Implementation of the k 0-standardization method for analysis of geological samples at the Neutron Activation Analysis Laboratory, São Paulo, Brazil

The Neutron Activation Analysis Laboratory (LAN-IPEN) has been analysing geological samples for many years with the INAA comparative method, for geochemical and environmental research. This study presents the results obtained in the implementation of the k ₀-standardization method at LAN-IPEN, for geological samples analysis, by using the program k ₀-IAEA, provided by the International Atomic Energy Agency (IAEA). The thermal to epithermal flux ratio f and the shape factor α of the epithermal flux distribution of the IEA-R1 nuclear reactor of IPEN were determined for the pneumatic irradiation facility and one selected irradiation position, for short and long irradiations, respectively. To obtain these factors, the “bare triple-monitor” method with ¹⁹⁷Au–⁹⁶Zr–⁹⁴Zr was used. In order to validate the methodology, the geological reference materials basalts JB-1 (GSJ) and BE-N (IWG-GIT), andesite AGV-1 (USGS), granite GS-N (ANRT), SOIL-7 (IAEA) and sediment Buffalo River Sediment (NIST–BRS-8704), which represent different geological matrices, were analysed. The concentration results obtained agreed with assigned, with bias <10 % except for Zn in AGV-1. The U-score test showed that all results, except Mg in JB-1, are within 95 % confidence interval. These results indicate excellent possibilities of using this parametric method at the LAN-IPEN for geochemical and environmental studies.     

k 0-INAA of biological matrices at IPEN neutron activation analysis laboratory,São Paulo,using the k0_IAEA software

This study presents the results obtained in the application of the k ₀-standardization method at the Neutron Activation Analysis Laboratory at IPEN (LAN-IPEN), for biological sample analysis, by using the k0_IAEA software, provided by the International Atomic Energy Agency (IAEA). The thermal to epithermal flux ratio f and the shape factor α of the epithermal flux distribution of the IEA-R1 nuclear reactor of IPEN were determined for the pneumatic irradiation facility and one selected irradiation position, for short and long irradiations, respectively. To obtain these factors, the “bare triple-monitor” method with ¹⁹⁷Au–⁹⁶Zr–⁹⁴Zr was used. To evaluate the accuracy of the results, bias (%) and E _n-number test were applied to the results obtained in the analysis of the biological reference materials NIST SRM 1547 peach leaves, INCT-MPH-2 mixed polish herbs and NIST SRM 1573a tomato leaves. Bias (%), for most elements, ranged from 0 to 30 %, in relation to certified values. E _n-number values showed that, with few exceptions (Na in NIST SRM 1547 and NIST SRM 1573a, and Al, Cr, Sc and Zn in INCT-MPH-2), the results were within a 95 % CI. These results pointed to the possibility of using the k ₀-INAA method with the k0_IAEA software for analysis of biological samples at LAN-IPEN.     

Experimental cross section evaluation for innovative 99Mo production via the (α,n) reaction on 96Zr target

The high-specific activity ⁹⁹Mo accelerator-based production, via the (α,n) reaction on ⁹⁶Zr-enriched target, has been investigated in the present work. The excitation function measurement has been performed in the energy range 8–34 MeV at the ARRONAX facility, using the well-known stacked foils technique on natural zirconium as target. A general good agreement in the cross section trend has been observed, once compared to former measurements. A different (i.e. higher) peak value and a shift of about 2 MeV towards larger energies have however been found. Assuming a fully enriched ⁹⁶Zr target irradiated by an α-beam at suitable energy (E = 25 MeV), the ⁹⁹Mo production yield has thus been estimated. At last the alternative production routes, based on the ⁹⁶Zr(α,n)⁹⁹Mo and ¹⁰⁰Mo(p,x)⁹⁹Mo/^99mTc reactions, are compared.     

