Zirconium stable isotope analysis of zircon by MC-ICP-MS: Methods and application to evaluating intra-crystalline zonation in a zircon megacryst

Zirconium (Zr) plays a key role in the development of phases like zircon (ZrSiO₄) and baddeleyite (ZrO₂) in magmatic systems. These minerals are crucial for the study of geologic time and crustal evolution, and their high resistivity to weathering and erosion results in their preservation on timescales of billions of years. Although zircon and baddeleyite may also preserve a robust record of Zr isotope behavior in high-temperature terrestrial environments, little is known about the factors that control Zr isotope partitioning in magmatic systems, the petrogenetic significance of fractionated compositions, or how these variations are recorded in Zr-rich accessory phases. Here, we describe a new analytical protocol for accurately determining the Zr stable isotope composition of zircon by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS), using the double-spike method to correct for procedural and instrumental mass bias. We apply this technique to test whether zircon crystallization in carbonatite magmatic systems is a driver of Zr isotope fractionation by interrogating the internal zonation of a zircon megacryst from the Mud Tank carbonatite (MTUR1). We find the MTUR1 megacryst to lack internal zoning within analytical uncertainties with a mean μ⁹⁴/⁹⁰Zr_(NIST) = −55 ± 28 ppm (2 SD, n = 151), which suggests that zircon crystallization is not a driver of Zr isotope fractionation in carbonatite magmas. This observation is in stark contrast with those made in silicate magmatic systems, raising the possibility that the bonding environment of Zr⁴⁺ ions may be fundamentally different in carbonatite vs. silicate melts. Because of its remarkable homogeneity, the MTUR1 megacryst is an ideal natural reference material for Zr isotopic analysis of zircon using both solution and spatially resolved methods. The reproducibility of a pure Zr solution and our chemically purified zircon fractions indicate that the external reproducibility of our method is on the order of ±28 ppm for μ⁹⁴/⁹⁰Zr, or ±7 ppm per amu, at 95% confidence

A general moment NRIXS approach to the determination of equilibrium Fe isotopic fractionation factors: application to goethite and jarosite

We measured the reduced partition function ratios for iron isotopes in goethite FeO(OH), potassium-jarosite KFe3(SO4)2(OH)6, and hydronium-jarosite (H3O)Fe3(SO4)2(OH)6, by Nuclear Resonant Inelastic X-Ray Scattering (NRIXS, also known as Nuclear Resonance Vibrational Spectroscopy -NRVS- or Nuclear Inelastic Scattering -NIS) at the Advanced Photon Source. These measurements were made on synthetic minerals enriched in 57Fe. A new method (i.e., the general moment approach) is presented to calculate {\beta}-factors from the moments of the NRIXS spectrum S(E). The first term in the moment expansion controls iron isotopic fractionation at high temperature and corresponds to the mean force constant of the iron bonds, a quantity that is readily measured and often reported in NRIXS studies.Comment: 38 pages, 2 tables, 8 figures. In press at Geochimica et Cosmochimica Acta. Appendix C contains new derivations relating the moments of the iron PDOS to the moments of the excitation probability function measured in Nuclear Resonant Inelastic X-ray Scatterin

The REE isotopic compositions of the Earth

Lanthanides are a group of 14 naturally occurring elements with atomic numbers ranging from 57 (La) to 74 (Lu), which are also known as rare earth elements (REE). REEs are ubiquitous in minerals and rocks. The chemical properties of REEs vary as smooth functions of their atomic numbers, a phenomenon known as the contraction of the lanthanides. This is the main control behind REE fractionation in minerals and rocks. The relative abundance of REEs is usually presented as the REE pattern by normalizing the concentrations in the sample to those in reference materials such as chondrites and shales

Developments in PF-HPLC (pneumatic-fluoropolymer high performance liquid chromatography)

Return missions are providing unique opportunities to deepen our knowledge of the formation and evolution of the solar system. The six Apollo missions have been critical in shaping our understanding of the Earth-Moon history [1], and the recent Genesis (solar wind; e.g., [2]), Stardust (cometary dust from Wild 2; e.g., [3,4]) and Hayabusa (dust from S-type asteroid from Itokawa; e.g., [5]) missions brought in a wealth of data

Zirconium stable isotope analysis of zircon by MC-ICP-MS: Methods and application to evaluating intra-crystalline zonation in a zircon megacryst

