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Electron probe microanalyzer measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~100 μg g(−1) level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimize electron beam current density, a rastered 50 × 100 μm electron beam was adequate and minimized sensitivity to small Al-rich contaminants. Reproducible analyses of eleven SIMS-cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 μg g(−1)• The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: lmilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination-sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.

X-ray standing wave fluorescence yield depth profiling was used to determine the solar wind implanted Fe and Ni fluences in a silicon-on-sapphire (SoS) Genesis collector (60326). An internal reference standardization method was developed based on fluorescence from Si and Al in the collector materials. Measured Fe fluence agreed well with that measured previously by us on a sapphire collector (50722) as well as SIMS results by Jurewicz et al. Measured Ni fluence was higher than expected by a factor of two; neither instrumental errors nor solar wind fractionation effects are considered significant perturbations to this value. Impurity Ni within the epitaxial Si layer, if present, could explain the high Ni fluences and therefore needs further investigation. As they stand, these results are consistent with minor temporally-variable Fe and Ni fractionation on the timescale of a year.

We have measured the isotopic composition and fluence of solar-wind nitrogen in a diamond-like-carbon collector from the Genesis B/C array. The B and C collector arrays on the Genesis spacecraft passively collected bulk solar wind for the entire collection period, and there is no need to correct data for instrumental fractionation during collection, unlike data from the Genesis “Concentrator.” This work validates isotopic measurements from the concentrator by Marty et al. (2010, 2011); nitrogen in the solar wind is depleted in ^(15)N relative to nitrogen in the Earth’s atmosphere. Specifically, our array data yield values for ^(15)N/^(14)N of (2.17 ± 0.37) × 10^(−3) and (2.12 ± 0.34) × 10^(−3), depending on data-reduction technique. This result contradicts preliminary results reported for previous measurements on B/C array materials by Pepin et al. (2009), so the discrepancy between Marty et al. (2010, 2011) and Pepin et al. (2009) was not due to fractionation of solar wind by the concentrator. Our measured value of ^(15)N/^(14)N in the solar wind shows that the Sun, and by extension the solar nebula, lie at the low-^(15)N/^(14)N end of the range of nitrogen isotopic compositions observed in the solar system. A global process (or combination of processes) must have operated in interstellar space and/or during the earliest stages of solar system formation to increase the ^(15)N/^(14)N ratio of the solar system solids. We also report a preliminary Genesis solar-wind nitrogen fluence of (2.57 ± 0.42) × 10^(12) cm^(−2). This value is higher than that derived by backside profiling of a Genesis silicon collector (Heber et al. 2011a).

We report concentrations and isotopic compositions of He, Ne, and Ar measured with high spatial resolution along a radial traverse of a silicon carbide (SiC) quadrant of the Genesis mission concentrator target. The Ne isotopic composition maps instrumental fractionation as a function of radial position in the target: the maximum observed isotopic fractionation is approximately 33‰ per mass unit between the center and periphery. The Ne fluence is enhanced by a factor of 43 at the target center and decreases to 5.5 times at the periphery relative to the bulk solar wind fluence. Neon isotopic profiles measured along all four arms of the "gold cross" mount which held the quadrants in the concentrator target demonstrate that the concentrator target was symmetrically irradiated during operation as designed. We used implantation experiments of Ne into SiC and gold to quantify backscatter loss and isotopic fractionation and compared measurements with numerical simulations from the code "stopping and range of ions in matter." The ^(20)Ne fluence curve as a function of radial distance on the target may be used to construct concentration factors relative to bulk solar wind for accurate corrections for solar wind fluences of other light elements to be measured in the concentrator target. The Ne isotopic composition as a function of the radial distance in the SiC quadrant provides a correction for the instrumental mass-dependent isotopic fractionation by the concentrator and can be used to correct measured solar wind oxygen and nitrogen isotopic compositions to obtain bulk solar wind isotopic compositions.

