Comparison of fluorine determination in biological and environmental samples by NAA, PAA and PIXE

Capabilities of instrumental neutron activation analysis (INAA), photon activation analysis with radiochemical separation (RPAA) and proton induced γ-ray emission (PIGE) for determination of fluorine in biological and environmental materials are compared in terms of detection limits, nuclear and other interferences. The lowest detection limit of 0.5 μg^.g^-1 was achieved by RPAA, the detection limit of the non destructive and interference-free PIGE method was by one order of magnitude higher, whereas two to three orders of magnitude higher detection limits compared to RPAA were obtained in INAA. A satisfactory agreement was found between the results obtained in this work and reference, mostly information values for several biological and environmental materials. However, higher values of two orders of magnitude were determined by RPAA and PIGE in NIST RM-8414 Bovine Muscle compared to the fluorine information value. The reason for this difference is the contamination of this material with Teflon, which occurred on its preparation and has not been taken into account in establishing the information value. This revised version was published online in August 2006 with corrections to the Cover Date.     

Raman spectroscopic analysis of the enigmatic Comper pigments

An early church decoration project carried out by Sir Ninian Comper in 1896–98, involving the rood screen and canopy in St. Mary’s, Egmanton, is currently undergoing restoration. Despite the rather prolific works of this famous ecclesiastical architect, there is little information available about the actual pigments that he used in his projects that gave rise to the special nomenclature “Comper green” and “Comper red”. Specimens of green, red, black, grey, white and blue paint from this work have been made available for Raman spectroscopic analysis, and their identification has been achieved for the first time. The characteristic red and green pigments used in Comper’s work, Comper green and Comper red, are both seen to be mixtures; in the former, Raman bands from chrome yellow (lead(II) chromate) and Prussian blue are identified, and the latter is confirmed as being a mixture of vermilion (mercury(II) sulfide) and barytes (barium sulfate). The other colours are found to represent a rich diversity of palette and include haematite, lead tin yellow (type II), lamp black, gypsum, anhydrite, hydrocerussite and calcite. The information from this first Raman spectroscopic study of Comper’s palette will assist the conservation and restoration of an important nineteenth century church decoration.     

Towards the differentiation of non-treated and treated corundum minerals by ion-beam-induced luminescence and other complementary techniques

Differentiation of treated and non-treated gemstones is a chief concern for major jewellery import companies. Low-quality corundum specimens coming from Asia appear to be often treated with heat, BeO or flux in order to enhance their properties as precious minerals. A set of corundum samples, rubies and sapphires from different origins, both treated and non-treated has been analysed at the Centre Européen d’Archéométrie, with ion-beam-induced luminescence (IBIL) and other complementary techniques such as Raman, proton-induced X-ray emission (PIXE), and proton-induced gamma-ray emission (PIGE). IBIL, also known as ionoluminescence, has been used before to detect impurities or defects inside synthetic materials and natural minerals; its use for the discrimination of gemstone simulants or synthetic analogues has been elsewhere discussed (Cavenago-Bignami Moneta, Gemología, Tomo I Piedras preciosas, perlas, corales, marfil. Ediciones Omega, Barcelona, 1991). PIXE has been frequently applied in the archaeometric field for material characterisation and provenance studies of minerals (Hughes, Ruby & sapphire. RWH Publishing, Fallbrook, 1997; Calvo del Castillo et al., Anal Bioanal Chem 387:869–878, 2007; Calligaro et al., NIM-B 189:320–327, 2002) and PIGE complements the elemental analysis by detecting light elements in these materials such as—and lighter than—sodium that cannot be identified with the PIXE technique (Sanchez et al., NIM-B 130:682–686, 1997; Emmett et al., Gems Gemology 39:84–135, 2003). The micro-Raman technique has also been used complementarily to ion beam analysis techniques for mineral characterisation (Novak et al., Appl Surf Sci 231–232:917–920, 2004). The aim of this study is to provide new means for systematic analysis of corundum gemstone-quality mineral, alternative to the traditional gemmologic methods; for this purpose, a Spanish jewellery import company supplied us with a number of natural corundum samples coming from different places (part of them treated as explained above). The PIXE elemental concentrations of the samples showed large quantities of calcium and lead in some cases that can be linked to treatment with fluxes or lead oxide. The plot of the chromium and iron concentration grouped the samples in various aggregates that corresponded to the different types of corundum analysed. Micro-Raman complemented the PIXE analysis corroborating the presence of lead oxides but the use of the PIGE technique was not successful for the detection of beryllium due to the low cross section of the nuclear reaction chosen for its identification. IBIL was capable of distinguishing between treated and non-treated samples of the same type based on the luminescent features of the materials. Work presented at the International Symposium on Luminescence Spectrometry 2008, September 7–11, Bologna, Italy     

