Content:

GMPV – Geochemistry, Mineralogy, Petrology & Volcanology

GMPV1.1 – Advances in nano- to micro-analytical tools to understand Earth processes

EGU21-14614 | vPICO presentations | GMPV1.1 | Highlight

Grain boundary character information via individual imaging or statistical analyses: complexion transitions and grain boundary segregation

Katharina Marquardt, David Dobson, Simon Hunt, and Ulrich Faul

Grain boundaries affect bulk properties of polycrystalline materials, such as electrical conductivity, melting or bulk viscosity. In the past two decades, observations of marked bulk material property changes have been associated with changes in the structure and composition of grain boundaries. This led to the term “grain boundary complexions” to mark the phase-like behaviour of grain boundaries while differing from phases in the sense of Gibbs (Cantwell 2014).

Here we introduce the principles of grain boundary structure to property relations and potent methods to study these. The focus is on the combination of structural, chemical and statistical analysis as obtainable using transmission electron microscopy and electron backscatter diffraction. Data from these complementary methods will be discussed on two systems; garnet and olivine polycrystals.

Past elasticity measurements showed that the Youngs modulus of garnet polycrystals changes as a function of sintering pressure (Hunt et al. 2016). Here we used high resolution transmission electron microscopy to study the structure of grain boundaries from polycrystals synthesized at low (4-8 GPa) and high (8-15) GPa sintering pressure. The HRTEM data were acquired using an image-corrected JEOL ARM 300 to achieve the highest resolution at low electron doses using a OneView camera. Our data indicate a grain boundary structural change occurs from “low-pressure” to “high pressure” grain boundaries, where the grain boundary facets change from >100 nm – 20 nm to 3-7 nm length scale, respectively. We conclude that sintering pressure affects grain-boundary strength and we will evaluate how this may influence anelastic energy loss of seismic waves through elastic or diffusional accommodation of grain-boundary sliding.

Polycrystalline olivine samples show different viscosity related to grain boundary segregation of impurities. To investigate if the distribution of grain boundaries is affected by grain boundary chemistry, we analysed grain orientation data from over 4x104 grains, corresponding to more than 6000 mm grain boundary length per sample. Using stereology, we extract the geometry of the interfacial network. The thus obtained grain boundary character distribution (GBCD) is discussed in relation to bulk viscosity.

How to cite: Marquardt, K., Dobson, D., Hunt, S., and Faul, U.: Grain boundary character information via individual imaging or statistical analyses: complexion transitions and grain boundary segregation, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-14614, https://doi.org/10.5194/egusphere-egu21-14614, 2021.

EGU21-6581 | vPICO presentations | GMPV1.1 | Highlight

Atom probe as a tool for understanding mineral physics and rock deformation: a case study of deformed wehrlite

Joseph Cukjati, Reid Cooper, Stephen Parman, Ningli Zhao, Austin Akey, and Fernando Laiginhas

Here we report Atom Probe Tomography (APT) analyses of grain and phase boundaries of laboratory-deformed, fine-grained mixtures of clinopyroxene and olivine (Zhao, et al., 2019).  The experiments show that the mixtures deform much more rapidly than either mineral endmember.  This enhanced deformation in the two-phase material is due to stress-driven reactions at the phase boundaries. Lower effective viscosities of phase mixtures may be critical to the initiation of plate tectonics and the formation of mantle shear zones.

The hypothesis presented here is that the ‘bulk rock’ – a wehrlite – deforms rapidly because conversion of one phase to the other occurs at phase boundaries (e.g., Sundberg & Cooper, 2008).  In this model, grain-scale transport of the shared (slowly-diffusing) mineralogical component Si4+ is not required.  The near-boundary gradients of olivine-insoluble ions are presented as evidence of the phase transformation which either dissolves olivine into clinopyroxene or vice versa.  

The resolving power of the APT makes it a promising tool for investigating the microphysics of rock deformation, bridging the atomic scale all the way to the plate-tectonic scale.

References:
Sundberg M, Cooper RF (2008) Crystallographic preferred orientation produced by diffusional creep of harzburgite: effects of chemical interactions among phases during plastic flow. J Geophys Res Solid Earth 113(12):B12208.
Zhao N, Hirth G, Cooper RF, Kruckenberg SC, Cukjati J (2019) Low viscosity of mantle rocks linked to phase boundary sliding. Earth Planet Sci Lett 517:83–94.

How to cite: Cukjati, J., Cooper, R., Parman, S., Zhao, N., Akey, A., and Laiginhas, F.: Atom probe as a tool for understanding mineral physics and rock deformation: a case study of deformed wehrlite, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-6581, https://doi.org/10.5194/egusphere-egu21-6581, 2021.

EGU21-2432 | vPICO presentations | GMPV1.1 | Highlight

Atomic scale structure of a plagioclase – magnetite interface

Ge Bian, Olga Ageeva, Gerlinde Habler, Vladimir Roddatis, and Rainer Abart

Magnetite (Mt) is the foremost carrier of rock natural remanent magnetization (NRM). Needle- and lath shaped Mt micro-inclusions in plagioclase (Pl) from gabbro often have systematic crystallographic- and shape orientation relationships (CORs, SORs) with the Pl host. The SORs of Mt leads to magnetic anisotropy which may bias the NRM of the Mt-Pl inclusion-host assemblage. Thus, the origin of the CORs and SORs between Mt and Pl is important for paleomagnetic reconstructions. In this context, the atomic structures of Mt-Pl interfaces are of particular interest.

The CORs and SORs between Mt and Pl were reported earlier and the underlying systematics was revealed from correlated optical and scanning electron microscopy (SEM) including electron back scattered diffraction (EBSD) analyses [1] (and references therein). The so-called plane normal type Mt micro-inclusions extend parallel to the Mt<111> direction, which is perpendicular to the densely packed Mt{222} oxygen layers that are parallel to one of seven Pl lattice planes with nearly identical d-spacings, namely Pl(112), Pl(-312), Pl(1-50), Pl(150), Pl(100), Pl(31-2) and Pl(1-12). Direct imaging of Mt-Pl interfaces has rarely been reported due to the beam sensitivity of Pl. Here we present the microscopic structure of a Mt-Pl interface along the inclusion elongation direction using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and integrated differential phase contrast STEM (iDPC-STEM) techniques.

The TEM foil was prepared using a focused Ga-ion beam (Ga-FIB) from a lath-shaped Mt micro-inclusion of 23 μm x 17 μm x 0.1 μm extending perpendicular to Mt{111}/Pl(-312). The foil is oriented so that the Mt<111>/Pl(-312)-pole are parallel and Mt{110}/Pl(150) planes are perpendicular to the foil.

The STEM images show that the Mt-Pl interface is perfectly straight and parallel to Mt{110}/Pl(150) and that it is devoid of steps. Electron diffraction patterns confirm that the elongation direction of the micro-inclusions is determined by the good fit of oxygen layers across the Pl-Mt interface. A 2.4% difference in the d-spacings between Pl(-312) and Mt{222} is likely accommodated by every about 42'nd Mt{222} plane forming an edge dislocation at the Mt-Pl interface. In addition, elastic strain is indicated by a deviation of d111/d110 of Mt from the strain free reference lattice. Moreover, lattice fringes in iDPC-STEM images reveal coherence between Pl(22-1) and Mt{111} planes without misfit dislocations. This additional coherence may explain the particularly strong alignment of Mt{111} and Pl(-312) reflected by the EBSD data.

In summary, the elongation directions of the Mt inclusions are determined by the alignment of important oxygen layers of both phases across the Mt-Pl interface, which is parallel to oxygen-rich lattice planes in both phases. Misfit dislocations are presumably introduced to compensate the 2.4% lattice misfit along the elongation direction. The well-organized interface structure ensures a low interfacial energy and is a viable explanation for the observed Mt-Pl CORs and SORs.  

Acknowledgement

Funding by FWF project I 3998-N29 and RFBR project 18-55-14003 is acknowledged.

Reference

[1] Ageeva et al (2020) Contrib. Mineral. Petrol. 175(10), 1-16.

How to cite: Bian, G., Ageeva, O., Habler, G., Roddatis, V., and Abart, R.: Atomic scale structure of a plagioclase – magnetite interface, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-2432, https://doi.org/10.5194/egusphere-egu21-2432, 2021.

EGU21-124 | vPICO presentations | GMPV1.1

TEM and LA-ICP-MS constraints on fluid-induced alteration of a zircon-xenotime intergrowth in pegmatite from Piława Górna (the Góry Sowie Block, SW Poland)

Fabian Tramm, Richard Wirth, Bartosz Budzyń, Jiří Sláma, Anja Schreiber, and Łukasz Birski

An intergrowth of zircon and xenotime, formed at ca. 2.09 Ga, was significantly altered after incorporation as a restite into pegmatite at ca. 370 Ma (Piława Górna, Góry Sowie Block, SW Poland; Budzyń et al., 2018). Alteration involved fluid-induced coupled dissolution-reprecipitation processes, which resulted in compositional alteration and development of patchy zoning and porosity in the xenotime and the rim of zircon. Diffusion-reaction processes affected the metamict core of zircon and resulted in nano- to microscale patchy zoning and submicron-scale porosity. This study evaluates the alteration processes with respect to structural and compositional characteristics by using TEM and LA-ICPMS trace element analysis.

Nanoscale observations revealed nanoporosity in the metamict core of zircon and a continuation of patchy zoning on a submicron level, which resulted from heterogeneous metamictization correlating with variation in U and Th contents. The altered xenotime and the zircon rim are dominated by microporosity filled with a variety of secondary phases such as U, Th, Pb and Fe rich oxides and silicates. In rare cases, secondary PbS formed nano inclusions in zircon, occasionally surrounded by amorphous apatite. Aside of known substitution mechanisms in xenotime, such as thorite and cheralite components, a correlation of Zr with LREE and Si contents indicates substitution of the zircon component. Furthermore, the zircon-xenotime interface revealed dissolution pits, filled with secondary zircon that formed at the expense of primary xenotime via coupled dissolution-reprecipitation reactions. This indicates local penetration of the fluid-mineral reaction front into xenotime. Major (Si, Zr and P) and trace elements, including U, Th and Pb, which are geochronologically relevant, have been mobilized in the metamict core of zircon due to alteration induced by an alkali-rich fluid with high activities of F, Na and Ca. The altered xenotime and porous rim of zircon were affected by alteration induced by a fluid containing Fe, which resulted in precipitation of Fe-rich phases, such as Fe-oxides and silicates often accompanied by relevant contents of Pb. In conclusion, nanoscale structural observations and LA-ICP-MS trace element data support the complex geochronological implications of the altered zircon-xenotime intergrowth, emphasising the necessity of understanding alteration processes of zircon and xenotime taking into account element transport and thus the disturbance of their geochronological clock.

Acknowledgements: This work was supported by the National Science Centre grant no. 2017/27/B/ST10/00813.

References:

BudzyńB., Sláma J., Kozub-Budzyń G.A., Konečný P., HolickýI., RzepaG.,Jastrzębski M. (2018) Lithos 310-311, 65-85.

How to cite: Tramm, F., Wirth, R., Budzyń, B., Sláma, J., Schreiber, A., and Birski, Ł.: TEM and LA-ICP-MS constraints on fluid-induced alteration of a zircon-xenotime intergrowth in pegmatite from Piława Górna (the Góry Sowie Block, SW Poland), EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-124, https://doi.org/10.5194/egusphere-egu21-124, 2021.

EGU21-9404 | vPICO presentations | GMPV1.1

Trace-element migration during crystal-plastic deformation in UHP rutile: dislocations in low-angle boundaries as high-diffusivity pathways.

Rick Verberne, Hugo van Schrojenstein Lantman, Steven Reddy, Matteo Alvaro, David Wallis, Denis Fougerouse, Antonio Langone, Marco Scambelluri, David Saxey, and William Rickard

The trace-element composition of rutile is commonly used to constrain P-T-t conditions for a wide range of metamorphic systems. Recent studies have highlighted the importance of micro- and nanostructures in the redistribution of trace elements in rutile via high-diffusivity pathways and dislocation-impurity associations. In this contribution, we investigate the effect of crystal-plastic deformation of rutile on its composition by combining microstructural and petrological analyses with atom probe tomography. The studied sample is from an omphacite vein of the ultrahigh-pressure metamorphic Lago di Cignana unit, Western Alps, Italy. Zr-in-rutile thermometry and inclusions of quartz in rutile and of coesite in omphacite constrain rutile deformation to around the prograde HP-UHP boundary at 500–550 °C. Crystal-plastic deformation of a large rutile grain resulted in low-angle boundaries that generate a total misorientation of ~25°. Dislocations constituting the low-angle boundary are enriched in common (Fe, Zr) and uncommon trace elements (Ca). The Ca is interpreted to be derived from the grain exterior, suggesting diffusion of trace elements along the dislocation cores. The potential for dislocation microstructures to act as fast diffusion pathways must be evaluated when applying traditional geochemical analyses as compositional disturbances caused by the presence of dislocation might lead to erroneous interpretations.

How to cite: Verberne, R., van Schrojenstein Lantman, H., Reddy, S., Alvaro, M., Wallis, D., Fougerouse, D., Langone, A., Scambelluri, M., Saxey, D., and Rickard, W.: Trace-element migration during crystal-plastic deformation in UHP rutile: dislocations in low-angle boundaries as high-diffusivity pathways., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-9404, https://doi.org/10.5194/egusphere-egu21-9404, 2021.

EGU21-3100 | vPICO presentations | GMPV1.1

Zircon recrystallisation microstructures andthe implications for U-Pb dating

Jasper Huijsmans, Maartje Hamers, Martyn Drury, and Jim Lee

Uranium-lead dating of zircon has been used extensively in geochronological studies based on the widespread occurrence of zircon and its resistance to chemical and physical weathering. Previous research has shown that despite their apparent robustness, many zircons contain evidence for recrystallisation, such as the replacement of the primary oscillatory zoning by unzoned zircon. This replacement is characterised by rims, patches and embayments of unzoned zircon which can either completely replace the primary zoning or preserve faint remnants within the unzoned zircon.  In some samples, the unzoned zircon contains lower U and Pb concentrations, implying that the zircon U-Pb age may be reset during the replacement (Pidgeon, 1992). Interestingly, zircons have also been found in which there is no apparent difference in U-Pb age between the zoned and unzoned zircon (Schaltegger et al., 1999). To better understand the replacement of zoned by unzoned zircon, it is important to study the microstructures present within recrystallised zircon to understand possible mechanisms causing recrystallisation. Multiple mechanisms may explain the trace element distribution within (partially) recrystallised zircon: annealing of radiation damaged (metamict) zircon, annealing of lattice strain imposed by alternating U concentrations in oscillatory zoning, enhanced diffusion along fast-diffusivity pathways (such as low-angle subgrain boundaries or fractures) and coupled dissolution-reprecipitation.  The mechanism(s) by which zircons recrystallise remain poorly understood, as well as the effect of the formation of different microstructures on corresponding zircon U-Pb dates. Understanding these phenomena is therefore of vital importance for correctly interpreting U-Pb ages in zircon.

This work focusses on investigating the microstructures that are present within recrystallised zircons from both metamorphic and igneous environments from the Jack Hills, Australia (Pidgeon, 1992) and the island of Lewis and Harris, Scotland (Van  Breemen  et  al.   1971). Suites of zircons from these areas have been imaged with cathodoluminescence, which is a powerful tool for obtaining high resolution images of the internal structures of zircons. Within these suites, zircons are present which show complex zoning patterns and (partial) recrystallisation; these will be studied in greater detail using EDS, EBSD and SHRIMP. Preliminary results of EDS on the inclusions show that inclusions are composed of feldspars, thorite, quartz and apatite, which were most likely included during the primary crystallisation of the zircon. EBSD measurements will provide additional data on the crystallographic orientation of recrystallized zones and the state of metamictization of the zircons, and may show if zircon has deformed crystal-plastically forming subgrain boundaries.

 

References

Pidgeon, R. T. (1992). Recrystallisation of oscillatory zoned zircon: some geochronological and petrological implications. Contributions to Mineralogy and Petrology, 110(4), 463-472.

Schaltegger, U., Fanning, C. M., Günther, D., Maurin, J. C., Schulmann, K., & Gebauer, D. (1999). Growth, annealing and recrystallization of zircon and preservation of monazite in high-grade metamorphism: conventional and in-situ U-Pb isotope, cathodoluminescence and microchemical evidence. Contributions to Mineralogy and Petrology, 134(2-3), 186-201.

Van Breemen, O., Aftalion, M., & Pidgeon, R. (1971). The age of the granitic injection complex of harris,outer hebrides.Scottish Journal of Geology,7(2), 139–152.

How to cite: Huijsmans, J., Hamers, M., Drury, M., and Lee, J.: Zircon recrystallisation microstructures andthe implications for U-Pb dating, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-3100, https://doi.org/10.5194/egusphere-egu21-3100, 2021.

EGU21-7327 | vPICO presentations | GMPV1.1

Insights into chemical mobility in titanite driven by low-temperature crystal-plastic deformation

Nicholas Udy and Michael Stearns

The U-Pb system in titanite has been shown to be reset during a variety of high-temperature processes including high-temperature deformation, but post-deformation modification and recovery of crystal-lattice strain have so far made U-Pb equilibration mechanism from deformed titanites equivocal. Microstructures, including mechanical twinning and subgrain rotation recrystallization are more likely to be preserved at low-temperatures, but the systematics of chemical equilibration have not been established for these conditions. This study identifies progressive crystallographic misorientation and deformation twins in titanite porphyroclasts from the Wasatch Fault Zone, Utah, USA. The microstructures, mapped using electron backscatter diffraction (EBSD), developed at ~11 km depth during 300–400 ºC crystal-plastic deformation within the ductile fault zone. These microstructural maps were used to guide laser ablation-split stream ICP-MS analysis: U-Pb isotopes measured in tandem with major and trace element contents. Despite the low temperature, U-Pb and trace element contents in titanite equilibrated, at least partially, during deformation. Both major and trace elements in titanite also likely partitioned with a fluid and in response to the (re)crystallization of other mineral phases in the fault zone. Chemical zoning and crystal lattice recovery suggestive of fluid-aided recrystallization are absent, and the main mechanism for this resetting may instead be an enhancement of element mobility along microstructure dislocations. These processes are interpreted to record complex open-system behavior of titanite caused by crystal-plastic deformation during the initiation of the WFZ. This presentation will summarize the comparative analysis of microstructure by EBSD and titanite chemistry by LASS-ICP-MS, and how it bears on the understanding of elemental mobility in titanite during low-temperature crystal-plastic deformation.

How to cite: Udy, N. and Stearns, M.: Insights into chemical mobility in titanite driven by low-temperature crystal-plastic deformation, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-7327, https://doi.org/10.5194/egusphere-egu21-7327, 2021.

EGU21-10775 | vPICO presentations | GMPV1.1

Meyer-Neldel Rule on thermal stability parameters (trap depth and frequency factor) of luminescence signals in quartz

Zuzanna Kabacińska, Alida Timar-Gabor, and Benny Guralnik

Thermally activated processes can be described mathematically by the Arrhenius equation. The Meyer-Neldel Rule (MNR), or compensation law, linearly relates the pre-exponent term to the logarithm of the excitation enthalpy for processes that are thermally driven in an Arrhenian manner. This empirical rule was observed in many areas of materials science, in physics, chemistry, and biology. In geosciences it was found to uphold in hydrogen diffusion (Jones 2014a) and proton conduction (Jones 2014b) in minerals.

