Isotopic Mass Fractionation Research Articles

GEOTRACES IC1 (BATS) contamination‐prone trace element isotopes Cd, Fe, Pb, Zn, Cu, and Mo intercalibration

We report data on the isotopic composition of cadmium, copper, iron, lead, zinc, and molybdenum at the GEOTRACES IC1 BATS Atlantic intercalibration station. In general, the between lab and within‐lab precisions are adequate to resolve global gradients and vertical gradients at this station for Cd, Fe, Pb, and Zn. Cd and Zn isotopes show clear variations in the upper water column and more subtle variations in the deep water; these variations are attributable, in part, to progressive mass fractionation of isotopes by Rayleigh distillation from biogenic uptake and/or adsorption. Fe isotope variability is attributed to heavier crustal dust and hydrothermal sources and light Fe from reducing sediments. Pb isotope variability results from temporal changes in anthropogenic source isotopic compositions and the relative contributions of U.S. and European Pb sources. Cu and Mo isotope variability is more subtle and close to analytical precision. Although the present situation is adequate for proceeding with GEOTRACES, it should be possible to improve the within‐lab and between‐lab precisions for some of these properties.

Determination of SIMS matrix effects on oxygen isotopic compositions in carbonates

Carbonates have variable chemical composition and crystal structure, which can affect the accuracy of in situ (SIMS) isotopic measurements. Carbonate reference materials (calcite, dolomite, ankerite, magnesite, siderite, and rhodochrosite) were characterised for δ18O by IRMS, and for the chemical composition by electron microprobe, and then used to evaluate the SIMS instrumental mass fractionation (IMF) of oxygen isotopes. A clear relationship between the IMF and the MgO (wt%) content was observed during two different sessions for low Fe- and Mn-carbonates. For Fe- and Mn-bearing carbonates (i.e. more than 1 wt%), Fe and Mn contents have to be taken into account for IMF correction. Due to the highly variable Mg content in carbonates, calibration using suitable carbonate reference materials with different Mg contents (i.e.calcite, dolomite, and magnesite) seems to be the best solution for performing accurate δ18O measurements by SIMS. This matrix correction is not universally applied. Therefore the overall significance of uncorrected published δ18O values from high Mg-carbonates has to be taken with caution. There are numerous applications of this method covering domains as varied as environmental studies (stromatolites, high-Mg calcite corals), geothermometry involving calcite co-existing with dolomite, or siderite co-existing with ankerite, and cosmochemical studies of carbonate phases in meteorites.

Accurate and precise determination of stable Cr isotope compositions in carbonates by double spike MC-ICP-MS

Techniques for the separation of small quantities of Cr from carbonate material and for the analysis of stable Cr isotopes in carbonates by MC-ICP-MS are presented in this study. In comparison with previously published methods, we have developed a one-step Cr separation procedure that is relatively simple, and has a low blank (0.12–0.20 ng). Moreover, careful optimisation of the desolvating sample introduction system allows a significant increase in the sensitivity of our MC-ICP-MS technique compared to previous studies. Instrumental mass bias effects and fractionation of Cr isotopes during Cr separation are corrected using a carefully optimised 50Cr–54Cr double-spike method. Novel numerical simulations demonstrate that the effects of potential isobaric interferences from Ti, Fe and V are negligible, even if they are isotopically fractionated. Small deviations in the δ53Cr value of the NBS 979 standard between different analytical sessions are due to small deviations from exponential mass fractionation behaviour. The long-term reproducibility of δ53Cr for a spiked NBS 979 Cr isotope reference material is ±0.031‰ (2 S.D., n = 147). Analyses of carbonates reveal that they have δ53Cr values of 0.747 to 1.994‰, distinctly heavier than continental crust and the terrestrial mantle. The carbonates record Cr isotopic fractionation that may be used to understand redox reactions in the oceans. Although this study focuses on carbonate samples, our mass spectrometry technique can be applied to the analysis of any samples with low levels of Cr, including river waters and seawater.

