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Laser ablation multi-collector mass spectrometry (LA-MC-ICP-MS) has emerged as the technique of choice for in situ measurements of Sr isotopes in geological minerals. However, the method poses analytical challenges and there is no widely adopted standardised approach to collecting these data or correcting the numerous potential isobaric inferences. Here, we outline practical analytical procedures and data reduction strategies to help establish a consistent framework for collecting and correcting Sr isotope measurements in geological materials by LA-MC-ICP-MS. We characterise a new set of plagioclase reference materials, which are available for distribution to the community, and present a new data reduction scheme for the Iolite software package to correct isobaric interferences for different materials and analytical conditions. Our tests show that a combination of Kr-baseline subtraction, Rb-peak-stripping using βRb derived from a bracketing glass reference material, and a CaCa or CaAr correction for plagioclase and CaCa or CaAr + REE 2+ correction for rock glasses, yields the most accurate and precise 87Sr/ 86Sr measurements for these materials. Using the analytical and correction procedures outlined herein, spot analyses using a beam diameter of 100 μm or rastering with a 50–65 μm diameter beam can readily achieve 87Sr/ 86Sr measurements for materials with -1 Sr.

Recent advances in soil phosphorus (P) studies have revealed unique P hot spots and discrete micron-sized grains at soil microsites, but the significance of these so-called ‘hot spots’ and grains in P cycling and long-term supply is yet to be determined. We examined soil particles and pore space distribution at a micro-scale in two postglacial forest soils by laser ablation ICP-MS imaging. This allowed us to semi-quantitatively reveal both axial and lateral abundance, distribution, and co-localization of P with elements known to influence its chemical speciation (e.g., Si, Al, Mn, Ca, and Fe). The results show topsoil P to be co-localised predominantly with Si, Al, and Fe. However, in the subsoils, P was co-localised mainly with Ca, Si, Al, and Mg in spots within Si and Al-bearing minerals and with only Ca in discrete micron-sized grains. While the spots of P-Ca inclusions were ~ 1000 μm apart and present at 40–100 cm depth in Tärnsjö, the discrete grains of P-Ca were ~ 700–1200 μm apart and present at 90–100 cm depth in Tönnersjöheden. The P concentrations in these ‘hot spots’ and grains were 7 to 600 times greater than the average soil P concentrations, with the highest values (3434–8716 mmol P kg−1) occurring in the C horizons of the two soils. When combined with previous P speciation results obtained by synchrotron P K-edge XANES in the same soils, our work confirms geogenic apatite to have been dissolved in the topsoil and its P transformed to P adsorbed by Al-Si and Fe phases, and to organic P. Most importantly, our work shows subsoil spots of P-Ca inclusions and micron-sized grains to be a long-term source of P and Ca.

The Seve Nappe Complex (SNC) comprises continental rocks of Baltica that were subducted and exhumed during the Caledonian orogeny prior to collision with Laurentia. The tectonic history of the central SNC is investigated by applying in-situ zircon and monazite (Th-)U–Pb geochronology and trace element analysis to (ultra-)high pressure (UHP) paragneisses in the Avardo and Marsfjället gneisses. Zircons in the Avardo Gneiss exposed at Sippmikk creek exhibit xenocrystic cores with metamorphic rims. Cores show typical igneous REE profiles and were affected by partial Pb-loss. The rims have flat HREE profiles and are interpreted to have crystallized at 482.5 ± 3.7 Ma during biotite-dehydration melting and peritectic garnet growth. Monazites in the paragneiss are chemically homogeneous and record metamorphism at 420.6 ± 2.0 Ma. In the Marsfjället Gneiss exposed near Kittelfjäll, monazites exhibit complex zoning with cores enveloped by mantles and rims. The cores are interpreted to have crystallized at 481.6 ± 2.1 Ma, possibly during garnet resorption. The mantles and rims provide a dispersion of dates and are interpreted to have formed by melt-driven dissolution-reprecipitation of pre-existing monazites until 463.1 ± 1.8 Ma. Depletion of Y, HREE, and U in the mantles and rims compared to the cores record peritectic garnet and zircon growth. Altogether, the Avardo and Marsfjället gneisses show evidence of late Cambrian/early Ordovician partial melting (possibly in (U)HP conditions), Middle Ordovician (U)HP metamorphism, and late Silurian tectonism. These results indicate that the SNC underwent south-to-north oblique subduction in late Cambrian time, followed by progressive north-to-south exhumation to crustal levels prior to late Silurian continental collision.

Iron isotopic equilibration at the Trans-Atlantic Geotraverse hydrothermal field takes place over tens of thousands of years, with variable degrees of hydrothermal maturation throughout the active mound, according to iron isotope analyses of sulfide minerals. Sub-seafloor hydrothermal processes along volcanically active plate boundaries are integral to the formation of seafloor massive sulfide deposits and to oceanic iron cycling, yet the nature of their relationship is poorly understood. Here we apply iron isotope analysis to sulfide minerals from the Trans-Atlantic Geotraverse (TAG) mound and underlying stockwork, 26 degrees N Mid-Atlantic Ridge, to trace hydrothermal processes inside an actively-forming sulfide deposit in a sediment-free mid-ocean ridge setting. We show that data for recently formed chalcopyrite imply hydrothermal fluid-mound interactions cause small negative shifts (20 kyr evolution of the TAG complex. The identified processes may explain iron isotope variations found in fossil onshore sulfide deposits.