Trapped charge dating methods that use electron spin resonance (ESR) or optically or thermally stimulated luminescence (OSL and TL) are based on the dose-dependent accumulation of defects in minerals such as quartz and feldspar. The thermal stability of these defects in the age range investigated is a major prerequisite for accurate dating, while the accurate determination of the values of the trap depths and frequency factors play a major role in thermochronometry applications. 

The correlation of kinetic parameters for diffusion has been very recently established for irradiated oxides (Kotomin et al. 2018). A correlation between the activation energy and the frequency factor that satisfied the Meyer–Neldel rule was reported when the thermal stability of [AlO4/h+]0 and [TiO4/M+]0 ESR signals in quartz was studied as function of dose (Benzid and Timar-Gabor 2020). Here we compiled the optically stimulated luminescence (OSL) data published so far in this regard, and investigated experimentally the thermal stability of OSL signals for doses ranging from 10 to 10000 Gy in sedimentary quartz samples. We report a linear relationship between the natural logarithm of the preexponent term (the frequency factor) and the activation energy E, corresponding to a Meyer-Neldel energy of 45 meV, and a deviation from first order kinetics in the high dose range accompanied by an apparent decrease in thermal stability. The implications of these observations and the atomic and physical mechanisms are currently studied.

 

References

Benzid, K., Timar Gabor, A. 2020. The compensation effect (Meyer–Neldel rule) on [AlO4/h+]0 and [TiO4/M+]0 paramagnetic centers in irradiated sedimentary quartz. AIP Advances 10, 075114.

Kotomin, E., Kuzovkov, V., Popov, A. I., Maier, J., and Vila, R. 2018. Anomalous kinetics of diffusion-controlled defect annealing in irradiated ionic solids. J. Phys. Chem. A 122(1), 28–32

Jones, A. G. (2014a), Compensation of the Meyer-Neldel Compensation Law for H diffusion in minerals, Geochem. Geophys. Geosyst., 15, 2616–2631

Jones, A. G. (2014b), Reconciling different equations for proton conduction using the Meyer-Neldel compensation rule, Geochem. Geophys. Geosyst., 15, 337–349

How to cite: Kabacińska, Z., Timar-Gabor, A., and Guralnik, B.: Meyer-Neldel Rule on thermal stability parameters (trap depth and frequency factor) of luminescence signals in quartz, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10775, https://doi.org/10.5194/egusphere-egu21-10775, 2021.

Inclusions in garnets from the river Lešnica alluvion (Cer mountain area, Serbia),  were investigated in an effort to study their distribution within the garnet host and to estimate the mechanism of their origin. Garnets are often occurring in the Lešnica alluvion in a form of loosely separated crystals with preserved crystalline forms and as mildly rounded broken grains [1]. Their mineralogical determination was previously published by Milošević et al, [1]. Crystals, that have been extracted and separated from the sandy fraction, have exhibited the presence of various types of inclusions in their structure. Single and multiphase inclusions in the garnets were examined optically by petrographic methods followed by SEM-EDS method, applied for the chemical analyses of the individual inclusion, and LA-ICP-MS applied to determine distribution and content of trace elements in the host garnet.

Results from SEM-EDS method show that garnets are of the spessartine-almandine type with the incorporation of irregular inclusions determined as rare earth elements (REE) minerals (monazite, xenotime, columbite-tantalite) and accessory minerals that usually incorporate REE (titanite, apatite, and zircon) together with uranium oxide minerals. Other single-phase inclusions are often quartz and rutile. Size of inclusion varieties from grain to grain, between 5 and 40 µm, while their distribution doesn’t follow any pattern, random distribution. It has been noted that zircon and uranium oxide minerals are often found coupled and as multiphase inclusions while monazite, xenotime and columbite-tantalite minerals are observed as separate, single, inclusions. Chondrite normalized REE in the host garnets plotted on spider diagram show extreme depletions of large ion lithophile elements (LILE) and enrichment in high field strength elements (HFSE), with negative Ce, Nd and Eu anomaly. Single-phase and multiphase inclusions that are occurring in the same garnet host with a random distribution are suggesting different genetic relations.

[1] Milošević M., Kostić B., Vulić P., Jelić I. 2019. Garnets from river Lešnica alluvion, mountain Cer. II Kongres Geologa Bosne i Hercegovine sa medjunarodnim učešćem, Pp. 306-311

How to cite: Milošević, M. and Kostić, B.: Single and multi-phase inclusions in garnets from the Lešnica alluvion in the Internal Dinarides, Serbia, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-2423, https://doi.org/10.5194/egusphere-egu21-2423, 2021.

The proliferation of modern techniques available for petrologists has resulted in an explosion of detailed information on mineral compositions and processes over the last decade. One area of research that is undergoing dramatic advances is the non-destructive interrogation of samples in three dimensions through X-ray microscopy (XRM). Techniques such as ZEISS Versa and Ultra XRM can be performed at a variety of scales and resolutions, resulting in micro-to-nano scale information on geological samples. Such techniques can be correlated with each other i.e. expanding nanoscale resolution to a large sample or internal calibration of X-ray intensity to identify mineral assemblages, or even correlation with other techniques such as electron microscopy (EM). X-ray techniques are also particularly adaptable to digital resolution enhancements through software processes such as machine learning algorithms.

Collecting 3D information for petrological investigations can often require ground truthing of mineralogical and compositional interpretations. The more developed the 3D microscopy becomes, the more we are increasingly interested in features that are deeply buried within our samples. This means the corresponding techniques for excavating a region of interest also need to advance in both speed and accuracy.

The ZEISS Crossbeam-Laser (XBL) system provides a unique capability of rapidly excavating to a point of interest within a 3D sample volume. The XBL is already seeing use in material sciences, with a standard XB chamber with focussed Ion Beam (FIB) and Electron Microscopy (EM), and a correlated femtosecond laser chamber for rapid material removal. Sample data collected through XRM can be correlated to the XBL stage so that any internal features located by XRM have their coordinates automatically available in three dimensions. The femtosecond laser can excavate to a region of interest (RoI) within the sample within seconds or minutes, dramatically reducing preparation time compared to standard FIB/PFIB. The laser cut surface can be used for analysis techniques such as energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD), even prior to final polishing with the focussed ion beam (FIB).

Here we show the XRM-XBL workflow in high grade metamorphic rocks for identifying minerals in context for geochronology and micro-to-nano scale textures.

How to cite: Taylor, R.: Advances in 3D characterisation for correlative microscopy in geosciences, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-9597, https://doi.org/10.5194/egusphere-egu21-9597, 2021.

Geochemical, petrographic, and spectroscopic indices that vary with compositional changes in petroliferous organic matter (OM) during thermal maturation are key petroleum system parameters used to understand petroleum generation. In unconventional shale source-rock reservoirs, where multiple, highly dispersed OM types may be present in intimate contact with surrounding mineral phases, OM molecular composition (e.g., aromaticity) is especially useful for informing structure-reactivity relationships representative of different OM types. Here, we employ microscale, in situ, and correlative Raman and reflectance approaches to evaluate aromaticity evolution for a suite of OM types (i.e., liptinite, micrinite, solid bitumen, vitrinite, and inertinite) at the single particle level across an artificial thermal gradient. Our samples include a marginally mature (vitrinite reflectance ~0.5%) Late Cretaceous Boquillas Shale from south Texas, United States, and two hydrous pyrolysis (HP) residues following reaction of the raw Boquillas Shale sample at 300°C and 330°C for 72 hours. Our data indicate that: (i) liptinite, micrinite, solid bitumen, vitrinite, and inertinite particles exhibit different aromatic signatures in the raw shale sample and (ii) these OM types, with the exception of inertinite, effectively experience similar changes in aromatic structure with thermal advance. Data also reinforce the concept that reservoir temperature may be a secondary factor in controlling the molecular composition of inertinite. These findings inform a broader understanding of how different petroliferous OM types evolve throughout thermal reactions and further demonstrate that correlative Raman spectroscopy and reflection analyses, combined with careful organic petrography, can provide complimentary estimates of OM molecular composition and thermal maturity.

How to cite: Jubb, A., Birdwell, J., and Hackley, P.: Evaluating aromaticity changes with thermal stress at the single particle level for a suite of organic matter types from the Boquillas Shale (Texas, United States) via correlative Raman and reflection analyses, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-259, https://doi.org/10.5194/egusphere-egu21-259, 2021.

EGU21-1528 | vPICO presentations | GMPV1.1

A Raman spectroscopic study of the natural carbonophosphates Na3MCO3PO4 (M = Mn, Fe, and Mg)

Ekaterina Fomina, Evgeniy Kozlov, Mikhail Sidorov, and Vladimir Bocharov

Along with some other Na-minerals, carbonophosphates indicate a high initial Na activity in carbonatite and kimberlite melts, which is beneficial for petrological reconstructions. Because carbonophosphates are capable of incorporating large-ion lithophile and rare earth elements (REEs) in their structure, they can participate in the transport of these elements. Moreover, due to the presence of both [PO4]3− and [CO3]2− groups in carbonophosphates, these mineral phases play an important role in the Earth's global carbon and phosphate cycles. With all these properties, carbonophosphates have long attracted the attention of geologists. Raman spectroscopy appears to be one of the most suitable tools for their diagnosis, since they commonly present in rocks as small inclusions in other mineral grains. Despite this profit, only a few publications contain Raman characteristics of either natural or synthetic carbonophosphates.

We studied and compared Raman spectra of three natural carbonophosphate phases (sidorenkite, bonshtedtite, and bradleyite) with the general formula Na3MCO3PO4 (M = Mn, Fe, and Mg, correspondingly). These spectra showed from 21 to 24 vibrational bands, of which the two most intense (963±5 cm-1 и 1074±3 cm-1) correspond to the ν1(P–O) and ν1(C–O) modes. These two bands split due to the occurrence of isomorphic impurities. It was found that the crystallographic orientation of the sample influences the intensity of most bands. A natural increase in the Raman shift was observed for most bands assigned to the same vibrations (the smallest shift in the spectrum is characteristic of sidorenkite, an intermediate - of bonshtedtite, and the largest - of bradleyite).

We propose the following algorithm for the diagnosis of carbonophosphates:

  • Checking minerals for belonging to the group of carbonophosphates by the main bands and the characteristic profile of the spectrum;
  • Testing the hypothesis that the mineral of question is bradleyite based on the analysis of the estimated shift of the main bands;
  • Diagnosis of a mineral species by peaks located between the main bands;
  • Validation of the diagnostics by considering the position of the bands at 185±9 cm-1, 208±7 cm-1, 255±5 cm-1, and 725±6 cm-1.

The proposed algorithm allows one to perform Raman diagnostics of carbonophosphates in inclusions even in the absence of EPMA data. In the study of carbonatites, kimberlites, and other rocks, the diagnostics of the mineral species of the carbonophosphate group can be important in the petrological aspect.

This research was funded by the Russian Science Foundation, grant number 19-77-10039.

How to cite: Fomina, E., Kozlov, E., Sidorov, M., and Bocharov, V.: A Raman spectroscopic study of the natural carbonophosphates Na3MCO3PO4 (M = Mn, Fe, and Mg), EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-1528, https://doi.org/10.5194/egusphere-egu21-1528, 2021.

EGU21-2626 | vPICO presentations | GMPV1.1 | Highlight

The Potential Applications of Raman Spectroscopy in Unravelling Complex Palaeowildfire Ecosystems

Thomas Theurer, David Muirhead, David Jolley, and Dmitri Mauquoy

Raman spectroscopy represents a novel methodology of characterising plant-fire interactions through geological history, with enormous potential. Applications of Raman spectroscopy to charcoal have shown that this is an effective method of understanding intensity changes across palaeofire regimes. Such analyses have relied on the determination of appropriate Raman parameters, given their relationship with temperature of formation and microstructural changes in reference charcoals. Quantitative assessments of charcoal microstructure have also been successfully applied to the assessment of carbonaceous maturation under alternate thermal regimes, such as pyroclastic volcanism. Palaeowildfire systems in association with volcanism may present a complex history of thermal maturation, given interactions between detrital charcoals and volcanogenic deposition. However, whilst palaeofire and volcanic maturation of carbonaceous material are well understood individually, their interaction has yet to be characterised. Here we present the first analysis of palaeofire charcoals derived from volcanic ignition utilising Raman spectroscopy. Our results indicate that complex interactions between volcanism and palaeofire systems may be better understood by the characterisation of charcoal microstructure, alongside palaeobotanical and ecosystem studies. Understanding the unique relationship between wildfires and volcanism, and the impact that this has on the fossil record, may better assist our understanding of wildfire systems in deep history. Further still, this highlights the potential for better understanding the socioecological impacts of modern and future wildfire systems closely associated with volcanic centres. 

How to cite: Theurer, T., Muirhead, D., Jolley, D., and Mauquoy, D.: The Potential Applications of Raman Spectroscopy in Unravelling Complex Palaeowildfire Ecosystems, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-2626, https://doi.org/10.5194/egusphere-egu21-2626, 2021.

Over the last two decades, Raman microspectroscopy has known a spectacular development in various research fields of petrology opening new avenues for studies in sedimentology, metamorphism or magmatism and cosmochemistry. This has been made possible thanks to major technological improvements (e.g., Raman hyperspectral mapping) and a better theoretical approach (e.g., data processing and interpretation). Raman spectra are actually sensitive to even minor (chemical or structural) perturbations within chemical bonds in (even amorphous) solids, liquids, and gases. They can, thus, help identify, characterize, and differentiate between individual minerals, fluid inclusions, glasses, carbonaceous materials, solid solution phases, strain in minerals, and dissolved species in multi-component solutions. Such sensitivity and versatility make Raman a unique tool for petrology. Yet, it relies on a weak and subtle signal and a cautious approach is required to avoid pitfalls during the analysis and/or the interpretation of data. Some recent scientific milestones will be presented and discussed in various fields like geothermobarometry of metamorphic rocks, geochemistry of meteorites, speciation of deep fluids involved in fluid-rock interactions or the characterization of organic/mineral assemblages of astrobiological interest. For the particular c       ase of petrology, Raman microspectroscopy has the immense advantage that it requires minimal sample preparation, thus it can be performed in situ preserving the original microtexture of the sample with a rather high spatial resolution for analysis, typically 1 mm at 532 nm for modern systems. Therefore, this technique is now increasingly used to study poorly crystalline and chemically heterogeneous materials involved for instance in geochemical processes occuring at Earth surface. But it faces numerous challenges due to the reactivity of such phases making them fragile under the laser beam, or due to the quasi-systematic presence of intense backgrounds in the spectra overwhelming the Raman signal. The source of this background can be multiple as it can be observed with fine-grained samples and/or it can be generated by the presence of luminescence/fluorescence emission centers. More generally such background is not well understood although it is a major issue for Raman spectroscopy in many petrological applications. However, there too, recent technological developments, sometimes based on old ideas, offer new possibilities to investigate safely and accurately such materials : time-resolved spectroscopy and surface-enhanced Raman spectroscopy (SERS) will be presented as well as some applications for petrology of complex samples.

How to cite: Beyssac, O.: Raman spectroscopy for petrology : recent scientific milestones, technological trends and challenges, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-3416, https://doi.org/10.5194/egusphere-egu21-3416, 2021.

In recent decades increasing evidence was found for life under extreme conditions, e.g., near black smokers on the ocean floor. The synthesis and stability of vital molecules like adenosine triphosphate (ATP) and adenosine diphosphate (ADP) are essential to maintain the metabolism of all known organisms. The lifetime of these molecules in water is limited by the non-enzymatic hydrolysis reaction that becomes dominant at elevated temperatures. A better understanding of this mechanism will provide us insights of life at extreme conditions.

Previous studies determined the hydrolysis rate constants of ATP for several compositions, temperatures and pressures using quench experiments and subsequent analysis. So far, it was not tested whether quench artefacts might have affected those results. Therefore, the current study was performed to develop a method to follow the reaction in-situ with a high sampling rate at elevated temperatures. A confocal micro-Raman spectrometer and a hydrothermal diamond anvil cell were used to perform experiments at elevated temperatures and vapour pressure. Spectra were obtained in the range of 660 cm-1 to 1157 cm-1 as a function of time. Different solutions of ATP and ADP were measured at 353 K, 373 K, and 393 K, at starting pH values of 3 and 7. First findings are consistent with previous studies and show that with decreasing pH value the hydrolysis rate increases. The data indicate hydrolysis rate constants in the magnitude of 10-3 s-1 by 393 K, 10-4 s-1 by 373 K and 10-5 s-1 by 353 K. These initial observations show that this technique produces reliable kinetic data on this reaction. It also provides much better sampling statistics than quench experiments. 

The high reaction rates suggest that a mechanism exists to regulate this reaction at higher temperatures, which is necessary to allow metabolism under extreme conditions. Moreover, it is commonly known that ATP interacts with various metal ions with different effects on the reaction rate. An application of this method would be the quantification of the hydrolysis rate constant in chemically more complex systems.

How to cite: Moeller, C., Schmidt, C., Guyot, F., and Wilke, M.: A new in-situ method to determine the hydrolysis rate constant of adenosine triphosphate (ATP) by application of Raman spectroscopy in a hydrothermal diamond anvil cell, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-3419, https://doi.org/10.5194/egusphere-egu21-3419, 2021.

EGU21-7459 | vPICO presentations | GMPV1.1

An insight on the polyphase thermal history of the Ghomarides and Upper Sebtides in the Internal Rif (North Morocco) by means of Raman spectroscopy on organic matter

Andrea Schito, Achraf Atouabat, Rocco Calcagni, Sveva Corrado, David Muirhead, Claudia Romano, Alessandro Pozzi, Roberto Galimberti, and Amalia Spina

The correct assessment of maximum temperatures experienced by rocks is an essential tool to unravel the evolution of the thermal structure of the crust during the main phases of an orogenesis. Given to broad P-T stability field of classical metamorphic mineralogical indicators, maximum temperatures derived from the analyses of carbonaceous material dispersed in rocks by means of Raman spectroscopy has shown to be a suitable alternative to classical geothermometer. Initially developed for high metamorphic rocks the use of this tools has recently been extended also at lower metamorphic degree and diagenesis. This allowed us to extend the analyses of paleotemperatures experienced by rocks from Ghomarides and Sebtides from the Internal Rif in North Morocco with respect to previous works. Ghomaride and Sebtides in this portion of the Rif-Betic-Tell chain, represent respectively the upper and lower plates of a metamorphic core complex  and are composed, the first, by Paleozoic rocks with a partially preserved Mesozoic-Cenozoic cover and the second by lower Paleozoic to Triassic deep-crustal mica-schists, migmatites and granulites associated with peridotites (Beni Bousera complex).

Our data suggest that the uppermost Tiszgarine Unit of the Upper Sebtides experienced warmer condition than previously observed. Moreover, we calculate the maximum temperatures experienced by the Ghomarides  during both the Eo and Late Variscan cycles showing that differences in temperature exist among the vary units that compose the complex. Finally, in the southern area our data suggest a less severe alpine heating related to the emplacement of the Beni Bousera peridotite, than previously calculated.

