New results on Xi’an-AMS and sample preparation systems at Xi’an-AMS center

The Institute of Earth Environment of the Chinese Academy of Sciences and Xi’an Jiaotong University have jointly created an AMS center based on a 3 MV multi-element accelerator mass spectrometer (AMS). The main focus of the Xi’an-AMS center will be earth environmental studies, archeology and biomedical research. This paper summarizes that the end-user recognized features of the Xi’an-AMS and reports new results obtained during the final acceptance tests for nuclides ¹⁰Be and ²⁶Al, for which the background for ratio ¹⁰Be/⁹Be of 3.65 × 10⁻¹⁵ was demonstrated and the ²⁶Al precision test with terminal 3 MV was performed. We also introduce the new built graphite and BeO sample preparation systems and the preparation procedures. We also discuss the recent measurements obtained using our new machine after the acceptance tests.     

Forensic applications of C at CIRCE

The decreasing trend of the radiocarbon pulse produced during the atmospheric tests of nuclear weapons (bomb-carbon) coupled with high sensitivity accelerator mass spectrometry (AMS) measurements, drastically increased the precision of radiocarbon age determinations since the second part of the sixties, allowing the application of radiocarbon AMS to a wide range of studies previously not directly involving conventional radiocarbon dating (i.e. food authenticity, forensic, biochemistry). In the framework of authenticity evaluation of artworks, high precision radiocarbon (¹⁴C) AMS measurements (ΔR/R < 0.3%) reduce the conventional uncertainty of the dating to few decades, allowing precise age estimation of materials containing carbon (C). The Centre for Isotopic Research on Cultural and Environmental heritage (CIRCE) during its activity on AMS ¹⁴C dating achieved high precision measurements opening the opportunity to these kinds of applications. This paper presents the main results obtained from radiocarbon measurements on a set of bone samples analyzed for the determination of the post-mortem interval in the framework of an unsolved case investigated by the Rome prosecutor office. The chronological characterization of the wooden support of the “Acerenza portrait” is also presented with the aim to evaluate its age and to further investigate the possibility to attribute this artwork to Leonardo da Vinci.Bomb-¹⁴C dating on the lipid and collagen fractions of bones allows the evaluation of the year of the death of the individuals by means of ad hoc calibration data sheet with the typical few years precision and difference between collagen apparent age and the year of death appeared in agreement with the age of one individual estimated by dating of tooth collagen. Conventional radiocarbon dating on both wood and wood extracted cellulose leads to an estimation of the portrait wood board age (2σ) of 1459-1524 AD (57% relative probability), 1571-1631 AD interval (42% relative probability).and 1559-1563 AD (1% relative probability). These results attribute with the highest relative probability an age comprised within the life span of Leonardo (1452-1519) to the support.     

Applications of a compact ionization chamber in AMS at energies below 1 MeV/amu

The increasing demand for measuring long-lived radionuclides with small AMS machines at energies below 1 MeV per nucleon raises the need for compact detectors which still have a decent energy resolution and allow for a clear identification of the incident particles. Based on a design by the AMS group at the ETH Zurich a compact gas ionization chamber was built and installed at the 3 MV tandem AMS facility VERA (Vienna Environmental Research Accelerator). The main challenge in AMS is the detection of rare isotope species in the presence of strong isotopic and isobaric interferences. The task of the ionization chamber is the suppression of the unwanted isobar by separating the ions via their different stopping powers. Measurements of ³⁶Cl at VERA showed an achieved suppression of the unwanted stable isobar ³⁶S of 3 × 10⁻⁴ and measurements of ¹⁰Be showed an achieved suppression of ¹⁰B of at least 3 × 10⁻⁶. Additional suppression of the isobaric ions can be achieved by a degrader foil technique applied to ¹⁰Be measurements by G.M. Raisbeck. In combination with the new ionization chamber the achieved suppression of ¹⁰B is at least 10⁻¹⁰. Measurements of blank samples at VERA show that the background for AMS with ¹⁰Be is below 2 × 10⁻¹⁵.     

