolved emission spectroscopy and fast photography. The experiments were performed using two opposing parallel targets of Cu and C in vacuum, ablated with two synchronized ns lasers. The results showed an increased emission intensity from copper ions Cu II (368.65, 490.97, 493.16, 495.37 and 630.10 nm) and Cu III (374.47 and 379.08 nm) due to the ionization that occurs during collisions of Cu and C species. It was found that the optimum delay between pulses, which yields the maximum emission enhancement of Cu ions, depends on the sampling distance. On the other hand, the emission intensity of C lines, C II (426.70 nm), C III (406.99 and 464.74 nm) and C IV (465.83 nm), decreased and the formation of C₂ molecules was observed. A comparison between the temporal evolution of the individual plasmas and their collision performed by combining imaging and the time resolved emission diagnostics, revealed an increase of the electron temperature and electron density and the splitting of the plume into slow and fast components.     

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.     

Simultaneous determination of arsenic, selenium and mercury in foodstuffs by chemical vapour generation inductively coupled plasma optical emission spectroscopy

A procedure for the simultaneous determination of arsenic, selenium and mercury in foodstuffs has been developed. After a two-step microwave-assisted wet digestion in closed vessels, using concentrated nitric acid and hydrogen peroxide, the solution was analysed by inductively coupled plasma multichannel-based emission spectrometry using chemical vapour generation as the sample introduction system. All steps of the procedure, such as solid sample dissolution, pre-reduction to the suitable oxidation state, vapor generation, transport and atomization have been designed and optimised taking into account the concomitant presence of all the analytes considered. Temporal variation of analytical signals as well as interfering effects due to transition elements were also studied. Under the optimised operating conditions, the achieved detection limits for the simultaneous determination of arsenic, selenium and mercury in foodstuffs were 0.006, 0.023 and 0.018 microg g(-1), respectively, allowing their determination in real samples. Precision of the analytical procedure was 6.8% for arsenic, 5.2% for selenium and 7.7% for mercury (n=7). The accuracy and reliability of the method was verified by the analysis of both standard reference materials (rice flour and spinach leaves) and real samples (natural and Se-enriched rice).     

Separation and inductively coupled plasma optical emission spectrometric (ICP-OES) determination of trace impurities in nuclear grade uranium oxide

A simple and rapid inductively coupled plasma optical emission spectrometric method for the determination of trace level impurities like REEs, Y, Cd, Co, V, Mg, B, Ca, Cr, Mn, Ni, Cu, Zn and Al in uranium oxide samples is described. The method involves solvent extraction separation of uranium from 6 M HNO₃ acid medium using di (2-ethyl hexyl) phosphoric acid in toluene, which selectively separates uranium leaving behind the trace impurities in the aqueous media, for quantification by ICP-OES. The method has been applied to few synthetic samples and five certified reference U₃O₈ standards. The results are compared with other methods such as TBP-TOPO-CCl₄ and 1,2 diaminocyclohexane N,N,N′,N′-tetra acetic acid (CyDTA)–ammonium hydroxide (NH₄OH) separation techniques. Different experimental parameters like contact time, acidity, aqueous to organic ratio etc., are optimized for better and accurate results. The method is simple, rapid, accurate and precise for all the studied elements, showing a relative standard deviation of 1.5–12.0% at trace levels studied (5.5–12% at 0.2 μg/mL and 1.5–6.0% at 0.5 μg/mL), on the synthetic samples prepared from high purity oxides.     

Improving the analytical performances of inductively coupled plasma optical emission spectrometry by multivariate analysis techniques

The various multivariate analysis techniques which have been successfully applied to maximize the analytical performance of ICP-OES are reviewed. These include optimization procedures, spectral data processing and calibration methods as well as classification and pattern recognition techniques.     

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.     

Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination

A new synthesized modified mesoporous silica (MCM-41) using 5-nitro-2-furaldehyde (fural) was applied as an effective sorbent for the solid phase extraction of uranium(VI) and thorium(IV) ions from aqueous solution for the measurement by inductively coupled plasma optical emission spectrometry (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ions were investigated in batch method. Under optimal conditions, the analyte ions were sorbed by the sorbent at pH 5.5 and then eluted with 1.0 mL of 1.0 mol L⁻¹ HNO₃. The preconcentration factor was 100 for a 100 mL sample volume. The limits of detection (LOD) obtained for uranium(VI) and thorium(IV) were 0.3 μg L⁻¹. The maximum sorption capacity of the modified MCM-41 was found to be 47 and 49 mg g⁻¹ for uranium(VI) and thorium(IV), respectively. The sorbent exhibited good stability, reusability, high adsorption capacity and fast rate of equilibrium for sorption/desorption of uranium and thorium ions. The applicability of the synthesized sorbent was examined using CRM and real water samples.     

The determination of samarium, europium, gadolinium and dysprosium in uranium products by direct-current plasma emission spectrometry

Samarium, europium, gadolinium and dysprosium were separated from uranium-containing materials by means of solvent extraction with Alamine 336, followed by cation-exchange. The elements were determined in the sub-ppm range by means of direct-current plasma atomic-emission spectrometry.     

Elemental analysis of horse hair by optical emission spectroscopy

A spectrographic method is developed for the simultaneous determination of trace elements in horse hair. The quantitative estimates of elements Ag, Al, B, Ca, Cu, Fe, Mg, Mn, Na, P, Pb, Si, Ti, v, and Zn are reported and the precision of determination for some elements is given.     

On-line preconcentration and determination of chromium in parenteral solutions by inductively coupled plasma optical emission spectrometry

A method for the preconcentration and speciation of chromium was developed. On-line preconcentration and determination were obtained using inductively coupled plasma optical emission spectrometry (ICP-OES) coupled with flow injection. To determinate the chromium (III) present in parenteral solutions, chromium was retained on activated carbon at pH 5.0. On the other hand, a step of reduction was necessary in order to determine total chromium content. The Cr(VI) concentration was then determined by difference between the total chromium concentration and that of Cr(III). A sensitivity enrichment factor of 70-fold was obtained with respect to the chromium determination by ICP-OES without preconcentration. The detection limit for the preconcentration of 25 ml of sample was 29 ng l⁻¹. The precision for the 10 replicate determinations at the 5 μg l⁻¹ Cr level was 2.3% relative standard deviation, calculated with the peak heights. The calibration graph using the preconcentration method for chromium species was linear with a correlation coefficient of 0.9995 at levels near the detection limits up to at least 60 μg l⁻¹. The method can be applied to the determination and speciation of chromium in parenteral solutions.     

Separation and determination of molybdenum by inductively coupled plasma optical emission spectrometry using quercetin immobilization on silica gel

A new method is described for the separation of molybdenum based on its chelation in a column packed with quercetin, immobilized on silica gel in a slightly acidic medium (pH 5.0). Recovery ranged from 95% (NIST 1515 apple leaves) to 99% (deionized, distilled water; DDW) with an absolute blank of 27.5±1.6 pg obtained for the analysis of DDW. Detection limits, absolute and relative, based on a 5.0-ml sample volume were 4.8 pg and 1 ng l⁻¹, respectively. Results are presented for molybdenum determination in two standard reference materials, NIST 1515 and NIST 1547 peach leaves, using simple calibration curves for quantification. α-Benzoinoxime was used as the eluent.     