How to cite: Schito, A., Atouabat, A., Calcagni, R., Corrado, S., Muirhead, D., Romano, C., Pozzi, A., Galimberti, R., and Spina, A.: An insight on the polyphase thermal history of the Ghomarides and Upper Sebtides in the Internal Rif (North Morocco) by means of Raman spectroscopy on organic matter, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-7459, https://doi.org/10.5194/egusphere-egu21-7459, 2021.

EGU21-7530 | vPICO presentations | GMPV1.1

In situ Raman spectroscopic technique for high-pressure studies of mineral and fluid inclusions formation 

Nadezda Chertkova, Anna Spivak, Egor Zakharchenko, Yuriy Litvin, Oleg Safonov, and Anastasiia Burova

Rapid development of in situ experimental techniques provides researchers with new opportunities to model geological processes, which take place deep in the Earth’s interior. Raman spectroscopy is considered a powerful analytical tool for investigation of the samples subjected to high pressures in a diamond anvil cell, since in such experiments phase assemblages can be determined in real time using measured Raman spectra.

In this study, we describe experimental methods for in situ observation and spectroscopic analysis of fluids and minerals, which constitute environment for diamond growth, at the upper mantle pressure conditions. Experiments were conducted in the externally heated, “piston-cylinder” type diamond anvil cell at pressures exceeding 6 GPa and temperatures up to 600 degree C. Phase relationships and fluid speciation were monitored during experiments to reconstruct the environment and mechanism of inclusions formation. Compared to other analytical tools, commonly used in combination with diamond anvil cell apparatus, Raman spectroscopy offers several advantages, such as short sample preparation time, non-destructive characterization of the phases observed in the sample chamber and relatively short measurement time.

This work was supported by grant No. 20-77-00079 from the Russian Science Foundation.

How to cite: Chertkova, N., Spivak, A., Zakharchenko, E., Litvin, Y., Safonov, O., and Burova, A.: In situ Raman spectroscopic technique for high-pressure studies of mineral and fluid inclusions formation , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-7530, https://doi.org/10.5194/egusphere-egu21-7530, 2021.

EGU21-7939 | vPICO presentations | GMPV1.1

Raman Spectral Trends in ‘low-temperature’ Carbonaceous Materials.

David Muirhead

Amorphous carbonaceous materials are typically those that would be considered immature, at temperatures below 300°C, in a typical sedimentary basin burial setting. Only recently has there been much discussion on the efficacy of Raman spectroscopy on amorphous carbon at temperatures below 300°C. Here we present data from a variety of published sources alongside our own data reviewing the apparent trends in amorphous carbon with some discussion related to thermal regime (intensity, duration), with case studies including intruded host rocks, fold and thrust belts and wildfires. We conclude that Raman spectroscopy can be applied successfully to ‘low-temperature’ carbonaceous material whilst noting the challenges faced to fully understand the physio-chemical mechanisms at these temperature ranges.

How to cite: Muirhead, D.: Raman Spectral Trends in ‘low-temperature’ Carbonaceous Materials., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-7939, https://doi.org/10.5194/egusphere-egu21-7939, 2021.

Carotenoid compounds such as β-carotene are some of the most prevalent organic molecules on Earth and are key biomarkers as there is no known abiogenic source. During diagenesis and thermal alteration, carbon undergoes well-documented changes in Raman spectra.

There has been little research into the transitional degradation of carotenoid spectra to where they are fully replaced by the carbon spectra as the main identifier of thermal maturity under Raman spectroscopy. This is an overlooked regime when discussing the search for life, terrestrial and extra-terrestrial, where current research (using Raman spectroscopy) either focuses on finding living organisms displaying common organic molecules, or looks for the elemental carbon evidence of extinct fossil life. The real world is not usually so polarised, so covering the transition between these modes of life detection will improve any detection analysis.

For this study the volcanic thermal spring system in Viterbo, Italy was used as a field-based laboratory. The high rate of carbonate precipitation in these thermal springs, the wide range of thermal regimes (58°C to 25°C), and the prevalence of fast-growing algae in the run-off streams, give excellent preservation of a range of organic matter states at directly measurable temperatures.

The results demonstrate how the Raman spectra of the carotenoid compounds change with hydration, death of the organism, and thermal alteration of the organic material. The relationship between the spectra of the carotenoid compound and the elemental carbon spectra in the transition zone is also shown.

This study expands on the use of Raman spectroscopy of carbon as a low-temperature geothermometer, and provides a framework for the spectral response of organic matter in an often-overlooked geological regime. It is anticipated that the fields of geothermal energy, climatology, geobiology and astrogeobiology, could all benefit from this study, incorporating this enhanced thermal alteration data into existing and future work.

How to cite: O'Donnell, A.: Searching for life in volcanic carbonate systems and the effect of temperature on organic molecules, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-9659, https://doi.org/10.5194/egusphere-egu21-9659, 2021.

Organic carbon in rocks undergoes nanostructural changes when exposed to increased temperatures or strain. These changes can be identified using Raman spectroscopy, giving information about thermal maturity and strain conditions. However, it is well documented that in a heterogeneous rock, strain can be highly localised, evident in microstructural variations such as strain shadows, sub-grain development, twinning, and the rotation and alignment of crystal axes. In this study we map microstructural textures in deformed calcite through optical microscopy and EBSD of calcite crystal axes. This textural map is compared to mapped Raman spectral parameters of organic carbon particles in the same thin section. A comparison of the maps allows assessment of the extent to which Raman spectral parameters and hence carbon nanostructure is influenced by strain at a sub-mm scale. The study highlights the sensitivity of organic carbon nanostructure to sub-mm scale changes in strain localisation within a single deformed carbonate sample.

How to cite: Kedar, L., Bond, C., and Muirhead, D.: Strain-related carbon ordering on a sub-mm scale: a comparison of carbonate microfabrics and organic carbon nanostructure within a single sample., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-9921, https://doi.org/10.5194/egusphere-egu21-9921, 2021.

EGU21-11092 | vPICO presentations | GMPV1.1

Raman Spectroscopy as a potential strain gauge

Clare Bond, Lauren Kedar, and David Muirhead

Raman Spectroscopy is increasingly being used to better understand a range of Earth Science processes. Notable recently is the application of Raman Spectroscopy to carbonaceous material in strained rocks. Here we investigate the changes in Raman Spectral response in strained material relative to an unstrained equivalent, drawing on examples from the published literature and our own work. We consider inconsistencies in the relative changes in Raman Spectral parameters of strained material and their potential causes. In doing so we look at some of the current methods for determining Raman Spectral parameters in rocks and what they might tell us about the strain state of carbon in a single rock sample. Finally, we consider the implications for use of Raman Spectroscopy of carbonaceous material as a geothermometer as well as a future potential strain gauge. 

How to cite: Bond, C., Kedar, L., and Muirhead, D.: Raman Spectroscopy as a potential strain gauge, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-11092, https://doi.org/10.5194/egusphere-egu21-11092, 2021.

GMPV4.1 – Evolution of the Earth's upper mantle: a petrological, geochemical and geodynamic perspective on lithospheric mantle xenoliths, orogenic and ophiolitic peridotites

EGU21-8450 | vPICO presentations | GMPV4.1

Depletion, metasomatism and refertilisation in the Sub-Continental Lithospheric Mantle beneath northern Victoria Land (Antarctica): a review

Massimo Coltorti, Costanza Bonadiman, Federico Casetta, Barbara Faccini, Pier Paolo Giacomoni, Beatrice Pelorosso, and Cristina Perinelli

Assessing the nature and evolution of the Sub-Continental Lithospheric Mantle (SCLM) is crucial to understand the dynamics of Earth’s interior and the global scale tectono-magmatic processes. The study of ultramafic xenoliths brought to the surface in specific context, such as northern Victoria Land (Antarctica), is a key to investigate how the SCLM bear witness of large-scale geodynamic episodes. Indeed, the Antarctica lithosphere was involved into three main tectono-magmatic episodes since Paleozoic, i.e. the 550-110 Ma Ross subduction, the Jurassic (~182 Ma) Ferrar magmatism and the Cenozoic alkaline magmatism responsible for the opening of the West Antarctic Rift System (WARS).

In this study, a review of the petrological and geochemical features of >200 mantle-derived and cumulate xenoliths brought to the surface at Baker Rocks, Greene Point, Handler Ridge, Harrow Peaks, Browning Pass and Mount Overlord enabled us to reconstruct the main depletion and enrichment processes that took place in the Antarctica SCLM. Strong depletion is recorded by Greene Point lherzolites and harzburgites (18-21%), which likely began melting in the garnet facies and terminated in the spinel facies (Perinelli et al. 2006), whereas mild melt extraction in the spinel stability field was hypothesized at Baker Rocks and Handler Ridge (12-16% and 7-13% melting, respectively). The onset of the Jurassic Ferrar large magmatic event is testified by both the refertilisation in Greene Point-Baker Rocks peridotites and the appearance of cumulate orthopyroxenites/olivine-websterites at Harrow Peaks and Baker Rocks. Late enrichment process/es took place in concomitance with the Cenozoic alkaline magmatism of the WARS, resulting in both cryptic and modal metasomatism and overprinting earlier chemical modifications. This metasomatism was particularly effective at Baker Rocks, as shown by the increase of clinopyroxene abundance, its trace element enrichment and the formation of amphibole disseminated and in veins. Clinopyroxene composition in Cenozoic cumulate rocks matches the enrichment path observed in the peridotites, supporting the link between the last metasomatic process and the recent alkaline magmatism.

Among mantle xenoliths populations, Greene Point record the highest T-P (870-1059 °C; 0.8-1.6 GPa) and the least oxidized conditions (fO2 down to -2/-3 ΔFMQ). Cumulate rocks yield the highest fO2 (up to +1.5 ΔFMQ), at T varying between 900 and 1150°C, approximating the conditions of crystallizing melts. No discrepancies in fO2 emerged between amphibole-bearing and amphibole-free peridotites, ruling out a strict correlation between amphibole stability, H2O activity and fO2. Nevertheless, the alkaline metasomatic event, which led to amphibole formation, caused a remarkable increase in the H2O content of the system. In fact, anhydrous peridotites preserve bulk H2O contents ≤128 ppm, while lherzolites with disseminated amphibole and hornblendites have H2O contents as up to 354-1120 ppm and 1.42 wt%, respectively.

 

Perinelli, C., et al. 2006. Geochemical and O-isotope constraints on the evolution of lithospheric mantle in the Ross Sea rift area (Antarctica). Contributions to Mineralogy and Petrology, 151(3), 245-266.

How to cite: Coltorti, M., Bonadiman, C., Casetta, F., Faccini, B., Giacomoni, P. P., Pelorosso, B., and Perinelli, C.: Depletion, metasomatism and refertilisation in the Sub-Continental Lithospheric Mantle beneath northern Victoria Land (Antarctica): a review, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-8450, https://doi.org/10.5194/egusphere-egu21-8450, 2021.

EGU21-10603 | vPICO presentations | GMPV4.1

Geochemical and petrophysical characterization of mantle metasomatism beneath the North Tanzanian Divergence, East African rift.

Adeline Clutier, Fleurice Parat, Michel Gregoire, Benoit Gibert, Stéphanie Gautier, and Christel Tiberi

The North Tanzanian Divergence (NTD) is the prolongation of the eastern branch of the East African Rift and is a place of intense volcanism. Numerous volcanoes erupted deep subalkaline to highly alkaline magmas, including the particular active natrocarbonatite Oldoinyo Lengai. On the North-South axis (Natron to Manyara basins), three highly alkaline volcanoes, Pello Hills, Lashaine and Labait, erupted melilite magmas that originated from low degree of partial melting of asthenospheric mantle (depth > 120 km). The particularity of these volcanoes is that they sampled numerous mantle xenoliths during ascent. This represents a unique opportunity to study the composition and the rheology of lithospheric mantle. Mantle xenoliths are deep garnet-bearing peridotites (120 km depth), amphibole and phlogopite peridotites and phlogopitites. They contain abundant hydrous minerals as isolated crystals or veins that attest to an important metasomatism beneath the NTD. Previous geochemical and petrological studies have highlighted interactions of alkaline magmas and the thick cratonic lithosphere as metasomatic agent. However, the presence and composition of magmas, the degree of metasomatism, and the role of metasomatism on mantle rheology below the NTD is still debated.

To characterize these previous parameters, in this study we performed geochemical and petrophysical analyses on metasomatized, fertile and refractory mantle xenoliths from Labait (on-craton volcano) and Pello Hills (in-rift volcano). Using mineral compositions and thermobarometer calibrations, we estimated the depth of mantle xenoliths between 40 and 140 km (14 to 47 kbar) and temperatures from 930 to 1340°C. EBSD analysis on thin sections indicate that peridotites and amphibole/phlogopite-bearing mantle xenoliths display a moderate to strong deformation induced crystal preferred orientation. In contrast, weak mineral orientations have been observed in phlogopite-amphibole-clinopyroxene-bearing veins. Calculation of seismic properties using MTEX program show that peridotites are seismically anisotropic, up to 12.4% for P-wave velocity (Vp) and 6.8% for S-wave velocity (Vs). The Vp and Vs in hydrous veins are lower than in peridotites (Vp: 7.5-7.9 and 8.3-9.6 km/s; Vs: 4.4-4.6 and 5.0-5.3 km/s respectively) and therefore the Vp and Vs velocities decrease with the increasing proportion of metasomatic minerals. We estimate that a peridotite with 20 vol.% metasomatic vein has a velocity decrease of 3.5% for Vp and 2.9% for Vs, compared to a fertile peridotite.

These geochemical and petrophysical approaches are important to understand P- and S-wave propagation in the lithospheric mantle beneath the NTD and more specifically in metasomatized lithospheric mantle. The new in situ data and models from mantle xenoliths will be compared to tomographic acquisition and discussed in term of temperature, presence of melt or metasomatism processes. Both petrophysical and geophysical data will help to precisely determine the structure and rheology of the lithospheric mantle, which may control the propagation of the rift at early stage rifting between the Tanzanian craton and the mobile Proterozoic belts.

How to cite: Clutier, A., Parat, F., Gregoire, M., Gibert, B., Gautier, S., and Tiberi, C.: Geochemical and petrophysical characterization of mantle metasomatism beneath the North Tanzanian Divergence, East African rift., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10603, https://doi.org/10.5194/egusphere-egu21-10603, 2021.

EGU21-1670 | vPICO presentations | GMPV4.1

Evolution of lithospheric mantle beneath mobile belt between two cratons: An example from the Oku Massif, Cameroon Volcanic Line (W Africa)

Jacek Puziewicz, Sylvin S. T. Tedonkenfack, Sonja Aulbach, Theodoros Ntaflos, Mary-Alix Kaczmarek, Anna Kukula, Magdalena Matusiak-Małek, and Małgorzata Ziobro

Cameroon Volcanic Line (CVL) is located in the western part of equatorial Africa and consists of volcanoes which were active from Eocene to recent, stretching ca. 1700 km from the Atlantic in the SW into the African continent in the NE. The continental part of the CVL is located on the Neoproterozoic Central African Orogenic Belt and is situated between the Congo craton and Sahara/Western Africa craton. Mantle peridotite xenoliths which occur locally in lavas of the CVL come from the spinel facies only, suggesting a relatively shallow lithosphere-asthenosphere boundary (LAB). This is supported by seismic studies, showing the LAB at 90-100 km.

In order to understand better the evolution of the lithospheric mantle beneath the CVL, we studied xenolith suite (16 xenoliths) from Befang in the Oku Massif (Tedonkenfack et al., submitted). The Befang xenoliths are almost entirely lherzolites which have cataclastic to weakly porphyroclastic texture. Harzburgites and websterites occur subordinately. Spinel is interstitial and has amoeboidal shape. The studied peridotites (14 lherzolites, 1 harzburgite) consist of minerals with almost constant composition (olivine Fo88.7-90.3, orthopyroxene Al 0.17-0.19 atoms per formula unit (a pfu), clinopyroxene Al 0.28-0.30 a pfu, spinel Cr# dominantly 0.09-0.11). Spinel of Cr# 0.15 occurs in one of the lherzolites, whereas that occurring in harzburgite has Cr# 0.19. Clinopyroxene REE patterns are similar to those of Depleted MORB Mantle (DMM) except LREEs, which vary from depleted to enriched. The A-type olivine fabric occurs in the EBSD-studied subset of 8 samples (one harzburgite and 7 lherzolites). Orthopyroxene shows deformation consistent with olivine. The fabric of LREE-enriched clinopyroxene is equivalent to those of orthopyroxene and olivine, whereas spinel and LREE-depleted clinopyroxene are oriented independently of the fabric of host rock.

These data, thermometry, phase relationships and phase equilibria diagrams suggest that the Befang mantle section was refertilised by MORB-like melt at pressures 1.0-1.4 GPa and temperatures slightly above 1200 – 1275 ºC. The olivine-orthopyroxene framework and LREE-enriched clinopyroxene preserve the fabric of protolith. On the other hand, the LREE-depleted clinopyroxene shows discordant orientation relative to olivine-orthopyroxene protolith framework, and amoeboidal spinel crystallized from the melt. The major element and REEs composition of pyroxenes occurring in the Befang peridotites indicate chemical reequilibration at temperatures 930 – 1000 ºC. Trace element modeling shows that websterites can be linked to Cenozoic volcanism. We speculate that they form veins in the lithospheric mantle. Our study therefore supports the origin of fertile SCLM via refertilization rather than by extraction of small melt fractions, and further emphasizes the involvement of depleted melts in this process, which contrasts with the incompatible element-enriched melts typically invoked in within-plate settings.

This study originated thanks to the project of Polish National Centre of Research NCN 2017/27/B/ST10/00365 to JP. The bilateral Austrian-Polish project WTZ PL 08/2018 enabled extensive microprobe work.

References:

Tedonkenfack SST, Puziewicz J, Aulbach S, Ntaflos T., Kaczmarek M-A, Matusiak-Małek M, Kukuła A, Ziobro M: Lithospheric mantle refertilization by DMM-derived melts beneath the Cameroon Volcanic Line – a case study of the Befang xenolith suite (Oku Volcanic Group, Cameroon). Submitted.

How to cite: Puziewicz, J., Tedonkenfack, S. S. T., Aulbach, S., Ntaflos, T., Kaczmarek, M.-A., Kukula, A., Matusiak-Małek, M., and Ziobro, M.: Evolution of lithospheric mantle beneath mobile belt between two cratons: An example from the Oku Massif, Cameroon Volcanic Line (W Africa), EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-1670, https://doi.org/10.5194/egusphere-egu21-1670, 2021.

EGU21-5234 | vPICO presentations | GMPV4.1

Lithospheric mantle beneath the Vogelsberg volcanic field (Central Germany) 

Małgorzata Ziobro, Jacek Puziewicz, Sonja Aulbach, Theodoros Ntaflos, Magdalena Matusiak-Małek, and Michel Grégoire

Vogelsberg is a Cenozoic volcanic field situated at the northern tip of the Upper Rhine Graben. It stretches over two major Variscan basement units: the Rheno-Hercynian Zone in the NW and the Saxo-Thuringian Zone in the SE. We studied peridotite xenoliths from Breitenborn, Nidda and Dreihausen (SE, central and NW part of Vogelsberg, respectively) in order to reveal the evolution of the subcontinental lithospheric mantle (SCLM) rejuvenated during a Cenozoic rifting episode.

