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In this study, we present a high precision and high spatial resolution in situ Fe isotope protocol using femtosecond (fs) laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS). The intermediate measurement precision obtained over a period of ca. 3 years for the USGS glass BIR‐1G against the Puratronic reference material is 0.17‰ (2s) for δ56Fe. Uncertainties achieved on individual analyses of glass and olivines were < 0.15‰ for δ56Fe. This high precision is associated with high spatial resolution of about 170 × 25 μm. Our results display good consistency between LA‐MC‐ICP‐MS and solution nebulisation MC‐ICP‐MS data from the literature. Obtained δ56Fe values on different USGS glasses (BIR‐1G, BHVO‐2G and BCR‐2G) show that these reference materials have homogenous Fe isotope ratio and therefore can be used as bracketing calibrators during laser ablation measurement sessions. On the other hand, the San Carlos Olivine displays high Fe isotope heterogeneity, and therefore cannot be considered as a good bracketing standard (calibrator). We also applied our fs‐LA‐MC‐ICP‐MS protocol to olivines and pyroxene from the Kerguelen Archipelago. This technique appears to be a relevant tool to resolve isotopic zoning in chemically zoned silicate phenocrysts, even of small size (< 1 mm). We demonstrate that within single lavas, olivine crystals display various zoning depending on their size, related to their residence time in the magma. Both equilibrium and diffusive processes were observed in olivine crystals from Kerguelen, uncovering complex histories. Hence, iron isotope ratio measurements by fs‐LA‐MC‐ICP‐MS open new possibilities for studying highly zoned silicate minerals in magmatic rocks to better understand their formation. [ABSTRACT FROM AUTHOR]

Despite the importance of structural control on metal stable isotope fractionation in inorganic and abiotic systems, the link between metal structural changes and related isotopic fractionation during reactions with organic surfaces and live cells remains poorly established. We conducted reversible adsorption of Fe(II) and Fe(III) on the surface of exopolysaccharide (EPS)-rich and EPS-poor Pseudomonas aureofaciens, and we allowed Fe intracellular uptake by growing cells. We analyzed the Fe isotopic composition of the remaining fluid and cell biomass, and compared the isotopic fractionation during adsorption and assimilation reaction with relative changes in Fe structural status between aqueous solution and bacterial cells, based on available and newly collected X-ray absorption spectroscopy (XAS) observations. Iron(III) adsorption onto P. aureofaciens at 2.8 ≤ pH ≤ 6.0 produced an enrichment of the cell surface in heavier isotopes with Δ57Fecell-solution ranging from +0.7 to +2.1‰, without a link to pH in EPS-rich cultures. In contrast, the magnitude of isotopic fractionation increased with pH in EPS-poor cultures. Iron(II) adsorption produced an even larger enrichment of the cell surface in heavier isotopes, by up to 3.2‰, tentatively linked to Fe(III) hydroxide precipitation. Intracellular assimilation of Fe(II) favored heavier isotopes and led to Δ57Fecell-solution of +0.8‰. In addition, Fe(III) cellular uptake produced an enrichment of the bacterial biomass in lighter isotopes with Δ57Fecell-solution of −1‰. The XAS analyses demonstrated the dominance of Fe(III)–phosphate complexes both at the cell surface and in the cell interior. We suggest that heavier isotope enrichment of the cell surface relative to the aqueous solution is due to strong Fe(III)–phosphoryl surface complexes and Fe complexation to ligands responsible for metal transfer from the surface to the inner cell. In case of Fe(II) adsorption or assimilation, its partial oxidation within the cell compartments may lead to cell enrichment in heavier isotopes. In contrast, loss of symmetry of assimilated Fe(III) relative to the aqueous Fe3+ ion and longer bonds of intracellular ions relative to aqueous Fe(III)–citrate or hydroxo-complexes could produce an enrichment of cells in lighter isotopes. The versatile nature of Fe(II) and Fe(III) fractionation without a distinct effect of pH and surface exopolysaccharide coverage suggests that, in natural soil and sedimentary environments, Fe isotope fractionation during interaction with heterotrophic bacteria will be primarily governed by Fe complexation with DOM and Fe redox status in the soil pore water. [ABSTRACT FROM AUTHOR]