Optimization of 89Zr production using Monte Carlo simulations

Zirconium-89 (⁸⁹Zr) can be produced in a cyclotron by focusing the proton beam on an yttrium-89 (⁸⁹Y) foil target. Optimal combination of beam energy and target assembly configuration enables maximum production of ⁸⁹Zr while minimizing the formation of contaminant nuclides such as ⁸⁸Zr and ⁸⁸Y to allow efficient and effective radiopharmaceutical labeling. Accurate modeling of the proton beam and the target is therefore an essential step to assure the best beam and target specification. We used the radiation transport code MCNPX to simulate the transport of protons through the irradiation assembly and the nuclear reaction code TALYS to obtain the production cross sections of various nuclides from proton-⁸⁹Y reactions. Results from simulating the irradiation of 14 mm diameter targets with aluminum (Al) degrader at 19.8 mA for 1 h suggested that the 0.15 mm thick one would produce 227 MBq while the 0.3 mm thick one would produce 413 MBq of ⁸⁹Zr with less than 1 % uncertainty. These results show excellent agreement with experimental work in literature. This work provides the basis for further experimental and theoretical assessments of the use of ⁸⁹Zr as radiopharmaceutical labels.     

Fabrication and characterization of an irradiation facility for large-sample geometry

An irradiation facility consisting of a modified beam port shielding plug has been designed, fabricated built and characterized for use in irradiating non-standard sample geometries. The shielding plug features a graphite moderator at the core end with a hole, or “well” drilled of sufficient diameter and depth to accommodate an eight ounce (227 gram) sample bottle. Added shielding behind the graphite consists of castable neutron- and -gamma-ray shielding. The modified shielding plug can be removed relatively quickly from its irradiation position to minimize personnel exposures. It is mounted in close proximity to the Ohio State University Research Reactor reactor core to allow performance of high-sensitivity neutron activation analysis studies. Using the SAND-II unfolding code, the energy-dependent neutron flux has been measured in the sample irradiation position. When operating at 100 % power, the total flux is 3.9 × 10¹² n/cm²/s. Of this, 55 % is thermal (<0.5 eV), 23 % is epithermal (>0.5 eV, <0.5 MeV), and 22 % is “fast” (>0.5 MeV). This makes the facility suitable for neutron activation studies. Recently it has been used for irradiation of filter papers collected in a study of particulate air pollution in the form of atmospheric particulate matter in an urban environment.     

Separation of Zr in the rubble waste generated at the Fukushima Daiichi Nuclear Power Station

Separation method of Zr using trans uranium resin (TRU resin) and tetra valent actinide resin (TEVA resin) was developed for the analysis of ⁹³Zr contained in the rubble waste. Zr, Nb, and U were quantitatively extracted on the TRU resin from 3 M HNO₃ and striped with 0.01 M HF, in addition, some part of Mo, Hg, Bi, and Th were also included in the stripping solution. The stripping solution was evaporated to eliminate HNO₃ and the residue was dissolved in 0.1 M HF. Finally, Zr was separated from Nb and Mo with the TEVA resin.     

Multiresidue Analysis of Pesticides in Vegetables and Citrus Fruits by LC–MS–MS

In this work, an analytical multiresidue method using liquid chromatography tandem-mass spectrometry (LC–MS–MS) with triple quadrupole in selected reaction monitoring (SRM) mode for the simultaneous determination of 54 pesticides in vegetables (pepper and tomato) and citrus fruits (orange and lemon) has been developed. The procedure involves initial single phase extraction of sample with acetonitrile by agitation, followed by liquid–liquid partition aided by “salting out” process using NaCl. The average recovery by the LC–MS–MS method obtained for these compounds varied from 65.5 to 114.5% with a relative standard deviation between 2.3 and 8.3%. The method presents good linearity over the range assayed 10–500 μg L^?1 (except famoxadone 50–1,000 μg L^?1) and the detection limits for the pesticides studied varied from 0.03 to 14.9 μg kg^?1. The proposed method was used to determine pesticide levels in vegetables and citrus fruit samples from different experimental orchards and greenhouses from the Region of Murcia.     

