Studies in heavy ion activation analysis

¹⁵N induced radioactivation was used to study the possible trace determination of light elements with 1Z17. 55 nuclear reactions were investigated with ion beam energies ranging from E_1ab=10 MeV to E_1ab=30 MeV. Three elements were found to be determinable non-destructively, selectively and sensitively: Li, Be and Mg. Nuclear interferences have also been defined and quantified. The technique has been tested by analyzing NBS standards. Finally, Li and Be have been determined in glass samples and Mg in various types of alumina.     

Etude des possibilites de dosage du lithium par activation au moyen de protons et de deutons de moyenne energie

The determination of lithium by measuring⁷Be, produced by proton or deuteron activation, has been studied. The extent of interference from boron or beryllium, which also form⁷Be, was measured. The calculated sensitivity limits when activating for one hour with 10μA beams of 14 MeV protons or 25 MeV deuterons are, for lithium, 1·10⁻¹ and 2.5·10⁻² ppm and for boron, 2·10⁻¹ and 1·10⁻¹ ppm, respectively.      

Synthesis and Characterization of a Magnesium Boryl and a Beryllium‐Substituted Diazaborole

Reaction of a lithium boryl, [(THF)₂Li{B(DAB)}] (DAB=[(DipNCH)₂]^2?, Dip=2,6‐diisopropylphenyl), with a dinuclear magnesium(I) compound [{(^MesNacnac)Mg}₂] (^MesNacnac=[HC(MeCNMes)₂]^?, Mes=mesityl) unexpectedly afforded a rare example of a terminal magnesium boryl species, [(^MesNacnac)(THF)Mg{B(DAB)}]. Attempts to prepare the magnesium boryl via a salt metathesis reaction between the lithium boryl and a β‐diketiminato magnesium iodide compound, instead led to an intractable mixture of products. Similarly, reaction of the lithium boryl with a β‐diketiminato beryllium bromide precursor, [(^DepNacnac)BeBr] (Dep=2,6‐diethylphenyl) did not give a beryllium boryl, but instead afforded an unprecedented example of a beryllium substituted diazaborole heterocycle, [{(^DepNacnac)Be(4‐DAB^?H)}BBr]. For sake of comparison, the same group 2 halide precursor compounds were treated with a potassium gallyl analogue of the lithium boryl, viz. [(tmeda)K{:Ga(DAB)}] (tmeda=N,N,N’,N’‐tetramethylethylenediamine), but no reactions were observed.     

Trace determination of beryllium by heavy ion activation analysis

A novel procedure for measuring the concentration of trace beryllium in different samples has been studied using¹¹B heavy ion activation analysis. The specific reaction,⁹Be/¹¹B, 2n/¹⁸F, is sensitive and selective when using a 10 MeV¹¹Be³⁺ bombardment energy. The detection limit for a nondestructive analysis is 0.1 ng for a 2 h irradiation in a A cm^–2 beam current. A precision of 12% was achieved at the 50 g g^–1 level. Beryllium has been determined in a standard beryllium-copper alloy NBS-SRM C1123. Glass samples containing up to 61 trace elements were also analyzed nondestructively. When using a clean vacuum irradiation chamber, the technique might allow ultra-trace determinations, dealing with solid samples of a few milligrams.     

Trace determination of lead by helium-4 activation analysis

The determination of lead via 30 MeV⁴He bombardment to produce the long-lived radioisotope²¹⁰Po was studied. The validity of the technique was tested by the analysis of a series of NBS glass samples doped with 61 different trace elements at nominal 500 to 1 ppm level concentrations. The measurement sensitivity of alpha counting with surface barrier detectors was evaluated. The detection limit was estimated at 0.1 ppm. The⁴He-activation technique coupled with -counting features a unique combination of sensitivity and accuracy for the trace determination of lead.     

Nuclear and atomic activation with heavy ion beams

Heavy ion activation has been studied as a method for determining hydrogen. The reactions used [e.g.¹H(⁷Li, n)⁷Be] are the “inverse” of well known reactions [e.g.⁷Li(p, n)⁷Be]. Nuclear activation parameters for the ion beams of interest (⁷Li²⁺,¹⁰B²⁺) have been studied. The analytical feasibility is demonstrated with the determination of hydrogen in titanium at the 100 and 30 ppm levels with relative precisions of 8 to 10%. Detection limits in titanium are in the 0.1 to 0.5 ppm range. Heavy ion bombardment is also accompanied by the emission of characteristic X-rays (“atomic” activation). The parameters governing X-ray emission and background production have been investigated. Experimental K and L X-ray yields from thick targets have been measured for many elements excited by Oⁿ⁺ beams of 0.5 to 7 MeV/amu and Kr⁷⁺ beams of 0.5 to 1 MeV/amu. The simultaneous determination of trace elements at levels of 10 to several 100 ppm in microsamples (∼10⁻⁵ g) is demonstrated on biological specimens. K and L X-ray yields and corresponding detection limits have also been measured with the⁷Li²⁺ and¹⁰B²⁺ beams used for the nuclear activation of hydrogen. With these beams (∼6 MeV/amu) simultaneous nuclear and atomic activation is possible, yielding an unusual multielement trace analysis capability covering hydrogen and medium and high Z elements.     