We present the first experimental radium mineral/melt partitioning data, specifically between anorthite and a CMAS melt at atmospheric pressure. ^(226)Ra disequilibria are an important chronometer of recent magmatic activity. Ion microprobe measurement of coexisting anorthite and glass phases produces a molar D_Ra = 0.040 ± 0.006 and D_(Ra)/D_(Ba) = 0.24 ± 0.05 at 1400 °C. Our results indicate that lattice strain partitioning models fit the divalent (Ca, Sr, Ba, Ra) partition coefficient data of this study well, supporting previous work on crustal melting and magma chamber dynamics that has relied on such models to approximate radium partitioning behavior in the absence of experimentally determined values.

Ion microprobe elemental and isotopic determinations can be precise but difficult to quantify. Error is introduced when the reference material and the sample to be analysed have different compositions. Mitigation of such “matrix effects” is possible using ion implants. If a compositionally homogeneous reference material is available which is “matrix-appropriate,” i.e., close in major element composition to the sample to be analysed, but having an unknown concentration of the element, E, to be determined, ion implantation can be used to introduce a known amount of an E isotope, calibrating the E concentration and producing a matrix-appropriate calibrator. Nominal implant fluences (ions cm^(−2)) are inaccurate by amounts up to approximately 30%. However, ion implantation gives uniform fluences over large areas, thus it is possible to “co-implant” an additional reference material of any bulk composition having known amounts of E, independently calibrating the implant fluence. Isotope-ratio measurement standards can be produced by implanting two different isotopes, but permil level precision requires post-implant calibration of the implant isotopic ratio. Examples discussed include: (1) standardising Li in melilite; (2) calibrating a ^(25)Mg implant fluence using NIST SRM 617 glass; and (3) using Si co-implanted with ^(25)Mg alongside NIST SRM 617 to produce a calibrated measurement of Mg in Si.

Apatite, titanite and olivine samples were bombarded with a ~ 150 MeV proton beam to produce ~ 10^8 atoms/mg of spallation ^3He. High-precision stepped-heating experiments were then performed in which the artificial ^3He and, for apatite and titanite, the natural radiogenic ^4He were measured to characterize the diffusive behavior of each isotope. Helium-3 diffusion coefficients are in excellent agreement with concurrently and/or previously determined He diffusion coefficients for each mineral. Our results indicate that proton-induced ^3He is uniformly distributed and that radiation damage associated with a proton fluence of ~ 5 x 10^(14) protons/cm^2 does not cause noticeable changes in ^4He diffusion behavior in at least apatite and titanite. Proton-induced ^3He can therefore be used to establish He diffusion coefficients in minerals with insufficient natural helium for analysis or those in which the natural ^4He distribution is inhomogeneous. In addition,step-heating ^4He/^3He analysis of a mineral with a uniform synthetic ^3He concentration provides a means by which a natural ^4He distribution can be determined.

International audience; A method to quantitatively determine the fluences of shallowly-implanted solar wind ions returned to Earth by the Genesis Discovery mission is described. Through backside depth-profiling, we recover nearly complete depth profiles of implanted solar wind for several nonvolatile elements, including Mg, Al, Ca, Cr, and, to a lesser extent, Na, in silicon targets that collected bulk solar wind and solar wind from specific velocity regimes. We also determine the fluences of the volatile elements C, N, and O in silicon targets that collected bulk solar wind. By the use of appropriately calibrated ion implanted standards, fluences as low as 2 x 10(10) atoms cm(-2) can be determined with precision and accuracy typically in the few percent range. Specific approaches to sample preparation, sputtering artifacts during depth profiling by secondary ion mass spectrometry, and quantification including the production of ion implant standards are discussed. (C) 2014 Elsevier B.V. All rights reserved.

RIMS depth profiles have been measured for Cr and Ca in Genesis solar wind collector made from Si and compared to such measurements for ion-implanted Si reference material. The presence of surface contamination has been shown to be a significant factor influencing the total Ca and Cr fluence measured in the Genesis collectors. A procedure to remove the contaminant signal from these depth profiles using the reference material implanted with a minor isotope demonstrated that 36% of the measured Ca fluence in our Genesis sample comes from terrestrial contamination.