Fabrication and characterization of enhanced hydrazine electrochemical sensor based on gold nanoparticles decorated on the vanadium oxide,ruthenium oxide nanomaterials,and carbon nanotubes composites

This work describes the synthesis of mixed oxide film of vanadium and ruthenium by pulsed deposition technique on multiwall carbon nanotubes and the decoration of gold nanoparticles on the mixed film. A ternary electrocatalyst has been developed for the electrochemical oxidation of hydrazine by combining two metal oxide mixtures with Au nanoparticles. Surface morphology and chemical composition of the electrode have been examined with SEM, EDX, HRTEM, EIS, and XRD. The peak current of hydrazine increased 9 times at the AuNPs/(VOx-RuOx)/CNT/GCE compared to the bare GCE, and the peak potential shifted to negative 848 mV. Linear sweep voltammetry (LSV) and amperometric techniques revealed that the AuNPs/(VOx-RuOx)/CNT/GCE displays linear concentration range 2.5–10000 µM (LSV) and the concentration range 0.03–100 µM (amperometry). The limit of detection (LOD) is 0.5 μM and 0.1 μM at (S/N = 3) for LSV and amperometric technique, respectively. The results obtained show a good RSD% of 2.1%–3.2% and reasonable recovery of 97%–108% of hydrazine detection.     

Electrocatalytic determination of chlorpromazine drug using Alizarin Red S as a mediator on the glassy carbon electrode

The anodic oxidation of chlorpromazine (CPZ) has been studied on a glassy carbon electrode by electrocatalytic effect of Alizarin Red S (ARS) as a homogenous mediator in universal buffer (pH = 2). The linear sweep voltammetry (LSV) studies showed that the catalytic current of this system depends on the concentration of CPZ. The magnitude of the peak current for ARS increased severely in the presence of CPZ, and proportional to CPZ concentration. The catalytic peak current was linearly dependent on CPZ concentration in the ranges of 10–500 μM and the detection limit was 5.16 μM by LSV. The diffusion coefficient of CPZ was estimated using chronoamperometry. The method also was used for estimation of catalytic rate constant at catalytic reaction between ARS and CPZ. The influences of potentially interfering substances on the current response of the system were examined. The importance of technique is because of its ability to electrocatalytic determination of CPZ with ARS as homogenous electrocatalyst, while it does not need to be prepared as for the modified electrode. The method was successfully applied for analysis of CPZ in solid pharmaceutical formulations.     

Simultaneous determination of low Z elements in barium borosilicate glass samples by in situ current normalized particle induced gamma-ray emission methods

Particle induced gamma-ray emission (PIGE) method using 4 MeV proton beam was utilized to analyze two types of barium borosilicate glass (BaBSG) samples for quantification of concentrations of low Z elements. The in situ current normalization method was applied in the analysis of eight samples containing varying concentration of F along with Si, B and Na. Charge normalized PIGE method was applied to determine concentrations of above low Z elements including Li and Al in samples having simulated nuclear waste from reprocessing of thoria spent fuel. Synthetic samples and NIST SRMs were used for method validation.     

Determination of total fluorine in five coal reference materials by proton-induced gamma-ray emission spectrometry

The direct non-destructive proton-induced gamma-ray emission (PIGE) technique with a germanium detector was applied to the determination of total fluorine concentration in five coal reference materials (BCR 40, NIST 1632b, NIST 1635, SARM 20 and USGS CLB-1). Duplicate analyses were made from five randomly selected bottles of each coal. Individual data are presented and some problems (calibration, proton stopping power, effects of sample heating by the proton beam, background estimation) which were encountered during this study are discussed. Sensitivity and reproducibility of the determinations, and homogeneity of the coal samples with respect to fluorine contents by analysis of variance were investigated. The present data are also compared with the few published values for these reference samples, including other PIGE data. The use of synthetic standards and spiked samples in the present study suggested that the PIGE method was more accurate than other techniques.     

