The heat transfer in the region of the Mauna Kea (Hawaii)—constraints from borehole temperature measurements and coupled thermo-hydraulic modeling

The objectives of this paper are an understanding of the thermal and hydraulic field because of a negative temperature gradient and cold temperatures in the 1-km-deep borehole of the Hawaiian Scientific Drilling Project (HSDP), located near the coast line. The temperature pattern is attributed to a superposition of thermal and hydraulic processes. In the deeper borehole (HSDP-2, depth 3.1 km) detailed temperature monitoring was performed. Temperature measurements reveal two different thermal regimes. The upper part is characterised by cold temperatures and a negative temperature gradient similar to those observed in the shallow pilot borehole. Below 1100 m, increasing temperatures are observed. Different processes, such as topographically driven groundwater flow, ingress of salt water and conductive heat flow are investigated by numerical modeling. A pure conductive scenario fails to match the temperature measurements, implying that both borehole sections are overprinted by advective conditions. Coupled fluid and heat flow modeling with solute transport yield results that agree with observed temperatures. The results of these simulations suggest that meteoric water flow from the mountain range controls the thermal conditions in the upper part of the borehole. Below this level, the thermal regime is additionally affected by circulation of salt water from the nearby ocean. Each of these flow systems has been observed at other locations: topographically driven fresh water at locations with pronounced topography and ingress of salt water is typical for islands or coastal areas. At Hawaii, they coincide and influence each other, resulting in a salt water interface occurring at greater depth than expected.     

GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

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.     

Deciphering formation processes of banded iron formations from the Transvaal and the Hamersley successions by combined Si and Fe isotope analysis using UV femtosecond laser ablation

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.     

In situ iron isotope ratio determination using UV-femtosecond laser ablation with application to hydrothermal ore formation processes

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.     

Matrix-independent Fe isotope ratio determination in silicates using UV femtosecond laser ablation

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 δ^56/54Fe and δ^57/54Fe values that agree with those from solution ICP-MS data within the measured precision. For high Cr concentration (⁵⁴Cr/⁵⁴Fe >0.0001), i.e. in the garnet and forsterite sample, δ^56/54Fe and δ^57/54Fe 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 δ^56/54Fe 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 δ^56/54Fe and 0.2‰ (2 SD) for δ^57/54Fe, 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 largely matrix-independent method, which provides a substantial advantage over commonly employed nanosecond laser ablation systems.     

Micro-scale tracing of Fe and Si isotope signatures in banded iron formation using femtosecond laser ablation

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 δ⁵⁶Fe values of 0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ⁵⁶Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ⁵⁶Fe 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 δ³⁰Si 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.