The thermal diffusion of an Mg implant in Si has been measured with SIMS and compared to RIMS (resonant ionisation mass spectrometry) measurements of Mg implantation and diffusion in Si wafers exposed to solar wind irradiation in the NASA Genesis mission. The Genesis samples show much more surface segregation that the samples annealed in the laboratory, due to diffusion and segregation of the implanted Mg to the heavily damaged near surface regions of the Genesis wafers. This Mg transport has been modeled by solving a set of stiff differential equations and found to agree with RIMS measurements for a Mg interstitial migration energy of 0.7 eV.

Regular, geometric, apparently crystallographically-controlled, sector zoning has been produced in synthetic anorthite crystallized from a liquid of Type B Ca,Al-rich inclusion (CAI) composition. Cathodoluminescence (CL) provides a rapid method for observing the sectors. Sharp discontinuities in Mg concentration always accompany sharp changes in CL intensity at sector boundaries. Although CL intensity anti-correlates with Mg concentration, there is not a well-defined quantitative relationship, and Mg concentration steps range from as little as 5% to almost a factor of 2 for different CL boundaries. When measurable, Na also tends to anti-correlate with CL brightness in a given crystal and thus correlates with Mg. The partition coefficients for Mg and Na can vary by up to a factor of 2 depending on the particular sector and thus are not constant for CAI anorthite which formed by fractional crystallization. In contrast, Ti (either Ti^+3 or Ti^+4) concentration is not a function of sector zoning and thus does not affect the CL intensity. The sector zoning and correlated chemical variations for synthetic anorthite are similar to those in natural anorthite from Type B CAIs. The CL intensity, boundary sharpness, and minor element zoning in synthetic anorthite are not affected by annealing at 850°C for three weeks. Overall, our observations suggest that the observed CL patterns and minor element zoning in Type B anorthite are igneous in origin and have not been modified by subsolidus reequilibration or alteration. This leads to the conclusion that the ^(26)Mg-^(26)Al systematics in CAIs (based almost entirely on anorthite) have not been modified by subsolidus reequilibration or alteration.

The Genesis mission Solar Wind Concentrator was built to enhance fluences of solar wind by an average of 20x over the 2.3 years that the mission exposed substrates to the solar wind. The Concentrator targets survived the hard landing upon return to Earth and were used to determine the isotopic composition of solar-wind—and hence solar—oxygen and nitrogen. Here we report on the flight operation of the instrument and on simulations of its performance. Concentration and fractionation patterns obtained from simulations are given for He, Li, N, O, Ne, Mg, Si, S, and Ar in SiC targets, and are compared with measured concentrations and isotope ratios for the noble gases. Carbon is also modeled for a Si target. Predicted differences in instrumental fractionation between elements are discussed. Additionally, as the Concentrator was designed only for ions ≤22 AMU, implications of analyzing elements as heavy as argon are discussed. Post-flight simulations of instrumental fractionation as a function of radial position on the targets incorporate solar-wind velocity and angular distributions measured in flight, and predict fractionation patterns for various elements and isotopes of interest. A tighter angular distribution, mostly due to better spacecraft spin stability than assumed in pre-flight modeling, results in a steeper isotopic fractionation gradient between the center and the perimeter of the targets. Using the distribution of solar-wind velocities encountered during flight, which are higher than those used in pre-flight modeling, results in elemental abundance patterns slightly less peaked at the center. Mean fractionations trend with atomic mass, with differences relative to the measured isotopes of neon of +4.1±0.9 ‰/amu for Li, between -0.4 and +2.8 ‰/amu for C, +1.9±0.7‰/amu for N, +1.3±0.4 ‰/amu for O, -7.5±0.4 ‰/amu for Mg, -8.9±0.6 ‰/amu for Si, and -22.0±0.7 ‰/amu for S (uncertainties reflect Monte Carlo statistics). The slopes of the fractionation trends depend to first order only on the relative differential mass ratio, Δ m/ m. This article and a companion paper (Reisenfeld et al. 2012, this issue) provide post-flight information necessary for the analysis of the Genesis solar wind samples, and thus serve to complement the Space Science Review volume, The Genesis Mission (v. 105, 2003).

