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Authigenic components in marine sediments are important archives for past environment reconstructions. However, defining reliable age constraints and assessing the effects of post-depositional overprints in Precambrian sequences are challenging. We demonstrate a new laser-based analytical approach that has the potential to rapidly and accurately evaluate the depositional and alteration histories of Proterozoic shales. Our study employs a novel application of in situ Rb-Sr dating coupled with simultaneous trace-element analysis using reaction-cell laser ablation–inductively coupled plasma–tandem mass spectrometry (LA-ICP-MS/MS). We present results from shales sourced from two wells in the Proterozoic McArthur Basin, northern Australia. These rocks have been widely used by previous studies as a key section for ancient biogeochemical and paleo-redox reconstructions. Shales from well UR5 yielded initial 87Sr/86Sr ratios, Rb-Sr ages, and rare earth element plus yttrium (REEY) patterns similar to those of a dolerite sampled from the same core. We propose that the UR5 samples chronicle hydrothermal alteration instigated by the dolerite intrusion. In contrast, a correlative shale from well UR6 yielded an age consistent with the expected depositional age (1577 ±56 Ma) with REEY and initial 87Sr/86Sr ratios similar to ca. 1.5 Ga seawater. We suggest that this sample records the minimum depositional age and early marine diagenetic history for this unit. This new technique can date Proterozoic shales quickly, cheaply, and with minimum sample preparation. Importantly, ages are triaged to differentiate between those recording primary marine versus secondary processes. This novel approach provides a potentially powerful tool for dating and fingerprinting the vast array of ancient marine shales for further studies of Earth systems through deep time.

The Seve Nappe Complex is a subduction-related high-grade metamorphic unit that was emplaced onto the margin of Baltica during Caledonian orogenesis. In this paper, the tectonometamorphic evolution of the Lower Seve Nappe in the Scandinavian Caledonides was characterized with the help of the continuous Collisional Orogeny in the Scandinavian Caledonides (COSC-1) drill core, using a combination of various P–T estimation techniques based on garnet–quartz mineral pairs (quartz-in-garnet and Ti-in-quartz [QuiG–TiQ]), conventional thermobarometry and thermodynamic modelling of phase equilibria. This multi-method approach yields complementary results and delivers critical data to constrain a comprehensive pressure–temperature–deformation–time (P–T–D–t) evolutionary path for the metasedimentary rocks of the Lower Seve Nappe. In the garnetiferous metasedimentary rocks, quartz inclusions in garnet preserve the P–T conditions of three distinct garnet growth stages corresponding to three metamorphic stages Ms1 to Ms3, including prograde and peak metamorphic conditions. Ms1 and Ms2 stages were constrained via quartz inclusions in garnet core and mantle. They are relatively close in the P–T space and could be considered as one single continuous prograde event occurring at epidote–amphibolite facies conditions of 460–520°C and 0.6–0.85 GPa. The growth of the garnet outermost rim defines the Ms3 stage at amphibolite facies conditions of 590–610°C and 1.13–1.18 GPa and corresponds to the peak metamorphic conditions. The microstructural analysis shows that the finite ductile strain pattern of the Lower Seve Nappe results from the superposition of four deformation phases. The initial phase D1 is defined by the S1 foliation that is still preserved as a curved inclusion trail in the garnet core. The D2 phase initiated contemporaneously with garnet core growth and the development of muscovite–biotite–plagioclase S2 foliation. Garnet outermost rim growth marks the end of the prograde path and peak metamorphic conditions. This stage is overprinted by the D3 phase and Ms4 stage associated with the development of the main regional metamorphic and mylonitic fabric S3 associated with C′-type shear bands along the retrograde path. Ms4 stage, which was constrained using traditional thermobarometric techniques, corresponds to the chemical re-equilibration of the metasedimentary minerals and occurred under amphibolite facies conditions at ~570–610°C and 0.78–1.00 GPa. The D3 phase is then generally weakly to strongly overprinted by later lower grade deformation D4 phase at greenschist facies conditions (Ms5). 40Ar/39Ar ages of syn-kinematic white mica and biotite indicate that the final stage of the thrusting of the Lower Seve Nappe and thus the timing of its emplacement onto the Offerdal Nappe occurred at c. 423 Ma. Collectively, these results are consistent with previous estimates of the timing and conditions of metamorphism derived from the Lower Seve Nappe especially in west-central Jämtland. However, application of QuiG–TiQ thermobarometry demonstrated that quartz inclusions in garnet can preserve different aspects of garnet growth, which are not accessible by traditional methods especially in complex terranes, and therefore provided new significant insights into the Lower Seve prograde evolution.

© 2022 Elsevier B.V.This study deals with the age and petrogenesis of mafic-ultramafic intrusions ranging in size from a few meters to 10 km within the Early Carboniferous high-grade gneisses of the Pulur Complex in the Eastern Pontides. The intrusions comprise dunite, wehrlite, gabbronorite, leucogabbro, anorthosite and ilmenite-bearing gabbronorite of cumulus origin, and are crosscut by dikes of ilmenite-bearing gabbronorite, leucogranite and microdiorite. U–Pb dating on zircons from gabbronorite, anorthosite and leucogranite yielded igneous crystallization ages of 322–326 Ma, indicating that the intrusions were emplaced ca. 5–7 Ma after the peak of high-grade metamorphism, and form part of the Late Carboniferous high-volume magmatism in the region. In most cumulate rocks, Cr–Al spinel, olivine and plagioclase were early crystallizing phases, followed by orthopyroxene, clinopyroxene and hornblende. Whole rock geochemical data suggest that wehrlite, gabbronorite, leucogabbro and anorthosite stem from a common magma, and ilmenite-bearing gabbronorite and dikes of leucogranite and microdiorite from different magmas. Application of mineral/melt partition coefficients to trace element compositions of clinopyroxene and hornblende in cumulate rocks suggests that the main cumulate body was derived from middle- to high-K calc-alkaline basic melts, and relatively late ilmenite-bearing gabbronorites from hypersthene-normative Ca-rich melts. All the rock types display radiogenic Sr and Pb isotopic signatures, and unradiogenic Nd isotopic ratios, which are indistinguishable from those of the coeval voluminous high-K calc-alkaline I-type granites in the region; the isotopic ratios are probably related to the metasomatism of the lithospheric mantle by sediment-derived melts. We suggest that the parental melts of the mafic-ultramafic intrusions and those of the high-K calc-alkaline granites were genetically related, and melts of the high-K calc-alkaline granites were probably derived from the melting of newly underplated calc-alkaline basic material at lower crustal depths, that were compositionally comparable to the parental magmas of the mafic-ultramafic intrusions.

The formation and evolution of Palaeoarchaean De Kraalen and Witrivier Greenstone Belts (DKGB and WGB) of the Kaapvaal Craton are poorly known. Here we report zircon and rutile in situ U-Pb ages and zircon Hf isotopic data from a variety of supracrustal rocks. The zircon cores from a metamafic amphibole-bearing gneiss from the DKGB give a protolith age of 3 441 ± 5 Ma, whereas the zircon mantle domains give a metamorphic age of 3 211 ± 16 Ma. The 176Hf/177Hft values for all zircon domains give a tight cluster around 0.280596 ± 0.00006 (2 SD). U-Pb analyses of zircon for an amphibolite intercalated with thin calc-silicate layers from the WGB give a single crystallisation age of 3 230 ± 3 Ma, but the Hf isotope ratios of these zircon grains define two different populations. The first population yields 176Hf/177Hf~3.23 Ga = 0.28064 ± 0.00004, corresponding to εHf~3.23 Ga = 2.4 ± 1.9 (2SD) and Hf model ages between ca. 3.51 to 3.30 Ga. These are Hf isotope characteristics for zircons from a relatively juvenile source extracted from a depleted mantle source ca. 0.28 to 0.07 Ga prior zircon crystallisation. The second population yields 176Hf/177Hf~3.23 Ga = 0.28093 ± 0.00004 with εHf~3.23 Ga = 8.1 ± 1.3 (2SD). These Hf data combined with the 206Pb/207Pb ages lead to isotope ratios that lie above those of Depleted Mantle. The unusually high Hf isotope signature for the cores of the zircons from the WGB amphibolite most likely represent a contribution from an early highly depleted mantle source. A rutile in situ U-Pb age of 3.085 Ga from a recrystallised quartzite indicate that the rocks from the DKGB experienced slow cooling following the 3.21 Ga metamorphic event or (partial) resetting due to elevated geothermal gradient caused by the ca. 3.1 Ga intrusions of the Vrede Granitiod Suite. The latter interpretation is preferred because ~145 Ma of slow cooling from the amphibolite facies conditions of peak metamorphism to the blocking temperature for mass diffusion of Pb in rutile is unlikely. While the Zr-in-rutile temperature of ca. 710°C at 7 kbar for DKGB most likely records the peak temperature of the ~3.23 to 3.21 Ga event. The trace element concentrations of the metamorphic rutile grains within the quartzite of the DKGB indicate that the source rock was enriched in Cr. Either due to silification during hydrothermal alteration of the (ultra)mafic country rock or during deposition in an atmosphere that allowed for chromite grains to be part of the sediment.