The Vogelsberg xenoliths are spinel harzburgites and clinopyroxene-poor spinel lherzolites. Most samples show grain size reduction leading to serial or porphyroclastic texture, or slight to well-defined foliation. All studied sites have similar major elements chemistry: olivine Fo 89.3-91.7%; orthopyroxene (opx) Mg# 0.89-0.92 and 0.06-0.25 atoms of Al pfu (per formula unit); clinopyroxene (cpx) Mg# 0.89-0.93 and 0.10-0.33 atoms of Al pfu. Spinel Cr# is highly variable: 0.18-0.45 for Breitenborn, 0.14-0.57 for Nidda and 0.11-0.61 for Dreihausen.

Vogelsberg peridotites exhibit a diversity of REE patterns:

(1) opx with a sinusoidal pattern, no cpx (Nidda, Dreihausen);

(2) cpx with flat patterns; coexisting opx with strong LREE-depletion, (La/Lu)N ~0.02 (Nidda, Dreihausen)

(3) cpx with flat, spoon-shaped patterns with La-Ce-enrichment (La/Pr)N ~4.3; opx similar to (2) but partly spoon-like, (Nd/Lu)N ~0.02 (Nidda, Breitenborn)

(4) cpx with different degree of LREE-enrichment, (La/Lu)N­ of 4-21.4; coexisting opx with mild LREE-depletion, (La/Lu)N of 0.1-0.3 (Breitenborn, Nidda, Dreihausen)

(5) cpx with flat HREE pattern and strongly LREE-depleted, (La/Eu)N ~0.03; coexisting opx similar to (2) but with (Ce/Lu)N ~0.001 (Breitenborn)

Temperatures calculated using REE content (TREE) [1] for the Breitenborn peridotites exhibit two ranges: 930-990°C and 1050-1130°C, for the Nidda ones: 880-930°C, 1000-1050°C and 1110-1150°C and for Dreihausen ones: 1140-1190°C. Temperatures calculated on the basis of pyroxene major element contents (TBKN) [2] are 40-90°C lower than TREE in Breitenborn and Nidda and lower by 10-55°C in Dreihausen.

The most common pyroxene REE patterns (type 4) are products of two-phase metasomatism: by Vogelsberg alkali basalt followed by a highly LREE-rich melt that further increased LREE contents in cpx, up to observed abundances. Strongly LREE-depleted opx (types 2, 3, 5) and cpx (type 5) patterns could be residues after partial melting of a fertile protolith, or products of metasomatism by melts derived from depleted MORB mantle. Cpx patterns of type 2 and 3 might have been once similar to type 5 but were later affected by the second phase of metasomatism: highly LREE-rich melt that increased chromatographically their LREE contents to variable degrees. The diversity of REE patterns and calculated temperatures shows that the SCLM beneath Vogelsberg is highly heterogeneous, probably due to spatial variability of deformation and percolation of hot melts connected with Cenozoic rifting.

 

This study was funded by Polish National Science Centre to MZ (UMO-2018/29/N/ST10/00259) and JP (UMO-2014/15/B/ST10/00095). EPMA analyses were done thanks to the Polish-Austrian projects WTZ PL/16 and WTZ PL 08/2018. MZ acknowledges the DAAD fellowship at Goethe University Frankfurt.

References

[1] Liang Y. et al. (2013). GeochimCosmochimActa 102, 246–260.

[2] Brey G. & Köhler T. (1990). JPetrol 31, 1353–1378.

How to cite: Ziobro, M., Puziewicz, J., Aulbach, S., Ntaflos, T., Matusiak-Małek, M., and Grégoire, M.: Lithospheric mantle beneath the Vogelsberg volcanic field (Central Germany) , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-5234, https://doi.org/10.5194/egusphere-egu21-5234, 2021.

EGU21-15992 | vPICO presentations | GMPV4.1

Metal enrichment as a result of SCLM metasomatism? Insight from ultramafic xenoliths from SW Poland.

Hubert Mazurek, Jakub Ciazela, Magdalena Matusiak-Małek, Bartosz Pieterek, Jacek Puziewicz, Marina Lazarov, Ingo Horn, and Theodoros Ntaflos

Migration of metals such as gold, silver and copper through the subcontinental lithospheric mantle (SCLM) can be tracked by the investigation of sulfides in mantle xenoliths. Therefore, to understand relations between the metal migration and metasomatism of silicate phases in the SCLM beneath SW Poland we studied sulfides in a set of mantle ultramafic xenoliths with variable metasomatic history. The xenoliths occur in the Cenozoic alkaline mafic volcanic rocks from the SW Poland (N Bohemian Massif).  

The studied sulfides occur in mantle rocks of variable history: 1) strongly depleted (group A0) to weakly metasomatized peridotites (Group A1); 2) strongly melt-metasomatized peridotites (Group B); 3) pyroxenites (Group C; for details of group definition see Matusiak-Małek et al., 2014, JoP). The metasomatism was of mixed silicate/carbonatite nature. The sulfides are either interstitial or enclosed in the silicates and form mostly globular monosulfide solid solution-chalcopyrite (mss-Ccp) assemblages typical of igneous sulfides separated and crystallized from mafic magmas, with mss partially re-equilibrated to exsolutions of pentlandite (Pn) and pyrrhotite (Po) when temperature dropped to <600°C (e.g., Craig and Kullerud, 1969, Econ. Geol. Monogr.).

The sulfide abundances increase from Group A (≤ 0.008 vol.‰) through Group B (up to 0.060 vol. ‰) to Group C (up to 0.963 vol.‰) xenoliths. The sulfides of Groups C (Po15–99Pn0–20Ccp0–70)and B (Po0–85Pn14–100Ccp0–27) are generally poorer in Ni compared to Group A (Po0–74Pn24–100Ccp0–35). Consequently, Ni/(Ni+Fe) in the Group C pentlandites (0.41–0.52) is lower than in those in Group A (0.45–0.69). Moreover, the sulfide grains of Group B are enriched in chalcophile elements (e.g., the median content of Zn is 90 ppm) compared to sulfides from Groups C (52 ppm Zn) and A (51 ppm of Zn). The same relations occur in PGE contents, e.g., Pt in Group B is 1.6 ppm, while in Groups C and A it is 0.1 and 1.3 ppm, respectively.  Observed differences in δ56Fe between the Groups are probably due to modal composition of bulk sulfide grains between Groups A (Ni-rich), B and C (Fe-Cu-rich). As no difference is observed between the grains of the same composition, any fractionation of Fe isotopes in sulfide melt seems to be possible only upon its differentiation from Ni-rich to Fe-Cu-rich.

The host peridotites were affected by strong depletion as the degree of partial melting was possibly ~30%. Thus, the observed enhanced sulfide modes in the metasomatized peridotites (Groups A1 and B) are most likely brought by the metasomatic melt. This is also evidenced by their Fe-Cu-rich composition, similar to that of the sulfides from the pyroxenites. In this view, melt metasomatism likely affects the chalcophile and highly-siderophile metal budget of the continental lithosphere.

 

The measurements of Fe isotopic ratios were financed from funds for years 2020-2024 within program “Diamond Grant” (DI2019 0093 49), the LAICPMS measurements were financed from 2016/23/N/ST10/00288 to J.C., and the EPMA analyses were done within the frame of the Polish-Austrian project WTZ PL/16 and WTZ PL 08/2018.

How to cite: Mazurek, H., Ciazela, J., Matusiak-Małek, M., Pieterek, B., Puziewicz, J., Lazarov, M., Horn, I., and Ntaflos, T.: Metal enrichment as a result of SCLM metasomatism? Insight from ultramafic xenoliths from SW Poland., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-15992, https://doi.org/10.5194/egusphere-egu21-15992, 2021.

EGU21-12817 | vPICO presentations | GMPV4.1

First assessment of the noble gas and CO2 isotopic composition of fluid inclusions hosted in mantle xenoliths from El Hierro (Canary Islands) 

Andres Sandoval Velasquez, Andrea Luca Rizzo, Alessandro Aiuppa, Maria Luce Frezzotti, Samantha Remigi, Eleazar Padrón, and Nemesio Pérez

Studying the isotopic composition of fluids trapped in mantle xenoliths opens avenues to understanding the origin and cycling of volatiles in the Earth’s upper mantle. Here, we present the first isotopic results for noble gases and CO2 in fluid inclusions (FI) trapped in mantle xenoliths from El Hierro the youngest island of the Canarian archipelago. Our results are based on 6 mantle xenolith samples (3 Spinel-lherzolites and 3 Spinel-harzburgites) collected from the El Julan cliff valley (Oglialoro et al., 2017), from which we hand-picked crystals of Ol, Opx, and Cpx. Isotopic determinations were performed at the INGV (Sezione di Palermo) noble gas and stable isotopes laboratories, following the preparation methods and analytical procedures described in Rizzo et al. (2018 and references therein).

The Ne-Ar isotopic compositions reveal the presence of an atmospheric component in the FI. Most of the samples exhibit 4He/20Ne ratios > 60, 20Ne/22Ne ratios between 9.84 and 10.49, 21Ne/22Ne ratios from 0.0295 to 0.0330, and 40Ar/36Ar > 800, suggesting mixing between MORB-like mantle fluids and an air-derived component. We argue this latter may (at least in part) derive from upper mantle recycling of atmospheric fluids via paleo-subduction event(s). Excluding samples possibly affected by diffusive fractionation processes, the average Rc/Ra ratio (3He/4He ratio corrected for atmospheric contamination) measured in El Hierro xenoliths is ~7.45 + 0.26 Ra, within the MORB range (8 + 1 Ra; Graham, 2002). The He homogeneous signature of these xenoliths agrees well with the 3He/4He compositions previously reported in lava phenocrysts and cumulates (Day and Hilton, 2011) and is slightly below the maximum ratios measured in groundwater samples during the 2012 volcanic unrest (~8.2 Ra; Padron et al., 2013). All these pieces of evidence argue against a primordial source involved in the local lithospheric mantle. Putting these data in the context of previous literature results for FI and surface gases in the Canary Islands (La Palma, La Gomera, Tenerife, Gran Canaria, and Lanzarote), we identify an eastward 3He/4He decreasing trend that parallels a corresponding increase of the oceanic crust thickness. In addition to the mantle heterogeneity, we propose that part of the 3He/4He east-to-west variation along the archipelago is caused by the variable thickness of the oceanic crust (and hence, different interactions with 4He-rich crustal fluids during emplacement).

The FI δ13C(CO2) isotopic composition ranges from -2.38 to -1.23‰ in pyroxenes and -0.2 to +2.0‰ in olivine. These unusually positive δ13C compositions support the existence of a recycled crustal carbon component in the local source mantle, likely pointing to mantle metasomatism (Oglialoro et al., 2017) from fluids carrying carbon from subducted sediments and/or altered oceanic crust (AOC).

How to cite: Sandoval Velasquez, A., Rizzo, A. L., Aiuppa, A., Frezzotti, M. L., Remigi, S., Padrón, E., and Pérez, N.: First assessment of the noble gas and CO2 isotopic composition of fluid inclusions hosted in mantle xenoliths from El Hierro (Canary Islands) , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12817, https://doi.org/10.5194/egusphere-egu21-12817, 2021.

EGU21-8810 | vPICO presentations | GMPV4.1

Pyroxenitic xenoliths from southern Scotland and what they tell us.

Magdalena Matusiak-Małek, Piotr Matczuk, Brian G.J. Upton, Theodoros Ntaflos, Sonja Aulbach, Jacek Puziewicz, and Anna Kukuła

Late Carboniferous/early Permian mafic volcanic rocks occurring in Scotland carry a broad spectrum of peridotitic and pyroxenitic xenoliths. The latter provide evidence of magmatic processes in the lower crust and the lithospheric mantle. In this study we present textural and compositional data on twenty-eight pyroxenitic xenoliths from six localities from southern Scotland (Midland Valley and Southern Uplands Terranes).

Most are interpreted as adcumulates (varying in grain size from fine to coarse) although some others are mesocumulates. They include both clinopyroxenites and websterites with variable amounts of olivine; phlogopite is present in only one sample. Cores of greenish clinopyroxene in three of the olivine clinopyroxenites are enveloped by brownish clinopyroxene, while one composite xenolith comprising coarse-grained olivine clinopyroxenite in sharp contact with harzburgite. Five groups, based on textural and mineralogical features were distinguished. Representatives of more than one group can be present in a single locality.

Most of the samples from the same textural group share similar chemical composition. In general, the clinopyroxenes are Ti,Al-diopside/augite with Mg#=0.74-0.86; where clinopyroxenes are zoned the rims have lower Mg# and higher Al content. The orthopyroxene is an Al (±Cr)-enstatite with Mg#=0.78-0.89, olivine (Fo76-77) is relatively NiO-rich (0.16-0.29 wt.%). In clinopyroxenites the pyroxenes are LREE-enriched (LaN/LuN=1.31-3.17) with convex-upward REE patterns (SmN/LuN=2.48-7.37).

The temperatures and pressures of clinopyroxene crystallization in most of the clinopyroxenites are 1220-1300°C and 1.08–1.30 GPa (Putirka, 2008), respectively. Only the composite xenolith and the coarse-grained clinopyroxenites recorded higher pressures (1.42 and 1.65-2.03 GPa, respectively). As the Moho beneath S Scotland is located at ~35 km (corresponding to ~1 GPa; Davis et al., 2012), most of the clinopyroxenites are considered to come from the uppermost portions of lithospheric mantle or lowermost continental crust; the coarse-grained clinopyroxenites and the composite xenolith sample lithospheric mantle.

Clinopyroxenites from the southern Scotland crystallized from alkaline basaltic magmas similar to those that entrained  them. Whilst Downes et al. (2007, 2001) had previously suggested this for clinopyroxenites from Midland Valley localities, our studies show that crystallization of mafic melts was more widespread. Strong chemical and textural variations in the pyroxenites together with relatively constant PT conditions of crystallization suggest that they formed either from melts of slightly different composition, perhaps in response to magma chamber processes such as magma replenishment and/ or mixing. While, the presence of mafic cumulates points to possible crustal underplating beneath S Scotland, the presence of a high-pressure clinopyroxenites and composite clinopyroxenitic-peridotitic xenolith imply that some of the pyroxenites originated in the lithospheric mantle.

Davis et al. (2012). Geoph.J. Int., 190, 705-725.

Downes et al., (2007). J. Geol. Soc., 164, 1217-1231.

Downes et al. (2001). Lithos, 58, 105-124.

Putirka et al. (2008). Rev. Min. Petr., 69, 61-120.

This study was funded by Polish National Science Centre to MMM no. DEC-2016/23/B/ST10/01905. EPMA analyses were done within the frame of the Polish-Austrian project WTZ PL/16 and WTZ PL 08/2018.

 

How to cite: Matusiak-Małek, M., Matczuk, P., Upton, B. G. J., Ntaflos, T., Aulbach, S., Puziewicz, J., and Kukuła, A.: Pyroxenitic xenoliths from southern Scotland and what they tell us., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-8810, https://doi.org/10.5194/egusphere-egu21-8810, 2021.

EGU21-10496 | vPICO presentations | GMPV4.1

Long-lived low Th/U Pacific-type isotopic mantle domain

Xijun Liu, Zhiguo Zhang, Pengde Liu, Yujia Song, and Yao Xiao

    The presence of Pacific-type and Indian-type mid-ocean ridge (MORB) isotopic source domains in the upper mantle is a clear manifestation of global-scale mantle compositional heterogeneities. The Indian-type mantle domain is a long-lived feature that can be traced back to, at least, the Palaeozoic Tethyan mantle domain. Little temporal constraints currently exist, however, regarding the longevity of Pacific-type mantle domain. The extinct Paleo-Asia Ocean (PAO), a subsidiary ocean of the Panthalassic Ocean that formed during the breakup of the Rodinia Supercontinent in Mesoproterozoic to Neoproterozoic, can provide a solution to this dilemma. Here, we report the first complete geochemical and Sr, Nd and high-precision Pb isotopic data set for representative mafic rock samples from ophiolites representing remnants of the PAO basement ranging in age from 275 to 624Ma to constrain the composition of their mantle provenance. Data suggest that the sub-PAO mantle has a similar long time-integrated, high Sm/Nd ratio as the global depleted upper mantle, but also shows typical Pacific MORB-like Pb isotopic compositions with lower 207Pb/204Pb(t) and 208Pb/204Pb(t) for given 206Pb/204Pb(t) ratios, and low radiogenic 208Pb*/206Pb*, indicating a long time-integrated, low Th/U ratios. Thus, the Pacific-type mantle domain, like the Indian-type mantle domain, is a long-lived secular mantle domain that can be traced back to early Paleozoic or even to the Neoproterozoic. Data further indicate that the Nd and Pb isotopic distinction between such two large-scale and long-term mantle domains is due to the different evolutionary and tectonic histories of the circum-Pacific (PAO, Paleo- and modern Pacific) and sub-Tethys-Indian oceanic mantle realms. The Panthalassic-Pacific ocean realm had remarkable permanency existing as a big ocean at lease throughout the Phanerozoic, that implies that continental materials were limit to recycle into underlying mantle, thus the underlying mantle was relative free of the continental material contamination and then produce the low time-integrated Th/U Pacific-type mantle domain. In contrast, the break-up of the Gondwana supercontinent makes the Tethys realms to experience repeated opening and closures, which transferred large volume of continental materials into the underlying mantle and then produce the high Th/U Indian-type mantle domain. Our results indicate that the high Sm/Nd and low Th/U ratio of Pacific-type mantle domain most likely are an inherited, long-standing intrinsic feature of the depleted upper mantle derived from the Earth's primordial mantle with less contamination of continental materials. In contrast, the large-scale and long-lived Indian-type mantle heterogeneity is produced by plate tectonic-driven continental material circulation in the upper mantle. Such a genetic link between plate tectonics and mantle chemical geodynamics is crucial to our understanding of how the Earth system works.

    This study was financially supported by the National Natural Science Foundation of China (92055208,41772059) and the CAS “Light of West China” Program (2018-XBYJRC-003).

How to cite: Liu, X., Zhang, Z., Liu, P., Song, Y., and Xiao, Y.: Long-lived low Th/U Pacific-type isotopic mantle domain, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10496, https://doi.org/10.5194/egusphere-egu21-10496, 2021.

EGU21-14751 | vPICO presentations | GMPV4.1

Pristine metasomatic melt preserved in mantle rocks of the Bohemian Massif

Alessia Borghini, Silvio Ferrero, Patrick J. O'Brien, Bernd Wunder, and Oscar Laurent

Melt inclusions of very unusual nature occur in garnets of eclogites of the Granulitgebirge, Bohemian Massif. This is one of the first direct characterization of a preserved metasomatic melt responsible for the formation of eclogites enclosed in garnet peridotites. The inclusions are micrometric, from glassy to fully crystalized as nanogranitoids and randomly distributed in the garnet core. Nanogranitoids contain kumdykolite/albite, phlogopite, osumilite and kokchetavite with a variable amount of quartz, pyroxene, carbonate and rare white mica. The melt has a granitic composition rather than basaltic or tonalitic/trondhjemitic as would be expected from the partial melting of ultramafic or mafic rocks and it is as well hydrous and peraluminous. The trace elements composition is also unusual for melts in mantle rocks with elements typical of continental crust (Cs, Li, B, Pb and Rb) and subduction zone (Th and U). Similar signatures, i.e. continental crust and subduction, are visible also in the whole rock trace elements in the form of high amounts of LILE and U. The eclogite major elements composition is similar to a Ca- and Fe - rich mafic rock akin more to the crust than to the mantle.