Plutonium measurements on the 1 MV AMS system at the Centro Nacional de Aceleradores (CNA)

Plutonium isotopes have been recently added to the list of radionuclides that can be measured with the new generation of compact AMS facilities. In this paper we present first experimental results concerning the development of the plutonium AMS technique at 680 kV on the 1 MV AMS system at the Centro Nacional de Aceleradores (CNA) in Sevilla, Spain. This is the first compact AMS machine designed and manufactured by High Voltage Engineering Europa. As we demonstrate, the obtained backgrounds for ^239,240Pu, of about 10⁶ atoms, and the ²³⁹Pu/²³⁸U mass suppression factor, in the range of 10⁻⁹, compare to the ones achieved on other AMS facilities. With the measurement of reference materials provided by the International Atomic Energy Agency (IAEA-375, IAEA-Soil-6, IAEA-381) and samples already studied on the 600 kV compact ETH/PSI AMS system at Zürich, we show that the CNA system can be perfectly used for the routine measurement of plutonium isotopes at environmental levels.     

Status of the compact 1 MV AMS facility at the Centro Nacional de Aceleradores (Spain)

Since February 2006, the new 1 MV multielement compact AMS facility SARA (Spanish Accelerator for Radionuclides Analyses) at the Centro Nacional de Aceleradores (CNA) in Sevilla (Spain) is fully operative. During the first one and a half year of operation, the viability of the system for the measurement of ¹⁰Be, ¹⁴C, ¹²⁹I and plutonium isotopes, ²³⁹Pu and ²⁴⁰Pu, has been evaluated. First results have demonstrated that, in terms of precision and detection limits, the performance of the device compares to other compact AMS facilities, although some progress can still be done in order to optimize its capacities. At this moment, background levels are in the order of 10⁻¹⁴ for ¹⁰Be/⁹Be, 10⁻¹³ for ¹²⁹I/¹²⁷I, 10⁻¹⁵ for ¹⁴C/¹²C (processed and unprocessed blank) and about 10⁶ atoms for plutonium isotopes: ²³⁹Pu, ²⁴⁰Pu and ²⁴²Pu. In this work, the current status of the AMS measurements at CNA for the above mentioned radionuclides is described.     

Towards more precise Be and Cl data from measurements at the 10 level: Influence of sample preparation

The spreading application of accelerator mass spectrometry (AMS) to the geosciences will require measurement of increasing numbers of samples with low ¹⁰Be/⁹Be and ³⁶Cl/Cl isotopic ratios. To distinguish radionuclide concentrations in samples from corresponding processing blanks, samples must be prepared using stable isotope carriers with low intrinsic radionuclide concentrations. Measurements at different AMS facilities have shown that commercially available ⁹Be carriers rarely meet these requirements and use of ⁹Be carriers prepared from Be-containing minerals such as Be₂SiO₄ is advisable. For precise determinations at the low 10⁻¹⁴ level, samples need to produce the highest ⁹Be currents possible. Measurements performed at the two AMS facilities in France show that mixing BeO with Nb powder generally yields higher ⁹Be currents than mixing with Ag powder. Contamination of BeO by other elements such as Ti or Al will reduce the current by a simple dilution effect, thus limiting the statistical precision with which ¹⁰Be can be determined. In the case of ³⁶Cl analyses, repeated water-leaching of calcite samples sufficiently removes all atmospheric ³⁶Cl contamination, allowing determination of terrestrial cosmogenic in situ produced ³⁶Cl concentrations for surface exposure dating.     

Protactinium-231: A new radionuclide for AMS

For the first time, an AMS system was used to determine concentrations of the actinide Protactinium-231. ²³¹Pa has widespread applications in the earth sciences. It can be used for U-series disequilibrium dating, and ²³¹Pa is an important tracer in Paleoceanography. The Pa isotopes were measured with the compact ETH/PSI-AMS facility TANDY operating at about 300 kV. The linearity of the AMS is documented with two standard-dilution experiments and first measurements of natural samples from very different climate archives are presented. Our results show that it is possible to determine ²³¹Pa amounts in the lower femtogram (1 fg = 10⁻¹⁵ g) range with the TANDY. In natural samples, ²³¹Pa concentrations between 1 and 4 pg/g (1 pg = 10⁻¹² g) were measured with an average total error of 3% (one sigma). The average over all reproducibility of these first measurements was better than 2% with clear potential for improvement.     