Made available in DSpace on 2022-05-01T09:47:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2022-04-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) We use a combination of several in situ techniques to assess the P-T-t path of high-pressure granulites from the Passos Nappe in the Southern Brasília Orogen (SE Brazil). Quantitative element mapping and single-element thermometers (Zr-in-rutile and Ti-in-quartz) are coupled with P-T pseudosections and monazite and rutile dating. Compositional and temperature maps, based on cathodoluminescence mapping and in situ analyses of Ti-in-quartz, are presented as a novel approach to evaluate crystallization temperature. The studied rocks have a pelitic protolith and record a peak pressure assemblage of garnet + kyanite + rutile + K-feldspar + quartz + melt ± plagioclase that formed at ~830°C and 1.2 GPa. Retrograde conditions of ~560°C and 0.6 GPa are determined based on the grossular content of garnet and the crystallization of biotite and ilmenite. Metamorphic peak conditions occurred ca. 635 Ma, according to monazite dating, with a younger date of ca. 615 Ma associated with later kyanite crystallization. Rutile ages of ca. 590 Ma are linked to the late retrograde stage (at ~600°C). Results show that the distribution of Ti-in-quartz is heterogeneous, decreasing in abundance towards the rim of crystals, though the higher temperatures constrained with Ti-in-quartz thermometry are broadly consistent with peak conditions. The peak pressure conditions are consistent with continental collision setting in the Southern Brasília Orogen and were followed by an early cooling/decompression stage and then by a slow cooling during exhumation and transport to shallower crustal levels. Department of Geology São Paulo State University Department of Mineralogy and Geotectonics University of São Paulo Institute of Geological Sciences University of Bern TEKTOS Research Group Faculdade de Geologia Universidade do Estado Rio de Janeiro (UERJ) Department of Earth Sciences University of Gothenburg Department of Geosciences Virginia Tech Department of Geology São Paulo State University CNPq: 141604/2018-2 FAPESP: 2015/05230-0 FAPESP: 2016/22627-3 CNPq: 305720/2001-1 CNPq: 311606/2019-9 CNPq: 486328/2013-9

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.

The scarcity of well-preserved and directly dateable sedimentary sequences is a major impediment to inferring the Earth’s paleo-environmental evolution. The authigenic mineral glauconite can potentially provide absolute stratigraphic ages for sedimentary sequences and constraints on paleo-depositional conditions. This requires improved approaches for measuring and interpreting glauconite formation ages. Here, glauconite from a Cretaceous shelfal sequence (Langenstein, northern Germany) was characterized using petrographical, geochemical (EMP), andmineralogical (XRD) screening methods before in situ Rb-Sr dating via LA-ICP-MS/MS. The obtained glauconite ages (~101 to 97 Ma) partly overlap with the depositional age of the Langenstein sequence (±3 Ma), but without the expected stratigraphic age progression, which we attribute to detrital and diagenetic illitic phase impurities inside the glauconites. Using a novel age deconvolution approach, which combines the new Rb-Sr dataset with published K-Ar ages, we recalculate the glauconite bulk ages to obtain stratigraphically significant ‘pure’ glauconite ages (~100 to 96 Ma). Thus, our results show that pristine ages can be preserved in mineralogically complex glauconite grains even under burial diagenetic conditions (T < 65 °C

Rheology of the continental lower crust plays an integral role in governing the style of continental extension. Temperature-dependent creep deformation in the lower crust decreases lithospheric strength and promotes coupling of deformation in the brittle crust and upper mantle; however, few constraints exist concerning the thermal evolution of extending lower crust. Here, we present a high-temperature thermochronological investigation of the Ivrea-Verbano Zone—archetypal continental lower crust that was attenuated during opening of the Alpine Tethys oceanic basin. Rutile U–Pb dates collected from three samples spanning the bottom ∼2-km of the crustal section are between ∼160 and ∼180 Ma, and exhibit near-rim zonations in Zr, Hf, Nb and Ta. Thermal-kinematic modeling of these data, combined with existing rutile U–Pb dates, show that the base of the Ivrea-Verbano Zone experienced heating on two timescales: conductive heating over ∼10 Myr, associated with thinning of the lithospheric mantle, and advective heating over

rom ca. 50 Ma to present, the western Pacific plate has been subducting under the Philippine Sea plate, forming the oceanic Izu-Bonin-Mariana (IBM) subduction system. It is the only known location where subduction zone products are presently being transported to the surface by serpentinite-mud volcanoes. A large serpentine mud “volcano” forms the South Chamorro Seamount and was successfully drilled by ODP during Leg 195. This returned mostly partially serpentinized harzburgites enclosed in serpentinite muds. In addition, limited numbers of small (1 mm–1 cm) fragments of rare blueschists were also discovered. U–Pb dating of zircon and rutile from one of these blueschist clasts give ages of 51.1 ± 1.2 Ma and 47.5 ± 2.0 Ma, respectively. These are interpreted to date prograde high-pressure metamorphism. Mineral equilibria modelling of the blueschist clast suggests the mineral assemblage formed at conditions of ∼1.6 GPa and ∼590 °C. We interpret that this high-pressure assemblage formed at a depth of ∼50 km within the subduction channel and was subsequently exhumed and entrained into the South Chamorro serpentinite volcano system at depths of ∼27 km. Consequently, we propose that the material erupted from the South Chamarro Seamount may be sampling far greater depths within the Mariana subduction system than previously thought. The apparent thermal gradient implied by the pressure–temperature modelling (∼370 °C/GPa) is slightly warmer than that predicted by typical subduction channel numerical models and other blueschists worldwide. The age of the blueschist suggests it formed during the arc initiation stages of the proto-Izu-Bonin-Mariana arc, with the P–T conditions recording thermally elevated conditions during initial stages of western Pacific plate subduction. This indicates the blueschist had prolonged residence time in the stable forearc as the system underwent east-directed rollback. The Mariana blueschist shows that subduction products can remain entrained in subduction channels for many millions of years prior to exhumation. Refereed/Peer-reviewed

Conventional dating of molybdenite (187Re-187Os) provides one of few options for direct dating of sulfide mineralization. Unfortunately, in situ dating of molybdenite is considered unreliable due to intra-granular decoupling of 187Re-187Os. In this study, we developed a new analytical protocol for studies of micron- to grain scale 187Re-187Os systematics in molybdenite. Online chemical separation using ICP-MS/MS technology enables in situ dating by β-decay systems (e.g., Rb-Sr and K-Ca in micas) using laser ablation. Here, the methodology is extended to the 187Re-187Os system, another β-decay system that cannot be resolved by mass spectrometry. Several reaction gases were evaluated, and production of OsCH2 by reaction with CH4 was found to produce strong separation of Os from Re. However, in contrast to the e.g., 87Rb-87Sr system, 1–2% of the parent isotope Re also reacted to ReCH2, leaving a significant interference. A mathematical correction of this remaining interference is possible, and 187Re-187Os (mass-shifted) can be measured accurately even for fairly extreme ratios. For laser ablation, standards were developed by pressing particulate pellets of conventionally dated molybdenite (Moly Hill and Merlin), because there are no appropriate reference materials available. Six natural molybdenite samples from a range of geological settings, containing > 10 ppm Re, were analyzed by 70 μm laser ablation spots, and ages were calibrated by analysis of molybdenite pellets. Contrary to our expectation, weighted average ages obtained were in agreement (within 1%) with conventional age determinations, with fairly good precision (from ~ 1 to 5% 2σ depending on Re concentration), suggesting limited or essentially nonexistent decoupling within crystals. Two important implications of this result are that decoupling Re-Os is not universal, and that our new analytical protocol is useful both for dating and for studies of decoupling. The benefit of in situ dating compared to conventional dating is, apart from lower cost and time consumption, the possibility of targeting smaller molybdenite crystals (≥ 100 μm) in thin sections and epoxy mounts. The youngest sample in the study is 920 Ma, but we see potential of dating significantly younger Re-rich molybdenite.