The peculiar melt composition and the lack of a clear residue of a melting reaction in the eclogites suggest that this melt is external, i.e. metasomatic. It infiltered the peridotites during subduction of the continental crust at mantle depth and aided the transformation of basic layers, already in the peridotite, to eclogite. In addition, similar trace elements patterns to the melt reported here can be found in the so-called durbachite -ultrapotassic melanosyenite present in the high-grade Variscan basement- and in the garnet peridotites and garnet pyroxenites of the T-7 borehole. In both case metasomatism was suggested but the agent was just inferred based on the geochemical signature. All these occurrences suggest that mantle contaminated by melts from deeply subducted continental crust is widespread beneath the Bohemian Massif.

How to cite: Borghini, A., Ferrero, S., O'Brien, P. J., Wunder, B., and Laurent, O.: Pristine metasomatic melt preserved in mantle rocks of the Bohemian Massif, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-14751, https://doi.org/10.5194/egusphere-egu21-14751, 2021.

EGU21-11060 | vPICO presentations | GMPV4.1

Multiple stages of serpentinization in mantle derived peridotites of the South Armorican Variscan suture zone

Geoffrey Aertgeerts, Didier Lahondère, Christophe Monnier, and Jean-Pierre Lorand

South Armorican mantle peridotites represent a great diversity of protoliths from supra-subduction zone to arc-fore arc ophiolites. In this study, we investigate the serpentinization of these protoliths. Numerous samples were collected in five different units, which represent ophiolitic dismembered pieces (Ty-Lan Peridotites (TLP) from the Audierne Complex, and Pont de Barel Peridotites (PBP), Folies Siffait Peridotites (FSP), l’Orgerais Peridotites (LOP) and Drain Peridotites (DP) from the Champtoceaux Complex). Field and microscopic observations together with Raman spectroscopy and electronic microprobe analysis (EMPA) allowed to identify several stages of serpentinization. All samples display a high rate of serpentinization, up to 80-90 %. Primary assemblage is represented by spinel (TLP, PBP, DP and LOP), olivine (TLP and FSP) and Ti-poor or Cr-rich pargasite (TLP and PBP). In all the samples, lizardite from olivine and bastites from pyroxene and amphibole characterize the first stage of serpentinization. It is associated with magnetite crystallization. No Al-rich lizardite meshe is identified by EMPA suggesting a low temperature (< 340°C) event. This serpentinization is followed by two generations of veins (V1 and V2). The V1 are Al-poor lizardite shear veins and crack-seal chrysotile veins characterize the V2. In PBP, microprobe mapping shows that V2 displays heterogeneous chemical chrysotile composition with significant variations of Al, Fe and Mg contents, suggesting metasomatism and/or variation of fluid composition during serpentinization. All these observations are closely similar to those of oceanic serpentinized peridotites. In the TLP, we identified a second stage of serpentinization characterized by antigorite after lizardite suggesting a high temperature event. In the OP, antigorite after lizardite was also identified. However, compared to the TLP ones, LOP antigorite is related to ductile (i.e., ultramylonite) deformations. This clearly indicates a high temperature stage of serpentinization (up to 500 °C). Furthermore, LOP ultramylonitized samples display one more chrysotile veins generation (V3) characterized by three distinct vein networks. The first one (V3a) is a crack-seal type vein network opened parallel to the main foliation. The second one (V3b) is perpendicular to the first one, whereas the third one (V3c) corresponds to tension gashes connected to C’ plans. This latter is perpendicular to V3a and V3b networks. The mylonitic foliation of LOP is similar to the surrounding micaschists schistosity, suggesting an orogenic high temperature stage of serpentinization. In the FSP, σ-type polycrystalline structures were identified. Lizardite meshes are progressively transposed and recrystallized into the foliation plan. This stage is associated with the crystallization of chlorite after tremolite, suggesting a retrograde stage of serpentinization during serpentinites exhumation. Finally, despite a great diversity of mantle-derived protoliths, our study shows that South-Armorican peridotites recorded a similar first low temperature oceanic stage of serpentinization. According to the Variscan history, it could have started during the Cambro-Ordovician for TLP, and during the Late Devonian for PBP, DP, LOP, FSP. Furthermore, some of these peridotites also recorded an orogenic serpentinization (LOP and FLP). Such observations provide new constraints that could be useful to a better understanding of the tectonometamorphic evolution of the South Armorican suture zones during the Variscan orogeny. 

How to cite: Aertgeerts, G., Lahondère, D., Monnier, C., and Lorand, J.-P.: Multiple stages of serpentinization in mantle derived peridotites of the South Armorican Variscan suture zone, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-11060, https://doi.org/10.5194/egusphere-egu21-11060, 2021.

EGU21-3319 | vPICO presentations | GMPV4.1

Rodingitization of mafic rocks from Central Evia (Greece) associated with serpentinite exhumation: Evidence from Petrological, Geochemical and Isotopic data 

Christos Karkalis, Andreas Magganas, Petros Koutsovitis, and Theodoros Ntaflos

In Central Evia island (Aegean-Greece) serpentinized ultramafic rocks appear as elongated thrust sheets or in the form of olistostromes incorporated within Maestrichtian-Paleocene flysch. These are crosscut by well-developed rodingite dykes that were derived from four main protoliths that include i) Boninites, ii) Island-arc Tholeiitic Basalts and Gabbros, iii) Alkaline basalts and iv) Calc-alkaline basalts. They mainly comprise of minerals that include (hydro)garnet + chlorite + clinopyroxene ± vesuvianite. Accessory minerals include spinel ± calcite ± prehnite ± amphibole ± orthopyroxene ± olivine ± quartz ± opaque Fe-Ti oxides. Rodingites that were formed at the expense of boninites and island-arc tholeiitic rocks were likely formed within a single rodingitization stage, since garnet is mainly grossular-rich and relict primary clinopyroxene has been preserved. The rodingitization of the alkaline and calc-alkaline basalts seems to have occurred as a multi-stage metasomatic process that occurred during the exhumation of the mafic-ultramafic mantle wedge complex. This resulted in the development of late-stage andradite, vesuvianite and in some cases of chlorite during derodingitization. In this case, successive reaction zones with variability in the participating mineral phases were developed.  Geochemical results reveal remarkable rare earth element (REE) enrichments, especially in the inner zones, likely being the result of successive diffusion and element transfer. Few rodingites are characterized as calcite-bearing, whose stable 13C-18O isotopic data points to the restricted involvement of late-stage mixed hydrothermal and seawater-related carbonation processes.

How to cite: Karkalis, C., Magganas, A., Koutsovitis, P., and Ntaflos, T.: Rodingitization of mafic rocks from Central Evia (Greece) associated with serpentinite exhumation: Evidence from Petrological, Geochemical and Isotopic data , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-3319, https://doi.org/10.5194/egusphere-egu21-3319, 2021.

Extensive magmatic activities were developed in  Central and Western Anatolia,  since middle miocene to quaternary times,   the most primitive lavas are situated in eastern end of Central (Sivas) and also western (Kula) Anatolia, besides Kula basalts are  one of the most recent basaltic rocks together with  basalts  from south-central Anatolia.   Although the magmatism is generally   observed at several different  locations, the recent   basaltic rocks in both of the regions   seem to be derived from  the melting  of the peridotite and pyroxenite  source  domains and the latter one  was ignored in previous studies as source component.

 The previous studies indicate that many of the basaltic rocks from Central and Western Anatolia  are related with spinel-garnet transition, but typical Tb/Yb(N) (>1.8; [1]) and Zn/Fe   (separates peridotite-derived (Zn/Fe <12; [2]) and pyroxenite-derived (Zn/Fe 13-20); [2] melts)  Co/Fe  ratios of the basaltic rocks from  several volcanic centers from Central and Western Anatolia  reveal that   melting from the single  source component  are not solely capable of  the producing  basaltic  rocks. 

 Sr-Nd and Pb isotopic  compositions  clearly display the distinction  of samples which are  linked to    asthenospheric source. The lead isotopic systematic  shows  no siginificant differences  among the Central and Western Anatolian basalts,  of all the samples are above the NHRL line and close to EM II  mantle component,  Sr- Nd  isotopes  also display similar compositions as well, the majority of the samples are in and close to mantle array,   but the  Sr isotopic composition   of  Miocene aged  Gediz and Simav lavas have high radiogenic values. 

Tb/Yb(N),  Zn/Fe ratios  and   as well as the Pb isotopic  compositions and REE-based melting model reveal  that Sivas, Erciyes Hasandağ, and Develidağ samples in central Anatolia,  and Kula, Gediz basalt in western Anatolia  seem to be  derived from the amalgamated melting of  pyroxenite and peridotite sources,   besides,  the sources melting is capable of  the producing     elemental variations in  basaltic rocks related with either lithospheric delamination or lithospheric  unstability

  • 1.Wang et al., 2002, J.Geophys.Res.vol:107,ECV 5 1-21
  • 2 .Le Roux, et al.,2011,EPSL, vol:307, 395-408

This study is financially supported by Hacettepe University, BAB project no: FHD-2018-17283

 

How to cite: Kurkcuoglu, B. and Yürür, T.: Sr-Nd-Pb isotopic significance of mantle source components from Central and Western Anatolia:  Melting  evidences   from peridotite and pyroxenite source  domains, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12162, https://doi.org/10.5194/egusphere-egu21-12162, 2021.

EGU21-14209 | vPICO presentations | GMPV4.1

A new tool to probe lithosphere evolution: OH signatures of pyroxenes

Jannick Ingrin

Four OH stretching bands in the frequency range 3300 – 3700 cm-1 dominate the infrared spectra of lithospheric pyroxenes. Depending on their metasomatic history or geodynamic origin, they have characteristic OH signatures. Pyroxenes from continental lithosphere that undergone “wet” metasomatism have distinct signature of those having undergone “dry” metasomatism. Pyroxenes from oceanic lithosphere have yet a third type of signature. Our most recent analyses of xenoliths and a critical review of the literature show that the phenomenon is widely distributed among continents and oceans. The phenomenon affects simultaneously opx and cpx from the same rock and various lithologies: peridotites, pyroxenites and granulites. In continental lithosphere, pyroxenes affected by “wet” metasomatism are dominated by OH bands at 3600 and 3415 cm-1 for opx and 3635 and 3445 cm-1 for cpx . Whereas pyroxenes affected by “dry” metasomatism are dominated by OH bands at 3570 and 3515 cm-1 for opx and 3595 and 3515 cm-1 for cpx. Opxs from oceanic lithosphere have OH spectra dominated by the band at 3415 cm-1, and with a smaller by bands at 3520 and 3570 cm-1 (Fig. 1).

In all these observations it was not possible to correlate the signatures with a specific major, minor or trace element. Therefore, the exact nature of the observed signatures remains unidentified. Notwithstanding, these OH signatures are representative of specific lithospheric events and offer a potential new benchmark for the study of lithospheric processes.

Fig.1 : Schematic diagram showing the 3 types of signatures for opx. Spectra from opxs in oceanic lithosphere are from Gose, J., Schmadicke, E. and Beran A.: Geology, 37, 543-546, 2009. Drawing of subduction is from WangZ-Z., Liu,J., Xia, Q-K., Hao Y_T. and Wang Q-Y.: Lithos, 360-361, 2020.

How to cite: Ingrin, J.: A new tool to probe lithosphere evolution: OH signatures of pyroxenes, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-14209, https://doi.org/10.5194/egusphere-egu21-14209, 2021.

EGU21-8372 | vPICO presentations | GMPV4.1

Ophiolitic peridotites in Xigaze (Tibet): Constraints on modes of melt transport in the mantle

Lingquan Zhao, Sumit Chakraborty, and Hans-Peter Schertl

The Xigaze ophiolite (Tibet), which occurs in the central segment of the Yarlung Zangbo Suture Zone, exposes a complete portion of a mantle sequence that consists essentially of fresh as well as serpentinized peridotites. We studied a sequence beneath the crustal section that exposes fresh, Cpx-bearing harzburgites and dunites that are underlain by serpentinized Cpx-bearing harzburgites and dunites. The rocks at the bottom are crosscut by dykes that have undergone different degrees of rodingitization. The modal compositions of peridotite from both fresh and serpentinized sections plot in abyssal upper mantle fields, with clinopyroxene modes less than 5 vol. %. Although harzburgites and dunites indicate that melt has been lost relative to primitive mantle compositions, the trace element patterns carry signatures of enrichment in incompatible elements, such as (i) “bowl-shaped” patterns of trace elements in silicate-Earth normalized spider diagrams, (ii) positive anomalies in highly incompatible trace elements such as Rb, Th, U, Ta, and (iii) enrichment of LREE in the clinopyroxenes from dunites and harzburgites. These features are indicative of complex melt transfer processes and cannot be produced by simple melt extraction. Petrographic studies reveal that harzburgite and dunite contain interstitial polyphase aggregates of olivine + Cpx + spinel + Opx and olivine + Cpx + Spinel, respectively. Experimental studies (e.g. Morgan and Liang, 2003) suggest that these aggregates represent frozen melt-rich components, indicating that fertile melt was percolating through the depleted harzburgite – dunite matrix. Presence of such “melt pods” would explain the trace element enrichment patterns of the bulk rock, as well as features such as reverse zoning (core: Cr, Fe2+ rich, rim: Al, Mg rich) of spinels in polyphase aggregates in fresh dunites. These results show that melt extraction from the mantle is not a single stage process, and that evidence of multiple melt pulses that propagated through a rock are preserved in the petrographic features as well as in the form of chemical signatures that indicate refertilization of initially depleted rocks.

How to cite: Zhao, L., Chakraborty, S., and Schertl, H.-P.: Ophiolitic peridotites in Xigaze (Tibet): Constraints on modes of melt transport in the mantle, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-8372, https://doi.org/10.5194/egusphere-egu21-8372, 2021.

EGU21-15299 | vPICO presentations | GMPV4.1

Supra-subduction mantle pyroxenites in an infant subduction system: the New Caledonia ophiolite record.

Elisa Ferrari, Arianna Secchiari, Alessandra Montanini, and Dominique Cluzel

Pyroxenites constitute the major form of heterogeneity in the upper mantle. Their occurrence in supra-subduction zone settings is mostly testified by veins and layers in refractory ophiolitic peridotites, where they represent a crucial witness of melt migration in the forearc/subarc environment [1,2]. The New Caledonia ophiolite hosts one of the largest forearc mantle section worldwide, providing a unique perspective into upper mantle processes. The sequence is dominated by ultra-depleted harzburgites [3], locally overlain by mafic-ultramafic cumulates [4,5,6]. The harzburgites are highly refractory residues that register a multi-phase evolution, including fluid-assisted melting in a forearc environment and contamination by fluid- and melt inputs triggered by Eocene subduction [1]. Pyroxenitic rocks intruding the harzburgites are only known in the Bogota peninsula shear zone, which records HT deformation along a paleotransform fault [7]. In this contribution, we report a comprehensive petrological and geochemical characterization on a new set of pyroxenites from this locality. The pyroxenites (~5-15 cm-thick) generally cut the peridotite foliation at variable angles, but concordant, locally boudinaged, layers also occur. Pyroxenite textures range from cumulitic to porphyroclastic or granoblastic-polygonal. The studied samples mostly consist of amphibole-bearing (5-44 vol.%) websterites, with variable amounts of orthopyroxene (27-67 vol.%) and almost constant clinopyroxene contents (~ 25-29 vol.%). Minor olivine-bearing orthopyroxenites are also present. Accessory phases include high-Ca (An= 82-86 mol%) plagioclase, Cr-rich spinel (Cr# = 50-61), sulfides and, occasionally, apatite. Pyroxenes displays high Mg# (Mg# Opx= 91-92; Mg# Cpx= 84-93), coupled with low Al2O3 contents (0.97-1.92 wt% and 1-2.42 wt% for orthopyroxene and clinopyroxene, respectively). Amphibole is high Mg# edenite. Application of conventional pyroxene thermometry yield equilibration temperatures ranging between 930-1040°C, comparable to the enclosing harzburgites (~ 950°C), whereas amphibole-plagioclase geothermometer provides lower temperatures (~ 800°C). Bulk rock composition of the websterites show variable Mg# (82-91) and REE concentrations ranging between 1 to 10 times chondritic values. They are characterized by flat to LREE-depleted (LaN/SmN 0.28-0.92) patterns, coupled to weak MREE-HREE fractionation (GdN/YbN = 1.73-1.92) and Eu negative anomalies. By contrast, orthopyroxenites display notably lower concentrations (0.1≤REE≤1 chondrite abundances). As a whole, clinopyroxene REE patterns of the websterites mirror bulk rocks at higher absolute values. Putative melts in equilibrium with clinopyroxene indicate strongly enriched compositions (up to 300 times chondritic values) coupled to variable LREE-HREE fractionation (LaN/LuN = 3-19) and flat to fractionated HREE (GdN/LuN 1-2). Such enriched liquids, which show some analogies with pre-obduction adakite-like dikes [8], have never been recorded in the MTZ cumulitic sequence of the New Caledonia ophiolite and shed new light on the magmatic activity in the early stage of subduction. 

[1] Varfalvy, Canad Mineral, 1997, 35 (2), 543-570.
[2] Berly et al., J. Petrol., 2006, 47(8), 1531-1555.
[3] Secchiari et al., Geosc. Front., 2020, 11(1), 37–55. [4]. 
[4] Marchesi et al., Chem. Geol., 2009, 266, 171-186.
[5] Pirard et al., J. Petrol., 2013, 54, 1759–1792.
[6] Secchiari et al., Contrib. Mineral. Petrol., 2018, 173(8), 66.
[7] Chatzaras et al., Geology, 2020, 48 (6): 569–573.
[8] Cluzel et al., Terra Nova, 2006, 6, 395–402.

How to cite: Ferrari, E., Secchiari, A., Montanini, A., and Cluzel, D.: Supra-subduction mantle pyroxenites in an infant subduction system: the New Caledonia ophiolite record., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-15299, https://doi.org/10.5194/egusphere-egu21-15299, 2021.

EGU21-15136 | vPICO presentations | GMPV4.1

Pyroxenites of Kukesi Massif, Mirdita Ophiolite – geological record for magmatic system in SSZ environment – preliminary results

Jakub Mikrut, Magdalena Matusiak-Małek, Jacek Puziewicz, and Kujtim Onuzi

Kukesi massif is located in the eastern part of the Mirdita Ophiolite (northern Albania), which marks suture after Neo-Thetyan ocean closure. It is formed of well-preserved mantle and crustal sections which exhibit Supra-Subduction Zone affinity (e.g. Dilek and Furnes 2009, Lithos). Lower part of the mantle section of the Kukesi massif consist mainly of harzburgites, whereas dunites are located close to Moho. Crustal section records transition from lower part formed by peridotites and pyroxenites (so called intermediate zone after Hoxha and Boullier 1995, Tectonophysics) to gabbros. In this study we focus on composition and origin of pyroxenites occurring in the mantle and lower crustal parts of the Kukesi massif.