Large Arctic rivers are important suppliers of iron to the Arctic Ocean. However, the sources of Fe-bearing particles in permafrost-dominated systems and the mechanisms driving this supply of Fe are poorly resolved. Here, Fe isotope ratios were used to determine the sources of Fe-bearing particles and colloids in the Lena River and tributaries. In samples collected after the spring floods, Fe-bearing particles (>0.22 µm) carried ∼70% of the Fe and have isotope ratios that are lower than, or similar to that of the continental crust. These particles are composed of a leachable Fe fraction of largely ferrihydrite, with isotope values of −1.40‰ to −0.12‰, and a fraction of clays and Fe oxides with continental crust values. Co-existing Fe-bearing colloids (

Much of the continental lithosphere developed during the Archean, which was an Eon of change in terms of global geodynamics and geochemical cycles. Uncovering the causal links between crust forming processes and prevailing geodynamic mechanisms is crucial for understanding the origins and composition of the present-day continental lithosphere. Pristine Archean crust is scarce yet can be found in cratons worldwide. Many of these occurrences comprise rocks of the tonalite-trondhjemite-granodiorite (TTG) suite, which represent a prevalent component of the Archean continental crust. TTGs are generally considered to have formed by partial melting of amphibolite or eclogite source rocks that had basaltic precursors originally extracted from a depleted mantle (e.g., [1]). The age of the source rocks (i.e., the time between the basalt extraction from the mantle and TTG formation) can be determined from the initial radiogenic isotope compositions of TTGs, provided that the P/D ratio of the source can be reliably estimated and is significantly different from that of the depleted mantle.Based on this principle, we estimated the age of basaltic sources of TTGs from cratons of different age and paleogeography from initial 87Sr/86Sr compositions determined by in-situ Sr isotope analysis of primary igneous apatite (LA-MC-ICPMS). The 87Sr/86Sr of these apatites show that prior to 3.4 Ga TTGs were derived from relatively old mafic sources and that the average time between formation of basaltic material from the mantle and subsequent remelting under amphibolite to eclogite facies conditions decreased drastically during the Paleoarchean. This secular change indicates a rapid global increase in the efficiency of TTG production or the emergence of a new TTG-forming process at c. 3.4 Ga [2].In this contribution we explore this hypothesis by comparing the 87Sr/86Sr signature of the TTGs with their trace-element compositions, as well as with 176Hf/177Hf zircon data for these rocks and contemporary TTGs from other studies. This combined geochronological, isotope and geochemical analyses will provide new constraints on the age of TTG sources during the Archean and will allow investigation into the nature and probable causes of the apparent rejuvenation at 3.4 Ga, as indicated by Sr isotopes.[1] Hoffmann, J.E. et al. (2011) Geochim. Cosmochim. Acta 75, 4157-4178.[2] Caton, S., et al., (in review) Chem. Geol.

Establishing temporal constraints of faulting is of importance for tectonic and seismicity reconstructions and predictions. Conventional fault dating techniques commonly use bulk samples of syn-kinematic illite and other K-bearing minerals in fault gouges, which results in mixed ages of repeatedly reactivated faults as well as grain-size dependent age variations. Here we present a new approach to resolve fault reactivation histories by applying high-spatial resolution Rb-Sr dating to fine-grained mineral slickenfibres in faults occurring in Paleoproterozoic crystalline rocks. Slickenfibre illite and/or K-feldspar together with co-genetic calcite and/or albite were targeted with 50 µm laser ablation triple quadrupole inductively coupled plasma mass spectrometry analyses (LA-ICP-MS/MS). The ages obtained disclose slickenfibre growth at several occasions spanning over 1 billion years, from at least 1527 Ma to 349 ± 9 Ma. The timing of these growth phases and the associated structural orientation information of the kinematic indicators on the fracture surfaces are linked to far-field tectonic events, including the Caledonian orogeny. Our approach links faulting to individual regional deformation events by minimizing age mixing through micro-scale analysis of individual grains and narrow crystal zones in common fault mineral assemblages.

Sub-seafloor hydrothermal processes along volcanically active plate boundaries are integral to the formation of seafloor massive sulfide (SMS) deposits and to oceanic Fe cycling, yet their nature is poorly understood. Here we apply Fe isotope analysis to sulfides from the TAG mound and underlying stockwork, 26°N Mid-Atlantic Ridge, to trace hydrothermal processes inside an actively-forming SMS deposit in a sediment-free mid-ocean ridge setting. We show that data for recently formed chalcopyrite imply fluid–mound interactions cause small negative shifts (< -0.1‰) to the δ56Fe signature of dissolved Fe released from TAG into the North Atlantic Ocean. Texturally resolved pyrite, in turn, preserves a δ56Fe range from − 1.27 to + 0.56‰ that reflects contrasting modes of formation (fluid–seawater mixing vs. fluid conductive cooling) and variable degrees of progressive hydrothermal maturation during the > 20 kyr evolution of the TAG complex. The identified processes may explain Fe isotope variations found in fossil onshore sulfide deposits.

In this paper, we present the 87Sr/86Sr data of 13 samples from horses from six Lithuanian burial sites dating from the 3rd to the 7th C AD. Alongside these data, we also publish the bioavailable 87Sr/86Sr data of 15 Lithuanian archaeological sites, based on 41 animals which enabled the construction of a reliable baseline for the Southeast Baltic area. The 87Sr/86Sr values partially confirmed the hypothesis that the unusually large horses found in Late Roman Period to Post-Migration Period burials are of non-local origin. Of the three non-local horses identified, two were among the largest specimens. However, the overlap of bioavailable 87Sr/86Sr data across different European regions does not permit us to establish whether the non-local horses originated from other areas in Lithuania or from more distant regions. With regards to the 87Sr/86Sr data, the place of origin of the non-local horses could be Southern Sweden. This encourages discussions on the possible directions of migration and compels us to rethink the current models that posit South and Central Europe as the main sources of migration. The results of the 87Sr/86Sr, δ13C, and δ15N analyses demonstrate that horses buried in the same cemetery had different mobility and feeding patterns. Differences could be due to the different function and sex of the horses as well as the lifestyle of their owners. The most sedentary horses were pregnant mares, while the extremely high δ15N of three horses may reflect additional fodder and probably a better diet.