Here we present major element, trace element, and oxygen isotope data for garnet from an amphibolitized eclogite block from Ring Mountain, Franciscan Complex, California, USA. Garnetite veins 1–5 cm thick are laterally continuous up to 10 m within an Mg-rich blackwall zone of the eclogite block. Complex major and trace element zoning patterns reveal multiple stages of garnet growth in both the matrix and garnetite veins. Similarities in major and trace element zoning between matrix and vein garnet suggest that crystallization of the garnetite veins began toward the end of matrix garnet core growth, and continued throughout the garnet growth history of the rock. Oscillatory zoning in rare-earth elements suggests garnet growth in pulses, with matrix-diffusion-limited growth in between pulses. Oxygen isotope analyses of matrix and vein garnet have a range in δ18O values of 5.3–11.1 ‰. Differences in δ18O values of up to ~ 4 ‰ between garnet core and rim are observed in both the matrix and vein; garnet cores range from 9.8 to 11.1 ‰ (median 10.4‰), garnet mantles range from 8.3 to 10.0 ‰ (median 9.7 ‰), and garnet rims range from 5.8 to 7.8 ‰ (median 6.7 ‰). Late-stage vein crystallization appears as a garnet “cement” that fills in a network of small (typically 5–50 µm) garnet cores, and likely crystallized from an amorphous phase. The low δ18O values of this latest stage of garnet growth are consistent with interaction with serpentinites, and likely represent the physical incorporation of the eclogite block into the serpentinite matrix melange.

Antarctic ice-sheet instability is recorded by ice-rafted debris (IRD) in mid- to high-latitude marine sediment, especially throughout climate transitions. The middle Miocene climatic transition (MMCT), 14.2 to 13.8 Ma, which marks the end of a significant warm period during the mid-Miocene, saw a rapid cooling of ca. 6-7 °C in the high-latitude Southern Ocean. This climatic shift was also accompanied by a global δ18O excursion of ca. 1‰, indicating a time of global cooling and significant Antarctic ice expansion (Shevenell et al., 2004). The MMCT is recorded by numerous IRD-rich sediment horizons in deep-sea sediment cores around the Antarctic margin, reflecting iceberg calving during times of ice-sheet instability. Resolving the locations of iceberg calving sites by detrital provenance analysis during the MMCT will be an important tool for forecasting effects of anthropogenic climate change.Here we present results of a multi-proxy provenance study by using K- and plagioclase feldspar, selected due to their relative abundance in clastic sediment, and tendency to incorporate Rb (Kfs only), Pb, and Sr at analytically useful concentrations, thus enabling source-terrane fingerprinting. While Pb-isotope fingerprinting is an established method for provenance analysis of glaciogenic sediment (Flowerdew et al., 2012), combining in-situ Sr-isotope fingerprinting with 87Rb/87Sr dating is a novel approach. These techniques are applied to deep-sea core ODP113-694, which was recovered from the Weddell Sea; as this is located ca. 750 km from the continental rise, in 4671.3 m of water. This location is ideal, as it acts as a major iceberg graveyard making it a key IRD depocenter (Barker, Kennett et al., 1988). Within the core, several IRD layers were identified and analysed with preliminary depositional ages of 14 to 14.4 Ma.We discuss the implications of our results in terms of location of active iceberg calving sites and further consider the viability of our multi-proxy provenance approach to the Antarctic offshore.Barker, P.F., Kennett, J.P., et al., 1988, Proc. Init. Repts. (Pt. A): ODP, 113, College Station, TX (Ocean Drilling Program).Flowerdew, M.J., et al., 2012, Chemical Geology, v. 292–293, p. 88–102, doi: 10.1016/j.chemgeo.2011.11.006.Shevenell, A.E., et al., 2004, Science, v. 305, p. 1766-1770, doi: 10.1126/science.1100061.

This study encompasses the ore mineralogy, textures and sulphide trace element chemistry of the Palaeoproterozoic Lovisa stratiform Zn-Pb deposit and the stratigraphically underlying Lovisa Fe Formation in the Bergslagen ore province (Sweden). We investigate the relative timing of formation and subsequent modifications of its ores in relation to the c. 1.87–1.80 Ga Svecokarelian orogeny. The Lovisa Zn-Pb deposit consists of several different ore types. The massive sphalerite-galena ore is distinctly deformed, exhibiting a multiple-scale “ball ore” texture with rounded silicate clasts within a deformed, fine-grained sulphide matrix. Underlying the massive ore is a locally folded, sphalerite-rich laminated ore, interpreted to represent a metamorphosed relict primary lamination. Several generations of sphalerite-galena fracture fillings and veins occur adjacent to the main ore zones and they cross-cut early ductile structures and metamorphic features. The trace element signatures of the sphalerite-galena infillings generally mimic those of the two main ore zones, thus supporting an origin by localised remobilisation of the primary sulphide ore and demonstrating limited trace element redistribution during this process. In contrast, discrete sulphosalt-rich fracture fillings cross-cutting earlier galena-chalcopyrite-rich fracture fillings and veinlets in the Lovisa Fe Formation suggest a significant but still relatively localised redistribution of metals. Trace element mapping of sulphides from the Lovisa Zn-Pb deposit reveals that inclusion-free overgrowths on pyrite crystals are locally Co-enriched compared to the cores, which resulted from the redistribution of Co during late metamorphic processes. Combined textural and geochemical evidence suggest that the originally syngenetic exhalative sulphide ore at Lovisa was locally strongly affected by polyphase deformation and remobilisation. This was initiated during the first stage of amphibolite facies grade regional metamorphism and deformation (D1, c. 1.87–1.85 Ga) but is mostly evident from the later stages (D2) and the evolution to retrograde and brittle conditions (c. 1.83–1.80 Ga and later).

Made available in DSpace on 2022-04-29T08:36:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-12-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) High-pressure metamafic rocks from the Passos Nappe, Southern Brasília Orogen, have been traditionally interpreted as highly retrogressed eclogites, even though no reliable P-T conditions were available thus far. In this work, samples from the least retrogressed sample were studied using petrography, mineral and whole-rock chemical analysis, thermodynamic modelling, and rutile U–Pb geochronology, with the objective of unravelling its metamorphic history. The studied rocks are, descriptively, hornblende-garnet-clinopyroxene schists. Garnet and hornblende occur in a matrix composed of clinopyroxene-plagioclase symplectite, with garnet being surrounded by plagioclase-hornblende coronas. A combination of thermodynamic modelling, Zr-in-rutile and Ti-in-quartz thermobarometry suggests peak temperature to be 725 ± 30 °C, attained at a minimum pressure of ≈16 kbar, and data from rutile and quartz crystals included in garnet qualitatively indicate an earlier stage at higher P and lower T, constraining a clockwise P-T path. No evidences of UHP metamorphism were found thus far. A lower intercept age of 579 ± 23 Ma was calculated from rutile data, which is identical, within uncertainty, to rutile ages obtained previously in units immediately above the rocks studied here. The data suggests that these rocks were submitted to a different P-T path compared to the adjacent units, and that they were subducted to depths of at least ≈60 km and tectonically emplaced amid the surrounding metapelitic rocks before 579 Ma, which is compatible with current models for the evolution of the Southern Brasilia Orogen. Department of Mineralogy and Geotectonics Institute of Geosciences University of São Paulo, Rua do Lago, 562 Department of Petrology and Metallogeny São Paulo State University, Av. 24A, 1515 Department of Earth Sciences University of Gothenburg, PO Box 460 Department of Petrology and Metallogeny São Paulo State University, Av. 24A, 1515 FAPESP: 13/04007-0 FAPESP: 15/05230-0 FAPESP: 16/22627-3 CNPq: 305720/2020-1 CNPq: 311606/2019-9 CNPq: 486328/2013-9