Silicon isotopic fractionation of CAI-like vacuum evaporation residues

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquids (Richter F. M., Davis A. M., Ebel D. S., and Hashimoto A. (2002) Elemental and isotopic fractionation of Type B CAIs: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521–540; Richter F. M., Janney P. E., Mendybaev R. A., Davis A. M., and Wadhwa M. (2007a) Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation. Geochim. Cosmochim. Acta 71, 5544–5564.). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, α Si, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that α Si = 0.98985 ± 0.00044 (2 σ) for 29Si/ 28Si with no resolvable variation with temperature over the temperature range of the experiments, 1600–1900 °C. This value is different from what has been reported for evaporation of liquid Mg 2SiO 4 (Davis A. M., Hashimoto A., Clayton R. N., and Mayeda T. K. (1990) Isotope mass fractionation during evaporation of Mg 2SiO 4. Nature 347, 655–658.) and of a melt with CI chondritic proportions of the major elements (Wang J., Davis A. M., Clayton R. N., Mayeda T. K., and Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO–MgO–SiO 2–CaO–Al 2O 3–TiO 2–REE melt system. Geochim. Cosmochim. Acta 65, 479–494.). There appears to be some compositional control on α Si, whereas no compositional effects have been reported for α Mg. We use the values of α Si and α Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.

Measurement of SIMS Instrumental Mass Fractionation of Pb Isotopes During Zircon Dating

An igneous zircon reference material (OG1) was characterised for U‐Pb isotopes by ID‐TIMS, and utilised to evaluate SIMS (SHRIMP) instrumental mass fractionation (IMF) of radiogenic Pb isotopes (207Pb*/206Pb*). The TIMS 207Pb*/206Pb* reference value for OG1 was 0.29907 ± 0.00011 (95% confidence limit), 3465.4 ± 0.6 Ma. The high 207Pb* (∼ 30 μg g−1), negligible common Pb, and isotopic homogeneity permitted precise (± 1–2‰) 207Pb*/206Pb* measurements within the analytical sessions. External reproducibility of mean 207Pb*/206Pb* ratios between sessions was demonstrated for one instrument, yielding a mean IMF of +0.87 ± 0.49‰. The mean 207Pb*/206Pb* ratios between instruments were dispersed beyond uncertainties, with session IMF values from +3.6 ± 1.7‰ to −2.4 ± 1.3‰, and a grand mean IMF value (twenty‐six sessions) of +0.70 ± 0.52‰, indicating a tendency towards elevated 207Pb*/206Pb*. The specific causes of variability in IMF are unclear, but generally reflect subtle differences in analytical conditions. The common practice in SIMS of assuming that IMF for Pb+ is insignificant could result in systematic age biases and underestimated uncertainties, of critical importance for precise correlation of Precambrian events. Nevertheless, a zircon RM such as OG1 can be readily incorporated into routine dating to improve 207Pb*/206Pb* accuracy and external reproducibility.

Neon isotopic measurements using high‐resolution, multicollector noble gas mass spectrometer: HELIX‐MC

We describe a new high‐resolution, multicollection, noble gas mass spectrometer, the HELIX‐MC, developed by GV instruments. The instrument uses a collector housing that holds five “MiniDual” detection systems, each detector containing two devices: a Faraday cup collector and channel electron multiplier. Each detector is 5.2 mm wide, which permits collecting adjacent beams separated by 1 atomic mass unit (amu) at mass 136. The HELIX‐MC operates at high mass resolution (m/Δm > 1500), which allows the interference of 40Ar++ on 20Ne+ to be resolved. We report the results of some tests on the “MiniDual” collectors, in which we have achieved precise Ne abundance and isotopic measurements. After a correction for doubly ionized CO2 (0.37–1.5%), our results show that the HELIX‐MC produces only very limited instrumental Ne isotopic mass fractionation (≈−0.5%.amu−1). The sensitivity of the HELIX‐MC for neon measurement performed on 1012 ohms collector is around 1.4 × 10−3 A torr−1 for quantities of 20Ne analyzed comprised between 1.27 × 10−15 and 4.71 × 10−15 moles. Within this range, the reproducibility of the isotopic measurements of standard gas falls in the range between 0.5 and 0.8% (1σ) for 20Ne/22Ne and 1 and 1.5% for 21Ne/22Ne over a period of several days. The machine characteristics for measuring He are also reported.