Measurements of the thermal neutron cross-sections and resonance integrals for 186W (n,γ) 187W and 98Mo (n,γ) 99Mo reactions

The thermal neutron cross-sections and resonance integrals of the ¹⁸⁶W (n,γ) ¹⁸⁷W and ⁹⁸Mo (n,γ) ⁹⁹Mo reactions in the thermal and 1/E regions, respectively, of a thermal reactor neutron spectrum have been experimentally determined by the activation method using ¹⁹⁷Au (n,γ) ¹⁹⁸Au reaction as a single comparator. The high purity natural W, Mo, and Zr foils; and Au wire diluted in aluminum, were irradiated without Cd shield in two neutron irradiation sites, characterized with different values for the thermal-to-epithermal flux ratios, f at the Second Egyptian Research Reactor (ETRR-2). The induced activities in the samples were measured by high-resolution γ-ray spectrometry with a calibrated germanium detector. Thermal neutron cross-sections for 2200 m/s neutrons and resonance integrals for the ¹⁸⁶W (n,γ) ¹⁸⁷W and ⁹⁸Mo (n,γ) ⁹⁹Mo reactions have been obtained relative to the reference values, σ₀ = 98.65 ± 0.09 b and I ₀ = 1500 ± 28 b for the ¹⁹⁷Au (n,γ) ¹⁹⁸Au reaction. The necessary correction factors for thermal neutron and resonance neutron self-shielding effects, and the epithermal flux index (α) were taken into account in the determinations. The results obtained were: σ₀ = 38.43 ± 0.4 b and I ₀ = 502 ± 65 b for ¹⁸⁶W (n,γ) ¹⁸⁷W, and σ₀ = 0.137 ± 0.014 band I ₀ = 6.47 ± 0.8 for ⁹⁸Mo (n,γ) ⁹⁹Mo. These results are discussed and compared with previous measurements and evaluated data in literature. The traditional method of determining thermal cross-sections and resonance integrals via neutron irradiation with and without Cd shield in one irradiation position was avoided in this work by neutron irradiation without Cd shield in at least two different neutron irradiation positions. This method provides alternative way for determining thermal cross-sections and resonance integrals simultaneously.     

Effect of Nb alloying additions on the characteristics of anodic oxide films on zirconium and their stability in NaOH solution

The characteristics of oxide films on Zr and Zr–Nb alloys (with Nb content of 2.5, 5, and 10 at.%) galvanostatically formed (at a current density of 100 μA cm^?2) in 0.5 M H₂SO₄ solution were investigated by means of electrochemical impedance spectroscopy. Electrochemical impedance spectroscopy spectra were interpreted in terms of an “equivalent circuit” with the circuit elements representing the electrochemical properties of a single layer oxide. The resistance of the oxide films was found to increase with increased Nb content in the alloy while the capacitance showed an opposite trend. The stability of the anodic oxide films grown in the sulfuric acid solution on Zr and Zr–Nb alloys was investigated by simultaneously measuring the electrode capacitance and resistance at a working frequency of 1 kHz as a function of exposure time to naturally aerated 3 M NaOH solution. Analyses of the electrode capacitance and resistance values indicated a decrease in chemical dissolution rate of the oxide films with the increase of Nb content in the alloy.     

Development and implementation of Høgdahl convention and Westcott formalism for k<Subscript>0</Subscript>-INAA application at Malaysian Nuclear Agency reactor

