Search

RATIONALE Boron isotopes are a powerful tool for pH reconstruction in marine carbonates and as tracer for fluid-mineral interaction in geochemistry. Micro-analytical approaches based on laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) often suffer from effects induced by the sample matrix. In this study, we investigated matrix-independent analyses of B isotopic ratios and applied this technique to cold-water corals. METHODS We employed a customized 193 nm femtosecond laser ablation system (Solstice, Spectra-Physics) coupled to a MC-ICP-MS (Nu Plasma II, Nu Instruments) equipped with electron multipliers for in situ measurements of B isotope ratios (11B/10B) at the micron-scale. We analyzed various reference materials of silicate and carbonate matrices using non-matrix match calibration without employing any correction mode. This approach was then applied to investigates defined increments in coral samples from a Chilean fjord. RESULTS We obtained accurate B isotope ratios with a precision of ± 0.9‰ (2 SD) for various reference materials including silicate glasses (GOR132-G, StHs6/80-G, ATHO-G, and NIST SRM 612), clay (IAEA-B-8) and carbonate (JCp-1) using the silicate glass NIST SRM 610 as calibration standard, which shows that neither laser-induced nor ICP-related matrix effects are detectable. The application to cold-water corals (Desmophyllum dianthus) reveal little intra-skeleton variations in δ11B with average values between 23.27 and 26.09‰. CONCLUSIONS Our instrumental set-up provides accurate and precise B isotopic ratios independently of the sample matrix at the micron-scale. This approach opens a wide field of application in geochemistry, including pH reconstruction in biogenic carbonates and deciphering processes related to fluid-mineral interaction.

Clay weathering in shales is an important component of the global Li budget because Li is mobilized from Li-rich clay minerals and shale represents about one quarter of the exposed rocks on Earth. We investigate Li isotopes and concentrations to explore implications and mechanisms of Li isotopic fractionation in Shale Hills, a first-order catchment developed entirely on shale in a temperate climate in the Appalachian Mountains, northeastern USA. The Li isotopic compositions (δ7Li) of aqueous Li in stream water and groundwater vary between 14.5 and 40.0‰. This range is more than half that observed in rivers globally. The δ7Li of aqueous Li increases with increasing Li retention in secondary minerals, which is simulated using a box model that considers pore fluid advection to be the dominant transport process, silicate dissolution to be the source of Li to the pore fluid, and uptake of Li by kaolinite, Fe-oxides, and interlayer sites of clays to be the sinks. The simulations suggest that only those deep groundwaters with δ7Li values of ∼15‰ are explainable as steady state values; those fluids with δ7Li values > 18‰, especially near-surface waters, can only be explained as time-dependent, transient signals in an evolving system. Lithium is highly retained in the residual solid phase during chemical weathering; however, bulk soils (0.5 ± 1.2‰ (1 SD)) and stream sediments (0.3‰) have similar, or higher, δ7Li values compared to average bedrock (−2.0‰). This is attributed to preferential removal of clay particles from soils. Soil clays are isotopically depleted in 7Li (δ7Li values down to −5.2‰) compared to parental material, and δ7Li values correlate with soil Li concentration, soil pH, and availability of exchangeable sites for Li as a function of landscape position (valley floor versus ridge top). The strong depletion of Li and clay minerals in soils compared to bedrock is attributed at least partly to loss of Li through export of fine-grained clay particles in subsurface water flow. This process might be enhanced as the upper weathering zone of this catchment is highly fractured due to former periglacial conditions. The Li isotopic composition of vegetation is similar to soil clay and both are distinct from mobile catchment water (soil pore water, stream and groundwater). Extrapolating from this catchment means that subsurface particle loss from shales could be significant today and in the past, affecting isotopic signatures of soils and water. For example, clay transformations together with removal of clay particles before re-dissolution support weathering conditions that lead to a low aqueous Li flux but to high δ7Li values in water.

