From Gabbro to Granulite and finally to Kyanite- and bimineralic Eclogite: A petrological, geochemical and mass balance approach to mantle eclogites

In this study, we present the phase transitions from gabbro into granulite and finally into kyanite-bearing and bimineralic eclogite. The investigated rock sample is a heterogeneous coexisting kyanite-bearing and bimineralic eclogite from the earth’s mantle collected at the Roberts Victor Diamond mine in South Africa. Plagioclase of the former granulite reacted completely out under low H2O activity (fH2O) to form these kyanite- bearing and bimineralic eclogites. To quantify the phase transitions of the original gabbroic precursor, which was first metamorphosed under H-T granulite facies conditions followed by metamorphism under Earth’s mantle conditions into both types of eclogite, a petrological, geochemical and a mass balance approach has been made. i) The results from our petrological approach show that Ca-rich garnet, which is coexistent with Ca-rich omphacite are the metastable phases from the original granulite in the kyanite-bearing relict while Mg-rich garnet, coexistent with Na-rich omphacite are the stable phases in the bimineralic eclogite part which took place at ~5.5 Gpa and ~1200°C. ii) Our geochemical results show a positive Eu anomaly in garnet from the kyanite-bearing part, which indicates that the igneous precursor of the granulite was a gabbro, probably formed as oceanic crust. Most of the REE show an excellent correlation with the major elements of the rock forming minerals during the plagioclase-out reaction of the former granulite. The LREE in garnet are removed during the formation of the bimineralic eclogite due to liquefying of the anorthite component in plagioclase of the former granulite. Whereas the HREE are enriched in garnets in the bimineralic part of the eclogite compared to those in the kyanite zone, and correlate with the Mg-Ca exchange between both garnet populations. iii) The results from our mass balance approach indicate that garnet in bimineralic eclogite was formed by 0.925 mole garnet and 0.075 mole plagioclase of the former granulite precursor. Whereas omphacite in the bimineralic eclogite have been formed by 0.625 mole clinopyroxene and 0.375 mole plagioclase of the earlier granulite. Following bimineralic eclogite forming reaction was calculated from our mass balance approach: 0.625 Cpx + 0.45 Plag + 0.925 Grs + 0.89 MgO + 1.15 CO2 = 1 Pyp + 1 Omph + 0.04 Ky + 1.15 Cc. The excess of MgO during final eclogitization interpreted to be added during mantle metasomatism. And finally, our results show that only those parts of the former granulite show the formation of bimineralic eclogite where water had access to the rock. The formation of the kyanite bearing eclogite out of the former granulite is just considered by liquefying of the anorthite component in plagioclase under very low H2O fugacity

The Magmatic to Hydrothermal Evolution of the Intrusive Mont Saint-Hilaire Complex: Insights into the Late-stage Evolution of Peralkaline Rocks

The Cretaceous Mont Saint-Hilaire complex (Quebec, Canada) comprises three major rock units that were emplaced in the following sequence: (I) gabbros; (II) diorites; (III) diverse partly agpaitic foid syenites. The major element compositions of the rock-forming minerals, age-corrected Nd and oxygen isotope data for mineral separates and trace element data of Fe-Mg silicates from the various lithologies imply a common source for all units. The distribution of the rare earth elements in clinopyroxene from the gabbros indicates an ocean island basalt type composition for the parental magma. Gabbros record temperatures of 1200 to 800°C, variable silica activities between 0·7 and 0·3, and fO2 values between −0·5 and +0·7 (log ΔFMQ, where FMQ is fayalite-magnetite-quartz). The diorites crystallized under uniform aSiO2 (aSiO2 = 0·4-0·5) and more reduced fO2 conditions (log ΔFMQ ~ −1) between ~1100 and ~800°C. Phase equilibria in various foid syenites indicate that silica activities decrease from 0·6-0·3 at ~1000°C to <0·3 at ~550°C. Release of an aqueous fluid during the transition to the hydrothermal stage caused aSiO2 to drop to very low values, which results from reduced SiO2 solubilities in aqueous fluids compared with silicate melts. During the hydrothermal stage, high water activities stabilized zeolite-group minerals. Fluid inclusions record a complex post-magmatic history, which includes trapping of an aqueous fluid that unmixed from the restitic foid syenitic magma. Cogenetic aqueous and carbonic fluid inclusions reflect heterogeneous trapping of coexisting immiscible external fluids in the latest evolutionary stage. The O and C isotope characteristics of fluid-inclusion hosted CO2 and late-stage carbonates imply that the surrounding limestones were the source of the external fluids. The mineral-rich syenitic rocks at Mont Saint-Hilaire evolved as follows: first, alkalis, high field strength and large ion lithophile elements were pre-enriched in the (late) magmatic and subsequent hydrothermal stages; second, percolation of external fluids in equilibrium with the carbonate host-rocks and mixing processes with internal fluids as well as fluid-rock interaction governed dissolution of pre-existing minerals, element transport and precipitation of mineral assemblages determined by locally variable parameters. It is this hydrothermal interplay between internal and external fluids that is responsible for the mineral wealth found at Mont Saint-Hilair