On the use of relative deceleration values for the determination of magnesium by PIGE

By spiking the sample and analyte standard with a compound containing a common non-analyte element, to which a relative deceleration property for 5 MeV protons has been ascribed, relative deceleration values for these target materials could be obtained by PIGE. These values are used to correct for matrix effects in elemental analysis using PIGE techniques. Following this approach, the determination of magnesium in the reference standards BSC 308, Cr XXXI, SARM 8 and SARM 9 was investigated by measuring the yield of the 390 keV²⁵Mg p(2,1) and 585 keV²⁵Mg p(1,0) -rays. Lithium carbonate was employed as the non-analyte spike and magnesium oxide as the analyte comparator.     

Ion beam analysis of elemental signatures in uranium dioxide samples: importance for nuclear forensics

In this paper the suitability of two non-destructive analytical techniques for identification of elemental signatures in samples containing uranium of different enrichments was studied. The measurements were based on particle induced X-ray emission (PIXE) and particle induced gamma-ray emission (PIGE) methods. The samples were irradiated by 3 and 5 MeV protons at the 3 MV Tandetron™ of Horia Hulubei National Institute for Physics and Nuclear Engineering. The characteristic X and gamma rays were measured using high purity germanium (HPGe) detectors. The GUPIX software was applied for processing the PIXE spectra, while a relative standardization was applied for PIGE analysis by using certified comparator standards and proton stopping powers calculated by SRIM.

     

Relationship between microhardness and fluorine contents on tooth enamel determined by PIGE analysis

The remineralization effect of fluoride has been measured by surface microhardness on tooth enamel. The purpose of this study was to investigate the relationship between microhardness and fluorine concentration on tooth enamel. Twelve sound bovine enamel specimens were prepared and immersed in 0.05% NaF solution for 1, 3, 6, 24 and 36 hours, respectively. The concentration of fluorine in specimens were measured by PIGE analysis and surface microhardness of each specimen was measured by surface microhardness tester. Fluorine concentration was increased by immersing time. There was no change in microhardness of each specimen by fluorine content. The results of this study suggest that there was no relationship between the fluorine concentration and surface microhardness in sound tooth enamel. PIGE analysis can be used effectively to assess the remineralization effect of fluorine content in tooth enamel.     

Chemical characterization of soda-lime glass samples by in situ current normalised PIGE and conventional INAA methods for forensic applications

Nuclear analytical methods namely in situ current normalised Particle Induced Gamma Ray Emission (PIGE) and conventional Instrumental Neutron Activation Analysis (INAA) were utilized for determining major, minor and trace concentrations of eighteen elements in five soda-lime (automobile) glass samples. Concentration of four major elements (Si, Na, Mg and Al) by PIGE and fourteen elements including ten trace elements by INAA were determined. For forensic application, major elements were used for confirming the class of glass samples, whereas concentration results of trace elements like transition and rare earth elements were utilized for finding similarity or differences among the glass samples.

     

Comparison of three analytical methods for quality control of clozapine tablets

Three different analytical methods for the quality control of clozapine in commercial formulations were developed and compared: a liquid chromatographic (LC) method with UV detection, a capillary zone electrophoretic (CZE) method, and a linear scan voltammetric (LSV) method. The isocratic LC procedure used a C18 reversed-phase column; the CZE method used an uncoated fused-silica capillary and phosphate buffer containing polyvinylpyrrolidone as the background electrolyte; the LSV method analyzed clozapine solutions with acidic phosphate buffer as the supporting electrolyte. The 3 methods gave similar and satisfactory results, in terms of precision and accuracy. Repeatability and intermediate precision were good (RSD% < 2.2) and accuracy, resulting from recovery studies, was between 98 and 102%. The rapidity of analysis was high for all 3 methods, especially for the LSV.     