In situ measurements of calcium isotopes by ion microprobe in carbonates and application to foraminifera

An analytical procedure has been developed for the in situ measurement of calcium isotope composition of carbonates with a spatial resolution of 15–20 μm on a Caméca IMS 1270 ion microprobe. By using two Faraday cup detectors, the 40Ca and 44Ca can be measured simultaneously, improving the internal reproducibility. Instrumental mass fractionation (IMF) of calcium isotopes was observed to be independent of primary ion beam intensity and of the Mg content of the carbonate, but can depend on vacuum conditions. Three calcite reference materials were used in this study (ENS 0, MEX and BRET 105E) and their δ 44Ca values relative to NIST915a were reproducible within a typical 1 σ standard deviation of ≈ 0.15‰. This analytical procedure was applied to planktonic foraminifera, Globorotalia inflata, dated at 2.8 Ma from Shatsky Rise (ODP leg 198). The range of measured δ 44Ca within a single test is 1.7‰. This intratest variation can be attributed to several processes such as temperature variation, ontogenic effects or differences between primary and secondary calcite (i.e. calcite precipitated by different biomineralization processes). Despite this intratest variation, the averages δ 44Ca for each foraminifer are similar and are in agreement with published δ 44Ca values measured for this age. This study shows that in situ δ 44Ca measurements in tests of foraminifera are an appropriate tool for investigating biomineralization processes.

Kinetic isotope effect during reduction of iron from a silicate melt

Iron isotopic compositions measured in chondrules from various chondrites vary between δ 57Fe/ 54Fe = +0.9‰ and −2.0‰, a larger range than for igneous rocks. Whether these compositions were inherited from chondrule precursors, resulted from the chondrule-forming process itself or were produced by later parent body alteration is as yet unclear. Since iron metal is a common phase in some chondrules, it is important to explore a possible link between the metal formation process and the observed iron isotope mass fractionation. In this experimental study we have heated a fayalite-rich composition under reducing conditions for heating times ranging from 2 min to 6 h. We performed chemical and iron isotope analyses of the product phases, iron metal and silicate glass. We demonstrated a lack of evaporation of Fe from the silicate melt in similar isothermal experiments performed under non-reducing conditions. Therefore, the measured isotopic mass fractionation in the glass, ranging between −0.32‰ and +3.0‰, is attributed to the reduction process. It is explained by the faster transport of lighter iron isotopes to the surface where reduction occurs, and is analogous to kinetic isotope fractionation observed in diffusion couples [Richter, F.M., Davis, A.M., Depaolo, D.J., Watson, E.B., 2003. Isotope fractionation by chemical diffusion between molten basalt and rhyolite. Geochim. Cosmochim. Acta 67, 3905–3923]. The metal phase contains 90–99.8% of the Fe in the system and lacks significant isotopic mass fractionation, with values remaining similar to that of the starting material throughout. The maximum iron isotope mass fractionation in the glass was achieved within 1 h and was followed by an isotopic exchange and re-equilibration with the metal phase (incomplete at ∼6 h). This study demonstrates that reduction of silicates at high temperatures can trigger iron isotopic fractionation comparable in its bulk range to that observed in chondrules. Furthermore, if metal in Type I chondrules was formed by reduction of Fe silicate, our observed isotopic fractionations constrain chondrule formation times to approximately 60 min, consistent with previous work.

Vapor pressures and evaporation coefficients for melts of ferromagnesian chondrule-like compositions