Translating burial and exhumation histories from the petrological and geochronological record of high-pressure assemblages in subduction channels is key to understanding subduction channel processes. Convective return flow, either serpentinite or sediment hosted, has been suggested as a potential mechanism to retrieve rocks from significant depths and exhume them. Numerical modelling predicts that during convective flow, subducted material can be cycled within a serpentinite-filled subduction channel. Geochronological and petrological evidences for such cycling during subduction are preserved in lawsonite eclogite from serpentinite melange in the Southern New England Orogen, eastern Australia. Ar–Ar, Rb–Sr phengite and U–Pb titanite geochronology, supported by phase equilibrium forward modelling and mineral zoning, suggest Cambro–Ordovician eclogite underwent two stages of burial separated by a stage of partial exhumation. The initial subduction of the eclogite at ca. 490 Ma formed porphyroblastic prograde-zoned garnet and lawsonite at approximate P–T conditions of at least 2.9 GPa and 600 °C. Partial exhumation to at least 2.0 GPa and 500 °C is recorded by garnet dissolution. Reburial of the eclogite resulted in growth of new Mg-rich garnet rims, growth of new prograde-zoned phengite and recrystallization of titanite at P–T conditions of approximately 2.7 GPa and 590 °C. U–Pb titanite, and Ar–Ar and Rb–Sr phengite ages constrain the timing of reburial to ca. 450 Ma. This was followed by a second exhumation event at approximately 1.9 GPa and 520 °C. These conditions fall along a cold approximate geotherm of 230 °C/GPa. The inferred changes in pressure suggest the lawsonite eclogite underwent depth cycling within the subduction channel. Geochronological data indicate that partial exhumation and reburial occurred over ca. 50 M y., providing some estimation on the timescales of material convective cycling in the subduction channel Refereed/Peer-reviewed

The Barberton Greenstone Belt (BGB) is a well-preserved remnant of Paleo- to Mesoarchean crust. The oldest supracrustal rocks of the BGB consist of the 3.5-3.3 Ga Onverwacht Group. These rocks form a NE-SW trending belt deformed and metamorphosed largely under lower greenschist-facies conditions. In the southern BGB, the Komati Fault separates the structurally uppermost, lower greenschist-facies Onverwacht Group from its stratigraphically lowest components – the Sandspruit and Theespruit Formations (hereafter referred to as Lower Onverwacht Group), which occur south of the Komati Fault and have been metamorphosed under high-pressure amphibolite-facies conditions. The Lower Onverwacht Group rocks occur as a band along the southern edge of the greenstone belt and as septa between several ca. 3.55, 3.45 and 3.23 Ga Tonalite-Trondhjemite-Granodiorite plutons. The Lower Onverwacht Group rocks record a complex history of metamorphism and retrogression. An early phase of amphibolite-facies metamorphism is recorded at ca. 3.44 Ga by monazite in metasediments, whilst the main phase of the regional metamorphism occurred at ca. 3.23 Ga (e.g. Cutts et al., 2014).The rocks targeted in this study have felsic metavolcanic protoliths and occur as a greenstone remnant within deformed and undeformed phases of 3.45 Ga Trondhjemites. They contain cm-sized garnets and the mineralogy of the samples indicate amphibolite-facies peak metamorphism. The garnets show major element growth zonation from core to rim (Alm0.63-0.80 Grs0.15-0.08Pyr0.0.05-0.09Sps0.17-0.0.03). U-Pb rutile geochronology gives an age at 3.15 Ga and Zr-in-rutile thermometry yields a temperature of ca. 640 °C (at 5 kbar). The rutile grains contain small, pristine zircon inclusions and the rutile is assumed to have grown in equilibrium with both zircon and quartz as buffer phases. The amphibolite-facies assemblage and the Zr-in-rutile temperature indicate that the rutile dates are cooling ages, which are difficult to interpret without information on the age of peak metamorphism of the samples. The objective of this study is to attempt to elucidate the early metamorphic record of these samples by directly dating the large garnet grains using in situ U-Pb laser-ablation inductively-coupled-plasma mass-spectrometry geochronology. Ongoing research shows that low-U garnet is datable by this method (Albert Roper et al., 2018). Preliminary results have been obtained from a different Lower Onverwacht Group sample, yielding a 3.45 Ga age for the garnet core and a 3.22 Ga age for the garnet rim (Cutts et al, unpublished data). The results indicate that U-Pb in rutile and in garnet from Archaean greenstones can be used in order to date metamorphic events. This is especially relevant when other potential datable accessory minerals, such as zircon or monazite, are not present. ReferencesCutts et al., 2014. Geological Society of America Bulletin 126, 251–270.Albert Roper et al., 2018. Goldschmidt Abstracts, 2018, 32.

The Sakarya Zone (northern Turkey) is a Gondwana-derived continental block accreted to northern Laurussia during the Carboniferous, and is regarded as the eastward extension of Armorica. Timing of its detachment from the northern margin of Gondwana, thus opening of the Paleo-Tethys, is poorly known. Here, we report on metagranite and amphibolite with Silurian igneous crystallization ages from the Early Carboniferous high-temperature/middle to low-pressure amphibolite-facies metamorphic rocks of the Sancakaya Massif within the Sakarya Zone (NW Turkey). The metagranite-amphibolite complex is exposed mainly along the southern margin of the Sancakaya Massif over an area of ca. 12 km by 15 km. The metagranite contains preserved domains of porphyric texture, indicative of derivation from a former granite porphyry. The amphibolite is devoid of any relict igneous texture. Both the metagranite and amphibolite are crosscut by late up to 50 cm thick felsic veins. Uranium-Pb dating on igneous zircons from both metagranite and amphibolite yielded Silurian ages of ca. 419 +/- 6 to 434 +/- 7 Ma (2 sigma), and on those from a felsic vein an age of 319 +/- 5 Ma (2 sigma) (Late Carboniferous). Geochemically, amphibolite displays anorogenic transitional tholeiitic to alkaline signatures. Initial cHf values of the igneous zircons from both metagranite and amphibolite show a large variation with medial values of -16 to -9 and + 3 to +6, respectively. Thus, the protoliths of amphibolite were derived from melts of depleted mantle, and those of the metagranite, on the other hand, from melts of reworked crustal material. We suggest that the Silurian anorogenic magmatism is related to a rifting event at the northern margin of Gondwana leading to the detachment of the Sakarya Zone and hence placing an age on the initial opening of the Paleo-Tethys. This interpretation is based on (i) the presence of Late Silurian to Devonian deep-sea sedimentary blocks in the PaleoTethyan accretionary complexes, and (ii) the resemblance of the U-Pb age spectra of detrital zircons in the metadastic sequence of the Sancakaya Massif to those of Cambro-Ordovician sandstones in Jordan (Gondwana), and (iii) the local occurrence of anorogenic A-type granites of Late Ordovician-Silurian age in the AnatolideTauride Block, a continental block which rifted from Gondwana during the Early Triassic. Wholly anorogenic nature of the Late Ordovician to Silurian igneous rocks in the Sancakaya Massif and reported in literature does not support the opening of the Paleo-Tethys as back-arc ocean, as suggested in most paleogeographic reconstructions. (C) 2019 Elsevier B.V. All rights reserved.