The metamorphosed, stratiform, c. 1.9 Ga Zinkgruvan Zn-Pb-Ag deposit is one of Europe’s largest producers of Zn. Since 2010, disseminated Cu mineralization is also mined from dolomite marble in a hydrothermal vent-proximal position in the stratigraphic footwall. Local enrichments of Co and REE exist in the vent-proximal mineralization types, albeit their distribution is poorly known. This contribution provides new data on the distribution of Co and REE within the Zinkgruvan deposit.LA-ICP-MS analysis suggest that lattice-bound cobalt in sphalerite range between 44 ppm and 1372 ppm, with the lowest and highest values occurring in distal and proximal mineralization, respectively. Proximal Co-rich sphalerite is always Fe-rich. Lattice-bound Co also occur in pyrrhotite; ranging from 52 ppm in distal ore to 1608 ppm in proximal ore. There is a concurrent increase in lattice-bound Ni from 3 ppm to 529 ppm. In proximal ore, Co is also hosted by cobalt minerals such as costibite (27.37 wt.% Co), safflorite (16.21 wt.% Co), nickeline (7.54 wt.% Co), cobaltite (32.74 wt.% Co) and cobaltpentlandite (25.49 wt.% Co). Automated quantitative mineralogy suggest that these minerals are highly subordinate to sphalerite (LA-ICP-MS analysis show that accessory apatite in proximal, marble-hosted Cu mineralization carries a few thousand ppm ∑REE, but locally up to c. 1.6 wt.% ∑REE. The apatite can be subdivided into two types. Type 1 apatite is characterized by dumbbell-shaped chondrite-normalized REE profiles with relative enrichment of in particular Sm-Tb, depletion of Yb-Lu relative to La-Pr, local positive Gd anomalies, and weak positive to negative Eu anomalies. Type 2 apatite is characterized by flat to negatively sloping REE profiles from La to Gd and relative HREE depletion. Additional REE is hosted by monazite. Type 1 apatite was only found as a gangue to Cu mineralization. The Type 1 apatite REE signature is characteristic of hydrothermal apatite, and a direct genetic association with vent-proximal Cu mineralization can be inferred.Comparison with published REE contents in apatite suggest that vent-proximal Zinkgruvan apatite is locally as REE-rich as apatite from Kiruna-type apatite iron oxide deposits, and more REE-rich than apatite in other metamorphosed sediment-hosted sulphide deposits in the world, such as the Gamsberg deposit (RSA).

Earth’s crust contains a substantial proportion of global biomass, hosting microbial life up to several kilometers depth. Yet, knowledge of the evolution and extent of life in this environment remains elusive and patchy. Here we present isotopic, molecular and morphological signatures for deep ancient life in vein mineral specimens from mines distributed across the Precambrian Fennoscandian shield. Stable carbon isotopic signatures of calcite indicate microbial methanogenesis. In addition, sulfur isotope variability in pyrite, supported by stable carbon isotopic signatures of methyl-branched fatty acids, suggest subsequent bacterial sulfate reduction. Carbonate geochronology constrains the timing of these processes to the Cenozoic. We suggest that signatures of an ancient deep biosphere and long-term microbial activity are present throughout this shield. We suggest that microbes may have been active in the continental igneous crust over geological timescales, and that subsurface investigations may be valuable in the search for extra-terrestrial life. Cenozoic signatures of life in calcite and pyrite deposits suggest deep biosphere activity throughout the Fennoscandian Shield, as revealed by isotopic, molecular and morphological analyses of mineral specimens.

The first find of microdiamond in the Nordøyane ultra-high-pressure (UHP) domain of the Western Gneiss Region (WGR) of the Scandinavian Caledonides reshaped tectonic models for the region. Nevertheless, in spite of much progress regarding the meaning and significance of this find, the history of rock that the diamonds were found in is complex and still largely ambiguous. To investigate this, we report U–Pb zircon ages obtained from the exact crushed sample material in which metamorphic diamond was first found. The grains exhibit complicated internal zoning with distinct detrital cores overgrown by metamorphic rims. The cores yielded a range of ages from the Archaean to the late Neoproterozoic / early Cambrian. This detrital zircon age spectrum is broadly similar to detrital signatures recorded by metasedimentary rocks of the Lower and Middle allochthons elsewhere within the orogen. Thus, our dating results support the previously proposed affinity of the studied gneiss to the Seve–Blåhø Nappe of the Middle Allochthon. Metamorphic rims yielded a well-defined peak at 447 ± 2 Ma and a broad population that ranges between c. 437 and 423 Ma. The data reveal a prolonged metamorphic history of the Fjørtoft gneiss that is far more complex then would be expected for a UHP rock that has seen a single burial and exhumation cycle. The data are consistent with a model involving multiple such cycles, which would provide renewed support for the dunk tectonics model that has been postulated for the region.

The origin of giant Kiruna-type iron ores has been debated for nearly 100 years. This study employs extensive stable isotope data from Kiruna-type ores worldwide and magmatic and hydrothermal reference materials to show that iconic Kiruna-type ores originate primarily from ortho-magmatic processes.

The burial and exhumation of continental crust during collisional orogeny exert a strong controlon the dynamics of mountain belts and plateaus. Constraining the rates and style of exhumation of dee ...

U-Pb isotope systems have been used to constrain the timing of formation, alteration, and oxidation of U minerals from the meta-granitic bedrock at Forsmark, eastern Sweden. Secondary ion mass spectrometry (SIMS) has been used to collect U-Pb data from uraninite. Discordant data suggest a ~1.8 Ga emplacement of uraninite-bearing pegmatites and an event of uraninite alteration at ~1.6 Ga. The latter age is contemporaneous with the Gothian orogeny in Scandinavia, which was associated with hydrothermal fluid circulation in the Fennoscandian Shield. Ca-uranyl silicates haiweeite and uranophane predominately formed 1.3–1.2 Ga, contemporaneous with the emplacement of the Satakunta complex of the Central Scandinavian Dolerite Group. A Palaeozoic group of Ca-U(VI)-silicates is also present, which indicates that the geochemical composition of geologic fluids was heterogeneous throughout the fracture network during this time. Low Pb concentrations in the U(VI) silicates of several samples are compatible with a recent (

