Trace-element analysis of argyle diamonds using instrumental neutron activation analysis

Thirty four elements were determined by instrumental neutron activation analysis in colourless, brown, and pink diamonds, with and without inclusions. These were compared with data obtained for similar elements in the host lamproite rock. The natural radioactivity of these samples was measured by instrumental techniques, and found to be negligible.     

Properties of hybridized DNA arrays on single-crystalline undoped and boron-doped (100) diamonds studied by atomic force microscopy in electrolytes

Properties of hybridized deoxyribonucleic acid (DNA) arrays on single-crystalline undoped and boron-doped diamonds are studied at the microscopic level by atomic force microscopy (AFM) in buffered electrolytic solutions. DNA is linked to diamond via aminodecene molecules (TFAAD) that are attached to undoped diamonds by a photochemical reaction and via nitrophenyl-diazonium molecules attached electrochemically to boron-doped diamonds. Both H-terminated and oxidized diamond surfaces are used in this process. On H-terminated surfaces, AFM measurements detect compact DNA layers. By analyzing phase and height contrast in AFM, a DNA layer height of 76 A is determined on the photochemically functionalized diamonds and a DNA layer height of up to 92 A is determined on the electrochemically functionalized diamonds. Based on the layer thickness, the DNA chains are tilted under the angle of 31 degrees . The morphology of the DNA layers exhibits long-range (30-50 nm) undulations of 20 A in height and a nanoroughness of 8 A. Using Hertz's model for calculating the contact area of the AFM tip on a DNA layer and a geometrical model of DNA arrangement on diamond yields the DNA density on diamonds of 6 x 10(12) cm(-2) on both photochemically and electrochemically functionalized diamonds. The structure of these dense DNA layers is not significantly influenced by variations in buffer salinity of 1-300 mM NaCl. DNA molecules can be removed from the diamond surface by contact-mode AFM with forces >or= 45 nN and >or= 76 nN on photochemically and electrochemically functionalized diamonds, respectively, indicating that DNA is bonded covalently and stronger on diamond than on gold substrates. The DNA arrangement and bonding strength are similar on oxidized diamond surfaces when using an electrochemical process. On oxidized surfaces after photochemical processing, DNA is bonded noncovalently as deduced from the removal force < 6 nN. The presence of hybridized DNA as well as the selective removal of DNA by AFM scanning are corroborated by fluorescence microscopy.     

Characterisation of diamond coatings with different morphologies by Raman spectroscopy using various laser wavelengths

Since the beginning of low-pressure diamond synthesis, Raman spectroscopy has been widely used to identify and characterise the quality of diamonds. The diamond crystal is characterised by a Raman peak at about 1,332 cm^-1. Other peaks are associated with miscellaneous carbon structures, e.g. graphite and amorphous phases. In recent years, both well-faceted crystalline diamonds and nanocrystalline and ultrananocrystalline diamonds have been investigated. For these fine-grained materials, the diamond peak at 1,332 cm^-1 disappears and the intensities of peaks at other wavelengths increase. To study the influence of the Raman laser wavelength, three lasers were used (472.681 nm, blue; 532.1 nm, green; 632.81 nm, red). For well-faceted diamonds, the Raman spectra with blue and green laser light were similar. A shift of the peak maxima and different intensities were observed. With use of the red laser, a strong luminescence peak and low peak intensities for the various carbon-related peaks occurred. When the diamond morphology changes from well-faceted to fine-grained ballas diamond, the spectra are similar for all three lasers.     

Hot atom effect on the leachability of elements in solid waste

The effect of neutron irradiation on the leachability of elements in solid wastes comprising of coal fly ash, hospital and municipal incinerator ashes was studied. There was a marked increase in leachability in the neutron irradiated wastes compared to non-irradiated wastes especially for elements such as As, Cd, Co, Cr, Sm and Zn. For elements such as Fe and Sm there was no significant difference in the leachabilities in the irradiated and non-irradiated wastes. The possible causes of this scenario and implications are discussed.     