In this study we studied 9 samples. They have composition of olivine websterite, clinopyroxenite, orthopyroxenite, hornblende-clinopyroxenite and websterite. Five of the analyzed samples have mantle origin (M): we studied (M)-olivine websterites and (M)-clinopyroxenite from harzburgitic part, as well as two (M)-orthopyroxenitic veins (one with clinopyroxenitic central part - composite vein) with minor amphibole cross-cutting dunites from one locality. From intermediate zone in crustal (C) part we collected (C)-hornblende-clinopyroxenites and (C)-websterite. 

Clinopyroxene composition is homogeneous in (M)-olivine-websterites (Mg#=84.5-87 and 88.8-90.5; Al=0.07-0.1 and 0.05-0.07, respectively), (M)-clinopyroxenite (Mg#=84-86, Al=0.04-0.08), (C)-hornblende-clinopyroxenites (Mg#=88.5-91, Al=0.08-0.12a.p.f.u.) and (C)-websterite (Mg#=87-88; Al=0.13-0.16a.p.f.u.). It differs widely between (M)-orthopyroxenitic veins: from Mg#=85-94 and Al=0.02-0.08 a.p.f.u  in clinopyroxenitic part of composite vein to Mg#=93.6-95 and Al=0.01-0.03 in the purely orthopyroxenitic one. Orthopyroxene from two samples of  (M)-olivine websterites have either Mg#=83 and Al~0.07 a.p.f.u (Foolivine=81.5) or Mg#=87  and Al~0.04 a.p.f.u (Foolivine=86). Orthopyroxene composition in composite(M)-vein varies in wide ranges (Mg#=83-89; Al=0.04-0.08 a.p.f.u.); the other vein is homogeneous (Mg#=90-91, Al=0.02-0.03 a.p.f.u, Foolivine=86.8-90); in (C)-websterite orthopyroxene has Mg#=82.4-84 and Al=0.12-0.14 a.p.f.u. Amphibole has composition of tremolite-actinolite. Spinel, where present, is highly chromian (Cr#=0.59-0.80).

Clinopyroxene is LREE-depleted in most of the samples, the (La/Lu)N=0.03-0.08. It is also LREE-depleted in (M)-clinopyroxenite ((La/Lu)N=0.05-0.23), but the contents of trace elements are higher than in other samples (eg. LuN=0.79-2.75 vs. 0.40-0.85). In (M)-veins the LREE contents are approximately at primitive mantle level ((La/Lu)N=0.28-1.66).  Clinopyroxene in all samples has positive Th-U, Pb and Sr anomalies and negative Ta and Zr anomalies, but concentrations of trace elements is significantly higher in (M) clinopyroxenite and veins.

The presence of tremolite and actinolite points to a retrogressive metamorphism which affected the rocks. The LREE-depleted nature of clinopyroxene forming all the pyroxenites and presence of orthopyroxene  point to crystallization of the rocks from tholeiitic melt, but variations in Mg# and REE content in clinopyroxene may reflect formation either from different generations of melts or from melts fractionated due to reactive percolation.  Variations in composition of the parental melts is visible even in a scale of one outcrop, which is demonstrated by (M)-orthopyroxenite veins with various modal composition and mineral major and trace elements compositions.

This study was financed from scientific funds for years 2018-2022 as a project within program “Diamond Grant” (DI 024748).

How to cite: Mikrut, J., Matusiak-Małek, M., Puziewicz, J., and Onuzi, K.: Pyroxenites of Kukesi Massif, Mirdita Ophiolite – geological record for magmatic system in SSZ environment – preliminary results, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-15136, https://doi.org/10.5194/egusphere-egu21-15136, 2021.

The Masirah ophiolite is one of the few true ocean ridge ophiolites that have been preserved (Rollinson, 2017) and lacks any indication that it formed in a subduction environment. The Masirah ophiolite in south-eastern Oman is a different and older ophiolite from the more famous northern Oman ophiolite. Chromite and copper ores comprise large deposits in the Samail ophiolite, northern Oman. In comparison, chromite and copper deposits have not been described in previous reports or previous exploration in Masirah ophiolite. Rollinson (2017) has proposed that the apparent absence of chromitites in the mantle section of Masirah ophiolite is an important discriminant between subduction related and ocean ridge ophiolites.  However, during recent studies on the Batain ophiolite mélange, and Masirah ophiolite, several chromitite pods have been discovered. The chromitites occur as separated small concordant, lenticular pods (3–10 m in thickness), which have been extensively altered and deformed, with the host pyroxenite serpentinites serpentinized harzburgites and dunites. The largest chromitite pods found within the pyroxenite and dunite of Masirah are up to 10 m across.  Unusual minerals and mineral inclusions (orthopyroxene, clinopyroxene, amphibole, phlogopite, serpentine, native Fe, FeO, alloy, sulfide, calcite, laurite, celestine and halite) within chromite have been observed in the chromitites from the  Masirah ophiolites.  The existence of hydrous silicate inclusions in the chromite calls for a role of hydration during chromite genesis. Both  phlogopite and hornblende were possibly formed from alkali-rich hydrous fluids/melts trapped within the chromite during the chromitite formation. High-T green hornblende and phlogopite included in the chromites is evidence of the introduction of water in the magma at the end of the chromite crystallization. Such paragenesis points to the presence of hydrous fluids during the activity of the shear bands. The chromitites parental magmas are rich in K, Na, LREE, B, Cs, Pb, Sr, Li, Rb and U relative to HREE, reflecting the alkalic fluids/melts that prevailed during the chromitites genesis.

The mineral inclusions  in association with host peridotites may have been brought by the uprising asthenosphere at mid-oceanic ridges due to the mantle convection. It appears that this chromite has been formed through reaction between amid-ocean-ridge basalt-melt with depleted harzburgite in the uppermost mantle.  The chromitite deposits have similar cr# (55-62% Al-chromitites), mg# Al2O3 and TiO2 contents to spinels found in MORB, and have been interpreted as having formed in amid-ocean ridge setting.  This suggests that this chromitites is residual from lower degree, partial melting of peridotite, which produced low-Cr# chromitites at the Moho transition zone, possibly in a mid-ocean-ridge setting. The chemistry of both mineral inclusions and chromite   suggests MORB-related tectonic setting for the chromitites that were crystallized at 1000 °C–1300 °C under pressures <3 GPa . The host peridotites were generated during the proto-Indian Ocean MORB extension and emplaced as a result of the obduction of the ophiolite over the Oman Continental margin during Late Cretaceous-Early Paleocene.

Rollinson, H., 2017. Geoscience Frontiers, 8: 1253–1262.

How to cite: Nasir, S.: New  podiform chromitites Occurrence from the Masirah Ophiolite, Oman, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-72, https://doi.org/10.5194/egusphere-egu21-72, 2021.

EGU21-15840 | vPICO presentations | GMPV4.1

Sequential geochemical extractions and mineralogy of Fe-bearing minerals in carbonatized mantle rocks in the Samail Ophiolite, Oman 

Zena Severin, Jessica L. Till, and Oman Drilling Project Phase 1 Science Party

Within the Samail Ophiolite, Oman, there are intervals of listvenite outcrops between layers of serpentinite zones above the basal thrust zone, atop the metamorphic sole. Near the base of the ophiolite mantle section, some peridotites underwent 100% carbonation from metasomatic introduction of CO2-bearing fluids <200°C to form listvenites during the time of emplacement (97 ± 29 Ma, Falk and Kelemen, 2015). The carbonate rocks comprise mostly magnesite and/or dolomite, quartz, Cr-spinel, and Fe-(hydr)oxides; with carbonates as the sole Mg-minerals and quartz as the only silicate phase. The aim of this study is to chemically and petrographically investigate the Fe-bearing minerals within the fluid-altered mantle rocks in drill core samples from hole BT1B of the ICDP Oman Drilling Project. Sequential chemical extractions are useful for recognizing iron pools based on the minerology. We investigated the quantities of Fe-oxide/hydroxide phases through a series of chemical extractions (Poulton and Canfield, 2005) via atomic absorption spectroscopy in addition to optical microscope, SEM/EDS, EPMA/WDS and ICP analysis. Extractions performed at room temperature and one at 50°C included: carbonate-associated Fe (sodium acetate) targeting siderite, HCl-extractable Fe(II), reducible oxides (citrate-dithionite) targeting hematite and possible goethite, and magnetite (oxalate). Carbonate-based Fe in the listvenites from a sodium acetate extraction ranges from 12-28 mg/g, while the same extraction performed at 50°C for twice as long resulted in higher proportions of carbonate-associated Fe (15-35 mg/g). Easily reducible iron quantities from the diluted HCl solution extraction display the lowest overall Fe fractions (0.75-5.5 mg/g) following the room temperature acetate and 0.63-1.7 mg/g after the 50°C acetate extraction. Fe in reducible oxides extracted by dithionite ranged from 1.4-15 mg/g with similar result after both a room-temperature acetate and a 50°C acetate step. Oxalate extraction succeeding the room-temperature acetate yielded magnetite concentrations of 1.9-8.0 mg/g, while the increased temperature and time in the first step (acetate extraction) were followed by significantly lower amounts of Fe extracted by oxalate (0.47- 3.6 mg/g). Additionally, the same extractions were performed on a pure siderite sample from Greenland. For siderite samples crushed a week prior to analysis, the carbonate-associated Fe in sodium acetate extract was 165±17 mg/g; the sidenote yielded 42 wt% of overall extracted Fe (392±33 mg/g). This is only slightly lower than the expected 48.2 wt% of Fe for a pure siderite sample. Dilute HCl extractions display results of 126±5.4 mg/g, dithionite solution extracted 25±0.5 mg/g and oxalate proportions were 76±9 mg/g. Due to possible oxidation of siderite to magnetite occurring during the time between powdering the samples and analysis, the full dissolution of siderite may not be fully represented in only the acetate. Microprobe data shows a total amount of FeO in carbonates as 1.3-10.8 wt%. This is more than or similar to the acetate and HCl proportions of Fe which represent carbonate associated minerals in the listvenites. Data obtained from EMPA and ICP will additionally be discussed in relation to the Fe-oxide phases with relation to the listvenites minerology.

How to cite: Severin, Z., Till, J. L., and Phase 1 Science Party, O. D. P.: Sequential geochemical extractions and mineralogy of Fe-bearing minerals in carbonatized mantle rocks in the Samail Ophiolite, Oman , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-15840, https://doi.org/10.5194/egusphere-egu21-15840, 2021.

EGU21-14475 | vPICO presentations | GMPV4.1

Trace element composition of clinopyroxene in gabbros and dolerites of the Tortuga Ophiolitic Complex, southernmost Patagonia.

Fernanda Torres Garcia, Mauricio Calderón, Leonardo Fadel Cury, Thomas Theye, Joachim Opitz, Diego Rojo, Joaquín Hopfenblatt, and Francisco Fuentes

During the Upper Jurassic-Lower Cretaceous times the western margin of Gondwana in southern Patagonia experienced extreme lithospheric extension and generation of rift and marginal back-arc basins. The ophiolitic complexes of the Rocas Verdes basin comprises incomplete ophiolite pseudostratigraphy lacking ultramafic rocks. The Tortuga Ophiolitic Complex, the southernmost seafloor remnant of the Rocas Verdes basin, record the most advanced evolutionary stage of the back-arc basin evolution in a mid-ocean ridge-type setting. The base of the Tortuga Complex consists of massive and layered gabbros, most of which are two pyroxene and olivine gabbros, leucogabbros, and clinopyroxene troctolites intruded by dikes of basalt and diabase with chilled margins. We present new major and trace element composition of clinopyroxene from the gabbros and sheeted dikes complexes to assess the geochemical affinity of parental basaltic magmas. Clinopyroxene in gabbros is mostly augite and have Al contents of 0.06-0.14 a.p.f.u. and Mg# of 80-92. Clinopyroxene in dolerites in the sheeted dike unit (augite and diopside) have Al content of 0.11-0.12 a.p.f.u. and Mg# of 85-92. Some immobile trace elements (e.g. Zr, Ti, Y) are sensitive to the degree of partial melting and mantle source composition, and can be used as a proxy for distinguishing tectonic environments. The Ti+Cr vs. Ca diagram, coupled with moderate-high TiO2 content of clinopyroxene (0.4-1.4 wt.%) suggests their generation in mid-oceanic ridge-type environment (cf. Beccaluva et al., 1989).  The high Ti/Zr ratios (of ~4-11) coupled with low Zr contents (~0.2-1.1) are expected for higher degrees of partial melting or for melting of more depleted mantle sources. Conversely, low Zr/Y ratios (0.05-0.13) plot between the range of arc basalts. Chondrite-normalized REE patterns in clinopyroxene display a strong depletion of LREE compared to HREE and have an almost flat pattern in the MREE to HREE with a positive Eu (Eu*= 0.9-1.1) anomaly, indicating that clinopyroxene crystallized from a strongly depleted mid-ocean-ridge-type basalt, formed by extensive fractional melting of the mantle source and/or fractional crystallization and accumulation of anhydrous phases. The general trend of the incompatible trace elements patterns exhibit depletion in LILEs, minor HFSEs depletion, positive anomaly of Rb and negative anomalies in Ba, Zr, Ti and Nb, consistent with their generation from a refractory mantle source barely influenced by subduction components derived from the oceanic slab. This agrees with basalt generation in a back-arc basin located far away from the convergent margin. This study was supported by the Fondecyt grant 1161818 and the Anillo Project ACT-105.

How to cite: Torres Garcia, F., Calderón, M., Fadel Cury, L., Theye, T., Opitz, J., Rojo, D., Hopfenblatt, J., and Fuentes, F.: Trace element composition of clinopyroxene in gabbros and dolerites of the Tortuga Ophiolitic Complex, southernmost Patagonia., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-14475, https://doi.org/10.5194/egusphere-egu21-14475, 2021.

EGU21-5975 | vPICO presentations | GMPV4.1

Spatial variability in Karoo dolerites

Arnold Kotze and R. James Roberts

AD Kotze and RJ Roberts

Department of Geology, University of Pretoria, Hatfield, Pretoria, South Africa; u04541686@tuks.co.za

The Karoo Large Igneous Province (KLIP) in South Africa consists of both a spatially limited extrusive basalt suite (Drakensberg Group) and a spatially extensive dolerite suite, both generally considered to be remarkable homogenous and of a “low-Ti” character (Luttinen, 2018). The homogeneity of the rocks requires that statistical analysis is necessary to look for spatial and geochemical trends in the data, which may yield clues to the mantle processes producing the 60 000 km2 expanse of basaltic magma. In this project, data derived from several locations are used as proxies to check for lateral variability in the Karoo dolerites. A principal component analysis (PCA) on trace element data using a covariance matrix was performed, and comparisons based on variables that are 1) common to the Karoo dolerites and Lesotho basalts and, 2) responsible for the most amount of variation to the data set are made. Trace element modelling is then used to test different mantle melting scenarios possibly responsible for the variation seen in the dolerites.

Principal component analyses revealed several trace elements are responsible for most of the variability in the dolerites. Cr and Ni has the strongest positive loading on Component 1 whereas Cr and Ba has the strongest positive loading on Component 2. Ba has a strong negative loading on Component 1. Cu, Sr, V and Zr do impart an appreciable amount of variation to the data, but all four variables have weak negative loadings on both components. Interestingly, the activity of Cu and V seems to be the inverse of that of Cr and Ni.

Due to the nature of a PCA, this work is afforded an opportunity to place the geochemistry of the Karoo dolerites within a larger geodynamic context without bias. From the observed variation, the activity of Ba and Cr is interpreted as an assimilation-oxidation process, whereas the Ni signature reflects the mantle origin of the magmas. Further modelling of these processes will allow the testing of suggested mechanisms for the formation of the KLIP, especially whether the magmatism is plume-related or related to the foundering of crustal blocks.

Luttinen, A., 2018. Bilateral geochemical asymmetry in the Karoo large igneous province. Scientific Reports, 8(5223).

How to cite: Kotze, A. and Roberts, R. J.: Spatial variability in Karoo dolerites, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-5975, https://doi.org/10.5194/egusphere-egu21-5975, 2021.

GMPV4.2 – Understanding planetary crusts and mantles: Recent advances in planetary sciences

EGU21-10624 | vPICO presentations | GMPV4.2

Modelling the ascent of picritic lunar magmas

Marissa Lo, Giuseppe La Spina, Katherine Joy, Margherita Polacci, and Mike Burton

Quantifying the volatile content of the lunar interior is valuable for understanding the formation, thermal evolution, and magmatic evolution of the Earth and Moon. Petrological modelling and geochemical measurements have been used to study the volatile composition of the lunar interior. Improvements to analytical instruments have facilitated more precise measurements of the volatile content of lunar samples and meteorites, however, several problems remain with these measurements, hence, the volatile content of lunar magmas has yet to be constrained with certainty. We propose a volcanological approach for inferring the volatile contents of different lunar magmas.

            A terrestrial magma ascent model has been modified for lunar applications. Numerous parameters were adjusted for lunar conditions, including: magma major element composition, from low-Ti (green and yellow glasses) to high-Ti (orange, red, and black glasses); H2O content; CO content; gravity; and pressure. The model calculated values for gas exsolution, viscosity, mass flow rate, and several other ascent processes, from a depth of 10 km to the surface. Using these results, we will assess the effect of varying magmatic volatile content on lunar magma ascent processes. We will also compare and contrast our results with existing models for lunar magma ascent, as well as models for magma ascent on other planetary bodies. Future work will involve modelling eruptions, using results from the magma ascent model, and verifying the results of the models using images and digital elevation models of the lunar surface.

How to cite: Lo, M., La Spina, G., Joy, K., Polacci, M., and Burton, M.: Modelling the ascent of picritic lunar magmas, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10624, https://doi.org/10.5194/egusphere-egu21-10624, 2021.

EGU21-1123 | vPICO presentations | GMPV4.2

The behaviour of MgO in a giant impact setting

Tim Bögels and Razvan Caracas

The Earth-Moon system and its formation is a topic of great scientific interest, and great debate over the past decades. The giant impact hypothesis is the currently accepted model to explain the formation of our moon. Accordingly, a mars-sized impactor collides with the proto-earth. This giant impact vaporized a significant portion of the impactor and the proto-earth, creating a large accretionary disk from which the moon subsequently formed. Currently, there is a large effort to build reliable thermodynamic descriptors for the building materials of the two bodies involved in the impact. Understanding the behavior of major rock-forming minerals under these extreme conditions is vital for increasing the accuracy of these models.

Magnesium oxide, MgO, is one of the fundamental building blocks for rocky planets. It is an archetype material of ionic solids and a well-known refractory material. Because of its relevance it has been studied extensively; experimental and theoretical results have been produced up to pressures of 800 GPa and temperatures reaching 20000 K. These pressure and temperature regions are of great interest for the planetary sciences, studying planetary interiors. The transformation of the face-centered B1 phase to the body-centered B2 phase and the associated melting curve have been modelled numerous times. In contrast, we know very little of the liquid behaviour of MgO under pressure, let alone at the low pressures found in accretionary disks.

Here we investigate the low-density high-temperature regime characteristic of after-shock isentropic release. We explore the subcritical and the supercritical regimes of MgO using ab initio molecular dynamics. We determine the position of the critical point and examine the structural and transport properties in the sub- and supercritical regimes. We find an elevated critical temperature in comparison with previously studied magnesium-silicates, in agreement to the refractory nature of MgO. Furthermore, we provide insight into the speciation of liquid MgO and the liquid-gas separation. We see a shift in Mg-O speciation towards lower degrees of coordination as the temperature is increased from 4000K to 10000K. This shift in speciation is less pronounced at higher densities. The majority of the chemical species forming the incipient gas phase consist of isolated Mg and O ions and some MgO and O2.