The boron isotopic composition (δ11B) of benthic foraminifera provides a valuable tool to reconstruct past deep-water pH. As the abundance of monospecific species might be limited in sediments, microanalytical techniques can help to overcome this problem, but such studies on benthic foraminiferal δ11B are sparse. In addition, microanalytics provide information on the distribution of δ11B at high spatial resolution to increase the knowledge of e.g. biomineralization processes. For this study, we investigated the intra- and inter-shell δ11B variability of the epibenthic species Cibicidoides wuellerstorfi, which is widely used in paleoceanography, by secondary ion mass spectrometry (SIMS) and femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS). While the average δ11B values obtained from these different techniques agree remarkably well with bulk solution values to within ± 0.1 ‰, a relatively large intra-shell variability was observed. Based on multiple measurements within single shells, the SIMS and LA data suggest median variations of 4.8 ‰ and 1.3 ‰ (2σ), respectively, where the larger spread for SIMS is attributed to the smaller volume of calcite being analyzed in each run. When analytical uncertainties and volume-dependent differences in δ11B variations are taken into account for these methods, the intra-shell variability is presumably in the order of ~ 3 ‰ and ~ 0.4 ‰ (2σ) on a ~ 20 µm and 100 µm scale, respectively. In comparison, the δ11B variability between shells exhibits a total range of ~ 3 ‰ for both techniques, suggesting that several shells need to be analyzed for accurate mean δ11B values. Based on a simple resampling method, we conclude that ~ 7 shells of C. wuellerstorfi must be analyzed using LA-MC-ICPMS to obtain an accurate average value within ± 0.5 ‰ (2σ) to resolve pH variations of ~ 0.1. Based on our findings, we suggest to prefer the conventional bulk solution MC-ICPMS over the in-situ methods for e.g. paleo-pH studies. However, SIMS and LA provide powerful tools for high-resolution paleoreconstructions, or for investigating ontogenetic trends in δ11B, possibly due to vital effects during chamber formation.

Stream chemistry reflects the mixture of complex biogeochemical reactions that vary across space and time within watersheds. For example, streams experience changing hydrologic connectivity to heterogeneous water sources under different flow regimes; however, it remains unclear how seasonal flow paths link these different sources and regulate concentration-discharge behavior, i.e., changes in stream solute concentration as a function of discharge. At the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO) in central Pennsylvania, USA, concentrations of chemostatic solutes (K, Mg, Na, Si, Cl) vary little across a wide range of discharge values while concentrations of chemodynamic solutes (Fe, Mn, Ca) decrease sharply with increasing stream discharge. To elucidate controls on chemodynamic solute behavior, we investigated the chemistry of surface water and shallow subsurface water at the SSHCZO in early autumn when discharge was negligible and concentrations of chemodynamic solutes were high. Dissolved ions, colloids, and micron-sized particles were extracted from hillslope soils and stream sediments to evaluate how elements were mobilized into pore waters and transported from hillslopes to the stream. During the study period when flow was intermittent, the stream consisted of isolated puddles that were chemically variable along the length of the channel. Inputs of subsurface water to the stream were limited to an area of upwelling near the stream headwaters, and the water table remained over a meter below the stream bed along the rest of the channel. Chemodynamic elements Fe and Mn were preferentially mobilized from organic-rich soils as a mixture of dissolved ions, colloids, and micron-sized particles; consequently, subsurface water draining organic-rich soils in the upper catchment was enriched in Fe and Mn. Conversely, Ca increased towards the catchment outlet and was primarily mobilized from stream sediments as Ca2+. Concentrations of chemostatic solutes were relatively invariable throughout the catchment. We conclude that chemodynamic behavior at SSHCZO is driven by seasonally variable connectivity between the stream and hillslope soils. During the dry season, stream water derives from a shallow perched water table (interflow) that upwells to generate metal-rich stream headwaters. High concentrations of soluble Fe and Mn at low discharge occur when metal-rich headwaters are flushed to the catchment outlet during periodic rain events. Interflow during the dry season originates from water that infiltrates through organic-rich swales; thus, metals in the stream at low flow are ultimately derived from convergent hillslopes where biological processes have concentrated and/or mobilized these chemodynamic elements. In contrast, high concentrations of Ca2+ at low discharge are likely mobilized from stream sediments that contain secondary calcite precipitates. We infer that chemodynamic solutes are diluted at high discharge primarily due to increased flow through planar hillslopes. This study highlights how spatially heterogeneous biogeochemistry and seasonally variable flow paths regulate concentration-discharge behavior within catchments.