Unravelling the timing and rate of subduction-zone metamorphism requires linking the composition of petrogenetic indicator minerals in blueschists and eclogites to time. Garnet is a key mineral in this regard, not in the least because it best records P-T conditions and changes therein and can be dated, using either Lu-Hf or Sm-Nd chronology. Bulk-grain garnet ages are the norm and can provide important and precise time constraints on reactions across both facies. Domain dating, i.e., dating of individual growth zones, moves beyond that. Domain dating by combining mechanical micro-milling and Sm-Nd chronology yielded important constraints on garnet-growth and fluid-release rates for blueschists (e.g., Dragovic et al., 2015). Developing this method for Lu-Hf chronology and, importantly, for "common-sized" garnet (≤1 cm) provides an important opportunity to further explore the potential of this approach.We combined a low-loss micro-sampling technique in laser cutting with a refined Lu-Hf routine to precisely date multiple growth zones of a sub-cm-sized garnet in a blueschist. The targeted grain from a glaucophane-bearing micaschist from Syros Island, Greece, was chemically characterized by major- and trace-element mapping (EPMA, LA-ICPMS) and five zones were extracted using a laser mill. The three core and inner mantle zones are chemically comparable and identical in age within a 0.1 Myr precision (2σ). The outer two zones are chemically distinct and are resolvably younger (0.2-0.8 Myr). The timing of these two major garnet-growth episodes, together with the variations in trace-element chemistry, constrain important fluid-release reactions, such as chloritoid-breakdown. The data show that the integral history of garnet growth in subduction zones may be extremely short ( Dragovic, B., Baxter, E.F. and Caddick, M.J., 2015. Pulsed dehydration and garnet growth during subduction revealed by zoned garnet geochronology and thermodynamic modeling, Sifnos, Greece. Earth and Planetary Science Letters, 413, pp.111-122.

To better understand the subduction–exhumation cycles of the Baltoscandian margin that reached (U)HP depths during the Caledonian orogeny, we have performed in-situ U-(Th-)Pb dating coupled with REE analysis of zircon and ± monazite in four samples from the supracrustal rocks of the Blåhø Nappe on Gossa island in the Western Gneiss Region (WGR) of Norway. We dated two garnet-plagioclase-biotite gneisses and two garnet-plagioclase-amphibole gneisses. Our research focused on deciphering the early metamorphic evolution of these complex rocks that have been overprinted by exhumation-related structures and pervasive retrogressive metamorphism.The dated zircon grains are spherical or slightly elongated in shape, some of which display clear multi-stage growth features. Only one grain armored by garnet preserved an older detrital core that yielded early Neoproterozoic dates between 1.1-1.0 Ga. This grain does not provide any Caledonian signal. Younger individual 206Pb/238U dates show three distinct populations that yield three concordia ages, each obtained from distinctly different compositional domains, the oldest from cores and the two youngest from overgrowths. The cores are characterized by HREE enrichment (high Lu/Gd ratios ca. 14.5), high Th/U ratios (> 0.1), and large Eu anomalies. They yield a concordia age of 474 ± 6.4 Ma. These cores can be rimmed by two different types of zircon overgrowth. The first overgrowth type (1) displays the same REE pattern as the cores and gives a concordia age of 444± 4.3 Ma. The second overgrowth type (2) shows a very weak Eu anomaly, no HREE enrichment (low Lu/Gd ratios ca. 2.37) and a very low Th/U ratios (Funded by the National Science Centre (Poland) project no. 2014/14/E/ST10/00321.

Kiruna-type apatite-iron-oxide ores are key iron sources for modern industry. The origin of the Kiruna-type apatite-iron-oxide ores remains ambiguous, however, despite a long history of study and a concurrently intense scientific debate. Diverse ore-forming processes have been discussed, comprising low-temperature hydrothermal processes versus a high-temperature origin from magma or magmatic fluids. We present an extensive set of new and combined iron and oxygen isotope data from magnetite of Kiruna-type ores from Sweden, Chile and Iran, and compare them with new global reference data from layered intrusions, active volcanic provinces, and established low-temperature and hydrothermal iron ores. We show that approximately 80% of the magnetite from the investigated Kiruna-type ores exhibit δ56Fe and δ18O ratios that overlap with the volcanic and plutonic reference materials (> 800 °C), whereas ~20%, mainly vein-hosted and disseminated magnetite, match the low-temperature reference samples (≤400 °C). Thus, Kiruna-type ores are dominantly magmatic in origin, but may contain late-stage hydrothermal magnetite populations that can locally overprint primary high-temperature magmatic signatures [1] . [1] Troll, V.R., Weis, F.A., Jonsson, E. et al. Global Fe–O isotope correlation reveals magmatic origin of Kiruna-type apatite-iron-oxide ores. Nature Communications 10, 1712 (2019) doi:10.1038/s41467-019-09244-4

Among the rocky planets of the solar system only the Earth has “granitic” continental crust. The timing and processes involved in the formation of Earth’s first extensive crust is still enigmatic. The chemical and isotope compositions of ancient crustal rocks preserve a record of their genesis. The Rb-Sr system proves to be an efficient proxy for the reconstruction of crust-mantle evolution since it can bring together information from seawater as preserved in chemical sedimentary rocks and information from magmatic rocks that can trace the time and extent of crust formation and concomitant mantle depletion during the Archaean eon. The Dharwar Craton in India preserves a suite of metamorphosed igneous and sedimentary rocks that record its early crustal evolution. To overcome the susceptibility for resetting and the difficulty in determining initial 87Sr/86Sr, the minerals barite and apatite are used to obtain precise and accurate 87Sr/86Sr, because these minerals preferentially incorporate Sr and exclude Rb and preserve the initial Sr isotope compositions at the time of their formation. Initial 87Sr/86Sr of apatite were obtained in situ using Laser Ablation Multi-Collector Inductively Coupled Plasma Mass Spectrometry. The robustness and only minor dispersion of the isotope ratios demonstrate the capability of matrix apatites in preserving initial Sr ratios. The least radiogenic value is used as the best estimate for the initial 87Sr/86Sr. The 87Sr/86Sr ratios of apatite from igneous rocks that formed from 3.5 Ga to 2.6 Ga constrain the Rb/Sr of the source over the whole time-span. A comparison of the Sr isotopes between seawater-derived barite and initial Sr isotope ratios in apatite from igneous rocks reveals that significant mafic to intermediate crust had formed by 3.2 Ga. Studying the entire Archaean time window, a dominantly mafic crust was the main source for the granitoid rocks in the Dharwar Craton from 3.5 to 3.1 Ga, whereas the rocks from 2.9 to 2.7 Ga were extracted dominantly from the depleted mantle.