Experiments were conducted in air and at low oxygen fugacity (f_O_2)) to evaluate Mg and Ti partitioning between anorthite and liquid (D_(Mg) and D_(Ti) in a synthetic composition similar to that of a Type B Ca, AI-rich inclusion (CAI). The starting material showed a range of compositions, which allowed assessment of the composition dependence of D_(Mg) and D_(Ti) in this system. Additional experiments using a homogeneous split of the same material investigated the effect of oxygen fugacity on the partitioning of Ti^(3+) and Ti^(4+) between anorthite and liquid. The low foe charges were purple, consistent with the presence of significant amounts of Ti^(3+).This was verified by electron spin resonance (ESR) spectra, and quantitative estimates of Ti^(3+) contents were obtained using ESR. The Ti and Mg partition coefficients in the air run using the homogeneous starting material are similar (0.034 and 0.036, respectively) and consistent with those determined in other studies. However, D_(Ti) at low f_(O_2) is slightly greater than D_(Ti) in the air experiments. Using Ti^(3+)/total Ti from the ESR measurements, D_(Ti^(3+)) is calculated to be about 0.040. The range of compositions reveal a clustering of D_(Mg) and D_(Ti) within charges, but a wide range of D_s between charges of different composition. A well-defined inverse correlation exists between D_(Mg) and D_(Ti). This variation is not due to temperature-dependence, but is instead due to the dependence of D_(Mg) and D_(Ti) on liquid composition (Si and Al in particular). D_(Mg) correlates positively with Si content and negatively with Al content, while D_(Ti) shows the opposite correlations. The results of these experiments have interesting implications for the petrogenesis of Type B CAIs and for substitution mechanisms of Mg, Ti^(4+), and Ti^(3+) into anorthite. Crystallization models for Type B CAIs permit certain predictions concerning trace element systematics in plagioclase. The Mg and Ti systematics are best explained by a fractional crystallization model where plagioclase crystallizes very late (>95% crystallization), and D_(Ti^(3+)). is equal to D_(Ti^(4+)). The results from our experiments support this model for the relative partitioning of Ti^(4+) and Ti^(3+) between plagioclase and liquid. In addition, the dependence of D_(Mg), and D_(Ti) on the Si content of a Type B CAI liquid helps explain systematics expected during late-stage crystallization of plagioclase. The composition dependence of D_(Mg) and D_(Ti) also allows assessment of substitution mechanisms in anorthite using a crystallization reaction approach. Using these methods, a plausible mechanism for Mg involves substitution for tetrahedral A1 by the reaction Mg^(2+) + Si^(4+) = 2AI^(3+), consistent with that proposed by previous workers. The systematics are also consistent with Ti^(4+) and Ti^(3+) substitution for tetrahedral Si^(4+) by the reactions 2Al^(3+) + Ti^(4+) = Ca^(2+) + 2Si^(4+) and Al^(3+) + Ti^(3+) = Ca^(2+) + Si^(4+), respectively.

Total reflection X-ray fluorescence spectrometry (TXRF) was used to analyze residual surface contamination on Genesis solar wind samples and to evaluate different cleaning methods. To gauge the suitability of a cleaning method, two samples were analyzed following cleaning by lab-based TXRF. The analysis comprised an overview and a crude manual mapping of the samples by orienting them with respect to the incident X-ray beam in such a way that different regions were covered. The results show that cleaning with concentrated hydrochloric acid and a combination of hydrochloric acid and hydrofluoric acid decreased persistent inorganic contaminants substantially on one sample. The application of CO2 snow for surface cleaning tested on the other sample appears to be effective in removing one persistent Genesis contaminant, namely germanium. Unfortunately, the TXRF analysis results of the second sample were impacted by relatively high background contamination. This was mostly due to the relatively small sample size and that the solar wind collector was already mounted with silver glue for resonance ion mass spectrometry (RIMS) on an aluminium stub. Further studies are planned to eliminate this problem. In an effort to identify the location of very persistent contaminants, selected samples were also subjected to environmental scanning electron microscopy. The results showed excellent agreement with TXRF analysis.