The boron isotopic composition of planktonic foraminiferal shell calcite ( δ 11 B Cc ) provides valuable information on the pH of ambient water at the time of calcification. Hence, δ 11 B Cc of fossil surface-dwelling planktonic foraminifera can be used to reconstruct ancient aqueous p CO 2 if information on a second carbonate system parameter, temperature and salinity is available. However, pH and p CO 2 of surface waters may vary seasonally, largely due to changes in temperature, DIC, and alkalinity. As also the shell fluxes of planktonic foraminifera show species-specific seasonal patterns that are linked to intra-annual changes in temperature, it is obvious that δ 11 B Cc of a certain species reflects the pH and thus p CO 2 biased towards a specific time period within a year. This is important to consider for the interpretation of fossil δ 11 B Cc records that may mirror seasonal pH signals. Here we present new Multi-Collector Inductively Coupled Mass Spectrometry (MC-ICPMS) δ 11 B Cc coretop data for the planktonic foraminifera species Globigerina bulloides , Globigerinoides ruber , Trilobatus sacculifer and Orbulina universa and compare them with δ 11 B borate derived from seasonally resolved carbonate system parameters. We show that the inferred season-adjusted δ 11 B Cc / δ 11 B borate relationships are similar to existing calibrations and can be combined with published δ 11 B Cc field and culture data to augment paleo-pH calibrations. To test the applicability of these calibrations, we used a core drilled on the Walvis Ridge in the Southeast Atlantic spanning the last 330,000 years to reconstruct changes in surface-water p CO 2 . The reconstruction based on G. bulloides , which reflects the austral spring season, was shown to yield values that closely resemble the Vostok ice-core data indicating that surface-water p CO 2 was close to equilibrium with the atmosphere during the cooler spring season. In contrast, p CO 2 estimated from δ 11 B Cc of O. universa , T. sacculifer and G. ruber that predominantly lived during the warmer seasons, exhibits up to ∼50 ppmv higher values than the Vostok ice-core data. This is probably due to the higher austral summer and fall temperatures, as shown by Mg/Ca to be on average ∼4 °C higher than during the cooler spring season, accounting for an increase in p CO 2 of ∼4% per 1 °C. Our results demonstrate that paleo-pH estimates based on δ 11 B Cc contain a significant seasonal signal reflecting the habitat preference of the recording foraminifera species.

The application of multiple isotope proxies on the same location within a Critical Zone (CZ), which we term “CZ-tope”, elucidates the interactions of geochemical, geomorphological, hydrological and biological processes together with anthropogenic influences in the CZ across widely disparate timescales. We exemplify the CZ-tope approach by summarizing the emerging hypotheses developed from isotopic measurements at the Susquehanna Shale Hills CZ Observatory (SSHCZO), Pennsylvania (U.S.A). At SSHCZO, measurements of U-series isotopes and meteoric 10Be in regolith provide evidence that the catchment is approaching a steady state at the ridgetops where regolith production is balanced by erosive loss. Isotopic measurements of δ13C, 87Sr/86Sr, and δ34S in the regolith, bedrock and water, together with 3H, δ2H and δ18O in various water reservoirs (precipitation, soil water, stream water and groundwater) support the hypothesis that nested reaction fronts have developed in the subsurface over timescales of millennia. Combinations of U-series and meteoric 10Be in bedrock and regolith and measurements of soil water δ18O led to the hypothesis that freeze-thaw is the dominant soil creep mechanism controlling regolith fluxes and hillslopes. Utilizing the CZ-tope approach of measuring δ26Mg, δ56Fe and δ11B isotopes on identical samples, we also developed a working hypothesis that particle transport in the subsurface represents a significant weathering loss from the catchment. Likewise, the use of δ18O, Ge/Si and 87Sr/86Sr ratios in xylem source waters (precipitation, soil, stream- and ground-), along with 87Sr/86Sr ratios from soils, led to the hypothesis that O isotope fractionation occurs near clay surfaces. Finally, analyses of 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb and 137Cs in soil from hillslope profiles have also revealed the imprint of widespread human activity. CZ-tope — the interpretation of multiple elements' isotopic ratios quantified for identical samples in one landscape — thus paints an emerging picture of SSHCZO as a relatively fast-eroding but slow-weathering landscape in which: i) nutrients are tightly cycled by vegetation, ii) soils move downslope largely by freeze-thaw, iii) subsurface particle transport is an important flux for mass loss, iv) mobile and immobile reservoirs act to fractionate water and cations into trees and stream water, and v) the imprint of humans is manifested in the metal contents of the topsoil.