Development of a high intensity Al beam from SiC targets for accelerated beam experiments at ISAC

An intense beam of ^26gAl has been developed for accelerated beam experiments at TRIUMF’s ISAC facility. Studies of the on-line production of Al radionuclides from thick silicon carbide targets have been performed as part of a program of beam development for astrophysical reaction studies at ISAC. While the release of short-lived Al nuclides from SiC was found to be slow, development of new target material forms and high-power target containers has allowed operation of SiC targets with proton currents of up to 70 μA on target. In addition, operation with the TRIUMF resonant ionization laser ion source (TRILIS) has produced ^26gAl beam intensities of 5.1 × 10¹⁰ s⁻¹.     

Pure ionization cross section of helium and ionization mechanism

Pure target ionization was investigated for 0.4-6.4 MeV C^q+(q = 1-4) + He and O^q+(q = 1-4) + He collisions. The double-to-single target ionization ratios R₂₁ were measured using coincidence techniques. We compare our results with existing experimental results and find they are in good agreement. The ratio R₂₁ is nearly independent of projectile charge state. The relation of R₂₁ ∼ V is analyzed using the over barrier model (OBM) and ionization probability, which is described in our extended over barrier model. Our calculation agrees well with the experimental results.     

Natural and anthropogenic U in environmental samples

The interaction of thermal neutrons with ²³⁵U results in fission with a probability of ∼85% and in the formation of ²³⁶U (t_1/2 = 2.3 × 10⁷ yr) with a probability of ∼15%. While anthropogenic ²³⁶U is, therefore, present in spent nuclear fuel at levels of ²³⁶U/U up to 10⁻², the expected natural ratios in the pre-anthropogenic environment range from 10⁻¹⁴ to 10⁻¹⁰. At VERA, systematic investigations suggest a detection limit below ²³⁶U/U = 5 × 10⁻¹² for samples of 0.5 mg U, while chemistry blanks of ∼2 × 10⁷ atoms ²³⁶U per sample limit the sensitivity for smaller samples. We have found natural isotopic ratios in uranium reagents separated before the onset of human nuclear activities, in uranium ores from various origins and in water from a subsurface well in Bad Gastein, Austria. Anthropogenic contamination was clearly visible in soil and rivulet samples from Salzburg, Austria, whereas river sediments from Garigliano river (Southern Italy) were close to the detection limit. Finally, our natural in-house standard Vienna-KkU was calibrated against a certified reference material (IRMM REIMEP-18 A).     

Study of Al measurement on the Shanghai Mini-cyclotron based AMS

We present a modification to the ¹⁴C-dedicated SMCAMS (Shanghai mini-cyclotron based AMS) system to allow the measurement of ²⁶Al for biomedical applications with the existing devices. This is accomplished by determining the turn number, harmonic number and RF frequency theoretically and then making the appropriate orbit programming and beam optics calculation and experimental adjustments. The tests were conducted using pencil graphite (for the carbon pilot beam), Al₂O₃ powder and metal aluminum to accelerate ions with mass number of 24, 25, 26 and 27. The frequency response curves for those ions are shown. Finally, the Al₂O₃ standard sample with a known isotope ratio of 1.0 × 10⁻¹⁰ is measured. The ²⁶Al⁻ ions are detected and its frequency response curve shows the peak of ²⁶Al⁻ though very weak is well separated from the most neighboring interfering molecular ions ²⁵MgH⁻.     

Small-mass graphite preparation by sealed tube zinc reduction method for AMS 14C measurements

Previous work has demonstrated that the sealed tube Zn reduction method for converting CO₂ to graphite for AMS ¹⁴C measurements produces targets that can be measured with high precision and low background for samples of about 1 mg C down to approximately 0.1 mg C at the Keck Carbon Cycle AMS facility at the University of California, Irvine (KCCAMS). Now a modified method has been developed to prepare small-mass samples ranging from 0.015 to 0.1 mg C. In this modified method, the volume of the sealed reactor tube is reduced to ～1.9 cm³, and the amounts of Zn and TiH₂ reagents are reduced proportionally. The amount of Fe catalyst used remains the same to ensure a long lasting current in the AMS. Small-mass samples prepared by this method generally yield ¹²C⁺¹ currents of about 0.5 μA per 1 μg C. An in situ simultaneous AMS δ¹³C measurement allows for correction of both graphitization and machine-induced isotopic fractionation, and is a prerequisite for high precision and accurate measurements using the Zn reducing method. Corrections for modern-carbon and dead-carbon background components are applied to samples based on small-mass samples of a ¹⁴C free material and of a modern standard covering the sample size range. It was discovered during additional investigation into lowering the modern-carbon background component that baking assembled reactor tubes at 300 °C for 1 h prior to use resulted in significantly lower modern-carbon background values. The accuracy and precision of small-mass samples prepared by this method are size dependent, but is usually ±10–15‰ for the smallest samples (0.015–0.02 mg C), based on duplicate measurements of primary and secondary standards.     

A new value for the half-life of Be by Heavy-Ion Elastic Recoil Detection and liquid scintillation counting

The importance of ¹⁰Be in different applications of accelerator mass spectrometry (AMS) is well-known. In this context the half-life of ¹⁰Be has a crucial impact, and an accurate and precise determination of the half-life is a prerequisite for many of the applications of ¹⁰Be in cosmic-ray and earth science research. Recently, the value of the ¹⁰Be half-life has been the centre of much debate. In order to overcome uncertainties inherent in previous determinations, we introduced a new method of high accuracy and precision. An aliquot of our highly enriched ¹⁰Be master solution was serially diluted with increasing well-known masses of ⁹Be. We then determined the initial ¹⁰Be concentration by least square fit to the series of measurements of the resultant ¹⁰Be/⁹Be ratio. In order to minimize uncertainties because of mass bias which plague other low-energy mass spectrometric methods, we used for the first time Heavy-Ion Elastic Recoil Detection (HI-ERD) for the determination of the ¹⁰Be/⁹Be isotopic ratios, a technique which does not suffer from difficult to control mass fractionation. The specific activity of the master solution was measured by means of accurate liquid scintillation counting (LSC). The resultant combination of the ¹⁰Be concentration and activity yields a ¹⁰Be half-life of T_1/2 = 1.388 ± 0.018 (1 s, 1.30%) Ma. In a parallel but independent study (Chmeleff et al. [11]), found a value of 1.386 ± 0.016 (1.15%) Ma. Our recommended weighted mean and mean standard error for the new value for ¹⁰Be half-life based on these two independent measurements is 1.387 ± 0.012 (0.87%) Ma.     

Proton induced γ-ray emission yields for the analysis of light elements in aerosol samples in an external beam set-up

The PIXE technique is a reliable tool for the characterisation of thin aerosol samples, but it can underestimate the lightest measurable elements, like Na, Mg, Al, Si and P, owing to the absorption of their X-rays inside the sample. The PIGE technique is a valid help to determine corrections for such effect: in order to perform PIGE measurements relative to thin reference standards in an external beam set-up, we measured, at the external beam facility of the Tandetron accelerator of the LABEC laboratory in Florence, the γ-ray yields as a function of the proton beam energy for the reactions ¹⁹F(p,p′γ)¹⁹F (E_γ = 110 and 197 keV), ²³Na(p,p′γ)²³Na (E_γ = 440 keV) and ²⁷Al(p,p′γ)²⁷Al (E_γ = 843 and 1013 keV), in the proton energy range from 3 to 5 MeV. The measured yields are shown, and the determined most suitable energies for performing PIGE quantification of Na and Al are reported, together with the corresponding minimum detection limits (MDLs). The results of some test on PIGE accuracy and an evaluation of self-absorption effects in PIXE measurements on thin aerosol samples are also presented.     

A versatile integrated system for thermoluminescence and optically stimulated luminescence measurements

A versatile integrated reader system for TL and OSL measurements of phosphor materials has been described for luminescence research applications. The developed integrated reader system works either in TL or OSL or TL-OSL mode. In the OSL operation, besides the conventional CW-OSL, POSL and LM-OSL modes a novel non-linear OSL (NL-OSL) method has been incorporated in the reader system. The optical stimulation unit consists of four high power LEDs fitted in four channels and optically focused on the sample. Each of the LED is capable of delivering up to 80 mW/cm² light power at the sample position. The LEDs with peak wavelength λ_p ≈ 470 nm and 530 nm and Δλ ≈ 20 nm have been used for optical stimulation of the samples. A PID temperature controller has been used for generating and controlling user defined heating profiles for the TL measurements in the reader system. The reader system covers a wide dynamic dose range of 10 μGy to 10³ Gy for TL/OSL measurements. The OSL grade α-Al₂O₃:C phosphor was used to test the reader system and investigate its impact on low dose assessment for personnel and environmental monitoring. The design concept of the reader system and the results of dose measurements are discussed.     

Monte Carlo study of ion-induced backward and forward secondary electron emission from thin Al foil

A direct Monte Carlo program has been developed to calculate the backward (γ_b) and forward (γ_f) electron emission yields from 20 nm thick Al foil for impact of C⁺, Al⁺, Ar⁺, Cu⁺ and Kr⁺ ions having energies in the range of 0.1-10 keV/amu. The program incorporates the excitation of target electrons by projectile ions, recoiling target atoms and fast primary electrons. The program can be used to calculate the electron yields, distribution of electron excitation points in the target and other physical parameters of the emitted electrons. The calculated backward electron emission yield and the Meckbach factor R = γ_f/γ_b are compared with the available experimental data, and a good agreement is found. In addition, the effect of projectile energy and mass on the longitudinal and lateral distribution of the excitation points of the electrons emitted from front and back of Al target has been investigated.     

In situ ERDA measurements of hydrogen isotope concentrations in palladium at atmospheric pressure

In situ elastic recoil detection analysis (ERDA) measurements in gases at atmospheric pressure have been carried out using 15 MeV ⁴He ion beams. The beams are extracted through a molybdenum foil having a thickness of 5 μm. The maximum depth of analysis is about 4 μm for the palladium hydride and palladium deuteride (PdH_x and PdD_x, x = 0.7-0.8) samples. The temperature of the samples rises stepwise from room temperature to 180 °C. ERDA spectra are obtained every 2 min. Hydrogen and deuterium in the samples are discharged in the temperature range of 120-140 °C in a vacuum. Decrease in the hydrogen concentration in the PdH_x sample heated in a vacuum follows a first order in the value of x and an apparent activation energy of discharge of hydrogen is 1.05 eV. On the other hand, the hydrogen and deuterium concentrations decrease at about 80 °C in air. No isotope effects are observed in both a vacuum and air. The temperature at which the hydrogen concentration decreases in helium gas is almost the same as that in a vacuum. It indicates that hydrogen and deuterium atoms are discharged by chemical reactions with air and that there are no effects of cooling of the thermocouple by convection of air.     

Si AMS measurement with ΔE-Q3D method

Accelerator mass spectrometry (AMS) is one of the most promising methods for the measurement of trace amount of ³²Si for its advantages of small sample size, short measurement time and extremely high sensitivity. However, the isobaric interference from ³²S often badly hinders the AMS measurement of ³²Si. The ΔE-Q3D detection technique established in this work brought about an overall suppression factor of larger than 10¹² for ³²S. As a result, a sensitivity of better than 1 × 10⁻¹⁴ (³²Si/Si) has been achieved, based on the measurement of a blank sample.     

Thermal and structural properties of low-fluence irradiated graphite

The release of Wigner energy from graphite irradiated by fast neutrons at a TRIGA Mark II research reactor has been studied by differential scanning calorimetry and simultaneous differential scanning calorimetry / synchrotron powder X-ray diffraction between 25 and 725 °C at a heating rate of 10 °C min⁻¹. The graphite, having been subject to a fast-neutron fluence from 5.67 × 10²⁰ to 1.13 × 10²² n m⁻² at a fast-neutron flux (E > 0.1 MeV) of 7.88 × 10¹⁶ n m⁻² s⁻¹ and at temperatures not exceeding 100 °C, exhibits Wigner energies ranging from 1.2 to 21.8 J g⁻¹ and a Wigner energy accumulation rate of 1.9 × 10⁻²¹ J g⁻¹ n⁻¹ m². The differential-scanning-calorimeter curves exhibit, in addition to the well known peak at ∼200 °C, a pronounced fine structure consisting of additional peaks at ∼150, ∼230, and ∼280 °C. These peaks correspond to activation energies of 1.31, 1.47, 1.57, and 1.72 eV, respectively. Crystal structure of the samples is intact. The dependence of the c lattice parameter on temperature between 25 and 725 °C as determined by Rietveld refinement leads to the expected microscopic thermal expansion coefficient along the c axis of ∼26 × 10⁻⁶ °C⁻¹. At 200 °C, coinciding with the maximum in the differential-scanning-calorimeter curves, no measurable changes in the rate of thermal expansion have been detected - unlike its decrease previously seen in more highly irradiated graphite.