ALBERT

Description: Despite the large number of successful applications of laser ablation, elemental and isotopic fractionation coupled to inductively coupled plasma mass spectrometry (ICP-MS) remain as the main limitations for many applications of this technique in the fields of analytical chemistry and Earth Sciences. A substantial effort has been made to control such fractionations, which are well-established features of nanosecond laser ablation systems. Technological advancements made over the past decade now allow the ablation of solids by femtosecond laser pulses in the deep ultraviolet (UV) region at wavelengths less than 200 nm. Here the use of femtosecond laser ablation and its effects on elemental and isotopic fractionation is investigated. The Pb/U system is used to illustrate elemental fractionation and stable Fe isotopes are used to illustrate isotopic fractionation. No elemental fractionation is observed beyond the precision of the multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements. Without a matrix match between standard and sample, elemental fractionation is absent even when using different laser ablation protocols for standardization and samples (spot versus raster). Furthermore, we found that laser ablation-induced isotope ratio drifts, commonly observed during nanosecond laser ablation, are undetectable during ultraviolet femtosecond laser ablation. So far the precision obtained for Fe isotope ratio determinations is 0.1‰ (2 standard deviation) for the 56Fe/54Fe ratio. This is close to that obtainable by solution multiple-collector inductively coupled plasma mass spectrometry. The accuracy of the results appears to be independent of the matrix used for standardization. The resulting smaller particle sizes reduce fractionation processes. Femtosecond laser ablation carries the potential to solve some of the difficulties encountered during the two prior decades since the introduction of laser ablation.

Description: UV femtosecond laser ablation coupled to MC-ICP-MS provides a promising in situ tool to investigate elemental and isotope ratios by non-matrix-matched calibration. In this study, we investigate Fe isotope composition in siliceous matrices including biotite, hornblende, garnet, fayalite and forsterite (San Carlos Olivine), and an oceanic Fe–Mn crust using the iron reference material IRMM-014 for calibration. To test the accuracy of the laser ablation data, Fe isotope compositions were obtained independently by solution ICP-MS after chromatographic separation of Fe. Sample materials with low Cr content, i.e. biotite, hornblende, fayalite and the Fe–Mn crust, reveal δ56/54Fe and δ57/54Fe values that agree with those from solution ICP-MS data within the measured precision. For high Cr concentration (54Cr/54Fe N0.0001), i.e. in the garnet and forsterite sample, δ56/54Fe and δ57/54Fe values were derived from 57Fe/56Fe ratios as correction of the isobaric interference of 54Cr on 54Fe is unsatisfactory. This approach provides accurate results for both minerals. Moreover, the garnet crystal exhibits isotopic zonation with differences of 0.3‰ in δ56/54Fe showing that substantial heterogeneities exist in high-temperature metamorphic minerals. Multiple analyses of homogeneous sample materials reveal a repeatability of 0.1‰ (2 SD) for δ56/54Fe and 0.2‰ (2 SD) for δ57/54Fe, respectively. This study adds to the observations of Horn et al. (2006) who have shown that the determination of Fe isotope ratios in various matrices including iron alloys, iron oxides and hydroxides, iron sulfide and iron carbonates can be performed with high accuracy and precision at high spatial resolution using UV femtosecond laser ablation ICP-MS. These results demonstrate that femtosecond laser ablation ICP-MS is a largelymatrix-independentmethod, which provides a substantial advantage over commonly employed nanosecond laser ablation systems.