To further develop boron isotopes as a tool for understanding shale weathering, we explored patterns of boron concentrations and isotopes across the forested Susquehanna Shale Hills Critical Zone Observatory (CZO). We present boron measurements for all watershed components that provided a foundation for examining water-rock interactions in a shale dominated watershed, including water compartments (e.g., precipitation, stream water, groundwater) and solid compartments (e.g., soil, bedrock, stream sediments, suspended load, and leaf litter). Results show boron isotopes (δ11B) in the bedrock (− 4.6‰) and soil (− 5.9 to - 4.2‰) were very similar. All waters were enriched in 11B by comparison: precipitation (7.2 to 22.6‰), stream (10.3 to 15.5‰), and groundwater (2.2 to 17.4‰). Modeling revealed that isotopic fractionation observed in the surface water and groundwater could mainly be explained by water-rock interactions including clay mineral dissolution (e.g., chlorite) and coprecipitation/adsorption processes (e.g., coatings on illite particles), likely in the near surface soils (~2 m deep). We found that leaching, the loss of boron from vegetation to stream water, plays a secondary role. Specifically, such leaching likely contributes the equivalent of 10 to 26% of the B fluxes from the watershed outlet. Boron mass balance between bedrock and precipitation inputs and the exported flux of dissolved and solid pools identified a “missing” isotopically light solid flux (δ11B of −12.2 ± 5.3‰ at ~4.4 ± 3.8 mol/ha/y of B; uncertainty reported as 2 SD). We did not sample any pool with this isotopic signature. Here our data suggest the composition of this pool is more likely related to precipitation of secondary clays rather than adsorption or (co)precipitation on Fe oxides. We propose two hypotheses to explain the missing light B pool: 1) a significant portion of the particles carrying the missing 10B are not sampled because they enter groundwater at depth and are transported out of the catchment under the stream; and/or 2) the inputs and outputs of boron are not operating at steady state in the catchment today, suggesting that the missing boron particles were lost in the past in proportions higher than today. When this B budget is paired with studies of δ26Mg and δ56Fe from Shale Hills, both of which also show missing isotopic pools, the pattern indicates a fundamental gap in understanding of shale weathering. We concluded that light B particles, presumably generated in the upper soils, are likely transported deep beneath the surface in the groundwater system or episodically in the past through riverine fluxes.

Silicon stable isotopes have emerged as a powerful proxy to investigate weathering because Si uptake from solution by secondary minerals or by the vegetation causes significant shifts in the isotope composition. In this study, we determined the Si isotope compositions of the principle Si pools within two small catchments located on sandstone and paragneiss, respectively, in the temperate Black Forest (Germany). At both settings, clay formation is dominated by mineral transformation preserving largely the signature of parental minerals with delta Si-30 values of around -0.7%. Bulk soils rich in primary minerals are similar to bulk parental material with delta Si-30 values close to -0.4%. Topsoils are partly different because organic matter degradation has promoted intense weathering leading to delta Si-30 values as low as -1.0%. Water samples expose highly dynamic weathering processes in the soil zone: 1) after spring snowmelt, increased release of DOC and high water fluxes trigger clay mineral dissolution which leads to delta Si-30 values down to -0.7% and 2) in course of the summer, Si uptake by the vegetation and secondary mineral formation drives dissolved Si to typical positive delta Si-30 values up to 1.1%. Groundwater with delta Si-30 values of around 0.4% records steady processes in bedrock reflecting plagioclase weathering together with kaolinite precipitation. An isotope mass balance approach reveals incongruent weathering conditions where denudation of Si is largely driven by physical erosion. Erosion of phytoliths contributes 3 to 21% to the total Si export flux, which is in the same order as the dissolved Si flux. These results elucidate the Si dynamics during weathering on catchments underlain of sedimentary origin, prevailing on the Earth surface and provide therefore valuable information to interpret the isotope signature of large river systems.