Determination of diamond

Analytical procedures are outlined for the determination of the diamond content of grinding wheels, drill crowns, saws, drills, hones, polishing powders and pastes, and other tools and materials employing industrial diamonds. Since the materials used as a matrix for industrial diamonds or a carrier for diamond abrasive powders may include a wide variety of metals, ceramics, plastics, cemented carbides, and organic pastes, the isolation and determination of diamond is often a rather complicated analytical task.     

Brown diamonds from an eclogite xenolith from Udachnaya kimberlite, Yakutia, Russia

We have performed petrographic and spectroscopic studies of brown diamonds from an eclogite xenolith from the Udachnaya pipe (Yakutia, Russia). Brown diamonds are randomly intermixed with colorless ones in the rock and often located at the grain boundaries of clinopyroxene and garnet. Brown diamonds can be characterized by a set of defects (H4, N2D and a line at 490.7 nm) which are absent in colorless diamonds. This set of defects is typical for plastically deformed diamonds and indicates that diamonds were likely annealed for a relatively short period after deformation had occurred. Excitation of brown colored zones with a 632.8 nm He-Ne laser produced the typical diamond band plus two additional bands at 1730 cm(-1) and 3350 cm(-1). These spectral features are not genuine Raman bands, and can be attributed to photoluminescence at ～710 nm (1.75 eV) and ～802 nm (1.54 eV). No Raman peak corresponding to graphite was observed in regions of brown coloration. Comparison with previous reports of brown diamonds from eclogites showed our eclogitic sample to have a typical structure without signs of apparent deformation. Two mechanisms with regard to diamond deformation are proposed: deformation of eclogite by external forces followed by subsequent recrystallization of silicates or, alternatively, deformation by local stress arising due to decompression and expansion of silicates during ascent of the xenolith to surface conditions.     

The application of INAA to the geochemical analysis of single diamonds

Instrumental neutron activation analysis (INAA) has been applied to the analysis of 62 small (0.01–0.5 carat), single, inclusion-bearing and inclusion-free diamonds from South Africa, Brazil and Colorado. Up to 40 elements were detected at the ppb and ppt levels in individual diamonds of the eclogitic (basaltic affinity) and the peridotitic (ultramafic) paragenesis. The data obtained in this study can be used to distinguish between diamonds from the eclogitic and peridotitic parageneses and provides geochemical information on the environment in which diamonds crystallize. Further, the technique may prove to be useful in fingerprinting diamonds of different provenance areas.     

Tracking nitrogen-to-nickel ratio and prevalent paramagnetic species in synthetic diamonds by electron spin resonance at 90 K

Nitrogen and nickel are the main impurities in the type Ib synthetic diamonds obtained under high pressure and high temperature conditions using nickel-containing catalysts. Nitrogen enters the synthesized diamond from the air. The nickel/nitrogen ratio for the two types of diamonds, obtained with and without an aluminum getter that prevents the diamond crystal lattice from nitrogen penetration, was studied by electron spin resonance at 90 K.     

Simultaneous determination of short-to-medium lived nuclides in Ghanaian food items using INAA and Compton suppression counting

Summary An instrumental neutron activation analysis (INAA) method was developed for the simultaneous determination of 19 elements in 10 individual food items from Ghana. The samples were irradiated for 1 minutes in a neutron flux of 2.5.     

Controle de la purete d'echantillons de nickel par spectrometrie-γ directement apres irradiation au moyen de neutrons thermiques

Purity control of high-purity nickel by direct γ-spectrometry after irradiation with thermal neutronsThe possibilities of analysing high-purity nickel samples by direct γ-spectrometry with a Ge(Li) detector after neutron activation are described. The samples (300—600 mg) are irradiated for 65 h in a thermal neutron flux of 5 X 10¹² n cm^-2 s^-1 and the matrix radioactivity is then allowed to decay for 30 h. It is possible to determine simultaneously 18 elements (the commonest impurities in nickel) by using standards containing known quantities of these elements irradiated under the same experimental conditions. Concentration limits are calculated for 15 elements based on the nuclear characteristics of the radio-isotopes which can be detected by neutron activation. It should be possible to determine 22 elements in nickel samples, at concentrations below 0.1 μg g^-1. The method is suitable for laboratories situated far from irradiation facilities.     