Zirconium (Zr) plays a key role in the development of phases like zircon (ZrSiO₄) and baddeleyite (ZrO₂) in magmatic systems. These minerals are crucial for the study of geologic time and crustal evolution, and their high resistivity to weathering and erosion results in their preservation on timescales of billions of years. Although zircon and baddeleyite may also preserve a robust record of Zr isotope behavior in high-temperature terrestrial environments, little is known about the factors that control Zr isotope partitioning in magmatic systems, the petrogenetic significance of fractionated compositions, or how these variations are recorded in Zr-rich accessory phases. Here, we describe a new analytical protocol for accurately determining the Zr stable isotope composition of zircon by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS), using the double-spike method to correct for procedural and instrumental mass bias. We apply this technique to test whether zircon crystallization in carbonatite magmatic systems is a driver of Zr isotope fractionation by interrogating the internal zonation of a zircon megacryst from the Mud Tank carbonatite (MTUR1). We find the MTUR1 megacryst to lack internal zoning within analytical uncertainties with a mean μ⁹⁴/⁹⁰Zr_(NIST) = −55 ± 28 ppm (2 SD, n = 151), which suggests that zircon crystallization is not a driver of Zr isotope fractionation in carbonatite magmas. This observation is in stark contrast with those made in silicate magmatic systems, raising the possibility that the bonding environment of Zr⁴⁺ ions may be fundamentally different in carbonatite vs. silicate melts. Because of its remarkable homogeneity, the MTUR1 megacryst is an ideal natural reference material for Zr isotopic analysis of zircon using both solution and spatially resolved methods. The reproducibility of a pure Zr solution and our chemically purified zircon fractions indicate that the external reproducibility of our method is on the order of ±28 ppm for μ⁹⁴/⁹⁰Zr, or ±7 ppm per amu, at 95% confidence

Calculation of thermal parameters of SiGe microbolometers

The thermal parameters of a SiGe microbolometer were calculated using numerical modeling. The calculated thermal conduction and thermal response time are in good agreement with the values found experimentally and range between 2x10$^-7$ and 7x10$^-8$ W/K and 1.5 and 4.5 ms, respectively. High sensitivity of microbolometer is achieved due to optimization of the thermal response time and thermal conduction by fitting the geometry of supporting heat-removing legs or by selection of a suitable material providing boundary thermal resistance higher than 8x10$^-3$ cm$^2$K/W at the SiGe interface.Comment: 11 pages, 6 figure

Development of an Automated All-Teflon HPLC System for the Analysis of Precious Geological and Extraterrestrial Materials

With the recent success of sample return missions such as Genesis (solar wind; e.g., [1-2]), Stardust (cometary dust particles; e.g., [3-5]) and Hayabusa (asteroid; e.g., [6-7]), as well as the recently announced OSIRIS-REx mission (estimated to collect more than 60 g of asteroidal material), it is clear that a new frontier of solar system research has been entered. Given the precious nature of these samples, it is also apparent that laboratory techniques need to be made as efficient as possible in order to maximize the information that we can gain from these unique and invaluable specimens. To determine the chemical and isotopic compositions of these samples, it is often necessary to separate and purify elements of cosmochemical interest from the host rocks. A widely used method for the chemical separation of elements, following sample digestion, is through column chromatography techniques

Uncooled IRFPA developments review

Abstract Today, large number of un cooled infrared detector developments are under progress due to the availability of silicon technology that enablesJealization of low cost 2D IR arrays. Development of such a structure involves a lot of trade-offs between the different parameters which characterize these detectors: • infrared flux absorption, • measurement of the temperature increase due to the incoming infrared flux absorption, • thermal insulation between detector and readout circuit, • readout of thermometer temperature variation. These trade-offs explain the number of different approaches that are under worldwide development. We present a rapid survey of the state of the art through these developments. LETlfUR has chosen resistive amorphous silicon as thermometer for his uncooled microbolometer development. After a first phase dedicated to the acquisition of the most important detector parameters in order to help the modeling and the technological development, an IRCMOS laboratory model (256 x 64 with a pitch of 50 I-Im) was realized and characterized. It was shown that NETD of 80 mK at ff1.25 Hz and 300 K background can be obtained with high thermal insulation (1.2 10 7 K/W)