To determine evaporation coefficients for the major gaseous species that evaporate from silicate melts, the Hertz–Knudsen equation was used to model the compositions of residues of chondrule analogs produced by evaporation in vacuum by Hashimoto [Hashimoto A. (1983) Evaporation metamorphism in the early solar nebula-evaporation experiments on the melt FeO–MgO–SiO 2–CaO–Al 2O 3 and chemical fractionations of primitive materials. Geochem. J. 17, 111–145] and Wang et al. [Wang J., Davis A. M., Clayton R. N., Mayeda T. K., Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO–MgO–SiO 2–CaO–Al 2O 3–TiO 2 rare earth element melt system. Geochim. Cosmochim. Acta 65, 479–494], in vacuum and in H 2 by Yu et al. [Yu Y., Hewins R. H., Alexander C. M. O’D., Wang J. (2003) Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts. Geochim. Cosmochim. Acta 67, 773–786], and in H 2 by Cohen et al. [Cohen B. A., Hewins R. H., Alexander C. M. O’D. (2004) The formation of chondrules by open-system melting of nebular condensates. Geochim. Cosmochim. Acta 68, 1661–1675]. Vapor pressures were calculated using the thermodynamic model of Ghiorso and Sack [Ghiorso M. S., Sack R. O. (1995) Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid–solid equilibria in magmatic systems at elevated temperatures and pressures. Contrib. Mineral. Petrol. 119, 197–212], except for the late, FeO-free stages of the Wang et al. (2001) and Cohen et al. (2004) experiments, where the CMAS activity model of Berman [Berman R. G. (1983) A thermodynamic model for multicomponent melts, with application to the system CaO–MgO–Al 2O 3–SiO 2. Ph.D. thesis, University of British Columbia] was used. From these vapor pressures, evaporation coefficients ( α) were obtained that give the best fits to the time variation of the residue compositions. Evaporation coefficients derived for Fe (g), Mg (g), and SiO (g) from the Hashimoto (1983) experiments are similar to those found by Alexander [Alexander C. M. O’D. (2004) Erratum. Meteoritics Planet. Sci. 39, 163] in his EQR treatment of the same data and also adequately describe the FeO-bearing stages of the Wang et al. (2001) experiments. From the Yu et al. (2003) experiments at 1723 K, α Na = 0.26 ± 0.05, and α K = 0.13 ± 0.02 in vacuum, and α Na = 0.042 ± 0.020, and α K = 0.017 ± 0.002 in 9 × 10 −5 bar H 2. In the FeO-free stages of the Wang et al. (2001) experiments, α Mg and α SiO are significantly different from their respective values in the FeO-bearing portions of the same experiments and from the vacuum values obtained at the same temperature by Richter [Richter F. M., Davis A. M., Ebel D. S., Hashimoto A. (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521–540] for CMAS compositions much lower in MgO. When corrected for temperature, the values of α Mg and α SiO that best describe the FeO-free stages of the Wang et al. (2001) experiments also adequately describe the FeO-free stage of the Cohen et al. (2004) H 2 experiments, but α Fe that best describes the FeO-bearing stage of the latter experiment differs significantly from the temperature-corrected value derived from the Hashimoto (1983) vacuum data.

Microanalysis of carbon isotope composition in organic matter by secondary ion mass spectrometry

An analytical procedure has been developed for the in situ measurement of carbon isotope composition of organic matter, with a spatial resolution of 20–30 μm, using a Cameca IMS 1270 ion microprobe. Instrumental mass fractionation (IMF) of carbon isotopes was observed to be independent of primary ion beam intensity and sputtering time, but did depend on vacuum conditions and on the chemical composition of the sample. To evaluate such “matrix effects”, a set of 9 standards representative of the natural chemical variability of organic matter was prepared, with H/C atomic ratios and organic carbon contents ( C org) ranging between 0.04 and 1.74 and between 41 and 100 wt.%, respectively. Under the analytical conditions tested, IMF was not found to be influenced by the presence of silicate mineral impurities in the organic matter, but variations in IMF up to 5‰ were observed over the set of standards with the magnitude of IMF negatively correlated to the H/C ratios of samples. Aliphaticity ratios determined using Fourier transform infrared microspectroscopy provided an in situ estimation of H/C ratios with a spatial resolution barely exceeding that of the ion microprobe and permit a correction for matrix effects with a standard error of ± 0.2‰ (1 σ). Taking into account all sources of uncertainty, ion microprobe δ 13C were accurately determined with a ± 0.7‰ (1 σ) total uncertainty. The mechanism for the matrix effect of H/C ratios upon IMF is still to be determined but it is likely related to the difference in proportion of atomic vs. molecular carbon ions observed between samples of different H/C ratios.