Place: Sopot Publisher: Polish Acad Sciences Inst Oceanology WOS:000528728600003; International audience; Concentrations of a large set of major and trace elements, and Sr, Nd and Pb isotope ratios were measured in Holocene sediments cored in the western deep Black Sea in order to unravel: (1) the controls of element enrichment, and (2) sources of the detrital component. The transition of the basin from oxic to euxinic resulted in enrichment or depletion in a number of elements in the deep-sea sediments. Authigenic Fe enrichment appears to depend on the amount of Fe mobilized from the sediment through the benthic redox shuttle mechanism and free H2S in the water column (degree of “euxinization”). Manganese enrichment is controlled by diagenetic reactions within the sediment: the dissolution of Mn minerals, Mn2+ diffusion upward and reprecipitation. Barium enrichment is also controlled by diagenetic reactions, sulfate reduction and methanogenesis, that take place above and below the sulfate-methane transition, respectively. The major part of V, Co, Ni, Cu, Zn, Cr, Mo, Cd and Sb is inferred to have co-precipitated with Fe in the euxinic deep waters and to have been incorporated into authigenic Fe-sulfides. Basin reservoir effect additionally influences the Mo enrichment. The U enrichment is interpreted to have a different origin in the two organic-rich stratigraphic units (II and I). It is inferred to be: (i) at the expense of the U inventory of the deepwater pool and a result of inorganic reduction of U at euxinic conditions in the lower Unit II; and (ii) at the expense of the U inventory of the surface water pool and a result of biogenic uptake and transfer to the sediment by the plankton in the upper Unit I. The high field strength elements are closely linked to the detrital component and their depletion in the organic-rich sediments reflects a dilution of the detrital component by the biogenic one. The enrichments of REE, Sn and Th are likely controlled by adsorption on clay minerals. Sr-Nd-Pb isotope compositions of the alumino-silicate component of the studied sediments are relatively uniform. They are most likely controlled by riverine suspended matter supplied mainly in the NW Black Sea (Danube Delta) and transported southward by marine currents, and to a lesser degree by suspended matter from the small rivers draining SE Bulgaria and NW Turkey. Wind-blown dust from the Sahara Desert appears to have a minor contribution to the alumino-silicate component of the sediments. The slight shift in the Pb isotopes in Unit I upper layers is possibly caused by the addition of anthropogenic Pb.

Current models for the properties of Hadean-Eoarchean crust encompass a full range of possibilities, involving crust that is anywhere from thick and differentiated to thin and mafic. New data are needed to test and refine these models, and, ultimately, to determine how continents were first formed. The Rb-Sr system provides a potentially powerful proxy for crustal evolution and composition. However, this system has thus far been underutilized in studies on early crustal evolution due to its susceptibility to re-equilibration. Overcoming this issue requires new analytical approaches to micro-sample ancient Sr-rich mineral relics that may retain primary Rb-Sr systematics, allowing for the precise and accurate determination of initial 87Sr/86Sr values. In this study, we used a novel application of laser-ablation multi-collector inductively coupled plasma mass spectrometry to determine the Sr isotope composition of apatite inclusions in >3.6 Ga zircon grains from Eoarchean granodiorite gneisses of the Acasta Gneiss Complex, Slave Province, Canada. The 87Rb-corrected 87Sr/86Sr values of these inclusions are largely identical and are distinctly different from values obtained from altered matrix apatite. The inclusion data provide the first direct estimate of initial 87Sr/86Sr for these ancient rocks. Combining this result with information on the protolith and source-extraction age yields estimates for the range of Rb/Sr values, and by extension composition, that the source of these rocks may have had. The data indicate that continental crust containing over 60 wt% of SiO2 was present in the ca. 4.2 Ga source of the Acasta Gneiss Complex. Thus vestiges of evolved crust must have existed within the primitive proto-continents that were present on the Hadean Earth.

The Arabian Shield comprises early Neoproterozoic to Cambrian (∼850–530 Ma) tectonostratigraphic terranes formed by the closure and accretion of juvenile volcanic arcs and back-arc basins associated with Gondwana assembly. Unlike the Nubian Shield which preserves crustal isotopic signatures, the Arabian Shield is distinctly juvenile with the exception of the Paleoproterozoic (∼1800–1670 Ma) Khida subterrane in Saudi Arabia and the terranes of Yemen. This study presents the first combined zircon U-Pb, O and Hf isotope data of metavolcanic and metasedimentary rocks from southwestern most Saudi Arabia, near the Yemen border – a region thought to contain some of the oldest (>815 Ma) lithologies in Saudi Arabia, including the Atura Formation and the Tayyah Belt. One volcaniclastic metasediment sample from the Atura Formation yields zircon U-Pb age peaks of 741, 672, 646 Ma (n = 131), δ18O(V-SMOW) ranging from 4.6 to 8.3‰ and ɛHf (t) from +7.7 to +12.5. Two samples from the Tayyah Belt include an older metasandstone and a late intruding granitic dyke which provides a minimum age for the Tayyah Belt. The former yields two significant U-Pb peaks of 812 (n = 8) and 999 (n = 6) Ma, δ18O and ɛHf (t) values ranging from 4.4 to 9.6‰ and −10.1 to +12.4, respectively; the later yields a concordia age of 645.8 [±1.7] Ma (n = 29), δ18O ranging from 5.7 to 6.6‰, and ɛHf (t) of +5.9 to +9.6. The zircon age and juvenile Hf signatures from the Atura Formation are consistent with the synorogenic phase in the Shield. Sedimentation was likely associated with arc volcanism during the previously documented eastward phase of accretion at ∼740–640 Ma and the closure of the Mozambique Ocean. In contrast, the data from the texturally more mature Tayyah Belt metasediment indicate a more distal, and more evolved crustal input at the time of sediment deposition which is unusual for the Saudi Arabian Shield. Consequently, the Tayyah metasediments are likely sourced from areas with greater continental affinity, such as the cratonic basement and/or reworked crust of the Sahara metacraton in NE Africa.