Kesebolite-(Ce), ideal formula CeCa2Mn(AsO4)[SiO3]3, is a new mineral (IMA No. 2019-097) recovered from mine dumps at the Kesebol Mn-(Fe-Cu) deposit in V&auml, stra G&ouml, taland, Sweden. It occurs with rhodonite, baryte, quartz, calcite, talc, andradite, rhodochrosite, K-feldspar, hematite, gasparite-(Ce), chernovite-(Y) and ferriakasakaite-(Ce). It forms mostly euhedral crystals, with lengthwise striation. The mineral is dark grayish-brown to brown, translucent, with light brown streak. It is optically biaxial (+), with weak pleochroism, and ncalc = 1.74. H = 5&ndash, 6 and VHN100 = 825. Fair cleavage is observed on {100}. The calculated density is 3.998(5) g&middot, cm&minus, 3. Kesebolite-(Ce) is monoclinic, P21/c, with unit-cell parameters from X-ray single-crystal diffraction data: a = 6.7382(3), b = 13.0368(6), c = 12.0958(6) &Aring, &beta, = 98.578(2)&deg, and V = 1050.66(9) &Aring, 3, with Z = 4. Strongest Bragg peaks in the X-ray powder pattern are: [I(%), d(&Aring, ) (hkl)] 100, 3.114 (20-2), 92, 2.924 (140), 84, 3.138 (041), 72, 2.908 (014), 57, 3.228 (210), 48, 2.856 (042), 48, 3.002 (132). The unique crystal structure was solved and refined to R1 = 4.6%. It consists of 6-periodic single silicate chains along (001), these are interconnected to infinite (010) strings of alternating, corner-sharing MnO6 and AsO4 polyhedra, altogether forming a trellis-like framework parallel to (100).

The U–Pb age and trace element composition of detrital rutile provide information about the metamorphic history of the source region that cannot be constrained by traditional U–Pb dating of detrital zircon. Previous provenance investigations focussed on only one of these methods. Based on a large LA-ICP-MS trace element and U–Pb isotopic dataset of detrital rutile and U–Pb isotopic data of detrital zircon from late Ordovician sedimentary rocks of Saxo-Thuringia, Germany, this paper discusses the application and significance of combining these methods in provenance investigations. U–Pb age spectra from the detrital zircons analysed show multiple age components (multimodal age spectra) in all samples. This is in contrast with the detrital rutile data, as only one sample yielded a multimodal U–Pb age distribution. Multimodal age spectra of detrital rutile are most likely preserved in sediments from (large) catchment areas with complex geological histories. They may also be related to specific sedimentation events, such as glacial washout during the retreat of large ice shields (e.g. the Hirnantian glaciation of Gondwana). Unimodal age spectra are however not restricted to small catchment areas, if the provenance region is characterized by a pervasive thermal overprint such as the Pan-African orogeny throughout Gondwana. Unimodal age distributions may further consist of overlapping age cluster detectable by different trace element composition of the detrital rutile grains. The combined U–Pb age and trace element data from detrital rutile grains demonstrate that rutile sourced from metapelitic rocks yield reliable and precise U–Pb ages. In contrast, detrital rutile classified to be of metamafic origin generally has too low uranium concentrations to be dated reliably by LA-ICP-MS. Detrital rutile records low- to medium-grade metamorphic events in the source region and therefore has the potential to better constrain the maximum depositional age of sedimentary rocks in comparison to U–Pb dating of detrital zircon.

Coralline algae have been used for sclerochronological studies throughout the last decade. These studies have focused on two different growth morphologies of the photosynthetic coralline algae: massive crusts forming small buildups on hard substrate, and free-living branching algal nodules, known as rhodoliths. The latter are generally found on soft-substrate, where they are frequently overturned by water movement and bottom feeding organisms, leaving one side of the rhodolith partially buried in the sediment at any given time. Here we test whether either of these growth morphologies is more suitable for proxy reconstructions by comparing Mg/Ca ratios – a temperature proxy – in multiple replicates of rhodoliths of Lithothamnion glaciale and in rhodoliths as well as encrusting specimens of Clathromorphum compactum. With both species being widespread throughout the Temperate and Arctic regions, we have chosen two North Atlantic localities at Nuuk Fjord, Greenland (Subarctic), and off the southeastern coast of Newfoundland, Canada (Temperate), for this study. Two to three Mg/Ca ratio transects spanning 18 years of growth were analysed on multiple specimens with encrusting morphologies and along different sides of rhodoliths using laser ablation inductively coupled mass spectrometry and compared to remotely sensed sea surface temperature (SST) data. The length of the common time span used for comparison was limited by growth interruptions in rhodoliths. Furthermore, our comparison is based on the assumption that rhodolith growth increments are annual – an assumption that has recently been challenged by mesocosm studies. Monthly Mg/Ca values from multiple transects within each individual were compared and in samples from Nuuk fjord significant correlations were found in 4 of 4 encrusting C. compactum, 4 of 4 C. compactum rhodoliths, and 2 of 3 L. glaciale rhodoliths. In Newfoundland significant correlations were found in 6 of 6 encrusting C. compactum comparisons (average: r = 0.61, p

The Birthday Reef was the most productive gold producer during historic mining of the Reefton goldfield on the west coast of the South Island of New Zealand. Deep exploration drill holes (up to 1.6 km long) intersected the mineralised quartz vein zone and adjacent hydrothermal alteration halo beneath the historic mine workings. The Paleozoic metasedimentary host rocks contain between 0.5 and 8 ppb Au and between 4 and 30 ppm As, and metamorphic pyrite typically contains 0.1 to 1 ppm Au in solid solution. The Au and As halo, above these background values, extends

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 …

The Palaeoproterozoic Transvaal and Olifantshoek Supergroups of South Africa contain some of the earliest hematite-rich sedimentary rocks (red-beds) and paleosols on record. The origin of these rocks has been variously attributed to surface processes under an oxygenated atmosphere that post-dated the ca. 2.3Ga Great Oxidation Event (GOE). Interpretations of their geochemical signatures, however, have been inconclusive with respect to the causes of the apparent K-enrichment that these rocks record. Here, we re-visit the basal Mapedi Formation of the Olifantshoek Supergroup and the unconformably underlying Drakenstein palaeo-weathering profile that develops against the Ongeluk Formation of the upper Transvaal Supergroup, and present new petrographic and geochemical data in an attempt to constrain the burial metasomatic history of these rocks. Apart from the strong hematitic nature and K-metasomatic overprint seen in both the Mapedi Formation and Ongeluk paleosol, a curious and hitherto unexplored enrichment in high-field strength elements (HFSEs: Ti, Nb, Y, Zr, REE, etc.) by several orders of magnitude higher than average shale characterizes the lower part of the Mapedi Formation as examined here. We show that such enrichments cannot be explained by normal source-to sink weathering processes, unless an unlikely provenance of special geochemical composition (i.e. alkali igneous rocks) is to be invoked. We conclude that the HFSE enrichment, K-metasomatism and evidently transgressive Fe-oxidation effects in the Mapedi shales can only be accounted for via post-depositional fluid-rock interaction, possibly involving F-bearing diagenetic brines. This opens the distinct possibility that such fluids may have also been implicated in alteration processes, enhanced Fe mobility and development of epigenetic hematitic iron-ores as seen at the Transvaal-Olifantshoek unconformity on regional scales. Copyright (c) 2017 John Wiley & Sons, Ltd.

An extensive microanalytical study of calcite precipitated from groundwater flowing into boreholes at >400 m depth in the Aspo Hard Rock Laboratory, Sweden, has been carried out. Hydrochemical variations in packed-off sections, isolating water-conducting fractures intersected by two boreholes, were documented over a period of 17 years. The extraction of the borehole equipment revealed calcite precipitation on the equipment. This mineral material enabled unique assessment of uptake of different trace elements by calcite during precipitation from granitoid fracture groundwater, at anoxic, low-temperature (c.a 14 °C), and neutral (pH: 7.4-7.7) conditions, under variable salinity (Cl: 2500-7000 mg/L) prevailing at these depths. Temporal hydrochemical variations could be traced by detailed micro-analytical transects in the calcites and the influence of metal speciation and complexation on partitioning into calcite could be assessed (e.g. explaining unexpectedly low incorporation of REEs). The resulting environment-specific partition coefficients for a large number of metals are relevant in models of radionuclide retention around proposed deep nuclear waste repositories in this kind of environment, particularly because 1) elements such as REEs act as natural analogues to actinides, and 2) existing coefficients established in laboratory or in other natural environments cannot be unreservedly applied to conditions in deep crystalline rocks.