Argon isotope fractionation induced by stepwise heating

Noble gas isotopes are widely used to elucidate the history of the rocks in which they have been trapped, either from distinct reservoirs or by accumulation following radioactive decay. To extract noble gases from their host rocks, stepwise heating is the most commonly used technique to deconvolve isotopically different components, e.g., atmospheric, in situ radiogenic, or excess radiogenic from mantle or crustal reservoirs. The accurate determination of the isotopic composition of these different components is of crucial importance, e.g., for ages obtained by 40Ar- 39Ar stepheating plateaus. However, diffusion theory-based model calculations predict that the stepwise thermal extraction process from mineral phases induces isotope fractionation and, hence, adulterates the original composition. Such effects are largely unconsidered, as they are small and a compelling experimental observation is lacking. We report the first unequivocal evidence for significant mass fractionation of argon isotopes during thermal extraction, observed on shungite, a carbon-rich Precambrian sedimentary rock. The degree of fractionation, as monitored by 38Ar/ 36Ar and 40Ar/ 36Ar ratios, very well agrees with theoretical predictions assuming an inverse square root dependence of diffusion coefficient and atomic mass, resulting in easier extraction of lighter isotopes. Hence, subatmospheric 40Ar/ 36Ar ratios obtained for argon extracted at low temperatures may not represent paleoatmospheric argon. Shungite argon resembles modern atmospheric composition, but constraints on the timing of trapping appear difficult to obtain, as shungites are multicomponent systems. In 40Ar- 39Ar stepwise heating, the isotope fractionation effect could cause systematic underestimations of plateau ages, between 0.15 and 0.4% depending on age, or considerably higher if samples contain appreciable atmospheric Ar. The magnitude of this effect is similar to the presently achieved uncertainties of this increasingly precise dating technique. Our results also indicate the importance of thermally activated diffusion as a possible fractionation mechanism, e.g., for hydrothermal gas exhalations, or for carbonaceous carrier phases such as “Q” in meteorites that have been suggested as carriers of highly fractionated noble gas residues from the early solar nebula.

The formation of chondrules by open-system melting of nebular condensates

Experiments were conducted under canonical nebular conditions to see whether the chemical compositions of the various chondrule types can be derived from a single CI-like starting material by open-system melting and evaporation. Experimental charges, produced at 1580 °C and PH2 of 1.31×10−5 atm over 1 to 18 hours, consisted of only two phases, porphyritic olivine crystals in glass. Sulfur, metallic-iron and alkalis were completely evaporated in the first minutes of the experiments and subsequently the main evaporating liquid oxides were FeO and SiO2. Olivines from short runs (2–4 hours) have compositions of Fo83-Fo89, as in Type IIA chondrules, while longer experimental runs (12–18 hours) produce ∼Fo99 olivine, similar to Type IA chondrules. The concentration of CaO in both olivine (up to 0.6 wt.%) and glass, and their Mg#, increased with increasing heating duration. Natural chondrules also show increasing CaO with decreasing S, alkalis, FeO and SiO2. The similarities in bulk chemistry, mineralogy and textures between Type IIA and IA chondrules and the experimental charges demonstrate that these chondrules could have formed by the evaporation of CI precursors. The formation of silica-rich chondrules (IIB and IB) by evaporation requires a more pyroxene-rich precursor.Based on the FeO evaporation rates measured here, Type IIA and IA chondrules, were heated for at least ∼0.5 and ∼3.5 h, respectively, if formed at 1580 °C and PH2 of 1.31×10−5 atm. Type II chondrules may have experienced higher cooling-rates and less evaporation than Type I.The experimental charges experienced free evaporation and exhibited heavy isotopic enrichments in silicon, as well as zero concentrations of S, Na and K, which are not observed in natural chondrules. However, experiments on potassium-rich melts at the same pressure but in closed capsules showed less evaporation of K, and less K isotopic mass fractionation, than expected as a function of decreasing cooling rate. Thus the environment in which chondrules formed is as important as the kinetic processes they experienced. If chondrule formation occurred under conditions in which evaporated gases remained in the vicinity of the residual melts, the extent of evaporation would be reduced and back reaction between the gas and the melt could contribute to the suppression of isotopic mass fractionation. Hence chondrule formation could have involved evaporative loss without Rayleigh fractionation. Volatile-rich Type II and volatile-poor Type I chondrules may have formed in domains with high and low chondrule concentrations, and high partial pressures of lithophile elements, respectively.

Ion Microprobe Analysis of Rb and Sr Isotopes in K-rich Minerals: An Attempt of Radiometric Dating