Crustal foundering is an important mechanism in the differentiation and recycling of continental crust. Nevertheless, little is known about the dynamics of the lower crust, the temporal scale of foundering and its role in the dynamics of active margins and orogens. This particularly applies to active settings where the lower crust is typically still buried and direct access is not possible. Crustal xenoliths derived from mantle depth in the Pamir provide a unique exception to this. The rocks are well-preserved and comprise a diverse set of lithologies, many of which re-equilibrated at high-pressure conditions before being erupted in their ultrapotassic host lavas. In this study, we explore the petrological and chronological record of eclogite and felsic granulite xenoliths. We utilized accessory minerals – zircon, monazite and rutile – for coupled in-situ trace-element analysis and U–(Th–)Pb chronology by laser-ablation (split-stream) inductively coupled plasma mass spectrometry. Each integrated analysis was done on single mineral zones and was performed in-situ in thin section to maintain textural context and the ability to interpret the data in this framework. Rutile thermo-chronology exclusively reflects eruption ( 11.17 ± 0.06 Ma ), which demonstrates the reliability of the U–Pb rutile thermo-chronometer and its ability to date magmatic processes. Conversely, zircon and monazite reveal a series of discrete age clusters between 55–11 Ma, with the youngest being identical to the age of eruption. Matching age populations between samples, despite a lack of overlapping ages for different chronometers within samples, exhibit the effectiveness of our multi-mineral approach. The REE systematics and age data for zircon and monazite, and Ti-in-zircon data together track the history of the rocks at a million-year resolution. The data reveal that the rocks resided at 30–40 km depth along a stable continental geotherm at 720–750 °C until 24–20 Ma, and were subsequently melted, densified, and buried to 80–90 km depth – 20 km deeper than the present-day Moho – at 930 ± 35 °C . The material descended rapidly, accelerating from 0.9–1.7 mm yr−1 to 4.7–5.8 mm yr−1 within 10–12 Myr, and continued descending after reaching mantle depth at 14–13 Ma. The data reflect the foundering of differentiated deep-crustal fragments (2.9–3.5 g cm−3) into a metasomatized and less dense mantle wedge. Through our new approach in constraining the burial history of rocks, we provided the first time-resolved record of this crustal-recycling process. Foundering introduced vestiges of old evolved crust into the mantle wedge over a relatively short period (c. 10 Myr). The recycling process could explain the variability in the degree of crustal contamination of mantle-derived magmatic rocks in the Pamir and neighboring Tibet during the Cenozoic without requiring a change in plate dynamics or source region.

Rutile (TiO2) is an important accessory mineral that, when present, offers a rich source of information about the rock units in which it is incorporated. It occurs in a variety of specific microstructural settings, contains significant amounts of several trace elements and is one of the classical minerals used for U–Pb age determination. Here, we focus on information obtainable from rutile in its original textural context. We do not present an exhaustive review on detrital rutile in clastic sediments, but note that an understanding of the petrochronology of rutile in its source rocks will aid interpretation of data obtained from detrital rutile. For further information on the important role of rutile in provenance studies, the reader is referred to previous reviews (e.g., Zack et al. 2004b; Meinhold 2010; Triebold et al. 2012). Coarse rutile is the only stable TiO2 polymorph under all crustal and upper mantle conditions, with the exception of certain hydrothermal environments (Smith et al. 2009). As such, we will focus on rutile rather than the polymorphs brookite, anatase and ultrahigh-pressure modifications. In this chapter, we first review rutile occurrences, trace element geochemistry, and U–Pb geochronology individually to illustrate the insights that can be gained from microstructures, chemistry and ages. Then, in the spirit of petrochronology, we show the interpretational power of combining these approaches, using the Ivrea Zone (Italy) as a case study. Finally, we suggest some areas of future research that would improve petrochronologic research using rutile. Rutile is a characteristic mineral in moderate- to high pressure metapelitic rocks, in high pressure metamorphosed mafic rocks, and in sedimentary rocks (e.g., Force 1980; Frost 1991; Zack et al. 2004b; Triebold et al. 2012). Rutile also occurs rarely in magmatic rocks, e.g., anorthosites, as well as in some hydrothermal systems. Coarse-grained …

Impact-generated hydrothermal systems have been suggested as favourable environments for deep microbial ecosystems on Earth, and possibly beyond. Fossil evidence from a handful of impact craters worldwide have been used to support this notion. However, as always with mineralized remains of microorganisms in crystalline rock, certain time constraints with respect to the ecosystems and their subsequent fossilization are difficult to obtain. Here we re-evaluate previously described fungal fossils from the Lockne crater (458 Ma), Sweden. Based on in-situ Rb/Sr dating of secondary calcite-albite-feldspar (356.6 &plusmn, 6.7 Ma) we conclude that the fungal colonization took place at least 100 Myr after the impact event, thus long after the impact-induced hydrothermal activity ceased. We also present microscale stable isotope data of 13C-enriched calcite suggesting the presence of methanogens contemporary with the fungi. Thus, the Lockne fungi fossils are not, as previously thought, related to the impact event, but nevertheless have colonized fractures that may have been formed or were reactivated by the impact. Instead, the Lockne fossils show similar features as recent findings of&nbsp, ancient microbial remains elsewhere in the fractured Swedish Precambrian basement and may thus represent a more general feature in this scarcely explored habitat than previously known.

Fractured rocks of impact craters may be suitable hosts for deep microbial communities on Earth and potentially other terrestrial planets, yet direct evidence remains elusive. Here, we present a study of the largest crater of Europe, the Devonian Siljan structure, showing that impact structures can be important unexplored hosts for long-term deep microbial activity. Secondary carbonate minerals dated to 80 ± 5 to 22 ± 3 million years, and thus postdating the impact by more than 300 million years, have isotopic signatures revealing both microbial methanogenesis and anaerobic oxidation of methane in the bedrock. Hydrocarbons mobilized from matured shale source rocks were utilized by subsurface microorganisms, leading to accumulation of microbial methane mixed with a thermogenic and possibly a minor abiotic gas fraction beneath a sedimentary cap rock at the crater rim. These new insights into crater hosted gas accumulation and microbial activity have implications for understanding the astrobiological consequences of impacts., Fractured rocks of impact craters have been suggested to be suitable hosts for deep microbial communities on Earth, and potentially other terrestrial planets, yet direct evidence remains elusive. Here, the authors show that the Siljan impact structure is host to long-term deep methane-cycling microbial activity.