The present work shows the development of k₀-instrumental neutron activation analysis (k₀-INAA) method at the Malaysian Nuclear Agency research reactor. To use the k₀-INAA method, two formalisms were regulated according to 1/ν and non-1/ν (n, γ) reaction nuclides. The reactor neutron spectrum parameters, the thermal to epithermal neutron flux ratio (f), the epithermal neutron flux shape factor (α) were measured using the bare bi-isotopic monitor and bare triple monitor methods, respectively, based on the Høgdahl convention. In addition, the modified spectral index \( r(\alpha )\sqrt {T_{n} /T_{0} } \), the Westcott \( g_{Lu} (T_{n} ) \) factor and the absolute neutron temperature T _n parameters were determined using the Westcott formalism. ¹⁷⁶Lu was used as non- 1/ν monitor while ¹⁹⁷Au, ⁹⁶Zr and ⁹⁴Zr were used as 1/ν monitors. The average values of \( r(\alpha )\sqrt {T_{n} /T_{0} } ,\,g_{Lu} (T_{n} ) \) and T _n were determined to be 0.1795 ± 0.0044, 1.9729 ± 0.0234 and 50.12 ± 3.21°C, respectively. The accuracy of the method was evaluated by analysing IAEA-Soil 7, IAEA-SL 1, NBS SRM 1633A-1 and IAEA-Soil 375 as reference materials. The results show an acceptable level of consistency.     

Cloud point extraction of Δ9-tetrahydrocannabinol from cannabis resin

A cloud point extraction coupled with high performance liquid chromatography (HPLC/UV) method was developed for the determination of Δ⁹-tetrahydrocannabinol (THC) in micellar phase. The nonionic surfactant “Dowfax 20B102” was used to extract and pre-concentrate THC from cannabis resin, prior to its determination with a HPLC–UV system (diode array detector) with isocratic elution. The parameters and variables affecting the extraction were investigated. Under optimum conditions (1 wt.% Dowfax 20B102, 1 wt.% Na₂SO₄, T?=?318 K, t?=?30 min), this method yielded a quite satisfactory recovery rate (~81 %). The limit of detection was 0.04 μg?mL^?1, and the relative standard deviation was less than 2 %. Compared with conventional solid–liquid extraction, this new method avoids the use of volatile organic solvents, therefore is environmentally safer.     

DFT study on mechanism of carbonyl hydrosilylation catalyzed by high-valent molybdenum (IV) hydrides

Density functional theory (DFT) calculations have been employed to investigate hydrosilylation of carbonyl compounds catalyzed by three high-valent molybdenum (VI) hydrides: Mo(NAr)H(Cp)(PMe₃) (1A), Mo(NAr)H(PMe₃)₃ (1B), and Mo(NAr)H (Tp)(PMe₃) (Tp?=?tris(pyrazolyl) borate) (1C). Three independent mechanisms have been explored. The first mechanism is “carbonyl insertion pathway”, in which the carbonyls insert into Mo?H bond to give a metal alkoxide complex. The second mechanism is the “ionic hydrosilylation pathway”, in which the carbonyls nucleophilically attacks η¹-silane molybdenum adduct. The third mechanism is [2 + 2] addition mechanism which was proposed to be favorable for the high-valent di-oxo molybdenum complex MoO₂Cl₂ catalyzing the hydrosilylation. Our studies have identified the “carbonyl insertion pathway” to be the preferable pathway for three molybdenum hydrides catalyzing hydrosilylation of carbonyls. For Mo(NAr)H (Tp)(PMe₃) (Tp?=?tris(pyrazolyl) borate), the proposed nonhydride mechanism experimentally is calculated to be more than 32.6?kcal/mol higher than the “carbonyl insertion pathway”. Our calculation results have derived meaningful mechanistic insights for the high-valent transition metal complexes catalyzing the reduction reaction.     

Improving neutron activation analysis accuracy for the measurement of gold in the characterization of heterogeneous catalysts using a TRIGA reactor

To measure the gold content of a catalyst accurately, neutron activation analysis (NAA) is one of the methods of choice. NAA is preferred for such heterogeneous catalysts because: (1) it requires minimal sample preparation; (2) NAA provides consistent and accurate results; and (3) in most cases results are obtained much quicker than competing methods. NAA is also used as a referee for the other elemental techniques when results do not fall within expected statistical uncertainties. However, at very high gold concentrations, applying NAA to determine the gold in a heterogeneous catalyst is more challenging than a routine NAA procedure. On the one hand, the neutron absorption cross section for gold is very high, resulting in significant self-shielding related errors. On the other hand, gold exhibits low energy resonance neutron absorptions. In this application the self-shielding minimization effort was handled more rigorously than the classic suppression of neutron flux within a specimen. This non-routine approach was used because: (1) for most applications, high accuracy, <3 % relative, is desired, (2) the low energy resonances of gold make its neutron reaction rate complex and (3) the TRIGA reactor flux profile used in this study contains both thermal and significant epithermal neutron fluxes. Accuracy and precision, using this new approach, are expected to improve from 15 % to better than 3 % relative uncertainty. This has been accomplished through a rigorous assessment of the observed effects of low energy resonance on the neutron flux spectral shape within the sample and designing an experiment to minimize the effects.     