Multivariate optimization of mercury determination by flow injection-cold vapor generation-inductively coupled plasma optical emission spectrometry

In this work a procedure for mercury determination by Flow Injection-Cold Vapor Generation-Inductively Coupled Plasma Optical Emission Spectrometry (FI-CVG-ICP OES) has been developed. The system uses a small homemade glass separator constructed to drive the Hg vapor to the plasma. An evolutionary operation factorial design was used to evaluate the optimal experimental conditions for mercury vapor generation, aiming at the low consumption of reagents, the improvement of the analytical signal and consequently greater sensitivity. The procedure allowed the determination of mercury and showed excellent linearity for the concentration range from 0.50 μg L(-1) to 100.0 μg L(-1), with Limits of Detection (LOD) and Quantification (LOQ) of 0.11 μg L(-1) and 0.36 μg L(-1), respectively, and a sampling rate of 36 analyses per hour. The optimized procedure showed good accuracy and precision, and the method was validated by the analysis of two certified reference materials: Buffalo River Sediment (NIST 2704) and human hair (IAEA 085). A good agreement with the certified values was achieved, with recovery values of 99% and 98% and relative standard deviation close to 2%.     

Isotope ratio determination in microgram levels of osmium by deuteron activation analysis

We have demonstrated the feasibility of determining isotope ratios in very small samples of osmium by deuteron activation in the Livermore Tandem Van de Graaff accelerator. The method involves determination of cross-section ratios by using several osmium isotope mixtures carefully prepared from electromagnetically-enriched osmium isotopes. The accuracy of this method was checked by a determination of the isotope ratios in naturally-occurring osmium. Our analysis demonstrated that an osmium specimen removed from a sample of commercial grade perrhenic acid contained only 0.4% natural osmium, the rest being radiogenic¹⁸⁷Os.Work performed under the auspices of the U. S. Department of Energy by the Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.     

Comparison of two lab-made spray chambers based on MSIS™ for simultaneous metal determination using vapor generation-inductively coupled plasma optical emission spectroscopy

The objective of this study is to evaluate the performance of two lab-made systems based on the Multimode Introduction System (MSIS™) and the modified MSIS™, to generate and introduce vapors of Ag, Cu, Cd, Cu, Ni, Sn, Zn, and also Au in the ICP torch. An univariate procedure was used to select the optimized working conditions (Ar flow, sample, reductant and waste flows, and reagent concentrations). Optimum conditions for working with modified MSIS were: nitric acid concentration 0.35 M, 8-hydroxyquinoline concentration: 40 mg L⁻¹, sodium borohydride concentration: 1.75% (w/v) + 0.4% (w/v) NaOH, argon purge flow to sweep the vapors to the torch: 1.2 L min⁻¹, sample flow and sodium borohydride flows: 2.3 L min⁻¹; waste flow: 7.7 mL min⁻¹. For the optimum working conditions for lab-made MSIS in dual mode the concentration of 8-hydroxyquinoline was 225 mg L⁻¹, the Ar purge flow was 0.75 L min⁻¹, and the conventional nebulization flow was 2.3 L min⁻¹. The sensitivity obtained was higher using the lab-made MSIS than using the lab-made modified MSIS or a forced outlet gas–liquid separator. The limits of detection were better for Au, Cd, Sn than those obtained using conventional nebulization; the measurements were precise (RSDs ≤ 5% in dual mode) and a good accuracy was obtained in the determination of Cd, Cu, Ni and Zn in a wastewater reference material using aqueous calibration and the lab-made MSIS in dual mode.     

Detection of boron nitride radicals by emission spectroscopy in a laser-induced plasma

Several vibrational bands of boron nitride radicals have been observed in a plasma produced by pulsed-laser ablation of a boron nitride target in low-pressure nitrogen or argon atmospheres. Using time- and space-resolved emission spectroscopic measurements with a high dynamic range, the most abundant isotopic species B¹¹N have been detected. The emission bands in the spectral range from 340 to 380 nm belong to the Δυ =−1, 0, +1 sequences of the triplet system (transition A³Π–X³Π). For positive identification, the molecular emission bands have been compared with synthetic spectra obtained by computer simulations. Furthermore, B¹⁰N emission bands have been reproduced by computer simulation using molecular constants which have been deduced from the B¹¹N constants. Nevertheless, the presence of the lower abundant isotopic radical B¹⁰N was not proved due the noise level which masked the low emission intensity of the B¹⁰N band heads.