Beryllium(II) Complexes with Bis(dimethylamino)phosphorylfluoride: A Multinuclear NMR (31P, 19F,and 9Be) Characterization in Solution

Complexes of beryllium chloride and nitrate with (Me₂N)₂P(O)F were characterized in solution by multinuclear NMR spectroscopy and in some cases by IR spectroscopy and conductimetry. ³¹P and ¹⁹F NMR spectra were informative of changes associated with complex formation revealing resonances consistent with different species in solution and suggest an equilibrium between these species in both beryllium derivatives. These compounds show narrow lines in the solution ⁹Be NMR spectra, indicative of a highly symmetric environment for beryllium. The presence of the different species was more pronounced in beryllium chloride complexes. The results are compared to those reported in the literature for hexamethylphosphoramide (HMPA).     

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.     

Particle-induced-gamma-ray-emission spectrometry applied to the determination of light elements in individual grains of granite minerals

The quantitative determination of Li, Be, B, F is feasible using a sensitive and non-destructive method by the analysis of the prompt -rays induced with charged particles (PIGE). The irradiation source is a Van de Graaff accelerator, and -analysis has to be performed during the irradiation. Measurements were made at the CERI laboratory in Orléans with the PIGE method using a 100×300 m² focused beam of 3MeV particles. Among the applications, micas along a drill core from the Beauvoir granite were analyzed. Bulk analyses of light elements in the drill core have previously been made. Coarse-grained micas were selected, individually irradiated and directly analyzed in polished thin sections from different elevations in the drill core. The sensitivity depends on the cross-sections of the nuclear reactions, on the particle current and on the duration of the irradiation. With a particle current irradiation of 25 nA during 1000 seconds, a 20 ppm limit of detection is reached for Be, 25 ppm for Li, 900 ppm for B and 450 ppm for F. A large variation of Be contents in the micas was found at equal drill hole elevations, and there was no strong correlation between whole-rock compositions and the mineral chemistry. The latter have been determined both by PIGE and by mineral separation and ICP analyses. On the other hand, a strong Li–F correlation was observed between the fluor-polylithionite and muscovite end-members, supporting previous analyses from equal elevation wells on sorted micas. Be–Li correlation is poorly defined, but the contents of the micas analyzed remained between the contents of bityite (Be–Li bearing mica) and lepidolites (Li-bearing micas) end-members. This suggests a solid-solution between the end-members, the extent of which is very narrow because the Be contents were not higher than 500 ppm. The detection limit is a function of the spatial resolution, because the current of the incident (or p) particles decreases with the impact size. The results show that the analysis of small individual grains of minerals with PIGE can thus be complementary to other analytical methods such as the electronic microprobe.     

Studies in heavy ion activation analysis

⁷Li induced radioactivation was used for the trace determination of hydrogen via the¹H(⁷Li, n)⁷ Be reaction. At 21 MeV⁷Li, only boron and magnesium present small nuclear interferences. An activation curve has been established by bombarding a stack of thin mylar foils. The comparison of this curve with the excitation function for the forward reaction, namely⁷Li(p, n)⁷ Be, shows that the recoil range from the superficial hydrogen atoms is only 1.7 mg·cm^–2, allowing post-irradiation etching. Hydrogen has been determined in titanium and lead bronze at the 100 ppm level with a relative precision of 6 to 10%. Studies of 32 potential interfering elements suggest the extension of Li activation to the trace determination of Na[²³Na(⁷Li,⁶Li)²⁴Na] and K[³⁹K(⁷Li, d)^44m,⁴⁴Sc].     

Studies in heavy ion activation analysis trace determination possibilities with9Be bombardment

⁹Be induced radioactivation was used to study the trace determination of 19 elements at 3 different ion beam energies (E_lab=14, 32 and 63 MeV⁹Be²⁺). Nine nuclear reactions, yielding radionuclides with half-lives longer than 2.5 m, present potential analytical features. Beside the very sensitive detection of B and N, the multielemental determination of Na, Si, Ca, Sc, and Zn is possible with a⁹Be ion beam of appropriate incident energy. Nuclear interferences have also been investigated and quantified.     