Non-destructive compositional analysis of sol–gel synthesized lithium titanate (Li2TiO3) by particle induced gamma-ray emission and instrumental neutron activation analysis

Lithium titanate, one of the important tritium breeding materials in D–T based fusion reactor under ITER programme, was synthesized through sol–gel route. For chemical quality control of finished product, it was necessary to quantify the lithium and titanium contents. As this ceramic sample is difficult to dissolve, non-destructive analytical methods are preferred for compositional analysis. In the present work, two non-destructive nuclear analytical methods namely particle induced gamma-ray emission (PIGE) using proton beam and instrumental neutron activation analysis (INAA) using reactor neutrons were standardized for the determination of lithium and titanium concentrations, respectively and applied to eleven samples of lithium titanate. To the best of our knowledge, Li quantification in lithium titanate sample is being reported for the first time using PIGE. For quantifications of Li and Ti, 478 keV prompt gamma-ray from ⁷Li (p, p′γ) ⁷Li and 320 keV gamma-ray from ⁵⁰Ti (n,γ) ⁵¹Ti were measured, respectively, by high resolution gamma-ray spectrometry. The PIGE and INAA methods were validated using several synthetic samples containing lithium and titanium, respectively. Concentrations of lithium and titanium and Li/Ti mole ratios were evaluated and compared with the stoichiometric concentration of Li₂TiO₃.     

Direct electrochemistry and electrocatalysis of hemoglobin immobilized by methacrylic acid

The direct electrochemistry of hemoglobin (Hb) incorporated in methacrylic acid (MAA) film on a paraffin-impregnated graphite electrode (PIGE) was described. A pair of well-defined and quasi-reversible cyclic voltametric peaks are obtained. The formal potentials (E ^0′) linearly depend on the pH of solution, indicating that the electron transfer was proton-coupled. Ultraviolet-visible (UV-Vis) spectra showed that the secondary structure of Hb in the MAA film was similar to individual Hb. The immobilized Hb retained its biological activity well and exhibited a nice response to the reduction of both NO₂⁻, and H₂O₂, on the basis of which a new biosensor has been developed. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 9, pp. 1079–1086. The text was submitted by the authors in English.     

Redox kinetics of adriamycin adsorbed on the surface of graphite and mercury electrodes

Kinetics of the surface redox reactions of adriamycin (doxorubicin hydrochloride) adsorbed on paraffin-impregnated graphite electrode (PIGE) and on mercury electrode is measured by square-wave voltammetry. In 0.9 mol/L KNO3 buffered to pH 4.65, the standard electrode reaction rate constants of the first quinone/hydroquinone redox couple (see Scheme 2) on PIGE and mercury are k(s1)=49+/-12 s(-1) and k(s1)=147+/-36 s(-1), respectively. Under the same conditions, the standard rate constant of the second redox couple on the PIGE is smaller than 4 s(-1) and the electron transfer coefficient of the reduction is alpha2=0.35.     

TOF-SIMS surface analysis of L-Tryptophan self assembled monolayer

This paper dealt with the preparation and characterization of self — assembled monolayersSAM-s of 1-hexadecanethiole and mercapto acetic acid on the silver nanostructure and subsequently the immobilization with amino acid L-Tryptophane. In order to achieve it, we used the electrodeposition of silver onto nanostructured surface of paraffin impregnated graphite electrode (PIGE). Subsequently, we assembled SAM by choosing the 1-hexadecanethiole and mercaptoacetic acid. These two kinds of SAM underwent the functionalization by L-Tryptophan. The observations of silver on PIGE surfaces were performed by scanning electron microscope (SEM). For surface analysis of the SAM functionalized by L-tryphophan, the TOF-SIMS technique was chosen. Finally, the fragmented ions of the immobilized-L-Tryptophan SAM were determined on the basis of suggested residues and three-dimensional structure. The residues show that the ability of L-Tryptophan to build homogeneous structure is better by mercaptoacetic acid SAM structure than by 1-hexadecanethiol. It was observed that L-Tryptophan built compact surface, which, due its chemical properties, can represent very interesting side regarding biocompatibility, homochirality and robustness in the area of life science.      