We report here in situ measurements of Rb and Sr isotopes in K-rich minerals (muscovite, phlogopite, and K-feldspar) using Sensitive High-Resolution Ion MicroProbe (SHRIMP). Several grains of the K-rich minerals were extracted from eight granitic rocks with various formation ages and mounted on epoxy-resin disks. Chemical compositions were measured by an electron probe microanalyzer (EPMA). Then they were set in the source chamber of SHRIMP. A 4-5 nA mass filtered O2- primary beam was used to sputter a 30-μm-diameter flat-bottomed crater and secondary positive ions were extracted by a 10 kV accelerating voltage for mass analysis. A mass resolution of 8900-9300 at 1% peak height was attained to reduce isobaric hydride interferences such as 87RbH+ on 88Sr+. The magnet was cyclically peak-stepped from mass 84 (84Sr and 28Si56Fe) to mass 88 (88Sr and 30Si58Fe), including the background, mass 85 for 85Rb and 29Si56Fe, mass 86 for 86Sr and 30Si56Fe, and mass 87 for 87Rb, 87Sr, and 29Si58Fe, respectively. No SiFe compounds of any mass number contributed significantly for the samples analyzed. Observed 87A/85A ratios (where A is an arbitrary element) were plotted against 88A/85A ratios for each sample. A least-square fitting was made in the diagram. The gradient and Y-intercept correspond to initial 87Sr/88Sr and initial 87Rb/85Rb ratios or present (87Rb/85Rb)+(87Sr*/85Rb) ratios, respectively, where “ * ” denotes radiogenic. The initial 87Sr/88Sr ratios are mostly consistent with the upper mantle 87Sr/88Sr ratios of various ages within experimental error. There is a positive correlation between the initial 87Rb/85Rb ratios and formation ages of the granitic rock samples, as it is expected from 87Rb decay. Further evaluation of the instrumental isotopic mass fractionation and relative sensitivities for Rb and Sr are required before the in situ 87Rb-87Sr measurement is routinely applied as a dating method.

Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts

The behavior of Na and K during evaporation from chondrule composition melts was studied using a vacuum furnace. Though Na is the less volatile of the two as an element, it is lost more rapidly than K from silicate melts. Mass fractionation of K isotopes was measured by ion microprobe and Rayleigh fractionation is observed for vacuum evaporation (10 −5 atm). With higher pressures of air, the K loss rate decreases but with increasing hydrogen pressure, K is lost more rapidly. δ 41K decreases with higher pressures, because of back reaction between melt and K in the gas. With long heating duration, the release of light K condensed within the furnace leads to interaction with the K-depleted melt and a further reduction of δ 41K. Natural chondrules differ in some ways from our experimental residues. Some (especially type IIA) have superchondritic Na and K, despite their assumed formation in nebular hydrogen, which enhances volatile loss, and chondrules do not show K isotopic fractionation. Type I chondrules in Semarkona (LL3.0) either plot on our evaporation trend, or are depleted in K but slightly enriched in Na, relative to K. In Bishunpur (LL3.1), type I chondrules are mostly K-depleted but moderately to strongly enriched in Na. In petrologic type 3.2 to 3.4 chondrites they are enriched in both K and Na, like type II chondrules. The alkali contents suggest type I chondrules experienced evaporation and subsequent metasomatism. Their normal δ 41K values suggest closed-system evaporation of a chondritic precursor in a gas with relatively high K pressures due to vaporization of dust accompanying chondrule precursor aggregates. Type II chondrules are volatile-rich, as well as unfractionated in K isotopes. They probably formed in a gas with higher pK than in the case of type I chondrules, due to heating of a more dust-rich parcel of gas.

Modelling isotope fractionation in thermal ionisation mass spectrometry filaments having diffusion controlled emission

An isotope mass fractionation model for thermal ionisation mass spectrometry (TIMS) based on transport modelling of uranium in platinum was applied to filaments with diffusion controlled emission. The diffusivity of uranium in platinum at different temperatures was determined by fitting signal data from uranium measurements to the diffusion model. By combining these data, an activation energy and a frequency factor for the diffusion of uranium in platinum was obtained. These data were then used to predict the fractionation of uranium as a function of time, K( t). The results from the model were compared with experimental fractionation data. A small and constant difference between the predicted and the experimental fractionation was observed. This residual K-factor ( K res) that the model did not account for was found to be 1.0055.

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (≪1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (∼1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.