Monazite is a common accessory phosphate mineral that occurs under a wide range of pressure and temperature conditions in sedimentary, metamorphic and igneous rocks. Monazite contains high amounts of Th and U, rendering single monazite grains suitable for in-situ U-Th/Pb dating using laser ablation inductively-coupled mass spectrometry (LA-ICP-MS). Two key aspects of monazite dating that are critical for accurate age data with maximum precision are (i) optimized instrumental conditions to minimize analytical scatter and (ii) a well characterized reference material to ensure the accuracy of the obtained aged. Here, we analyzed five monazite reference materials (USGS 44069, 94-222, MAdel, Moacir and Thompson Mine Monazite) for their U-Th/Pb ages using LA-ICP-MS technique and applied a variety of laser spot diameters and repetition rates to find the best operational conditions to achieve accurate age data while maintaining maximum precision. We find that a spot diameter of 10 &micro, m and a repetition rate of 10 Hz yield the most precise ages with a deviation of &plusmn, 2.0% from their respective high-precision U/Pb literature age data. Ages were reproduced in three different LA-ICP-MS laboratories using these parameters. Each reference material was tested for its suitability as a matrix-matched age reference material. For this, a rotating, iterative approach was adopted in which one reference monazite was used as calibration reference material against all others, which were treated as unknowns. The results reveal that USGS 44069, 94-222, Thompson Mine Monazite and MAdel all agree with their respective calculated ages and ID-TIMS reference ages and thus are suggested as suitable calibration reference materials. Moacir, however, appears slightly older than previously suggested (up to 4%), thus, caution is advised here when using Moacir as reference material for U-Th/Pb LA-ICP-MS dating in the absence of further absolute age calibration.

Volcanogenic massive sulfide deposits are enriched in metals that are either derived from hydrothermal alteration of the basement rocks or supplied by exsolution of metal-rich volatiles during magmatic differentiation. The extent to which each process contributes to metal enrichment in these deposits varies between different tectonic settings. Ocean Drilling Program Hole 786B recovered > 800 m of upper oceanic crust from a supra-subduction zone setting and includes a 30-m-thick mineralised zone. In situ S isotopic compositions of pyrite decrease from 5.9 ± 2.9‰ in the upper mineralised zone down to − 3.3 ± 2.1‰ in the extensively altered central mineralisation zone, potentially indicating strong magmatic fluid input in this area. Whole rock data and in situ trace element analyses in sulfide minerals show enrichment of Ag, As, Au, Bi, Mo, S, Se, Sb and Te in the mineralised zone. Evaluation of metal behaviour during magmatic differentiation and primary metal fertility of basement rocks suggests that degassing melt is the main source for the high Au, Se and S enrichment observed in the mineralised zone. Magmatic volatile exsolution occurred late during the magmatic differentiation (~ 2 wt.% MgO), concomitant with oxide crystallisation and metal depletion in the melt. Comparison of Ocean Drilling Program Hole 786B with volcanogenic massive sulfide deposits hosted by boninitic volcanic successions, such as in the Semail ophiolite, the Newfoundland Appalachians and the Flin Flon Belt, suggests that magmatic fluid exsolution could be a common mechanism for Au enrichment in bimodal mafic volcanogenic massive sulfide deposits.

The Rb-Sr beta-decay dating system is one of the most attractive tools in geochronology, as Rb is sufficiently abundant in common K-bearing minerals like biotite, muscovite and K-feldspar. This allows dating of a wide variety of rocks (e.g., volcanic, magmatic, metamorphic, sedimentary and hydrothermal environments) without the need of preconcentration, as is often required for U-Pb dating of zircon. However, this advantage was to date negatively counteracted by the lack of a suitable in-situ technique, as beta decay systems by nature have isobaric interferences of the daughter isotope by their respective parent isotope. A reaction cell sandwiched between two quadrupoles within an inductively coupled plasma mass spectrometer (ICP-MS) allows exactly this, the online chemical separation of two different elements. Coupled to a laser ablation (LA) system, in-situ Rb-Sr dating is therefore possible if a suitable reaction gas within the reaction cell can be found that separates Sr from Rb. We present here a simple procedure in which Rb-Sr ages can be obtained from a suite of individual phases in regular thin sections. Using the most established reaction gas, oxygen (O 2 ), it is possible to react part of the ablated Sr to SrO + while no RbO + is formed. Measurements of feldspars and micas with a spot size of 80 μm were calibrated against glass standards NIST SRM 610, BCR-2G and biotite from La Posta (California; 91.6 Ma). Results are presented for a variety of magmatic rocks with well-established thermal records: a sample each from the Klokken syenodiorite (Greenland; 1161 Ma), the Ulvo alkaligabbro (Sweden; 1256 Ma) and a pegmatite from the Bohus granite (Sweden; 920 Ma). Obtained in situ Rb-Sr isochron ages are accurate 87 Sr/ 86 Sr ratios are accurate The methodology outlined in this study has significant implications for Rb-Sr studies due to the high spatial resolution: (1) quality of measurements can be better controlled by avoiding alterations and inclusions, (2) large sample numbers can be investigated simply by using regular thin sections, (3) several mineral generations can be targeted that would not be distinguishable in mineral separates, and (4) isotope zonation within single crystals can be revealed. This will open the Rb-Sr dating system to new fields of study. For example, thermochronologic studies can use 87 Sr/ 86 Sr and 87 Rb/ 86 Sr zonation within crystals to better work out cooling and/or reheating paths. Further applications are in the field of provenance studies and temporal evolution of shear zones.

The Palaeoproterozoic Hartley Formation in the Olifantshoek Group was deposited in one of the rift-related Waterberg (sensu lato) red bed basins which formed on the Kaapvaal Craton after the 2.05 Ga Bushveld intrusions and coeval thermal event. The age of these basins is not well constrained due to the shortage of directly dateable rock types. The Hartley Formation contains rare quartz-porphyry lavas interbedded with the dominant basalts and these provide the means to date the formation by analyses of zircon. In this work zircon from one sample has been dated by six Th-U-Pb methods, namely Laser Ablation ICP Quadrupole Mass Spectrometry, Laser Ablation ICP High-resolution Mass Spectrometry, Laser Ablation ICP Multicollector Mass Spectrometry U-Pb (also Lu-Hf), Nordsim Ion probe U-Pb and Th-Pb; and Krogh method ID-TIMS. Our precise ages give a combined age of 1915.2 ± 1.1 Ma. Including one published ion probe date from the only other known occurrence of quartz porphyry, the results only agree if the quoted analytical errors are increased by 20%, which gives a combined result of 1915.6 ± 1.4 Ma. This is considered a reliable, precise and accurate age for the Hartley Formation and supersedes the published Kober method 207Pb/206Pb age of 1928 ± 4 Ma. The new Lu-Hf zircon data, supported by published whole rock Sm-Nd and Rb-Sr data, suggests that both the dominant basalts and the rare quartz porphyries of the Hartley Formation were derived from mafic source rocks which had been in the crustal domain from Archaean times. By contrast with the intracratonic rifts of the other Waterberg Basins, the Olifantshoek Supergroup reflects the development of a western passive margin as the Archaean Kaapvaal Craton rifted and drifted. This was followed by accretion of the Rehoboth Province along the Kalahari Line, accompanied by the development of the east-vergent Kheis Province thrust complex. This created a larger cratonic block against which the 1.2 Ga collisions of Namaqua-Natal terranes impacted. The Kheis Province now yields ~1.17 Ma cooling ages, reflecting the Namaqua collisions, but the true age of the Kheis event is still enigmatic.

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining 48Ti mass fractions in quartz by LA-ICP-MS at the 1 μg g−1 level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the low-CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g−1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of 48Ti as a normalising mass. Average titanium mass fraction from thirty-three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g−1 (2s) using 48Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of 48Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using 49Ti as an analyte.