Correction for ‘Measurement of number concentrations and sizes of Au nano-particles spiked into soil by laser ablation single particle ICPMS’ by Jani Tuoriniemi et al., J. Anal. At. Spectrom., 2020, 35, 1678–1686, DOI: 10.1039/D0JA00243G

The timing of diamond crystallization is generally inferred from radiometric dating of individual or multiple mineral inclusions in diamond, where ages are derived from isochrons or isotopic evolution models. Resulting ages often significantly predate the emplacement ages of host kimberlites, but age information from both approaches can be ambiguous due to long-lived mantle heterogeneities where mixing can mimic isochrons or in-situ aging. Direct dating of accessory mineral inclusions in diamonds, by contrast, has rarely been attempted because of the scarcity of such inclusions, requiring careful high grading of large amounts of diamond concentrates. Here, we report secondary ionization mass spectrometry (SIMS) U–Pb ages from a suite of rare rutile inclusions which were extracted from diamond in an eclogitic paragenesis from the Mir kimberlite pipe, Siberia. One population of rutile inclusions shows diamond crystal-shapes and was petrographically identified as completely enclosed in diamond prior to host burning for inclusion extraction. These rutile inclusions were screened for U abundances (0.24–23 μg/g U) and those with the highest U contents were dated, yielding a uniform U–Pb concordia age of 375.5 ± 7.0 Ma (error 95% confidence; mean square of weighted deviates MSWD = 0.74; number of spots n = 19). This age is nearly coeval with, but significantly (at the 95% confidence level) older than combined U–Pb rutile ages for rutile intergrown with polycrystalline fibrous diamond (362.9 ± 9.5 Ma; MSWD = 0.96; n = 7) and rutile from the eclogitic xenolith matrix (369 ± 16 Ma; MSWD = 0.30; n = 5). Rutile ages are consistent with published ages for kimberlite emplacement (ca. 360 Ma), but much younger than Re–Os sulfide isochron ages between ca. 913 Ma and 2.1 Ga for groups of individual inclusions in diamond from the same location. When assuming the oldest Re–Os sulfide age as the timing of rutile entrapment, diffusive Pb-loss from rutile inclusions over ca. 2 Ga would require diffusivities of Pb in diamond of >10−22 m2/s, as well as Pb partitioning coefficients between diamond and rutile at near or greater unity. Alternatively, if Pb is immobile in diamond, ancient rutile ages could have been reset due to processes other than volume diffusion through diamond (e.g., due to fluid migration along cracks). However, in this scenario it remains difficult to explain why all rutile inclusions dated here would have been located along cracks, whereas sulfide inclusions investigated in other studies were not. Another explanation is that rutile inclusions were entrapped at the time of diamond formation, and that this event is recorded by U–Pb rutile ages, whereas sulfides predate diamond crystallization and their Re–Os systematics were incompletely reset. Trace element heterogeneity in rutile suggests that they originated in chemically different environments, and thus rutile likely predates diamond formation. However, due to rapid diffusion of Pb in rutile, radiogenic Pb accumulated only after entrapment in diamond (for inclusions) or eruptive quenching (for intergrown or matrix rutile). Overall, rutile geochronology indicates that at least some diamond from the Mir pipe formed briefly (within the ca. 20 Ma age difference between U–Pb rutile ages for inclusions and intergrown/matrix rutile) before kimberlite eruption, supporting models that link diamond formation with carbon-rich precursors of kimberlite magmas.

The continental crust and sub-continental lithospheric mantle (SCLM) are co-dependent reservoirs in terms of their geochemistry, tectonics, and long-term evolution. Obtaining insight into the mechanisms of lithosphere formation and differentiation requires robust constraint on the complex petrological history of mantle rocks. This has proven difficult as samples from the deep mantle are rare and, although many may have formed in the Archean, no such age has been obtained directly from mantle-derived silicate minerals. Lutetium-hafnium geochronology of garnet has the potential of overcoming this limitation. In this study, this technique was applied on fragments of the SCLM exposed in the Norwegian Caledonides. The chronologic record of these rocks is rich and extensive, yet it is difficult to interpret and is, in part, inconsistent. Our Lu–Hf results from supersilicic pyrope in dunite provide the first Archean internal isochron ages for mantle rocks. These ages are consistent with a period of juvenile crust formation worldwide and provide a record of deeply sourced mantle upwellings from >350 km depth. Results from fertile rock types indicate that melting and isotope re-equilibration occurred in sync with two Proterozoic supercontinent break-up events that are recorded in the Laurentian and Baltic lithospheres. Together, the results indicate that since its extraction during a period of rapid Archean crustal growth, the SCLM appears to have largely been at petro-physical and chemical stasis, with the exception of major episodes of continental break-up. The evolution of the SCLM is thus, highly punctuated and ultimately controlled by the Wilson cycle.

Kiruna-type apatite-iron-oxide ores are key iron sources for modern industry, yet their origin remains controversial. Diverse ore-forming processes have been discussed, comprising low-temperature hydrothermal processes versus a high-temperature origin from magma or magmatic fluids. We present an extensive set of new and combined iron and oxygen isotope data from magnetite of Kiruna-type ores from Sweden, Chile and Iran, and compare them with new global reference data from layered intrusions, active volcanic provinces, and established low-temperature and hydrothermal iron ores. We show that approximately 80% of the magnetite from the investigated Kiruna-type ores exhibit δ56Fe and δ18O ratios that overlap with the volcanic and plutonic reference materials (> 800 °C), whereas ~20%, mainly vein-hosted and disseminated magnetite, match the low-temperature reference samples (≤400 °C). Thus, Kiruna-type ores are dominantly magmatic in origin, but may contain late-stage hydrothermal magnetite populations that can locally overprint primary high-temperature magmatic signatures., The origin of giant Kiruna-type iron ores has been debated for nearly 100 years. This study employs extensive stable isotope data from Kiruna-type ores worldwide and magmatic and hydrothermal reference materials to show that iconic Kiruna-type ores originate primarily from ortho-magmatic processes.