Measuremets of presolar grain in meteorite using neutron activation analysis with multi-parameter coincidence method

Neutron activation analysis with multi-parameter coincidence method was developed at the Japan Atomic Energy Agency (JAEA) and a non-destructive, ultra-high sensitive multi-elemental determination has been realized. The multi-parameter coincidence method is carried out with an array of 19 germanium detectors, GEMINI-II. Using this system, very weak γ-rays emitted from trace amounts of elements can be detected. The presolar grains were extracted from the Allende meteorite. Trace elements in the presolar diamonds were measured by neutron activation analysis with multi-parameter coincidence method.     

Indirect neutron absorptiometry

A preliminary account is given of the use of the neutron absorption of suitable elements (such as gadolinium) for the determination of non-absorbing elements (such as fluorine) by measuring the absorption of a dissolved precipitate (in the case quoted, gadolinium fluoride). This indirect determination by neutron absorption gives reproducible results rapidly and non-destructibly. The applications of the method are being studied.     

Application of on-line HPLC-ICP-MS for the determination of the nuclide abundances of lanthanides produced via spallation reactions in an irradiated tantalum target of a spallation neutron source

An analytical procedure has been developed for the determination of spallation nuclides in an irradiated tantalum target using HPLC coupled on-line to ICP-MS after dissolution and separation of the tantalum matrix. Pieces of tantalum were taken from different locations of the irradiated tantalum target which had been used as the target material in a spallation neutron source. Tantalum was dissolved in a HNO₃/HF mixture and the tantalum matrix was separated by liquid-liquid extraction so that only the spallation nuclides were left in the sample solutions. The major fraction of the spallation nuclides in the tantalum target are lanthanide metals in the μg g^–1 concentration range determined in the present study. Additional reaction products are formed by the irradiation of trace impurities in the original tantalum target. The nuclide abundances of the lanthanide metals measured in the tantalum target differ significantly from the natural isotopic composition so that a lot of isobaric interferences of long-lived radionuclides and stable isotopes in the mass spectrum are to be expected. Therefore, all the lanthanide metals had to be separated chemically prior to their mass spectrometric determination. The separation of all rare earth elements was performed by ion chromatography on-line to ICP-MS. The nuclide abundances of each lanthanide were determined using a sensitive double-focusing sector field inductively coupled plasma mass spectrometer. The nuclide abundances of the lanthanides in the irradiated tantalum target calculated theoretically and the experimental results obtained by on-line HPLC-ICP-MS proved to be in good agreement.     

Radioactivation analysis of aluminium,vanadium, copper,molybdenum, zinc and uranium in natural water samples using organic coprecipitants

A method is described for the determination of trace metal ions, V, Al, Cu, Mo Zn, and U, in natural water samples by neutron activation analysis, using organic coprecipitation as a preconcentration method. The preconcentration of trace elements was accomplished by converting the dissolved trace metal ions into the oxine chelates atpH 5.2 and extraction of the chelates witho-phenylphenol which is a liquid above 56 °C and solidifies at room temperature. After cooling the extraction system, the fine particles of the organic phase were collected on a millipore filter and the precipitate was air-dried in a clean environment. The solid extract was wrapped up in a sheet of clean polyethylene and subjected to neutron irradiation in a reactor for less than 10 min at a thermal flux of 2·10¹³ n·cm⁻²·sec⁻¹. γ-Ray spectrometry by a coaxial Ge(Li) detector connected to a 1024-channel PHA was performed on the irradiated sample without further chemical separation, and thus the ppb level concentration of the elements in natural water samples could be determined. The fundamental study of the collection of the trace elements is also described.     

Instrumental neutron activation analysis of some ancient punchmark coins from India

A nondestructive instrumental neutron activation analysis technique is applied for the analysis of precious ancient punchmark coins. Coins ranging between 8th century B.C. to 2nd century B.C. were irradiated with thermal neutrons in a²⁵²Cf neutron source facility and analyzed by comparator method of instrumental neutron activation analysis, using high purity germanium detector coupled to a multichannel analyzer, the activities being measured at photopeak energies of the corresponding radioisotopes. It is observed that punchmark coins are mainly of two types: copper or silver based. Other elements present in varying proportions are gold, arsenic and antimony.     