Halogen contents for the widely distributed reference glasses BHVO-2G, BIR-1G, BCR-2G, GSD-1G, GSE-1G, NIST SRM 610 and NIST SRM 612 were investigated by pyrohydrolysis combined with ion chromatography, total reflection X-ray fluorescence analysis, instrumental neutron activation analysis, the noble gas method, electron probe microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. Glasses BHVO-2G, GSD-1G and GSE-1G have halogen contents that can be reproduced at the 15% level by all bulk techniques and cover a significant range in halogen mass fractions for F (~ 20–300 μg g), Cl (~ 70–1220 μg g) and Br (~ 0.2–285 μg g) and I (~ 9–3560 ng g). The BIR-1G glass has low F (< 15 μg g), Cl (~ 20 μg g), Br (15 ng g) and I (3 ng g). The halogen contents for the silica-rich NIST SRM 610 and 612 glasses were poorly reproduced by the different techniques. The relatively high Cl, Br and I abundances in glasses GSD-1G and GSE-1G mean that these glasses are well suited for calibrating spatially resolved micro-analytical studies on silicate glasses, melt and fluid inclusions. Combined EPMA and laser ablation-inductively coupled plasma-mass spectrometry data for glass GSE-1G demonstrate homogeneity at the 10% level for Cl and Br.

In northwest Turkey, ophiolitic meta-gabbros are exposed on the Kazdag Massif located in the southern part of the Biga Peninsula. Trace element composition of rutile and Zr-in-rutile temperatures were determined for meta-gabbros from the Kazdag Massif. The Zr content of all rutiles range from 176 to 428 ppm and rutile grains usually have a homogeneous Zr distribution. The rutile grains from studied samples in the Kazdag Massif are dominated by subchondritic Nb/Ta (11–19) and Zr/Hf ratios (20–33). Nb/Ta and Zr/Hf show positive correlation, which is probably produced by silicate fractionation. The Nb/Ta and Zr/Hf ratios increase with a decrease in Ta and Hf contents. The core of rutile grains are generally characterized by low Nb/Ta ratios of 17–18 whereas the rims exhibit relatively high Nb/Ta ratios of 19–23. Trace element analyses in rutile suggest that these rutile grains were grown from metamorphic fluids. The P-T conditions of meta-gabbros were estimated by both Fe–Mg exchange and Zr-in-rutile thermometers, as well as by the Grt-Hb-Plg-Q geothermobarometer. The temperature range of 639 to 662 °C calculated at 9 kbar using the Zr-in-rutile thermometer is comparable with temperature estimates of the Fe-Mg exchange thermometer, which records amphibolite-facies metamorphism of intermediate P-T conditions. The P-T conditions of meta-ophiolitic rocks suggest that they occur as a different separate higher-pressure tectonic slice in the Kazdag metamorphic sequence. Amphibolite-facies metamorphism resulted from northward subduction of the Izmir-Ankara branch of the Neo-Tethyan Ocean under the Sakarya Zone. Metamorphism was followed by internal imbrication of the Kazdag metamorphic sequence resulting from southerly directed compression during the collision.

This provenance study focuses on detrital rutile grains from Jurassic sandstones of the Bayirkoy Formation in the central Sakarya Zone. Cr and Nb concentrations of detrital rutile grains in the Jurassic sandstones vary from 18 to 6855 μg/g and 70–13440 μg/g, respectively. Source area discrimination based on the Cr-Nb concentrations shows that 79 % of the detrital rutile grains originated from metapelitic and 21 % from metamafic rocks. The calculated rutile formation temperatures vary from 471 to 798 ℃ with an average temperature of 635 ℃ at P=10 kbar. Zr-in-rutile thermometer gives overlapping temperatures for all detrital rutile grains from both the metapelitic and metamafic sources. This demonstrates that most of the detrital rutiles sourced from metapelitic and metamafic rocks underwent similar metamorphic conditions and have similar metamorphic history. The U-Pb rutile dating yielded ages for the detrital rutiles in the time range of 346 to 319 Ma, which gives the age of metamorphism for the potential source rocks. Trace element compositions, Zr-in-rutile thermometer and U-Pb rutile geochronology show that detrital rutile grains were predominantly derived from early Carboniferous rocks that underwent metamorphism in amphibolite-facies conditions. Amphibolite-facies rocks of the Saricakaya Massif in the central Sakarya Zone seem to be the primary source lithologies for the detrital rutiles in the Jurassic Bayirkoy Formation as it comprises previously-mentioned source lithologies and has a close geographic position to the area studied. Carboniferous Variscan metamorphism was followed by emplacement of numerous post-collisional granitoids in the central Sakarya Zone.

Rare-earth elements play a crucial role in modern technologies and are necessary for a transition to a green economy. Potentially economic deposits of these elements are typically hosted in minerals such as monazite, bastnasite, and eudialyte (a complex Na-Ca-Fe-Zr silicate mineral with Cl), making these prime targets for geological research. Globally, rare-earth mineral deposits commonly show evidence of polyphase development and mineralisation processes, which need to be better understood to improve exploration strategies. The Norra Karr alkaline complex (Sweden) contains a globally significant deposit of rare-earth elements, hosted in the mineral eudialyte. In this study, we focussed on eudialyte crystals in undeformed, cross-cutting pegmatoid veins from Norra Karr. In order to determine their age, we refined an established micromilling method to enable sampling of minerals rich in rare-earth elements for precise analysis of major and trace elements, Nd isotope ratios, and Sm-Nd geochronology down to a scale of

The Western Dharwar Craton (WDC) and the Karwar Block (KB) in southern Peninsular India provide important windows to Earth’s early crustal evolution and continental growth as these domains likely represent fragments of the first landmass or supercontinent on our planet. Here we employ, for the first time, a coupled laser ablation zircon U-Pb dating and in-situ Rb-Sr dating of micas (biotite, muscovite) and feldspars to evaluate the Meso- to Neoarchean crustal evolution and Proterozoic magmatism/metamorphism in the Karwar Block. This novel approach based on integrated geochronological results show that the WDC and KB experienced (i) a major Mesoarchean continental growth event (c. 3.2 to 2.9 Ga), (ii) younger Neoarchean and Paleoproterozoic magmatism/migmatization (syn- and post-tectonic granite formation events at c. 2.8–2.6 Ga and 2.2 Ga, respectively), and (iii) Mesoproterozoic metamorphism/thermal imprint (as young as 1.2 Ga). The zircon eHf(t) values exhibit a range from +0.4 to +9.8 in amphibolite, hornblende gneiss and trondhjemite (3.28–3.08 Ga), as well as the +6.1 to +9.7 range for 2.96 Ga old zircons in porphyritic granite, which suggests juvenile source for the magmatism that constructed this crustal block. Overall, this study illustrates the benefits of using coupled zircon U-Pb and in-situ Rb-Sr mica and feldspar dating approaches, as the former (U/Pb) provides robust constraints or a ‘baseline age’ for initial crystallization of crustal sequences whereas the latter (Rb/Sr) is sensitive to younger magmatic and metamorphic events. Thus, the integration of these two laser ablation ICP-MS based geochronometers applied to crustal evolution studies, has the potential to provide more comprehensive insights into continental growth in the early Earth, and later magmatic and metamorphic history of the region.

Understanding metal scavenging by calcite in deep aquifers in granite is of importance for deciphering and modeling hydrochemical fluctuations and water–rock interaction in the upper crust and for retention mechanisms associated with underground repositories for toxic wastes. Metal scavenging into calcite has generally been established in the laboratory or in natural environments that cannot be unreservedly applied to conditions in deep crystalline rocks, an environment of broad interest for nuclear waste repositories. Here, we report a microanalytical study of calcite precipitated over a period of 17 years from anoxic, low-temperature (14 °C), neutral (pH: 7.4–7.7), and brackish (Cl: 1700–7100 mg/L) groundwater flowing in fractures at >400 m depth in granite rock. This enabled assessment of the trace metal uptake by calcite under these deep-seated conditions. Aquatic speciation modeling was carried out to assess influence of metal complexation on the partitioning into calcite. The resulting environment-specific partition coefficients were for several divalent ions in line with values obtained in controlled laboratory experiments, whereas for several other ions they differed substantially. High absolute uptake of rare earth elements and U(IV) suggests that coprecipitation into calcite can be an important sink for these metals and analogousactinides in the vicinity of geological repositories.