This research was supported by the European Research Council under EU Horizon 2020 research and innovation program (grant agreement 681818 – IMPACT to RC). We acknowledge access to supercomputing facilities via eDARI stl2816, PRACE RA4947, and Uninet2 NN9697K grants.

How to cite: Bögels, T. and Caracas, R.: The behaviour of MgO in a giant impact setting, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-1123, https://doi.org/10.5194/egusphere-egu21-1123, 2021.

EGU21-1145 | vPICO presentations | GMPV4.2

Partial core vaporization during giant impacts inferred from the entropy and the critical point of iron

Zhi Li, Razvan Caracas, and François Soubiran

The prevailing theory of the origin of the Moon is the giant impact hypothesis, in which a Mars-sized impactor collides with the proto-Earth in the late stage of accretion, and the Moon is subsequently formed from the proto-lunar disk made of the ejected materials. As the laboratory-scale experiments are not able to simulate planetary-scale impacts, our understanding of the giant impact mostly comes from hydrodynamic simulations. However, the results of these simulations heavily depend upon the available equation of state to describe the thermodynamic response of the constituent materials of the proto-Earth and impactor to shock waves.

 

Iron as a building block material of the terrestrial planets naturally received significant attention. But the major effort has been put to determine its phase diagram up to the Earth’s core conditions (126-360 GPa and 3000-7000 K) and beyond. The studies of iron at low densities are still scarce and the position of the critical point (CP) is uncertain. As the liquid-vapor dome ends at CP, the position of the latter determines the time evolution of the proto-lunar disk during its condensation.

 

In order to assess whether the core of the planets undergoes significant vaporization during a giant impact, we employ ab initio molecular-dynamics simulations to explore iron over a wide density region encompassing the critical point (CP) and the Hugoniot lines of the shocked iron cores. We determine the critical point of iron in the temperature range of 9000-9350 K, and the density range of 1.85-2.40 g/cm3, corresponding to a pressure range of 4-7 kbars [1]. This implies that the iron core of the proto-Earth may become supercritical after giant impacts. We show that the iron core of Theia partially vaporized during the Giant Impact. Part of this vapour may have remained in the disk, to eventually participate in the Moon’s small core. Similarly, during the late veneer stage a large fraction of the planetesimals have their cores undergoing partial vaporization. This would help to mix the highly siderophile elements into magma ponds or oceans.

 

References:

[1] Z. Li, R. Caracas, F. Soubiran, Partial core vaporization during Giant Impacts inferred from the entropy and the critical point of iron, Earth Planet. Sci. Letters, 2020, https://doi.org/10.1016/j.epsl.2020.116463

 

How to cite: Li, Z., Caracas, R., and Soubiran, F.: Partial core vaporization during giant impacts inferred from the entropy and the critical point of iron, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-1145, https://doi.org/10.5194/egusphere-egu21-1145, 2021.

EGU21-12352 | vPICO presentations | GMPV4.2

Trace and minor element variations in lunar granulites: Insights into lunar metamorphic conditions.

John Pernet-Fisher, Margaret Hartley, and Kathrine Joy

Metamorphic rocks on the Moon are an important yet under-studied suite of lunar lithologies that have been identified in the Apollo and lunar meteorite collections [1]. These rocks, with granoblastic textures, are generally referred to as granulites; however, unlike their terrestrial counterparts, they are considered to represent the products of only high-temperature (> 1000 oC) thermal metamorphism that completely re-crystallised their protolith(s). Lunar granulites are commonly sub-divided into two main compositional groups related to their protolith lithologies. The Fe-granulites, found at most Apollo landing sites, are generally accepted to derive from metamorphosed plagioclase-rich igneous cumulates, termed the ferroan anorthosite (FAN) suite. The FAN suite are important lithologies as they represent products of the primary lunar crust. The Mg-granulites are found mostly at the Apollo 16 landing site and within lunar meteorite samples; the protolith(s) of this latter group is not well understood [2].  Early studies have linked the protolith to secondary magmatic intrusions into the primary anorthositic crust (termed the Mg-suite); however, recent studies have tentatively connected the protolith to a Mg-rich variation of the primary crustal plagioclase cumulates (termed the MAN suite). The occurrence of MANs is controversial, it is unclear how the MAN suite fits into canonical lunar crustal formation models [3]. To investigate the protoliths of the granulite suites, we report in situ trace- and minor-element abundances for olivine and pyroxene grains within Fe- and Mg-granulites, determined by LA-ICP-MS and EPMA respectively. Trace-element data presented here indicate that the Mg-granulites are compositionally similar to the MAN suite. Furthermore, by comparing plagioclase trace-element data with peak metamorphic temperatures (calculated using two-pyroxene thermometers [4]), we find no relationship between metamorphic temperature and diagnostic trace-element signatures suggesting that both granulite suites experienced similar thermal metamorphic conditions. Additionally, we estimate the duration of metamorphic heating using experimentally derived diffusion rates of minor elements in minerals,  (such as Ca in olivine [5]). Both the calculated cooling rates and peak metamorphic temperatures can set constraints on the metamorphic heat source responsible for thermally annealing the Fe- and Mg-granulites. Specifically, we are able to assess whether the granulites formed as a result of shallow (<1 km) burial of the protolith by impact melt sheets or hot, impact-generated fall-back breccias [6]; or deep (> 1km) contact metamorphism of the protolith due to the emplacement of magma chambers or upwelling plutons within the lunar crust [7].

 

[1] Lindstrom & Lindstrom, 1986, JGR, 91(B4), 263-276 [2] Treiman et al. 2010. MaPS, 45, 163-180. [3] Gross et al. 2014, EPSL, 388, 318-328. [4] Brey & Köhler, 1990, J Pet, 31, 1353-1378. [5] Dohmen et al, 2007, PCM, 34, 389-407. [6] Cushing et al. 1999, MaPS, 34, 185-195. [7] Hudgins et al. 2011, Am Min, 96, 1673-1685.

How to cite: Pernet-Fisher, J., Hartley, M., and Joy, K.: Trace and minor element variations in lunar granulites: Insights into lunar metamorphic conditions., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12352, https://doi.org/10.5194/egusphere-egu21-12352, 2021.

EGU21-12247 | vPICO presentations | GMPV4.2

Origins and Implications of the Apollo 16 Breccia Noble Gas Suite

Mark C. Nottingham, Natalie M. Curran, John Pernet-Fisher, Ray Burgess, and Katherine H. Joy

The Apollo 16 landing site is dominated by regolith breccias; consolidated regolith palaeo-soils [5,7,8]. Each regolith soil (and, by extension, each regolith breccia) is composed of fragments of rock sourced from different impacts and lithological units [e.g. 2,3]. Because of this, these samples probe the impact history of the lunar surface across a wide range of time. McKay et al. (1986) reported the trapped argon isotope ratios (i.e., 40Ar/36ArTr) values of regolith breccias and used these values to semi-quantitatively model breccia formation ages [see also 4]. Two groups of regolith breccias were identified at the Apollo 16 landing site: (i) the ‘ancient’ group, lithified immature regolith (i.e., <30 Is/FeO), and (ii) a ‘younger’ group that generally have higher levels of maturity. Joy et al. (2011) used the 40Ar/36ArTr ratios to model that: (i) the ancient samples closed from soils to breccias between ~3.8 and 3.4 Ga, consistent with regolith developed and consolidated after the Imbrium basin-forming event, and during a time of declining basin-forming impacts, and (ii) that the young breccias were assembled in the Eratosthenian period between ~2.5 and 1.7 Ga, providing insight into post-basin bombardment impact processes.

A third set of regolith breccias identified by Jerde et al. (1987, 1990), (the soil-like breccias), have no reported noble gas or exposure age information. Joy et al. (2011) inferred that these samples were likely consolidated into breccias in the last 2 Ga (based on their Is/FeO maturity being similar to the Apollo 16 soils). They, therefore, may extend the current archive of impact and regolith processes into the Eratosthenian and Copernican periods.

Whole-rock samples were laser step heated and the extracted gases were measured using a Thermo Scientific Helix-MC noble gas magnetic sector mass spectrometer. Preliminary analysis of our data shows these breccias are dominated by a solar wind composition component, with minor spallation and radiogenic contributions. The concentrations of evolved gases suggest the samples are more similar in terms of noble gas budget to the present day Apollo 16 soil samples (based on analysis using data collated by Curran et al. 2020), than the ancient gas-poor Apollo 16 regolith breccias (McKay et al. 1986). Thus, these noble gas data are consistent with the petrological characterisation and Is/FeO classification [5,6] of these breccias being comparable to present day Apollo 16 soil samples. Solar wind composition gas concentrations comparable to present day soil samples suggest these new breccias represent consolidated regolith of comparable maturity, perhaps suggesting these soil-like breccias were formed around the same time period as the ‘younger’ group.

References: [1] Curran, N.M., et al., 2020, PSS, 182, 104823. [2] Donohue, P.H., et al., 2013, 44th LPSC, A#2897.; [3] Fagan, A.L., et al., 2013, GCA, 106, 429-445.; [4] Fagan, A.L., et al., 2014, Earth Moon Planets, 112, 59–71.; [5] Jerde, E.A., et al., 1987, J. Geophys. Res., 92(B4), E526– E536.; [6] Jerde, E.A., et al., 1990, EPSL, 98(1), 90-108.; [7] Joy, K.H., et al., 2011, GCA, 75(22), 7208-7225.; [8] McKay, D.S., et al., (1986), J. Geophys. Res., 91(B4), 277– 303.

How to cite: Nottingham, M. C., Curran, N. M., Pernet-Fisher, J., Burgess, R., and Joy, K. H.: Origins and Implications of the Apollo 16 Breccia Noble Gas Suite, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12247, https://doi.org/10.5194/egusphere-egu21-12247, 2021.

EGU21-10792 | vPICO presentations | GMPV4.2

Combined microstructural analysis and in-situ U-Pb chronology of baddeleyite within shergottites Northwest Africa (NWA) 7257, NWA 8679 and Zagami 

Leanne Staddon, James Darling, Winfried Schwarz, Natasha Stephen, Sheila Schuindt, Joseph Dunlop, and Kim Tait

Baddeleyite (monoclinic; m-ZrO2) is an important U-Pb chronometer within mafic lithologies from many planetary bodies. Recent in-situ U-Pb dating of micro-baddeleyite within shergottites has been key in confirming recent magmatic activity on Mars. However, despite a high U-Pb closure temperature (≥900 °C) and the retention of robust U-Pb isotope systematics to ~57 GPa within experimental studies, up to 80% Pb loss within baddeleyite has been reported from the highly-shocked shergottite Northwest Africa (NWA) 5298. Significantly, U-Pb isotopic disturbance has been shown to be strongly linked with baddeleyite internal microstructure, generated by partial to complete reversion from meta-stable, high P-T zirconia polymorphs during shock metamorphism. NWA 5298 has experienced elevated shock metamorphism, and particularly post-shock temperatures, in comparison to many other shergottites; in the absence of microstructural analyses, the magnitude of baddeleyite U-Pb isotopic disturbance within more moderately shocked shergottites remains unknown.

To address this, we combine electron backscatter diffraction (EBSD) microstructural analysis and in-situ U-Pb chronology of baddeleyite within three enriched shergottites: NWA 7257, NWA 8679 and Zagami. Studied samples have undergone shock conditions typical of shergottites, with complete transformation of plagioclase to maskelynite and pervasive fracturing of pyroxene, phosphates and oxides. Small veinlets of shock melt cross-cut NWA 8679 and Zagami, and shock melt pockets are present in all samples. Baddeleyite is abundant and ubiquitously associated with late-stage igneous assemblages, rather than shock melt.

We document a wide range of baddeleyite microstructures. These include crystal-plastically deformed magmatic twins, domains with a marked decrease in crystallinity, and complex, nanostructured domains with orthogonal orientation relationships that are interpreted to have resulted from complete reversion from high P-T polymorphs. Magmatic twins are only locally preserved due to shock heterogeneity. Despite this, and in contrast to NWA 5298, we find no link between baddeleyite microstructure and U-Pb isotope systematics. Analyses fall along well-defined discordia within Tera-Wasserburg plots for each sample, with the U-Pb isotopic composition of analyses controlled by overlap with surrounding phases and fractures rather than baddeleyite microstructure. We therefore determine two new, microstructurally constrained ages from discordia lower intercepts: 195 ± 15 Ma (95% confidence; MSWD 5.6) for NWA 7257 and 220 ± 23 Ma (95% confidence; MSWD 2.2) for NWA 8679. For Zagami, our findings support the previously reported magmatic crystallisation age of ~180 Ma. These results provide further confirmation that high post-shock temperatures are required to induce resolvable U-Pb isotopic disturbance baddeleyite, even within highly shocked samples, and that reversion from high P-T zirconia polymorphs alone does not necessitate U-Pb isotopic disturbance. While we caution the continued requirement for detailed microstructural analyses of baddeleyite prior to isotopic analyses, this study underlines the utility of baddeleyite chronology within martian meteorites and other shocked planetary materials.

How to cite: Staddon, L., Darling, J., Schwarz, W., Stephen, N., Schuindt, S., Dunlop, J., and Tait, K.: Combined microstructural analysis and in-situ U-Pb chronology of baddeleyite within shergottites Northwest Africa (NWA) 7257, NWA 8679 and Zagami , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10792, https://doi.org/10.5194/egusphere-egu21-10792, 2021.

EGU21-12820 | vPICO presentations | GMPV4.2

Volatile depletion and evolution of Vesta from coupled Cu-Zn isotope systematics

Jasmeet K. Dhaliwal, James M.D. Day, John B. Creech, and Frederic Moynier

The moderately volatile elements, Cu and Zn, are not strongly affected by magmatic differentiation [1, 2] and are important tracers of volatile depletion in planetary bodies, particularly low-mass, airless bodies [3]. New isotopic ratio and abundance measurements for both Cu and Zn are presented for eucrites to more fully understand volatile depletion processes that affected the parent-body of the howardite-eucrite-diogenite (HED) meteorites, the asteroid 4-Vesta. Zinc isotope ratios are reported for twenty-eight eucrite samples, which along with prior data [4] yield a range of δ66Zn from -1.8 to +6.3 ‰, excluding one outlier, PCA 82502 (δ66Zn = -7.8 ‰) and a Zn concentration range from 0.3 to 3.8 p.p.m. Heavy Zn isotopic ratios (positive δ66Zn compositions) in eucrites form a negative trend with Zn concentration, reflecting volatile depletion processes on Vesta that are similar to the Moon [5, 6]. Within the combined sample set, eleven eucrites have light Zn isotopic compositions from δ66Zn of -0.02 to -7.8 ‰, with the majority having more negative compositions than likely chondritic precursors (maximum δ66Zn of ~ -0.2 ‰ [7]). These samples are interpreted to reflect condensates formed subsequent to surface volatilization and outgassing, such as during impact bombardment. Measurements of Cu compositions are also reported for nineteen of the samples, yielding a range of δ65Cu from -1.6 to +0.9 ‰, and range of Cu concentrations from 0.2 to 2.8 p.p.m., with the exception of Stannern (Cu > 10 ppm). As with Zn, negative Cu isotopic ratios that are lighter than chondritic compositions (δ65Cu ~ -0.5 ‰ [8]) are attributed to recondensation that occurred following impact-induced vaporization (cf. [9]). Within the wide ranges of Zn and Cu isotopic compositions measured in eucrites, most samples cluster within ~ 0 ‰ < δ66Zn < +3 ‰ and ~ 0.2 ‰ < δ65Cu < +0.9 ‰. This range is interpreted to reflect volatile depletion processes similar to those that affected the Moon (BSM: δ66Zn +1.4 ± 0.5‰ [5, 6, 10, 11] and δ65Cu = +0.92 ± 0.16‰ [9-11]). The greater heterogeneity in eucrite Zn and Cu isotopic compositions compared to lunar samples can be attributed to the smaller size of the HED parent asteroid, which may have experienced more limited homogenization of these signatures following volatile depletion and for eucrites which have experienced complex impact addition and metamorphic processes.  

[1] Chen et al. (2013) EPSL, 369, 34-42. [2] Savage et al. (2015) Geochemical Perspective Letters, 1, 53-64. [3] Day and Moynier (2014) Philisophical Transactions of the Royal Society A, 372, p.20130259. [4] Paniello et al. (2012) GCA, 86, 76-87. [5] Paniello et al. (2012) Nature, 490, 376-379. [6] Kato et al. 2015 Nature Communications, 6, 1-4. [7] Luck et al. (2005) GCA 69, 5351-5363. [8] Luck et al. (2003) GCA, 67¸143-151. [9] Day et al. (2019) GCA, 266, 131-143. [10] Moynier et al. (2006) GCA, 70, 6103-6117. [11] Herzog et al. (2009) GCA, 73, 5884-5904.

How to cite: Dhaliwal, J. K., Day, J. M. D., Creech, J. B., and Moynier, F.: Volatile depletion and evolution of Vesta from coupled Cu-Zn isotope systematics, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12820, https://doi.org/10.5194/egusphere-egu21-12820, 2021.

EGU21-1230 | vPICO presentations | GMPV4.2

Superheating and cooling rates effects on olivine growth in chondritic liquid: experimental and petrographic approach

Marion Auxerre, François Faure, and Delphine Lequin

Chondrules - major constituent of chondrites (primitive meteorites) - belong to the first object formed in the solar system. They are millimetre-sized igneous objects resulting from partial to complete fusion and are divided into main families: non-porphyritic and porphyritic (Gooding and Keil, 1981); the latter one is more abundant in chondrites. This study aims to reproduce thermal histories of macro-porphyritic olivine chondrules (PO) and to better constrain (thermal, temporal) the conditions reigning in the early solar system.

In general, PO chondrules are composed of numerous euhedral crystals of olivine and/or pyroxene suggesting an initially melting below their liquidus temperatures. By contrast, in our study, the macro-porphyritic olivine chondrule displays only one large euhedral olivine. The low number of olivine crystals indicates that chondrule suffered an initial step of superheating, limiting nucleation process (Lofgren, 1988; Hewins et al., 1988). Moreover, embayments observed in euhedral olivine show that olivine crystal began to growth rapidly and then the growth-rate decreased during the cooling. Therefore, our petrographic investigation proposes a first high temperature stage (ΔTliq = +10 °C) followed by a slow cooling.

To test this thermal history, experiments are performed to determine degree of superheating and cooling rate effect (i) on nucleation rate and (ii) on morphology of olivines formed during cooling. Preliminary results seem to confirm that macro-porphyritic olivine chondrules result from the slow cooling of a superheated initial chondritic liquid (Varela et al., 2006). Then these results allow to precise the beginning of the igneous processes (minimum thermal temperature and cooling rate) and to discuss the complete thermal evolution of the chondrule, by considering all other reaction textures observed in this chondrule: peritectic and oxidation reactions, quench texture and aqueous alteration.

 

References:

Gooding et al., (1981) Meteoritics, 16, No. I; Hewins et al., (1988) Meteoritics, 25, 309-318; Lofgren, (1988) Geochim. & Cosmochim. Ada, 50, 1715-1726; Varela et al., (2006) Icarus, 178 (2), 553–569.