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^(84),^(86)Kr and ^(129),^(132)Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ^3He/^4He: (4.64 ± 0.09) × 10^(−4), ^(20)Ne/^(22)Ne: 13.78 ± 0.03, ^(21)Ne/^(22)Ne: 0.0329 ± 0.0001, ^(36)Ar/^(38)Ar 5.47 ± 0.01. The elemental composition is:^4He/^(20)Ne: 656 ± 5, and ^(20)Ne/^(36)Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ^(86)Kr/^(84)Kr: 0.302 ± 0.003, ^(129)Xe/^(132)Xe: 1.05 ± 0.02, ^(36)Ar/^(84)Kr 2390 ± 150, and ^(84)Kr/^(132)Xe 9.5 ± 1.0. The ^3He/^4He and the ^4He/^(20)Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (~100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.

One of the primary objectives of the Genesis sample return mission is to measure the oxygen isotopic composition of the Sun to permil-level precision. The returned samples pose a unique analytical challenge, and around the world, there has been parallel development of several competing techniques to make the oxygen measurement on the Genesis concentrator samples. At UCLA, we have developed a hybrid instrument: a secondary ion mass spectrometer (SIMS) front-end combined with an accelerator mass spectrometer (AMS), whose purpose is to eliminate molecular interferences via dissociation. We describe here the current status of the development of the instrument and the remaining issues to address before we request the Genesis samples for analysis.

We have used an electron microprobe or scanning electron microscope to analyze the Ag produced by exposure of Ilford nuclear emulsions to ^(151)Sm beta particles. The low beam currents of the SEM yielded satisfactory results while the higher current density of the microprobe produced variable amounts of volatilization of the organic constituents of the emulsion. Nonlinearities in Ag counting rate vs. exposure time curves were found at both high and low Ag concentrations. Two different types (mechanisms?) of emulsion fading were observed, one operating on an hour, the other on a day, time scale. The low-Ag nonlinearities are perhaps explained by either dose-dependent short time scale fading or by the requirement of multiple hits to render some AgBr grains developable.

Using electron probe and ion probe techniques, experimental crystal-liquid partition coefficients (D) have been measured in meteoritic Ca,Al-rich inclusion (CAI) compositions for Mg, Zr, Y, and REEs in anorthite and perovskite. Partitioning data for Ti in anorthite and Al in perovskite are also reported. Where cross-comparisons are possible between electron and ion probe data, agreement is good. Concentration variations in anorthite for many elements are beyond what can be explained by fractional crystallization, but show well-defined interelement correlations which could reflect the temperature dependence of the D values or could result from liquid boundary layers. For anorthite our D values for REEs are lower, and they decrease more rapidly with decreasing ionic radius than most in the literature. Most of the older REE D patterns for plagioclase in the literature are too flat because of insufficient purity of mineral separates or because of analytical problems. New ion probe data for minor and trace elements in anorthite from type B CAIs permit detailed comparisons with fractional crystallization models based on the measured D values. For most comparisons, models and observations do not agree for amounts of crystallization less than 90%. It is possible that anorthite does not appear until after 95% crystallization, compared to about 40% which would be expected from isothermal equilibrium crystallization experiments. The LREEs are highly compatible elements in perovskite, but D values drop sharply for the HREEs, Y, and Zr. D values for REEs increase strongly from air to highly reducing conditions as coupled REE-Ti^(+3) substitutions become possible. Model calculations show that REE patterns in igneous perovskites from CAIs will reflect the D pattern, and the models can explain some REE patterns from compact type A CAIs. However, there are other sets of trace element data for perovskite in CAIs that cannot easily be explained by igneous processes.