Neutron activation analysis of rare earth impurities in metallic uranium

A method with a sensitivity of 2·10⁻⁷ to 1·10⁻¹⁰% has been developed for determining Yb, Ho, Dy, Gd, Eu, Sm and La impurities in metallic uranium by means of neutron activation. The method is based on a preliminary chromatographic separation of the total amount of rare earth elements from uranium by passing the solution in sulphuric acid through KU-2 cation exchange resin and eluting the traces of uranium retained by the resin with a solution of ascorbic acid. The rare earth impurities are then eluted from the resin with 4–5N HCl, evaporated, and irradiated for 20 hours with a neutron flux of 1.2·10¹³ n·cm⁻²·sec⁻¹. Subsequently the traces of the rare earth elements are co-precipitated with Fe(OH)₃, dissolved in concentrated HCl and separated from the iron and other impurities by passing the solution through Dowex 1X8 anion exchange resin in the chloride form. The individual rare earth elements are then separated from each other using KU-2 cation exchange resin and a solution of ammonium α-hydroxyisobutyrate as the eluant.     

Pollution of agricultural crops with lanthanides,thorium and uranium studied by instrumental and radiochemical neutron activation analysis

The lanthanide elements, Th and U were measured in soils and agricultural crops collected in an area polluted by emissions from a phosphate fertilizer plant. Concentrations of the above elements in the soil and crop samples were determined by instrumental neutron activation analysis (INAA). Selected crop samples were also analyzed using radiochemical neutron activation analysis (RNAA) based on alkaline-oxidative fusion of the irradiated samples followed by precipitation of REE oxalates. Elevated levels of lanthanides, Th and U were found in some samples, especially in wheat chaff and parsley.     

Towards routine NAA of materials rich in heavy elements with iterative gamma-ray attenuation and neutron self-shielding calculations

Solids and powders can be analysed directly and with good accuracy by neutron activation analysis without sample preparation because of the excellent penetrating powers of neutrons and gamma rays. However, if the sample contains high concentrations of gamma-absorbing heavy elements or neutron-absorbing elements, the analysis results must be corrected for neutron self-shielding and gamma-ray attenuation. These effects are coupled and depend on the chemical composition of the sample, which is the final result of the analysis. Thus, the correction calculation must be iterative. In this work we performed the first coupled iterative corrections of the two effects. Six test samples were prepared by mixing powders containing compounds of Cd, a neutron absorber, and the rare-earth elements Ce, Pr and Nd with concentrations as high as 47 %. The samples were irradiated in the SLOWPOKE research reactor and counted with a germanium gamma-ray detector. In the samples with the highest heavy element concentrations, the uncorrected Neutron activation analysis results were in error by as much as 55 %. The results were corrected iteratively using the neutron self-shielding model coupled with the gamma-ray attenuation model, and the final corrected results were accurate to 5 % or better.     

Radiation analytical material characterization of diamond layers deposited onto tungsten carbide

The characterization of diamonds deposited onto WC single crystals by means of the CVD-method is reported. Investigations were performed by scanning electron microscopy, X-ray diffraction methods and the Kossel reflection technique. Single diamond crystals were deposited in the form of icosahedrons. An orientation correlation between substrate single crystal and diamond crystals could not be proved. In the paper presented, reasons will be given for this fact.     

Chemical nucleation for CVD diamond growth.

A new nucleation method to form diamond by chemically pretreating silicon (111) surfaces is reported. The nucleation consists of binding covalently 2,2-divinyladamantane molecules on the silicon substrate. Then low-pressure diamond growth was performed for 2 h via microwave plasma CVD in a tubular deposition system. The resulting diamond layers presented a good cristallinity and the Raman spectra showed a single very sharp peak at 1331 cm(-1), indicating high-quality diamonds.