Ru(bpy)3<Superscript>2+</Superscript>/β-cyclodextrin-Au nanoparticles/nanographene functionalized nanocomposites-based thrombin electrochemiluminescence aptasensor

In this study, a functionalized nanocomposite-based electrochemiluminescence (ECL) sensor for detecting thrombin was developed. First, Ru(bpy)₃²⁺/β-cyclodextrin-Au nanoparticles (β-CD-AuNPs)/nanographene (NGP) composites were used to modify the glassy carbon electrode (GCE) surface, and then aptamers (TBA1 and TBA2 with a 1:1 M ratio) were labeled with ferrocene (Fc) acting as the probes and were attached to the composite via the host–guest recognition between β-CD and Fc. In the absence of thrombin, the quenching of Fc to [Ru(bpy)₃]²⁺ was maintained, and “signal-off” ECL was observed. However, because of the specific combination of the aptamer probes and thrombin, the configuration of aptamer probes changed and escaped from the electrode surface once thrombin appears, which results in the quenching disappearance, and the ECL signal was changed from “off” to “on.” Meanwhile, the application of nanocomposites amplified the effect of “signal-on.” By this strategy, thrombin was detected with high sensitivity and with a detection limit down to 0.23 pM. Moreover, the relatively simple ECL sensor exhibited excellent reproducibility with at least 6 cycles of recovering the original signal.     

Determination of trace molybdenum in biological and water samples by graphite furnace atomic absorption spectrometry after separation and preconcentration on immobilized titanium dioxide nanoparticles

A new method has been developed for the determination of trace molybdenum based on separation and preconcentration with TiO₂ nanoparticles immobilized on silica gel (immobilized TiO₂ nanoparticles) prior to its determination by graphite furnace atomic absorption spectrometry (GFAAS). The optimum experimental parameters for preconcentration of molybdenum, such as pH of the sample, sample flow rate and volume, eluent and interfering ions, have been investigated. Molybdenum can be quantitatively retained by immobilized TiO₂ nanoparticles at pH 1.0 and separated from the metal cations in the solution, then eluted completely with 0.5 mol L^?1 NaOH. The detection limit of this method for Mo was 0.6 ng L^?1 with an enrichment factor of 100, and the relative standard deviation (RSD) was 3.4% at the 10 ng mL^?1 Mo level. The method has been applied to the determination of trace amounts of Mo in biological and water samples with satisfactory results.     

Properties of PAN-TBP extraction chromatographic material

Three production routes of the preparation of a solid extractant based on tributylphosphate (TBP) embedded in the polyacrylonitrile matrix (PAN) have been studied. The method of direct PAN coagulation with TBP was found to be not viable due to the significant TBP solubility in the coagulation bath. The most suitable PAN-TBP solid extractant was prepared by the well-known impregnation method of ready-made neat PAN beads. The kinetics of uranium extraction from 3 mol L^?1 HNO₃, the effect of nitrate and nitric acids concentrations on the value of weight distribution coefficients D _g as well as the uranium “extraction isotherm” were determined for this material. Uranium extraction was rather fast, approximately 1 h was sufficient for the equilibrium achievement. Capacity for the uranium uptake, measured in batch experiments on PAN-TBP for 0.048 mol L^?1 of uranium in 3 mol L^?1 nitric acid, was found to be q = 0.363 mmol g^?1 (58 % of the theoretical capacity). It was concluded that PAN-TBP material behaves like TBP in liquid–liquid extraction. Extraction capacity determined in column experiments was lower (by about 23 %) than expected from the “extraction isotherm” due to the TBP leaching out of the column. The thus prepared material is therefore not very suitable for multicycle extraction and stripping and can be used once, particularly for the analytical purposes.     