CBNM - determination of Li in BCR reference materials RM 303 and RM 304 lyophilized serum by isotope dilution mass spectrometry (IDMS)

Summary Lithium was determined in two BCR Candidate Reference Materials 303 and 304 by Isotope Dilution Mass Spectrometry using the state-of-the-art performance of isotope-specific methods gained during previous certifications of ⁶LiF reference targets used for the determination of the neutron lifetime [1]. After reconstitution of the serum, four aliquots of each of the two candidate materials from four different bottles were spiked with a previously characterized enriched ⁶Li spike [2] which is now available as CBNM IRM-615 and has a certified ⁶Li/⁷ Li ratio of 21.78±0.12 and a certified lithium concentration of 4.001±0.028 mol/g solution. The serum aliquots were digested in an HNO₃/H₂O₂ mixture and after evaporation of the acid, the lithium was separated on a cation exchange column, eluted with 0.3 mol/L HCl and used as LiCl for mass spectrometric measurement on an NBS type thermal ionization mass spectrometer. Similarly an unknown sample BCR X, provided by BCR to check the performance of the certifying laboratories, was analyzed. In addition the chemical preparation method was controlled by assaying NBS (NIST) SRM 909. The chemical blank was determined by IDMS using ⁶Li enriched CBNM IRM-615. The measurements were corrected for isotopic fractionation using the Isotopic Reference Material CBNM IRM-016 chemically prepared in the same way as the samples. The CRM samples as well as the BCR X sample and the NBS SRM 909 were also analyzed for isotopic composition to verify whether they had indeed natural isotopic composition. The final results have an overall uncertainty of 1.2 and 1.5%, respectively. This overall uncertainty (on a 2s basis or an estimate thereof) takes into account all uncertainty contributions of statistical as well as of systematic nature (uncertainties on used reference materials, density and blank determinations). The final results compare favorably with the values proposed by BCR for certification, but have a smaller (better) uncertainty: CRM 303: (0.517 4±0.005 7) mmol/L, CRM 304: (0.987±0.014) mmol/L     

Determination of lithium and halogens and the significance of lithium to the understanding of cosmochemical processes

With a newly developed method fluorine and the other halogens have been measured in terrestrial, meteoritic and lunar samples. As a valuable byproduct lithium was determined also via teh reactions⁶Li (n,α)t→¹⁶O (t, n)¹⁸F. From our measurements the following new values for the “cosmic” abundance are derived (in atoms per 10⁶ Si atoms) F 750, Cl 4350, Br 8.83, and I 1.14. We could show that the Li/Be or Li/Zr ratios can be used to estimate the ratio of the Mg-silicates to the group of refractory elements and in course to calculate the bulk composition of the Moon and other planetary objects.     

A simple and sensitive particle induced gamma-ray emission method for non-destructive quantification of lithium in lithium doped Nd2Ti2O7 ceramic sample

A particle induced gamma-ray emission method using proton beam in conjunction with in situ current normalization approach was standardized for non-destructive determination of low Z element lithium and was applied for quantification of Li in lithium doped neodymium dititanate (Nd₂Ti₂O₇) ceramic sample. Thick pellets of heat treated samples, their precursors and Li standards were prepared separately by homogeneously mixing with cellulose and fixed amount of F used for in situ current normalization. For validation of the method, four synthetic samples were also analyzed. Samples and standards were irradiated with 4?MeV proton beam (~5?nA current) from folded tandem ion accelerator (FOTIA) BARC, Mumbai. Characteristic ??-rays of 478?keV from ⁷Li to 197?keV from ¹⁹F were measured by high resolution ??-ray spectrometry. The Li concentrations determined in the six samples were in the range of 0.29?C0.85?wt%. The Li contents in heat treated samples gave the idea about loss of Li compared to their precursors.     

Determination des fonctions d'excitation des reactions19F(p, α0)16O et7Li(p, α0)4He entre 150 et 1800 keV

The experimental device used is described. Excitation functions are given for an angle of observation 150° with respect to the incident beam. The possibilities of applying these reactions to the measurement of surface lithium and fluorine concentrations are considered. The detection limits for these two elements are shown to be 5·10⁻³ μg·cm⁻² with protons of energy between 1,350 and 1,500 keV. The method is compared with that based on the detection of prompt γ-rays from the reactions⁷Li(p, γ)⁸Be and¹⁹F(p, α γ)¹⁶O.      