Nanoscale Chemical Imaging by Photo-Induced Force Microscopy: Technical Aspects and Application to the Geosciences

Photo-induced force microscopy (PiFM) is a new-frontier technique that combines the advantages of atomic force microscopy with infrared spectroscopy and allows for the simultaneous acquisition of 3D topographic data with molecular chemical information at high spatial (~ 5 nm) and spectral (~ 1 cm−1) resolution at the nanoscale. This non-destructive technique is time efficient as it requires only conventional mirror-polishing and has fast mapping rates on the order of a few minutes that allow the study of dynamic processes via time series. Here, we review the method’s historical development, working principle, data acquisition, and evaluation, and provide a comparison with traditional geochemical methods. We review PiFM studies in the areas of materials science, chemistry and biology. In addition, we provide the first applications for geochemical samples including the visualization of faint growth zonation in zircons, the identification of fluid speciation in high-pressure experimental samples, and of nanoscale organic phases in biominerals. We demonstrate that PiFM analysis is a time- and cost-efficient technique combining high-resolution surface imaging with molecular chemical information at the nanoscale and, thus, complements and expands traditional geochemical methods.LMO is grateful for financial support through a Beate Mocek Prize awarded by the German Mineralogical Society. This study was supported by the Australian Research Council (DEJ: DP160102081, EB: FT110100685, SFF and MWF: FL180100134) and Macquarie University (MWF: MQRF0001074-2020). We thank both anonymous reviewers and handling editor Dr. Thomas Meisel for improving the final version of this review with their expert comments

Cold plumes trigger contamination of oceanic mantle wedges with continental crust-derived sediments: Evidence from chromitite zircon grains of eastern Cuban ophiolites

The origin of zircon grains, and other exotic minerals of typical crustal origin, in mantle-hosted ophiolitic chromitites are hotly debated. We report a population of zircon grains with ages ranging from Cretaceous (99 Ma) to Neoarchean (2750 Ma), separated from massive chromitite bodies hosted in the mantle section of the supra-subduction (SSZ)-type Mayarí-Baracoa Ophiolitic Belt in eastern Cuba. Most analyzed zircon grains (n = 20, 287 ± 3 Ma to 2750 ± 60 Ma) are older than the early Cretaceous age of the ophiolite body, show negative εHf(t) (−26 to −0.6) and occasional inclusions of quartz, K-feldspar, biotite, and apatite that indicate derivation from a granitic continental crust. In contrast, 5 mainly rounded zircon grains (297 ± 5 Ma to 2126 ± 27 Ma) show positive εHf(t) (+0.7 to +13.5) and occasional apatite inclusions, suggesting their possible crystallization from melts derived from juvenile (mantle) sources. Interestingly, younger zircon grains are mainly euhedral to subhedral crystals, whereas older zircon grains are predominantly rounded grains. A comparison of the ages and Hf isotopic compositions of the zircon grains with those of nearby exposed crustal terranes suggest that chromitite zircon grains are similar to those reported from terranes of Mexico and northern South America. Hence, chromitite zircon grains are interpreted as sedimentary-derived xenocrystic grains that were delivered into the mantle wedge beneath the Greater Antilles intra-oceanic volcanic arc by metasomatic fluids/melts during subduction processes. Thus, continental crust recycling by subduction could explain all populations of old xenocrystic zircon in Cretaceous mantle-hosted chromitites from eastern Cuba ophiolite. We integrate the results of this study with petrological-thermomechanical modeling and existing geodynamic models to propose that ancient zircon xenocrysts, with a wide spectrum of ages and Hf isotopic compositions, can be transferred to the mantle wedge above subducting slabs by cold plumes

MPI-Ding reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented