Depth profiling and standardization from the back side of a sample for accurate analyses: Emphasis on quantifying low-fluence, shallow implants in diamond-like carbon.

RATIONALE: Back-side thinning of wafers is used to eliminate issues with transient sputtering when analyzing near-surface element distributions. Precise and accurate calibrated implants are created by including a standard reference material during the implantation. Combining these methods allows accurate analysis of low-fluence, shallow features even if matrix effects are a concern. METHODS: Implanted Na (<2.0 × 1011 ions/cm2 , peaking <50 nm) in diamond-like carbon (DLC) film on silicon (solar wind returned by NASA's Genesis mission) was prepared for measurement as follows. Implanted surfaces of samples were epoxied to wafers and back-side-thinned using physical or chemical methods. Thinned samples were then implanted with reference ions for accurate quantification of the solar wind implant. Analyses used a CAMECA IMS 7f-GEO SIMS in depth-profiling mode. RESULTS: Back-side-implanted reference ions reduced the need to change sample mounts or stage position and could be spatially separated from the solar wind implant even when measuring monoisotopic ions. Matrix effects in DLC were mitigated and the need to find an identical piece of DLC for a reference implant was eliminated. Accuracy was only limited by the back-side technique itself. CONCLUSIONS: Combining back-side depth profiling with back-side-implanted internal standards aides quantification of shallow mono- and polyisotopic implants. This technique helps mitigate matrix effects and keeps measurement conditions consistent. Depth profile acquisition times are longer, but if sample matrices are homogeneous, procedural changes can decrease measurement times.

Best Practices for Determination of Initial 10Be/9Be in Early Solar System Materials by Secondary Ion Mass Spectrometry.

Beryllium-10 (t 1/2 = 1.4 Ma) is a short-lived radionuclide present in the early Solar System. It is produced solely by irradiation reactions and can provide constraints on the astrophysical environment of the Sun's formation. Calcium- and aluminium-rich inclusions (CAIs), the first solids formed in the Solar System, show clear evidence for live 10Be at their time of formation, but it is unclear whether they record the same initial 10Be/9Be ratio. In this study, we examine the secondary ion mass spectrometry methods used to determine the initial 10Be/9Be ratio in meteoritic inclusions. Based on analyses of synthesised matrix-matched glass reference materials, we show that the effects of differing major element bulk compositions on the secondary ion yields of Be and B are minor for relevant phases. We demonstrate the importance of using the mean square weighted deviation (MSWD) to interpret the significance of the initial 10Be/9Be value. For thirty-two CAIs, we re-calculated the regressions using literature data, finding that several have unacceptably high MSWD. We calculate the effects of possible sources of isotopic disturbance. Finally, we outline best practices for reporting 10Be-10B data, to enable a more refined determination of the initial 10Be/9Be ratio in the early Solar System.

Water on Mars: Insights from apatite in regolith breccia Northwest Africa 7034.

Determining the source of planetary water from the hydrogen isotope compositions of crustal samples is complicated by the overprinting of isotopically diverse source material by geologic and atmospheric processes. As Mars has no plate tectonics, crustal material, which may have isotopically exchanged with the martian atmosphere, is not recycled into the mantle keeping the water reservoirs in the mantle and atmosphere mostly isolated, buffered by the crust. As the only known martian samples that are regolith breccias with a composition representative of the average crust of Mars, Northwest Africa (NWA) 7034 and its paired stones provide an important opportunity to investigate the water content and hydrogen isotope composition of the martian crust. In particular, apatites in distinct clasts as well as the brecciated matrix of NWA 7034 record a complex history including magmatic and impact processes, and exchange with crustal fluids.

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements.

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. Using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclides generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Furthermore, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.

Ultrahydrous stishovite from high-pressure hydrothermal treatment of SiO2.

Stishovite (SiO(2) with the rutile structure and octahedrally coordinated silicon) is an important high-pressure mineral. It has previously been considered to be essentially anhydrous. In this study, hydrothermal treatment of silica glass and coesite at 350-550 °C near 10 GPa produces stishovite with significant amounts of H(2)O in its structure. A combination of methodologies (X-ray diffraction, thermal analysis, oxide melt solution calorimetry, secondary ion mass spectrometry, infrared and nuclear magnetic resonance spectroscopy) indicate the presence of 1.3 ± 0.2 wt % H(2)O and NMR suggests that the primary mechanism for the H(2)O uptake is a direct hydrogarnet-like substitution of 4H(+) for Si(4+), with the protons clustered as hydroxyls around a silicon vacancy. This substitution is accompanied by a substantial volume decrease for the system (SiO(2) + H(2)O), although the stishovite expands slightly, and it is only slightly unfavorable in energy. Stishovite could thus be a host for H(2)O at convergent plate boundaries, and in other relatively cool high-pressure environments.

Anomalous fractionation of sulfur isotopes during sputtering.

Secondary ion mass spectrometric (SIMS) measurements of sulfur isotope ratios obtained during sputtering with a Cs(+) beam and detection of negative secondary ions show a strong dependence of isotope fractionation on secondary ion energy for ions with approximately 2-10 eV excess kinetic energy (approximately 9 per thousand/eV), and a weak dependence for ions with approximately 10-approximately 350 eV (0.05 per thousand/eV). Variable collection of the low-energy ions could thus result in variable measured sulfur isotope ratios. Being aware of this behavior should allow the analyst to avoid such a problem. The fractionation of the isotopes does not appear to follow theoretical or measured behavior for positive ions, and suggests that, at least for sulfur, the process of negative secondary ion emission is incompletely understood and may require different theoretical models.