Finely acicular rutile intergrown with host quartz (rutilated quartz) is commonly found in hydrothermal veins, including the renown cleft mineral locations of the Swiss Alps. These Alpine cleft mineralizations reportedly formed between ~13.5 and 15.2 Ma (based on ages of rare hydrothermal monazite and titanite) at temperatures ( T ) of ~150–450 °C (based on fluid inclusions and bulk quartz-mineral oxygen isotope exchange equilibria), and pressures ( P ) of 0.5–2.5 kbar (estimated from a geothermal gradient of 30 °C/km). The potential of rutilated quartz as a thermochronometer, however, has not been harnessed previously. Here, we present the first results of age and T determinations for rutilated quartz from six locations in the Swiss Alps with vein country rocks that cover peak-metamorphic conditions between ~600 and with x = Zr ppm and R = 0.008314 (uncertainties scaled by the square root of the mean square of weighted deviates MSWD = 11; n = 9). This relationship supports previously recognized temperature-dependent Zr uptake in rutile, although widely used Zr-in-rutile thermometer calibrations based on high- T experiments are at variance with oxygen isotope exchange temperatures. By contrast, Ti-in-quartz lacks systematic relations with oxygen isotope temperatures. The discrepancy between low- T Ti-in-quartz thermometry on one side, and oxygen isotope and Zr-in-rutile thermometry on the other, suggests that Ti-in-quartz thermometry should be applied with caution for low- T (

We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission-track (AFT) thermochronology by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP-MS and laser ablation (LA) ICP-MS were employed. Two apatite crystals are potential reference materials for LA-ICP-MS analysis: a 1 cm3 fraction of a Durango crystal (7.5 μg g−1 U) and a 1 cm3 Mud Tank crystal (6.9 μg g−1 U). The relative standard deviation (1 RSD) of the U concentration determined by ID-ICP-MS of both apatite crystals was ≤ 1.5%, whereas 1 RSD for the LA-ICP-MS results was better than 4%, providing sufficient homogeneity for fission-track dating. The results on the U homogeneity for two different apatite samples are an important step towards establishing in situ dating routines for AFT analysis by LA-ICP-MS. Nous restituons des tests d'homogeneite sur des grands cristaux d'apatite naturelle afin d’evaluer leur potentiel en tant que materiaux de reference pour l'U en vue d'une application dans le domaine de la thermochronologie par traces de fission sur apatite (AFT) par spectrometrie de masse a plasma induit couplee a l'ablation laser (LA-ICP-MS). Les tests d'homogeneite incluent des mesures des concentrations en elements majeurs par microsonde electronique (EPMA), alors que pour la concentration en U, la dilution isotopique (ID) ainsi que l'ablation laser (LA) ICP-MS ont ete employees. Deux cristaux d'apatite sont des materiaux de reference possibles pour les analyses LA-ICP-MS: une fraction d'1 cm3 d'un cristal de Durango (7,5 µg g−1 U) et un cristal d'1 cm3 de Mud Tank (6,9 µg g−1 U). L’ecart type relatif (1 RSD) de la concentration en U determinee par ID-ICP-MS des deux cristaux d'apatite est ≤ 1,5%, tandis que celui pour les resultats LA-ICP-MS est inferieur a 4%, offrant ainsi une homogeneite suffisante pour les datations par la methode des traces de fission sur apatite. Les resultats concernant l'homogeneite de l'U pour deux echantillons differents d'apatite sont une etape importante vers la possibilite d'envisager des datations AFT in situ en routine par LA-ICP-MS.

Microorganisms produce and consume methane in terrestrial surface environments, sea sediments and, as indicated by recent discoveries, in fractured crystalline bedrock. These processes in the crystalline bedrock remain, however, unexplored both in terms of mechanisms and spatiotemporal distribution. Here we have studied these processes via a multi-method approach including microscale analysis of the stable isotope compositions of calcite and pyrite precipitated in bedrock fractures in the upper crust (down to 1.7 km) at three sites on the Baltic Shield. Microbial processes have caused an intriguing variability of the carbon isotopes in the calcites at all sites, with δ13C spanning as much as −93.1‰ (related to anaerobic oxidation of methane) to +36.5‰ (related to methanogenesis). Spatiotemporal coupling between the stable isotope measurements and radiometric age determinations (micro-scale dating using new high-spatial methods: LA-ICP-MS U–Pb for calcite and Rb–Sr for calcite and co-genetic adularia) enabled unprecedented direct timing constraints of the microbial processes to several periods throughout the Phanerozoic eon, dating back to Devonian times. These events have featured variable fluid salinities and temperatures as shown by fluid inclusions in the calcite; dominantly 70–85 °C brines in the Paleozoic and lower temperatures (

In northwest Turkey, high-pressure metamorphic rocks occur as exotic blocks within the cetmi m lange located on the south of the Biga Peninsula. Rutile chemistry and rutile thermometry obtained from the eclogite and associated garnet-mica schist in the cetmi m lange indicate significant trace element behaviour of subducted oceanic crust and source-rock lithology of detrital rutiles. Cr and Nb contents in detrital rutile from garnet-mica schist vary from 355 to 1026 pzig and 323 and 3319 g/g, respectively. According to the Cr-Nb discrimination diagram, the results show that 85% of the detrital rutiles derived from metapelitic and 15% from metamafic rocks. Temperatures calculated for detrital rutiles and rutiles in eclogite range from 540 degrees C to 624 degrees C with an average of 586 degrees C and 611 degrees C to 659 degrees C with an average of 630 degrees C at P = 2.3 GPa, respectively. The calculated formation temperatures suggest that detrital rutiles are derived from amphibolite- and eclogite-facies metamorphic rocks. Amphibolite-facies rocks of the Kazdag Massif could be the primary source rocks for the rutiles in the garnet-mica schist from the cetmi m lange. Nb/Ta ratios of metapelitic and metamafic rutiles fall between 7-24 and 11-25, respectively. Nb/Ta characteristics in detrital rutiles may reflect a change in source-rock lithology. However, Nb/Ta ratios of rutiles in eclogite vary from 9 to 22. The rutile grains from eclogites are dominated by subchondritic Nb/Ta ratios. It can be noted that subchondritic Nb/Ta may record rutile growth from local sinks of aqueous fluids from metamorphic dehydration. (C) 2017 Elsevier GmbH. All rights reserved.

WOS: 000408588700008, The East Anatolian plateau (Turkey) is extensively covered by Neogene to Quaternary volcanic-sedimentary rocks, and is characterized by an attenuated lithospheric mantle. Its pre-Neogene basement is commonly considered to consist entirely of Late Cretaceous to Oligocene oceanic accretionary complexes, formed at the junction of several continental blocks. Here we report on three main exposures of the pre-Neogene basement in this region. The exposed areas consist mainly of amphibolite-to granulite-facies metamorphic rocks, including marble, amphibolite, metapelite, metagranite, and metaquartzite. An upper amphibolite-to granulitefacies domain is equilibrated at similar to 0.7 GPa and similar to 800 degrees C at 83 +/- 2 Ma (2 sigma). U-Pb dating of magmatic zircons from the metagranite yielded a Late Ordovician-early Silurian protolith age (444 +/- 9 Ma, 2 sigma). The detrital zircons from one metaquartzite point to a Neoproterozoic-early Paleozoic provenance. Ophiolitic rocks tectonically sit on the metamorphic rocks. Both the metamorphic and ophiolitic rocks are in turn unconformably covered by lower Maastrichtian clastic rocks and reefal limestones, suggesting that the whole exhumation process and juxtaposition with the ophiolitic rocks had occurred by the early Maastrichtian. Several lines of evidence, such as (1) the absence of any indication of a former high-pressure metamorphism in the metamorphic rocks, (2) the allochthonous nature of the ophiolitic rocks, (3) the presence of metagranite with a Late Ordovician-early Silurian protolith age, and (4) the Neoproterozoic- early Paleozoic provenance of detrital zircons in the metaquartzite (in contrast to the dominance of late Paleozoic-Mesozoic crystalline rocks in the adjacent continental blocks) indicate a substantial component of continental basement beneath the Neogene to Quaternary cover. Thus, the loss of the lithospheric mantle probably resulted from lithospheric foundering processes beneath the plateau, rather than just slab steepening and break-off., Scientific and Technological Research Council of Turkey [114Y226], We greatly benefited from lively discussions with C. Sengor, A. Okay, and O. Gogus, and constructive reviews by B. Wernicke and two anonymous reviewers. This work was financially supported by the Scientific and Technological Research Council of Turkey (grant 114Y226).