Iron isotopes in hot springs along the Juan de Fuca Ridge

We present Fe isotope data for high temperature hydrothermal fluids, sulfides, and basalts from the Juan de Fuca Ridge, USGS basalt standard BCR-2 and the Canyon Diablo iron meteorite. The Fe isotopic compositions of all samples fall within a range of ∼1‰. However, there is a small but statistically significant isotopic variation between Fe dissolved in hydrothermal fluids and Fe in Canyon Diablo. Specifically, the hydrothermal fluids are lighter compared to Canyon Diablo, yielding δ56Fe (=[(56Fe/54Fe)sample/(56Fe/54Fe)Canyon Diablo−1]×1000) values from −0.30‰ to −0.77‰. In contrast, the BCR-2 basalt and Canyon Diablo are isotopically indistinguishable. Measurements of δ56Fe in Juan de Fuca Ridge basalts and sulfides suggest that Fe isotopes are fractionated in hydrothermal systems. However, the data do not exclude the possibility of small δ56Fe differences between the rocks from which fluid Fe is derived and other igneous Fe, in which case fractionation in igneous systems is indicated. Regardless, these results are evidence of non-biological mass fractionation of Fe isotopes in nature. Further, venting of hydrothermal fluids into the overlying water column could provide a source of isotopically light Fe to the deep oceans, contributing to Fe isotopic variations observed in deep-sea sediments.

Solvent extraction, ion chromatography, and mass spectrometry of molybdenum isotopes.

A procedure was developed that allows precise determination of molybdenum isotope abundances in natural samples. Purification of molybdenum was first achieved by solvent extraction using di(2-ethylhexyl) phosphate. Further separation of molybdenum from isobar nuclides was obtained by ion chromatography using AG1-X8 strongly basic anion exchanger. Finally, molybdenum isotopic composition was measured using a multiple collector inductively coupled plasma hexapole mass spectrometer. The abundances of molybdenum isotopes 92, 94, 95, 96, 97, 98, and 100 are 14.8428(510), 9.2498(157), 15.9303(133), 16.6787(37), 9.5534(83), 24.1346(394), and 9.6104(312) respectively, resulting in an atomic mass of 95.9304(45). After internal normalization for mass fractionation, no variation of the molybdenum isotopic composition is observed among terrestrial samples within a relative precision on the order of 0.00001-0.0001. This demonstrates the reliability of the method, which can be applied to searching for possible isotopic anomalies and mass fractionation.

Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO 2-CaO-Al 2O 3-TiO 2 rare earth element melt system

A synthetic material with solar elemental proportions of iron, magnesium, silicon, titanium, calcium, and aluminum oxides and doped with rare earth elements was evaporated in a vacuum furnace at 1800 and 2000°C for different durations to study its chemical and isotopic evolution during the evaporation process. It is demonstrated that kinetic evaporation of solar composition material can produce residues of calcium-, aluminum-rich inclusion bulk chemistry. The evaporation sequence of the main constituents in this solar composition material is iron > silicon ≈ magnesium > titanium. Calcium and aluminum remain unevaporated after evaporation of 95% of the solar composition material. The chemical fractionation between the gas and condensed phase is a function not only of temperature and pressure, but also of the bulk chemical composition of the condensed phase. During the evaporation process, cerium is almost as volatile as iron. The 2,000-fold cerium depletion found in some refractory inclusions in carbonaceous chondrites was reproduced in the evaporation experiment and can be readily explained as a result of evaporation of preexisting meteoritic material. Kinetic isotopic fractionation of magnesium, oxygen, and silicon follows the Rayleigh distillation law during the laboratory evaporation of synthetic solar composition material. This implies that the residue is well mixed during the evaporation process and that the evaporation kinetic processes (both chemical and isotopic) are surface reaction-controlled. The isotopic mass fractionation factors are lower than those predicted from theoretical calculations by using the square root of mass ratios of likely evaporating species. Thus, the surface reaction is more complicated than decomposition into single gas species of each element.

The Investigation of Isotopic Mass Fractionation Processes in the Primordial Solar Nebula and the Realization of in-situ Isotope Survey of Primitive Materials.

The problems in investigating the thermal history of the primordial solar nebula from the isotopic mass fractionation data are discussed based on the compiled data of primitive materials as well as on the results of reproducing experiments. The results of the experiments showed that isotopic mass fractionation is dominated by various conditions which may vary considerably in the nebula. The fractionation process is controlled for example by the state of the evaporation source, the rate of evaporation and the rate of source mixing as well as the molecular species of the gas phase. Hence at present, one cannot estimate the thermal origin of the large mass fractionation observed in the refractory inclusions of the primitive meteorites. In order to estimate the thermal history from the mass fractionation data, further experiments should be preformed to understand the kinetic behavior of molecules during the evaporation and condensation process in the nebula. At the same time, isotopic data should be accumulated over various mineral phases having different origins in the meteorite. The isotopic in-situ survey on sections of primitive material should be performed over a wide area with high spatial resolution for effective data accumulation.