During the early industrial revolution, mining and smelting of ores and coal combustion released significant amounts of lead (Pb) into the atmosphere. While many researchers have documented high Pb concentrations in topsoils due to gasoline combustion between 1940s and 1980s, little work has focused on the extent of Pb and other heavy metal deposition into soils during the early industrial period. Here, we report Pb, cadmium (Cd), and zinc (Zn) concentrations and Pb isotope ratios of soils, sediments, parent bedrock, and waters collected from a small, currently pristine watershed (Shale Hills Critical Zone Observatory) in Pennsylvania (United States of America). Our results show that Pb in the soil comprises an addition profile, i.e. more Pb is present in the soil than is present in the equivalent parent bedrock. All three investigated soil profiles at Shale Hills on the same hillslope have Pb inventories (∼400–600 μg cm−2) attributed to atmospheric deposition. Cd and Zn concentrations in these soils show similar addition profiles due to atmospheric deposition. Based on Pb isotopic ratios, the most likely source of the added Pb is coal burning and ore smelting during local iron production in the early 19th century, roughly coincident with the construction of the U.S. transcontinental railroad. Mass balance and diffusive transport modeling were used to quantify Pb deposition rates and redistribution. These model results are consistent with the hypothesis that from ∼1850s to 1920s, coal burning and ore smelting in local iron blasting furnaces significantly increased the local Pb emissions so that Pb deposition rates in soils were in the range of 6–10 μg cm−2 yr−1. These values are comparable to Pb deposition rates found in other areas with early and intensive industrial activities (e.g. since the ∼1860s in Australia). Our new Pb, Cd, and Zn concentrations and Pb isotope results, in combination with the previously observed manganese (Mn) enrichment at Shale Hills, document that early industrial point sources contaminated local soils with metals that remain even today in topsoils with large sorption capacities. Where these metals are retained, their depth profiles provide a mean to infer the history of metal additions and redistributions.

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD-1G and MPI-DING reference glasses. Thirteen different laboratories were involved using high-precision bulk (TIMS, MC-ICP-MS) and microanalytical (LA-MC-ICP-MS, LA-ICP-MS) techniques. Detailed studies were performed to demonstrate the large-scale and small-scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD-1G and the MPI-DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.

Major- and trace-element data and Nd isotope compositions for granitoid samples from the Grampian Highlands in Scotland show a systematic evolution in the composition of their sources in the course of the Caledonian Orogeny. Granitoids of 511–451 Ma, related to the collision of the Midland Valley island arc with the Grampian terrane, show S-type affinity and fractionated REE patterns with minor Eu anomalies and low initial ϵ Nd values of −14.1 to −11.2 suggesting melting of predominantly Dalradian metasediments. Subsequently formed granitoids of 425–406 Ma derived from an assumed Andean plate margin comprise a wide spectrum of rock types including I-type granite–granodiorite, and S-type granitoids, monzonites and alkali granites. The trace-element patterns of these rocks and the range of initial ϵ Nd values of −2.1 to −6.9 are consistent with melting of variably rejuvenated crust as found in continental margin settings. We conclude that the Grampian Highlands were affected by two major crust-modifying events during the Caledonian Orogeny: predominantly recycling of older crust during docking of the Midland Valley arc and addition of juvenile, mantle-derived material to the crust during the convergence of Avalonia with Laurentia.

A new method for the in situ measurement of stable Si isotope ratio using UV-femtosecond laser ablation connected to a multiple-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) has been established. The use of medium mass resolution mode (with a resolving power m /Δ m = 8000) permits to resolve spectral interferences on 28 Si, 29 Si and 30 Si allowing for determination of the 29 Si/ 28 Si and 30 Si/ 28 Si 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 μm side 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 δ 29 Si and δ 30 Si have been determined for the silicon isotope standard IRMM-017 ( δ 30 Si ± 2 S.D. = − 1.26 ± 0.24‰; n = 89) and BigBatch ( δ 30 Si = − 10.55 ± 0.42‰; n = 15), as well as San Carlos Olivine ( δ 30 Si = − 0.81 ± 0.19‰; n = 14), Caltech Rose Quartz ( δ 30 Si = 0.10 ± 0.13‰; n = 14) sponge needles ( Stylocordyla borealis ; δ 30 Si = − 2.19 ± 0.32‰; n = 14) and JER-diopside glass ( δ 30 Si = 0 ± 0.09‰; n = 14) samples. The overall repeatability achievable is 0.15‰ (2 S.D.) on δ 29 Si and 0.24‰ (2 S.D.) on δ 30 Si. 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 δ 30 Si = 1.93 × δ 29 Si. 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.