Recent studies reveal that organisms from all three domains of life&mdash, Archaea, Bacteria, and even Eukarya&mdash, can thrive under energy-poor, dark, and anoxic conditions at large depths in the fractured crystalline continental crust. There is a need for an increased understanding of the processes and lifeforms in this vast realm, for example, regarding the spatiotemporal extent and variability of the different processes in the crust. Here, we present a study that set out to detect signs of ancient microbial life in the Forsmark area&mdash, the target area for deep geological nuclear waste disposal in Sweden. Stable isotope compositions were determined with high spatial resolution analyses within mineral coatings, and mineralized remains of putative microorganisms were studied in several deep water-conducting fracture zones (down to 663 m depth), from which hydrochemical and gas data exist. Large isotopic variabilities of &delta, 13Ccalcite (&minus, 36.2 to +20.2&permil, V-PDB) and &delta, 34Spyrite (&minus, 11.7 to +37.8&permil, V-CDT) disclose discrete periods of methanogenesis, and potentially, anaerobic oxidation of methane and related microbial sulfate reduction at several depth intervals. Dominant calcite&ndash, water disequilibrium of &delta, 18O and 87Sr/86Sr precludes abundant recent precipitation. Instead, the mineral coatings largely reflect an ancient archive of episodic microbial processes in the fracture system, which, according to our microscale Rb&ndash, Sr dating of co-genetic adularia and calcite, date back to the mid-Paleozoic. Potential Quaternary precipitation exists mainly at ~400 m depth in one of the boreholes, where mineral&ndash, water compositions corresponded.

Paleogeographic reconstructions of India and Madagascar before their late Cretaceous rifting juxtapose the Antongil Block of Madagascar against the Deccan Traps of India, indicating that the Western Dharwar Craton extends below the Deccan lavas. Some recent studies have suggested that the South Maharashtra Shear Zone along the northern Konkan coast of India limits the northern extent of the Western Dharwar Craton, implying that the craton does not extend below the Deccan Traps, raising a question mark on paleogeographic reconstructions of India and Madagascar. The continuity of the Western Dharwar Craton north of the South Maharashtra Shear Zone below the Deccan Traps—or its lack thereof—is critical for validating tectonic models correlating Madagascar with India. In this study, zircons in tonalitic basement xenoliths hosted in Deccan Trap dykes were dated in situ, using the U-Pb isotope system. The data furnish U-Pb ages that define three populations at 2527 ± 6, 2456 ± 6, and 2379 ± 9 Ma. The 2527 ± 6 Ma ages correspond to the igneous crystallization of the tonalites, whereas the 2456 ± 6 and 2379 ± 9 Ma ages date metamorphic overprints. The results help to establish for the first time that the basement is a part of the Neoarchean granitoid suite of the Western Dharwar Craton, which extends northward up to at least Talvade in central and Kihim beach in the western Deccan. By implication, the South Maharashtra Shear Zone cannot be the northern limit of the Western Dharwar Craton. The granitoids are correlated with the Neoarchean felsic intrusions (2.57–2.49) of the Masaola suite in the Antongil Block of Madagascar, supporting the existence of a Neoarchean Greater Dharwar Craton comprising the Western Dharwar Craton and the Antongil-Masora Block.

The Southern Granulite Terrane of India exposes remnants of an interbanded sequence of orthoquartzite–metapelite–calcareous rocks across the enigmatic Palghat–Cauvery Shear Zone (PCSZ), which has been interpreted as a Pan-African terrane boundary representing the eastward extension of the Betsimisaraka Suture Zone of Madagascar. Zircon U–Pb geochronology of metasedimentary rocks from both sides of the PCSZ shows that the precursor sediments of these rocks were sourced from the Dharwar Craton and the adjoining parts of the Indian shield. The similarity of the provenance and the vestiges of Grenvillian-age orogenesis in some metasedimentary rocks contradict an interpretation that the PCSZ is a Pan-African terrane boundary. The lithological association and the likely basin formation age of the metasedimentary rocks of the Southern Granulite Terrane show remarkable similarity to the rock assemblage and timing of sedimentation of the Palaeoproterozoic to Neoproterozoic shallow-marine deposits of the Purana basins lying several hundred kilometres north of this terrane. Integrating the existing geological information, it is postulated that the shallow-marine sediments were deposited on a unified land-mass consisting of a large part of Madagascar and the Indian shield that existed before Neoproterozoic time, part of which was later involved in the Pan-African orogeny. Supplementary material: Details of the zircon U–Pb LA-MC-ICP-MS analyses of samples are available at http://www.geolsoc.org.uk/SUP18793 .

The palaeo-Pacific margin of Gondwana in the present-day south–central Andes is marked by tectonic activity related to subduction and terrane accretion. We present detrital zircon U–Pb data encompassing the Palaeozoic era in northern Chile and northwestern Argentina. Cathodoluminescence images reveal dominantly magmatic zircon barely affected by abrasion and displaying only one growth phase. The main age clusters for these zircon grains are Ediacaran to Palaeozoic with an additional peak at 1.3–0.9 Ga and they can be correlated with ‘Grenvillian’ age, and the Brasiliano, Pampean, and Famatinian orogenies. The zircon data reveal main transport from the nearby Ordovician Famatinian arc and related rocks. The Silurian sandstone units are more comparable with Cambrian units, with Brasiliano and Transamazonian ages (2.2–1.9 Ga) being more common, because the Silurian deposits were situated within or east of the (extinct) Famatinian arc. Hence, the arc acted as a transport barrier throughout Palaeozoic time. The complete suite of zircon ages does not record the accretions of exotic terranes or the Palaeozoic glacial periods. We conclude that the transport system along the palaeo-Pacific margin of Gondwana remained stable for c . 0.3 byr and that provenance data do not necessarily reflect the interior of a continent. Hence, inherited geomorphological features must be taken into account when detrital mineral ages are interpreted. Supplementary material: U–Pb data, CL images, and detailed geological maps are available at www.geolsoc.org.uk/SUP18796.