Substoichiometric isotope dilution analysis of iron in biological materials by the 8-quinolinol-extraction

A highly precise and accurate method for the determination of minor amounts of iron by substoichiometric isotope dilution analysis is described. The constant amount of Fe(III) is substoichiometrically extracted with 2·10⁻⁴M oxine in chloroform from the aqueous phase of pH 9.2–10.0 containing 6·10⁻³M tartrate. The interfering ions such as Mn(II), Co(II), Ni(II), Cu(II), and Zn(II), can be removed by the preliminary extraction of Fe(III) from 7.5M hydrochloric acid solutions into isopropyl ether. The present method has been applied to the determination of iron in biological standard reference materials, i.e., the NBS Spinach (SRM-1570) and the NIES Pepperbush (SRM No. 1), and the results obtained are 548±9 ppm (NBS certified value: 550±20 ppm) and 193±4 ppm, respectively.     

Spectrophotometric determination of trace amounts of beryllium using 1,8-dihydroxyanthrone as a new chromogenic reagent

A simple, rapid, and sensitive spectrophotometric method for the trace level determination of beryllium based on the formation of a 1:2 complex with anthralin (1,8-dihydroxyanthrone) as a new reagent is developed. A spectrophotometric method was used to determine the acidity constant and stepwise proton dissociation of the reagent. The experimental conditions for determining beryllium including the influences of pH, reagent concentration and time were evaluated and optimized. Under the optimum experimental conditions, the molar absorptivity of the complex is 0.47 × 10⁴ l mol^?1 cm^?1 at 545 nm. Calibration graph was linear in the range of 0.04–1.04 μg ml^?1 with a detection limit of 0.012 μg ml^?1 and a %RSD of 0.43%, for 5 replicate determinations at 0.48 μg ml^?1 of Be(II). The interferring effect of some cations and anions was also studied. The method was applied for the determination of beryllium in beryl, silicate rock and alloys. Ethylenediaminetetraacetic acid (EDTA) was used for masking interfering ions.     

Electronic and geometric structure analysis of neutral and anionic metal nitric chalcogens: The case of MNX series (M=Li,Na, Be and X=O,S, Se,Te)

Coupled cluster and multireference configuration approaches are employed to study the electronic and geometric structures of mono-coordinated complexes of lithium, sodium, and beryllium with nitric oxide and its isovalent NS, NSe, and NTe species. Ground and low-lying excited states were examined for both linear-bonded and side-bonded isomers. We show that the ionic M⁺NX⁻ (M=Li, Na, Be and X=O, S, Se, Te) picture is a more natural representation and can account for the symmetry of the low−lying electronic states as Σ⁻, Δ, and Σ⁺, the smaller excitation energies and the larger binding energies for heavier X. An additional electron binds to the positively charged Li and Na terminal creating stable anions. The electron affinity (EA) of LiNX and NaNX species is in the 0.5–0.8 eV range. Despite the negative EA of beryllium and the very small EA of NO, the BeNO molecule has an EA of ~1.0 eV, which is increased to ~1.5 eV for the heavier BeNX species. This is attributed to the fact that the additional electron goes to the beryllium end for BeNO but to a π(MN) π*(NX) orbital of the rest species. Our accurate results contradict previous findings and serve as a guide for future experimental studies. © 2019 Wiley Periodicals, Inc.     

Spectrophotometric determination of beryllium and zirconium using chromotrope-2C

Summary Disodium salt of o-carboxyphenylazo chromotropic acid (chromotrope 2C) has been used for the colorimetric determination of microamounts of beryllium and zirconium. The red-violet complexes show maximum absorption at 580 nm and the colour systems obey Beer's law from 0.025 to 0.375 ppm of beryllium and 2 to 12 ppm of zirconium. The optimum concentration ranges are from 0.125 to 0.375 ppm for beryllium and from 4 to 12 ppm for zirconium, where the percent relative errors per 1% absolute photometric error are, respectively, 3.014 and 3.22. The sensitivity of the reactions per cm² are 0.00067 g Be and 0.027 g Zr. The complexes, with the metal to reagent ratio of 11, have instability constants as 2.836 · 10^–6 for beryllium and 6.026 · 10^–6 for zirconium.     

Determination of oxygen with reactor neutrons

Oxygen in silicon was determined by the secondary nuclear reactions of⁶Li(n, α)T and¹⁶O(t, n)¹⁸F. Lithium fluoride was deposited in vacuum on fused quartz, covered with the sample and irradiated in a nuclear reactor. The depth profiles of¹⁸F in fused quartz and in silicon were observed, and enough depth to eliminate surface oxygen was estimated. On the basis of these results, oxygen was determined by the average cross-section method. Oxygen concentration in CZ silicon with various growing condition was 5–26 ppm and was consistent with those determined by the infrared absorption method. The detection limit of oxygen in silicon is 5 ppm.