Description: The feasibility of in situ stable Fe isotope ratio measurements using UV-femtosecond laser ablation connected to a multiple-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been investigated. Different types of matrices, independently determined by solution MC-ICP-MS after chromatographic separation of Fe, have been analysed by laser ablation using the isotopically certified iron reference material IRMM-014 as the bracketing standard. The samples have been pure iron metal (JM Puratronic), Fe-meteorites (North Chile, Glenormiston and Toluca), the meteorite phases kamacite and taenite in Toluca and Fe-sulphides. Furthermore, Fe isotope ratios from hydrothermal hematite, siderite and goethite from an old mining area in the Schwarzwald, Germany, and of magnetite from the metamorphic Biwabik iron formation have been determined. The results show that a precision of better than 0.1‰ (2 sigma) can be achieved with laser ablation and that all the results obtained agree with those determined by solution ICP to better than 0.1‰. This precision and accuracy is achievable in both raster and spot ablation mode. A matrix-matched bracketing standard is not required, and all these materials can be measured accurately against a metal standard. The hydrothermal minerals show significant Fe isotope zonations. In some samples the range of δ56Fe in a single aggregate encompasses the entire spectrum of ratios found by bulk solution analyses in multiple samples distributed over the whole mining district. For example, isotopic zonations found in secondary fibrous hematites show a continuous change in the δ56Fe values from -0.5‰ in the core to -1.8‰ in the rim. Primary hydrothermal siderite shows the reverse pattern with lighter values in the core than in the rim. While the siderite is thought to record primary fluid histories, the hematite pattern is interpreted as a reworked isotopic signature generated by oxic dissolution of primary zoned siderite and immediate close range re-precipitation of the oxidized Fe. Abrupt changes are documented for secondary goethite showing a distinct overgrowth that is 0.4‰ lighter than the core of the grain. If indeed Fe isotopes in secondary minerals from hydrothermal ore deposits record the initial isotopic signatures of their precursor minerals, and these in turn record hydrothermal fluid histories, then the tools are in place for a detailed reconstruction of the deposit‘s genesis. We expect similar observations from other Fe-rich deposits formed at intermediate and low-temperatures (e.g. banded iron formations). Laser ablation now provides us with the spatial resolution that adds a further dimension to our interpretation of stable Fe-isotope fractionation.

Description: A new method for the in situ measurement of stable Si isotope ratio using UV-femtosecond laser ablation connected to a multiplecollector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been established. The use of medium mass resolution mode (with a resolving powerm/Δm=8000) permits to resolve spectral interferences on 28Si, 29Si and 30Si allowing for determination of the 29Si/28Si and 30Si/28Si ratios with high accuracy and precision on wide, interference-free plateaus. A three-isotope plot demonstrated that interferences, if existing, are negligible for Si isotope ratios. The laser spot size is 35 μm and measurements are made using square rasters of 150 μmside length. Different types of elemental Si, Si-oxide and silicate matrices have been analysed by laser ablation using the international standard NBS28 as the bracketing standard. Thus δ29Si and δ30Si have been determined for the silicon isotope standard IRMM-017 (δ30Si±2 S.D.=−1.26±0.24‰; n=89) and BigBatch (δ30Si=−10.55±0.42‰; n=15), as well as San Carlos Olivine (δ30Si=−0.81±0.19‰; n=14), Caltech Rose Quartz (δ30Si=0.10±0.13‰; n=14) sponge needles (Stylocordyla borealis; δ30Si=−2.19±0.32‰; n=14) and JER-diopside glass (δ30Si=0±0.09‰; n=14) samples. The overall repeatability achievable is 0.15‰ (2 S.D.) on δ29Si and 0.24‰ (2 S.D.) on δ30Si. The silicon isotope standard IRMM-018 has also been measured and was confirmed to be heterogeneous. The two isotope ratios follow an equilibrium mass-dependent fractionation law which can be represented as δ30Si=1.93× δ29Si. Published extractions methods have been used to wet-chemically purify Si from the JER-diopside glass. The Si extracted was presented as Si-gel and ablated like a solid. The results show excellent agreement with in situ measurements of this glass that confirms that this technique can be employed to a wide variety of matrices, including Si purified from solution. The new technique presents a viable alternative to solution MC-ICP-MS for bulk measurements and the most precise technique so far for in situ measurement of Si isotope ratios.

Description: We have detected micrometer-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using a UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite-carbonate-chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter layer trends giving overall uniform 56Fe values of ~0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however their individual 56Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and 56Fe end member values are 0.4‰ for siderite and -0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with 30Si values that range between -1.0 and -2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate-chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite-carbonate-chert 48 layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF's diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.