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe–Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower δ56Fe values by 0.2‰–0.5‰ as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite–ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including β-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the δ56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite–ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

This study presents the first Si isotope data of the principle Si pools in soils determined by a UV femtosecond laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). This method reveals accurate and precise Si isotope data on bulk materials, and at high spatial resolution, on the mineral scale. The following Si pools have been investigated: a) the Si source to soils on all major silicate minerals on thin sections from bedrock fragments in the soil profiles; b) bulk soils (particle size

To investigate the genesis of BIFs, we have determined the Fe and Si isotope composition of coexisting mineral phases in samples from the ∼2.5 billion year old Kuruman Iron Formation (Transvaal Supergroup, South Africa) and Dales Gorges Member of the Brockman Iron Formation (Hamersley Group, Australia) by UV femtosecond laser ablation coupled to a MC-ICP-MS. Chert yields a total range of δ30Si between −1.3‰ and −0.8‰, but the Si isotope compositions are uniform in each core section examined. This uniformity suggests that Si precipitated from well-mixed seawater far removed from its sources such as hydrothermal vents or continental drainage. The Fe isotope composition of Fe-bearing mineral phases is much more heterogeneous compared to Si with δ56Fe values of −2.2‰ to 0‰. This heterogeneity is likely due to variable degrees of partial Fe(II) oxidation in surface waters, precipitation of different mineral phases and post-depositional Fe redistribution. Magnetite exhibits negative δ56Fe values, which can be attributed to a variety of diagenetic pathways: the light Fe isotope composition was inherited from the Fe(III) precursor, heavy Fe(II) was lost by abiotic reduction of the Fe(III) precursor or light Fe(II) was gained from external fluids. Micrometer-scale heterogeneities of δ56Fe in Fe oxides are attributed to variable degrees of Fe(II) oxidation or to isotope exchange upon Fe(II) adsorption within the water column and to Fe redistribution during diagenesis. Diagenetic Fe(III) reduction caused by oxidation of organic matter and Fe redistribution is supported by the C isotope composition of a carbonate-rich sample containing primary siderite. These carbonates yield δ13C values of ∼−10‰, which hints at a mixed carbon source in the seawater of both organic and inorganic carbon. The ancient seawater composition is estimated to have a minimum range in δ56Fe of −0.8‰ to 0‰, assuming that hematite and siderite have preserved their primary Fe isotope signature. The long-term near-zero Fe isotope composition of the Hamersley and Transvaal BIFs is in balance with the assumed composition of the Fe sources. The negative Fe isotope composition of the investigated BIF samples, however, indicates either a perturbation of the steady state, or they have to be balanced spatially by deposition of isotopically heavy Fe. In the case of Si, the negative Si isotope signature of these BIFs stands in marked contrast to the assumed source composition. The deviation from potential source composition requires a complementary sink of isotopically heavy Si in order to maintain steady state in the basin. Perturbing the steady state by extraordinary hydrothermal activity or continental weathering in contrast would have led to precipitation of light Si isotopes from seawater. Combining an explanation for both elements, a likely scenario is a steady state ocean basin with two sinks. When all published Fe isotope records including BIFs, microbial carbonates, shales and sedimentary pyrites, are considered, a complementary sink for heavy Fe isotopes must have existed in Precambrian ocean basins. This Fe sink could have been pelagic sediments, which however are not preserved. For Si, such a complementary sink for heavy Si isotopes might have been provided by other chert deposits within the basin.

We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an 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 d 56 Fe values of � 0.9&, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual d 56 Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and d 56 Fe 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 d 30 Si 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 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.

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.