With the aim to better understand the cause of the iron isotope heterogeneity of mantle-derived bulk peridotites, we compared the petrological, geochemical and iron isotope composition of four xenolith suites from different geodynamic settings; sub-arc mantle (Patagonia); subcontinental lithospheric mantle (Cameroon), oceanic mantle (Kerguelen) and cratonic mantle (South Africa). Although correlations were not easy to obtain and remain scattered because these rocks record successive geological events, those found between δ[sup.57]Fe, Mg#, some major and trace element contents of rocks and minerals highlight the processes responsible for the Fe isotope heterogeneity. While partial melting processes only account for moderate Fe isotope variations in the mantle (0.9 ‰). The kinetic nature of rapid metasomatic exchanges between low viscosity melts/fluids and their wall-rocks peridotite in the mantle is the likely explanation for this large range. There are a variety of responses of Fe isotope signatures depending on the nature of the metasomatic processes, allowing for a more detailed study of metasomatism in the mantle with Fe isotopes. The current database on the iron isotope composition of peridotite xenoliths and mafic eruptive rocks highlights that most basalts have their main source deeper than the lithospheric mantle. Finally, it is concluded that due to a complex geological history, Fe isotope compositions of mantle xenoliths are too scattered to define a mean isotopic composition with enough accuracy to assess whether the bulk silicate Earth has a mean δ[sup.57]Fe that is chondritic, or if it is ~0.1 % above chondrites as initially proposed. Keywords Iron isotopes * Mantle peridotites * Metasomatism * Melt extraction, Introduction Studies conducted over the past decade on the iron isotope geochemistry have illustrated that it potentially brings important information pertaining to the formation and differentiation of terrestrial planets, such [...]

This work demonstrates the feasibility of the measurement of the isotopic composition of dissolved iron in seawater for an iron concentration range, 0.05-1 nmol [L.sup.-1], allowing measurements in most oceanic waters, including Fe depleted waters of high nutrient low chlorophyll areas. It presents a detailed description of our previously published protocol, with significant improvements on detection limit and blank contribution. Iron is preconcentrated using a nitriloacetic acid superflow resin and purified using an AG 1- x 4 anion exchange resin. The isotopic ratios are measured with a multicollector-inductively coupled plasma mass spectrometer (MC-ICPMS) Neptune, coupled with a desolvator (Aridus II or Apex-Q), usinga [sup.57]Fe [sup.58]Fe double spike mass bias correction. A Monte Carlo test shows that optimum precision is obtained for a double spike composed of approximately 50% [sup.57]Fe and 50% [sup.58]Fe and a sample to double spike quantity ratio of approximately 1. Total procedural yield is 91 [+ or -] 25% (2SD, n = 55) for sample sizes from 20 to 2 L. The procedural blank ranges from 1.4 to 1.1 ng, for sample sizes ranging from 20 to 2 L, respectively, which, converted into Fe concentrations, corresponds to blank contributions of 0.001 and 0.010 nmol [L.sup.-1], respectively. Measurement precision determined from replicate measurements of seawater samples and standard solutions is 0.08%0 ([delta][sup.56]Fe, 2SD). The precision is sufficient to clearly detect and quantify isotopic variations in the oceans, which so far have been observed to span 2.5 [per thousand] and thus opens new perspectives to elucidate the oceanic iron cycle. 10.1021/ac1002504

We compared the analytical performance of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The benefit of ultrafast lasers was evaluated regarding thermal-induced chemical fractionation, that is otherwise well known to limit LA-ICPMS. Both lasers had a Gaussian beam energy profile and were tested using the same ablation system and ICPMS analyzer. Resulting crater morphologies and analytical signals showed more straightforward femtosecond laser ablation processes, with minimal thermal effects. Despite a less stable energy output, the ultrafast laser yielded elemental (Pb/U, Pb/Th) and Pb isotopic ratios that were more precise, repeatable, and accurate, even when compared to the best analytical conditions for the nanosecond laser. Measurements on NIST glasses, monazites, and zircon also showed that femtosecond LA-ICPMS calibration was less matrix-matched dependent and therefore more versatile.