ABSTRACT
The use of new silicon single crystals highly enriched in 28Si recently produced for the upcoming redetermination of the Avogadro constant requires knowledge of their molar masses. The isotopic composition data are collected independently in different laboratories but all using the virtual element technique with multicollector inductively coupled plasma mass spectrometers. In this framework, the comparison of the results with an independent measurement of the amount of at least one of the depleted isotopes is useful to limit hidden systematic errors. To this aim, the 30Si mole fraction of a sample of the new material was measured using a relative measurement protocol based on instrumental neutron activation analysis. The protocol is similar to that previously applied with the AVO28 silicon material used for the last determination of the Avogadro constant value with the exception that unknown and standard samples are not coirradiated. The x(30Si) = 5.701 × 10-7 mol mol-1 estimate is close to the expected one and is given with a standard uncertainty of 8.8 × 10-9 mol mol-1. This value, if adopted, gives a contribution to the relative standard uncertainty of the Avogadro constant of 6.3 × 10-10.
ABSTRACT
The practical realization of the unit of mass is possible by manufacturing a perfect one-kilogram sphere from a 28Si-enriched single crystal. The mass of the sphere can be determined in terms of a fixed value of the Planck constant by counting the number of silicon atoms in the core of the single crystal. To reach the target 2.0 × 10-8 relative standard uncertainty, the mass of the surface layer and the mass deficit due to point defects such as impurities and vacancies must be investigated and corrected for. A sample of a 28Si-enriched single crystal produced to test the possibility of obtaining material at a scale useful to the dissemination of mass standards was measured by instrumental neutron activation analysis to check the purity with respect to a large number of possible contaminant elements. The results collected in a neutron activation experiment performed with the high thermal neutron flux available at the 20 MW OPAL research reactor are described. The data collected in this study showed that the produced material has a purity level never achieved with silicon used to manufacture previous one-kilogram spheres.
ABSTRACT
At present, counting atoms in a one-kilogram sphere made of (28)Si-enriched silicon allows the determination of the Avogadro constant with the 2.0 × 10(-8) relative standard uncertainty required for the realization of the definition of the new kilogram. With the exception of carbon, oxygen, boron, nitrogen, and hydrogen, the claimed uncertainty is based on the postulation that the silicon material used to manufacture the sphere was above a particular level of purity. Two samples of the silicon were measured using instrumental neutron activation analysis to collect experimental data to test the purity assumption. The results obtained in two experiments carried out using different research reactor neutron sources are reported. The analysis confirmed that the silicon material was of sufficient purity by quantifying the ultratrace concentration of 12 elements and determining the detection limits of another 54 elements.
ABSTRACT
This paper investigates the use of a method based on Cu decoration and neutron activation to determine the total volume of voids in a silicon single crystal. A measurement protocol was developed and tested in an experiment carried out with a 5 cm3 volume and 10 g mass high-purity natural silicon sample. The few percent uncertainty reached in the determination of the Cu concentration, at a 1014 cm-3 level, makes this method a candidate to set an upper limit to the concentration of the vacancies contributing to the void volume in the enriched silicon material used to determine the Avogadro constant.
ABSTRACT
The latest determination of the Avogadro constant, carried out by counting the atoms in a pure silicon crystal highly enriched in (28)Si, reached the target 2 × 10(-8) relative uncertainty required for the redefinition of the kilogram based on the Planck constant. The knowledge of the isotopic composition of the enriched silicon material is central; it is measured by isotope dilution mass spectrometry. In this work, an independent estimate of the (30)Si mole fraction was obtained by applying a relative measurement protocol based on Instrumental Neutron Activation Analysis. The amount of (30)Si isotope was determined by counting the 1266.1 keV γ-photons emitted during the radioactive decay of the radioisotope (31)Si produced via the neutron capture reaction (30)Si(n,γ)(31)Si. The x((30)Si) = 1.043(19) × 10(-6) mol mol(-1) is consistent with the value currently adopted by the International Avogadro Coordination.
ABSTRACT
Background: The purpose of this paper is to study the dependence of Co levels in hair on Co levels in blood after metal-on-metal (MoM) hip replacement and prove the suitability of hair analysis coupled to blood analysis in the decision process regarding implant revision evaluation. Methods: Hair samples of 19 MoM patients having both well-functioning and malfunctioning implants and Co mass concentration levels in blood between 0.2 µg L-1 and 221.0 µg L-1 were included. A method based on inductively coupled plasma mass spectrometry was validated and used to measure the Co level in hair. Results: The Co mass fraction in the hair of patients ranged between 0.011 mg kg-1 and 0.712 mg kg-1. A correlation analysis showed a statistically significant positive correlation (r = 0.932, P < .001) between Co in the hair and that in the blood in the full-level range and a statistically nonsignificant positive correlation (r = 0.595, P = .091) in the low-level range. Conclusions: A correlation between the Co level in the hair and that in the blood exists when the latter is clearly above the 7 µg L-1 mass concentration threshold suggested for implant revision evaluation. The correlation disappears when the Co level in blood approaches or falls down the mass concentration threshold and that in the hair approaches or falls within the normal population range of 0.004-0.14 mg kg-1. Accordingly, clinicians could consider a hair analysis coupled to a blood analysis to assess the revision of malfunctioning MoM implants that release metals in patient's body.
ABSTRACT
The commerce of illegal and counterfeit medicinal products on internet is a serious criminal problem. Drugs for erectile dysfunction such as phosphodiesterase type 5 inhibitor are the most commonly counterfeited medicines in Europe. The search of possible toxic chemical substances in seized products is needed. Moreover, the profiling of the material can be the source of relevant forensic information. For the first time a combined approach based on liquid chromatography (LC) coupled to high resolution mass spectrometry (HRMS) and instrumental neutron activation analysis (INAA) is proposed and tested, allowing characterisation of both authentic and illegal pharmaceuticals containing sildenafil seized in Italy. LC-HRMS allowed the detection and identification of unknown impurities not reported on labels in illegal products and the quantitation of the sildenafil. INAA showed to be suitable to provide both qualitative and quantitative information for forensic purposes on 23 elements, allowing discrimination between legal and illegal products.