Multitechnique characterization of lapis lazuli for provenance study

Lapis lazuli is one of the oldest precious stone, being used for glyptic as early as 7,000 years ago: jewels, amulets, seals, and inlays are examples of objects produced using this material. Only a few sources of lapis lazuli exist in the world due to the low probability of geological conditions in which it can form, so that the possibility to associate the raw material to man-made objects helps to reconstruct trade routes. Since art objects produced using lapis lazuli are valuable, only nondestructive investigations can be carried out to identify the provenance of the raw materials. Ionoluminescence (IL) is a good candidate for this task. Similar to cathodoluminescence (CL), IL consists in the collection of luminescence spectra induced by megaelectronvolt ion (usually protons) irradiation. The main advantage of IL consists in the possibility of working in air while measuring simultaneously the composition of major and trace elements by means of complementary ion beam analysis techniques like particle-induced X-ray emission (PIXE) or particle-induced gamma-ray emission (PIGE). In the present work, a systematic study of the luminescence properties of lapis lazuli under charged particle irradiation is reported. In the first phase, a multitechnique approach was adopted (CL, scanning electron microscopy with microanalysis, micro-Raman) to characterize luminescent minerals. This characterization was propaedeutic for IL/PIXE/PIGE measurements carried out on significant areas selected on the basis of results obtained previously. Criteria to identify provenance of lapis lazuli from four of the main sources (Afghanistan, Pamir Mountains in Tajikistan, Chile, and Siberia) were proposed.     

Proton-induced prompt gamma-ray emission for determination of light elements in human bone

Proton-induced prompt gamma-ray emission (PIGE) analysis has been used for the determination of light elements in human dense bone samples. Li, B, N, O, F, Na, Mg, Al, P and Ca peaks were detected. Smoothed, freeze-dried samples were irradiated in vacuo by 2.4 MeV protons and the induced prompt gamma rays recorded with a 110 cm³ Ge(Li) detector. Absolute concentrations were calculated on the basis of both calibration standards and pure element gamma-ray yields. The mean (±1 S. D.) concentrations as ppm or weight % obtained for 15 dense bone samples were: B 8.0 (3.3)ppm, N 12.2 (0.8)%, O 34.8 (2.3)%, F 639 (417)ppm, Na 5763 (371)ppm, Mg 2078 (290)ppm, P 9.26 (0.50)% and Ca 20.4 (1.3)%. The detection limits obtained without any prior concentration of the bone samples were: 0.3 ppm for Li, 2.0 ppm for B, 1.0% for N, 1.0% for O, 1.0 ppm for F, 3.0 ppm for Na, 50 ppm for Mg, 22 ppm for Al, 600 ppm for P and 0.8% for Ca. Detection limits for other light elements (4≤Z≤21) have also been estimated.     

Application of a Single-Wall Carbon Nano-Tube Film Electrode to the Determination of Trace Amounts of Folic Acid

Single-wall carbon nano-tubes were used to modify the surface of a glassy carbon electrode (GC) and applied in the determination of folic acid with voltammetry. The experiments demonstrated that the presence of a carbon nano-tube film on the electrode greatly increased the reduction peak current of folic acid. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used in a comparative investigation of the electrochemical reduction of folic acid with the film electrode. Effects of pH on the peak current and the peak potential were studied in the pH range of 4.0–8.0 with Britton-Robinson buffer solution. The reduction peak current was found to be linearly related to folic acid concentration over the range of 1 × 10⁻⁸ to 1 × 10⁻⁴ mol L⁻¹ with a detection limit of 1 × 10⁻⁹ mol L⁻¹ after 5 min accumulation. The film electrode provides an efficient way for eliminating interferences from some inorganic and organic species in the solution. The high sensitivity, selectivity and stability of the film electrode demonstrate its practical application from a simple and rapid determination of folic acid in tablets.     

PIGE-PIXE analysis of Nigerian tar sands

As a rapidly growing vast country, there is need in Nigeria to develop alternative energy sources to meet its ever increasing energy demands. Tar sands apart from its popular use as a source of asphaltic material for road surfacing is a new energy raw material in Nigeria. The immense industrial applications and utilization of the by-products of tar sands provide great incentives for its development. PIGE and PIXE techniques were employed for the determination of the major, minor and trace elemental concentrations in Nigerian tar sands including sulfur which occurs as pyrites, organic sulfur and sulfates. Proton beams produced by the 7 MV CN and 2.5 MV AN 200 Van de Graaff accelerators at I.N.F.N. Laboratori Nazionali di Legnaro (LNL) at Padova, Italy, were used for the PIGE and PIXE analysis, respectively. Results of this novel study are presented, discussed, and compared with some data from previous worker and values from Athabasca (Canada).