Evaluation of “method uncertainty” in the calibration of piston pipettes (micropipettes) using the gravimetric method in accordance with the procedure of ISO 8655-6

The gravimetric method specified by ISO 8655-6 is a standard method for calibrating piston pipettes (micropipettes). The quality of the calibration can be assessed by uncertainty evaluation, the procedure for which is described in ISO/Technical Report (TR) 20461. However, the existence of “method uncertainty” due to ambiguity in the calibration operation, which is not described in the TR, has been found in various experiments, such as the interlaboratory comparison of CCM.FF-K4.2.2011. In this report, the “method standard uncertainty” is quantified as exp(?4.51 + 0.36 ln(V ^nom/μL) + 0.05{ln(V ^nom/μL)}²) μL for a nominal volume, V ^nom, in the range from 2 μL to 10000 μL. Furthermore, the reported values in an interlaboratory comparison are confirmed to be consistent using the quantified method standard uncertainty.     

An Eicosanuclear Heterothiometallic Mo/S/Cu Cluster: Synthesis and Third-Order Nonlinear Optical Property

A potassium-crownether host–guest cation-templated synthetic method was used to build a heterothiometallic Mo/S/Cu cluster {[(K ? dibenzo-18-crown-6)(NMP)₂]₂[(K ? dibenzo-18-crown-6)(NMP)]₂[Mo₈S₃₂Cu₁₂]·H₂O} (1). 1 was structurally determined by X-ray single crystal and powder diffractions. The anionic Mo/S/Cu cluster [Mo₈S₃₂Cu₁₂]^4? exhibits a unique octameric eicosanuclear supra-cubane-like architecture. Potassium-crownether cations show “satellite-receiver”-shaped and hexagonal-pyramidal configurations. Moreover, the third-order nonlinear optical (NLO) property was studied through Z-scan method (532 nm, 4 ns pulses), which reveals that 1 possesses effective NLO absorptive and refractive properties.     

Complete thermal and epithermal neutron self-shielding corrections for NAA using a spreadsheet

An analytical expression has been developed to calculate the neutron self-shielding in a cylindrical sample using the elemental thermal neutron absorption cross sections, σ _abs , and the newly-defined epithermal neutron absorption cross-sections, σ _abs,ep . The σ _abs,ep were measured experimentally for 13 nuclides and calculated from resonance parameters for 76 nuclides. Agreement between the two was good to about 20% in most cases. A spreadsheet program was written to use these nuclear parameters to perform iterative self-shielding corrections of concentrations measured by NAA. In cases with up to 30% self-shielding, the correction factors had uncertainties varying from 2% to 3%.     

Highly Sensitive LC Method with Automated Co-Sense System and Fluorescence Detection for Determination of Sertraline in Human Plasma

A highly sensitive LC method with column-switching “Co-sense” system and fluorescence detection has been proposed for trace determination of sertraline in human plasma. A simple pre-column derivatization procedure with 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole reagent was employed. Fluxetine was used as an internal standard. Under the optimum chromatographic conditions, a linear relationship with good correlation coefficient (r = 0.9997) was found between the peak area ratio and sertraline concentration in the range of 5–5,000 ng mL^?1. The limit of detection and limit of quantitation were 1.41 and 4.28 ng mL^?1, respectively. The intra- and inter-assay precisions were satisfactory; the relative standard deviations did not exceed 5.63%. The accuracy of the method was proved; the recovery of sertraline from the spiked human plasma was 99.76–102.62 ± 2.19–5.63%. The proposed method had high throughput as the analysis involved simple sample pre-treatment procedure and short run-time (~12 min). The results demonstrated that the method would have a great value if applied in bioavailability and pharmacokinetic studies for sertraline.