How to cite: Auxerre, M., Faure, F., and Lequin, D.: Superheating and cooling rates effects on olivine growth in chondritic liquid: experimental and petrographic approach, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-1230, https://doi.org/10.5194/egusphere-egu21-1230, 2021.

EGU21-1751 | vPICO presentations | GMPV4.2

A rare free silica-bearing micrometeorite

Dafilgo Fernandes

Extraterrestrial dust that reaches the Earth’s surface has shown to represent the diverse types of samples from different precursors, namely, asteroid complexes and cometary bodies from the solar system. A substantial amount of this dust that strikes the upper atmosphere is believed to have been lost due to frictional heating with air molecules. Cosmic spherules that are melted particles are some of the widely recognized micrometeorites that survived this catastrophic entry process; however, their primordial characteristics are altered from their precursors making it difficult to identify the precursors. An individual peculiar spherule MS-I35-P204 recovered from the Antarctica blue ice has been identified. The spherule has been segregated using magnetic separation method, mounted in epoxy, and examined using SEM, subsequently analysed under electron microprobe. It is surrounded by a thin magnetite rim, and also holds a single kamacite bead that protrudes out at its top. The interior mineralogy mostly constitutes of a bulk pyroxene normative glass (MnO>2wt%) with several vesicles. The rare mineral phase is a skeletal aggregate of free silica, bearing Fe nuggets embedded in a glass. An isolated narrow lath of forsterite appears to be chondritic and is observed as relict grain that is associated with an anomalous low Ca pyroxene (MnO ~1.3 wt%, FeO~13 wt%). Earlier, free silica has been reported in some chondritic meteorites particularly the Enstatite and Ordinary group, and also in some carbonaceous chondrites such as CM, CR, CH, and K. It profoundly forms a pod that encloses the ferromagnesian silicate in silica-bearing chondrules. The unusual mineral assemblage seen in this spherule thereby appears to constrain probably the unique type of its contributor which need to be studied.

How to cite: Fernandes, D.: A rare free silica-bearing micrometeorite, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-1751, https://doi.org/10.5194/egusphere-egu21-1751, 2021.

GMPV5.1 – Solving geoscience problems using mineralogy

Nitrogen cycling between the Earth’s surface and interior influences atmosphere evolution, climate and habitability of our planet. Nitrogen transport process in the Earth’s interior is a key part of the cycling, which remains enigmatic. Silicate minerals are the main carriers of nitrogen mainly in the form of ammonium. Thus, untangling interactions of ammonium and lattice of the host minerals at the deep Earth’s conditions, is essential for understanding nitrogen transport process.

Feldspar, the most abundant mineral in the Earth’s crust, is a carrier of nitrogen to the deep Earth. Nitrogen is incorporated as ammonium in the M site of feldspar framework. To investigate interactions of ammonium and lattice at high temperatures, we conducted FTIR, Raman and XRD spectra measurements at high temperatures to 1000 oC on an ammonium-bearing feldspar, and revealed ammonium diffusivities and impacts on the lattice. The results show that diffusivities of ammonium at 800, 900 and 1000 oC are comparable to those of hydroxyl in feldspar, but much slower than structural molecular water. Importantly, ammonium in the M site of feldspar seems more stable than that in the layered site of phengite previously reported. Moreover, ammonium-bearing feldspar has smaller temperature-induced Raman mode wavenumber shifts and thermal expansion coefficients, as compared with ammonium-free feldspar.

The above results suggest interactions of ammonium and lattice of the silicate minerals at high temperatures. Thermal stabilities of ammonium depend on structure of the host silicates, and thermal stabilities of the host silicates are in turn affected by ammonium incorporated.

How to cite: Yang, Y.: Interactions of ammonium and lattice of feldspar at high temperatures, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-13827, https://doi.org/10.5194/egusphere-egu21-13827, 2021.

EGU21-13814 | vPICO presentations | GMPV5.1

Topotaxial intergrowth and origin of antiperthite in monzogranite 

Yueting Song and Shanrong Zhao

The crystallographic orientation of antiperthite (squared alkali feldspar inclusions grow inside plagioclase host) in Tiantangzai monzogranite from Dabie Mountain was investigated. The morphology of alkali feldspar inclusions is hexahedron, three pairs of parallel faces are controlled by the (010), (001) and (110) planes of the host plagioclase, respectively. Some plagioclase develops albite polysynthetic twin, defined the twinned individuals as Pl(1) and Pl(2), respectively; some alkali feldspar inclusions are related by Carlsbad twin, the twinned individuals are also defined as Kfs(1) and Kfs(2), respectively. Pl(1) is oriented similarly to Kfs(1). The topotaxial relationship between Pl(2) and Kfs(1) is similar to albite-twin. The topotaxial relationship between Kfs(2) and Pl(1) is similar to Carlsbad-twin. Kfs(2) and Pl(2) would form a topotaxial relationship similar to Carlsbad-albite-twin. Pl(1) generally becomes thinner or disappears in the regions where alkali feldspar inclusions developed. The development sequence of the alkali feldspar inclusions and the polysynthetic albite twin needs to be further investigated. Electron microprobe line scanning shows a homogeneous K, Ca and Na distribution in a single plagioclase grain with inclusions developed, suggesting that the origin of alkali feldspar inclusion may not be related to exsolution. The fractures in the host plagioclase are well developed, but most fractures do not pass through the embedded alkali feldspar. The precipitated alkali feldspar may be a result of alkali-bearing fluids penetrating through fractures and replacing plagioclase. The rim of some larger anhedral alkali feldspar inclusions has many voids, the local average misorientation map indicates there is a rectangular area with low misorientation difference inside the anhedral inclusions. The anhedral alkali feldspar inclusions are presumed to form by secondary replacement on top of the original rectangular inclusions.

How to cite: Song, Y. and Zhao, S.: Topotaxial intergrowth and origin of antiperthite in monzogranite , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-13814, https://doi.org/10.5194/egusphere-egu21-13814, 2021.

EGU21-12665 | vPICO presentations | GMPV5.1

Orientation relationships between magnetite micro-inclusions and plagioclase host 

Olga Ageeva, Ge Bian, Gerlinde Habler, and Rainer Abart

Magnetite micro-inclusions in silicate minerals are important carriers of the remanent magnetization of rocks. Their shape orientation relationships (SOR) and crystallographic orientation relationships (COR) to the host crystal are of interest in the context of the bulk magnetic properties of the inclusion-host assemblage. We investigated the SOR and COR of magnetite (MT) micro-inclusions in plagioclase (PL) from oceanic gabbro using correlated optical microscopy, scanning electron microscopy, Electron backscatter diffraction analysis and Transmission electron microscopy.

In the mm-sized PL crystals of the investigated gabbros MT is present as equant, needle- and lath-shaped (sub)micrometer sized inclusions. More than 95% of the needle-shaped inclusions show SOR and specific COR to the plagioclase host. Most of the needles are elongated perpendicular to one of the MT{111} planes, which is aligned parallel to one of the (112), (1-12), (-312), (-3-12), (150), (1-50) or (100) planes of plagioclase. These inclusions are classified as “plane-normal type”. The needle elongation parallel to MT<111>, which is the easy direction of magnetization, ensures high magnetic susceptibility of these inclusions. The underlying formation mechanism is related to the parallel alignment of oxygen layers with similar lattice spacing across the MT-PL interfaces that are parallel to the elongation direction [1].

Apart from the SOR and the alignment of a MT{111} with one of the PL low index planes, the MT crystals rotate about the needle elongation direction. The rotation angles are statistically distributed with several maxima representing specific orientation relationships. In some cases one of the MT<001> axes is aligned with PL[14 10 7] or PL[-14 10 -7], which ensures that FeO6 octahedra of MT well fit into channels // [001] of PL, which are formed by six membered rings of SiO4 and AlO4 tetrahedra [2]. This COR is referred to as the “nucleation orientation” of magnetite with respect to PL. There are several other possibilities to fit FeO6 octahedra into the [001] channels of PL, but the alignment stated above allows for the additional parallel alignment of one of the MT{111} with one of the above mentioned low index lattice planes of PL. MT crystals with one of these nucleation orientations can undergo directional growth to develop laths and needles. MT crystals with other nucleation orientations that do not allow for the parallel alignment of MT{111} with the above mentioned PL lattice planes, do not significantly grow and form the equant inclusions.

For some needles one or more of the MT{011} planes that are parallel to the needle elongation direction, are aligned with low-index planes of plagioclase such as PL (112), PL(150), PL(1-50) etc., and form MT facets. This situation corresponds to achievement of the best possible match between the two crystal lattices. This can either be generated during primary growth or during re-equilibration of the micro-inclusions and the plagioclase host.

Funding by RFBR project 18-55-14003 and Austrian Science fund (FWF): I 3998-N29 is acknowledged.

Reference

[1] Ageeva et al (2020) Contrib. Mineral. Petrol. 175(10), 1-16.

[2] Wenk et al (2011) Am. Min. 96, 1316-1324

How to cite: Ageeva, O., Bian, G., Habler, G., and Abart, R.: Orientation relationships between magnetite micro-inclusions and plagioclase host , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12665, https://doi.org/10.5194/egusphere-egu21-12665, 2021.

EGU21-10116 | vPICO presentations | GMPV5.1

Using electron backscatter diffraction to determine the formation mechanism of mineral inclusions in garnet

Thomas Griffiths, Victoria Kohn, Rainer Abart, and Gerlinde Habler

Determining the origin of mineral inclusions is a key problem in petrology. Assuming different inclusion formation mechanisms can lead to dramatically different petrological interpretations. Crystallographic orientation relationships (CORs), systematic relationships between the crystallographic orientations of crystals sharing boundary segments, are sensitive to the mechanisms of inclusion formation. Electron backscatter diffraction (EBSD) in the scanning electron microscope yields highly spatially resolved information about host-inclusion CORs. EBSD point analyses allow collection of large COR datasets, while retaining a link to the location of every measured inclusion and any shape preferred orientation (SPO) relative to host crystallography and microstructures. Based on combined COR, SPO and location information, we can differentiate between multiple origin hypotheses where COR formation is predicted, and the large number of measurements achievable allows observation of the relative frequency of different CORs.

Acicular rutile inclusions in garnet with SPOs parallel to garnet crystal directions are often interpreted based on microstructures alone as products of exsolution, implying the existence of precursor Ti-bearing garnet. We studied rutile needles from metapegmatite garnets from two localities with separate geological histories. Rutile needles occur in zones that extend parallel to garnet {112} (both localities) and {110} (one locality) crystal planes. Needles are elongated parallel to <111> (both localities) and <100> (one locality) directions in the garnet hosts. The majority of needles show a “specific” (completely fixed) COR to the garnet host. Several different CORs can be found within a single garnet domain and the frequency of different CORs varies both between domains from the same locality and between localities. Despite the existence of several CORs, there is a systematic link between the rutile-garnet COR exhibited by a given needle inclusion and its elongation direction relative to the crystallography of both garnet and rutile.

A comparison with literature datasets of CORs from garnets with acicular rutile inclusions reveals that both the type and frequencies of rutile-garnet CORs found in metapegmatite garnets differ strongly from those found in garnets of purely metamorphic origin. CORs judged to result in a poor alignment between rutile and garnet structures are considerably more frequent in the metapegmatite samples.

In garnets from one locality, the SPO of rutile needles does not favour all crystallographically equivalent garnet <111> directions equally. Instead, needles are preferentially elongated parallel to garnet <111> directions at high angles to the garnet facets defined by inclusion zoning. SPO and COR of the rutile needles thus depend on the orientation of the growing garnet interface, which is incompatible with an exsolution origin for these inclusions. Oriented nucleation of rutile at the garnet interface and subsequent simultaneous growth of both phases can account for these observations.

These results show the power of combining spatially resolved COR data with SPO information. An exsolution origin for rutile needles cannot be proposed based on needle SPO alone, and specific CORs are not necessarily indicative of an exsolution origin for rutile needles even if they occur together with an SPO relative to the garnet host.

We acknowledge funding by the Austrian Science Fund (FWF): I4285-N37.

How to cite: Griffiths, T., Kohn, V., Abart, R., and Habler, G.: Using electron backscatter diffraction to determine the formation mechanism of mineral inclusions in garnet, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10116, https://doi.org/10.5194/egusphere-egu21-10116, 2021.

EGU21-5066 | vPICO presentations | GMPV5.1

High-pressure crystal chemistry of four natural REE(As,P)O4 minerals from Mt. Cervandone, Italy

Francesco Pagliaro, Paolo Lotti, Alessandro Guastoni, Davide Comboni, G. Diego Gatta, Nicola Rotiroti, and Sula Milani

REE orthoarsenates and orthophosphates are common accessory minerals characterized by the general chemical formula REEXO4, where REE represents one of the lanthanides (La-Lu series), Y, Sc, Ca or Th, whereas X stands for As, P or Si. In the framework of a long-term project on the high-T/high-P crystal-chemistry and phase-stability of REE-bearing minerals, the high-pressure behavior of chernovite-(Y) (nominally YAsO4), xenotime-(Y) (nominally YPO4) gasparite-(Ce) (nominally CeAsO4) and monazite-(Ce) (nominally CePO4), has been studied. Chernovite-(Y) and xenotime-(Y) show a HREE- (Gd-Lu series) and Y-enrichment, and the same tetragonal symmetry (space group I41/amd), whereas gasparite-(Ce) and monazite-(Ce) share the same LREE (La-Eu) enrichment and monoclinic cell (space group P21/n). All these minerals occur at Mt. Cervandone (Western Alps, Italy), a renowned Alpine REE-bearing mineral deposit. The crystal chemistry of the four minerals has been studied via EPM-WDS analysis. Excluding gasparite-(Ce), which formation is bound to the replacement of the mineral synchisite-(Ce) (CaCe(CO3)2F), a sensible enrichment in Gd and Ho is observed. Moreover, the majority of the chernovite-(Y) show a variable amount of ThO2, up to 13 wt%, and phosphorous as substitute for arsenic in almost every proportion. In the case of the monoclinic series between monazite-(Ce) and gaparite-(Ce), no solid solution has been observed. Experiments at high-pressure were performed by in situ synchrotron X-ray diffraction using a diamond anvil cell. The high-pressure behavior of single crystals of xenotime-(Y), gasparite-(Ce) and monazite-(Ce) has been studied up to ~20 GPa, whereas that of chernovite-(Y) has been studied by powder diffraction up to 8.20(5) GPa. A II-order Birch-Murnaghan equation of state was fitted to the V-P data, within the phase stability field of the minerals, yielding the following bulk moduli: KP0,T0 = 125(3) GPa (βV0 = 0.0080(2) GPa-1) for chernovite-(Y); KP0,T0 = 145(2) GPa (βV0 = 0.0069(1) GPa-1) for xenotime-(Y);  KP0,T0 = 106.7(9) GPa (βV0 = 0.0094(1) GPa-1) for gasparite-(Ce), KP0,T0 = 121(2) GPa (βV0 = 0.0083(1) GPa-1) for monazite-(Ce). K’ = ∂KV/∂P = 4 (fixed) for all the minerals. Deformation mechanisms, at the atomic scale, were described on the basis of structure refinements.  

Acknowledgments: This research was partly funded by the PRIN2017 project “Mineral reactivity, a key to understand large-scale processes” (2017L83S77).

How to cite: Pagliaro, F., Lotti, P., Guastoni, A., Comboni, D., Gatta, G. D., Rotiroti, N., and Milani, S.: High-pressure crystal chemistry of four natural REE(As,P)O4 minerals from Mt. Cervandone, Italy, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-5066, https://doi.org/10.5194/egusphere-egu21-5066, 2021.

EGU21-10129 | vPICO presentations | GMPV5.1

Nano-sized particles and semimetal-rich melts in PGE-rich magmatic mineral systems 

José María González-Jiménez, Joaquín A. Proenza, Fernando Gervilla, and Rubén Piña

The results of several high temperature experiments predict that nanoparticles and nanomelts enriched in noble metals indeed exist in magmatic systems. Nanoparticles of Ru-Os-Ir or P-bearing sulfides alloys have been synthetized from S-free or S-undersaturated basaltic silicate melts at > 1000 °C at > 1000 °C. Pt-rich arsenide nanoparticles have also been synthesized in high-temperature sulfide melts well before the melt had reached a Pt–As concentration at which discrete Pt arsenide minerals become stable phases. More recently, the immiscibility of PGE-rich bismuthide melts within Ni-Fe-Cu sulfide liquids have also observed in high-temperature experiments, evidencing the key role played by nanomelts in controlling the PGE partitioning in magmatic mineral systems and their necessary existence for the formation of PGE-rich nanoparticles. However, many researches still remain convinced that these nanoparticles represent artifacts produced during quenching of experimental runs. The combination of focused ion beam micro-sampling techniques with high-resolution transmission electron microscopy (HRTEM) observations allowed the identification of PGE nanoparticles and nanominerals in magmatic base-metal sulfides from the PGE-Cr deposits from the Bushveld Complex in South Africa  and the eastern Cuban ophiolites. Moreover, nanometer sized of all six PGEs (Os, Ir, Rh, Ru, Pt, Pd) are relatively frequent natural quenched silicate melts preserved in mantle xenoliths. Collectively, all these observations made on natural rocks confirm the predictions of previous experiments on the possible formation of PGE mineral nanoparticles in magmatic systems rather to be result of low-temperature subsolidus re-equilibrium of magmatic minerals.

 

 

How to cite: González-Jiménez, J. M., Proenza, J. A., Gervilla, F., and Piña, R.: Nano-sized particles and semimetal-rich melts in PGE-rich magmatic mineral systems , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10129, https://doi.org/10.5194/egusphere-egu21-10129, 2021.

EGU21-10025 | vPICO presentations | GMPV5.1

Evaluating the effects of deformation on the chemistry of composite magnesioferrite-magnetite crystals by means of EBSD

Igor González-Pérez, Samuel Noval-Ruiz, Jose María González-Jímenez, Fernando Gervilla, Isabel Fanlo, and Fernando Tornos

Chemical signatures of magnetite are commonly used to track the evolution of mineralizing systems in many geological settings. However, the impact of deformation processes on magnetite chemistry remains still underexplored. Here, we report a rare case of composite crystals consisting of magnetite and magnesioferrite recording different degrees and styles of deformation in order to evaluate how deformation promotes chemical modification. The samples employed in this study come from two different Mg-skarn iron deposits (i.e., El Robledal and San Manuel) from the Serranía de Ronda (SW Spain). Chemical data acquired by Electron Probe Microprobe Analyzer (EPMA) and Field Emission Scanning Microscopy (FESEM) are contrasted against microstructural data obtained by using Electron Back-Scattered Diffraction (EBSD). Our results show that magnesioferrite crystals [Fe2+# (Fe2+/Fe2++Mg2+) = 0.22-0.46 and Fe3+# (Fe3+/Fe3++Al3+) = 0.99-1.00] from El Robledal deposit are characterized by a ductile deformation that led to different crystallographic orientation domains along with the replacement of magnesioferrite by magnetite (Fe2+# (Fe2+/Fe2++Mg2+) = 0.51-0.99 and Fe3+ (Fe3+/Fe3++Al3+) =0.98-1.00] via coupled dissolution – reprecipitation. A replacement of magnesioferrite [Fe2+# (Fe2+/Fe2++Mg2+) = 0.43-0.64 and Fe3+ (Fe3+/Fe3++Al3+) = 0.99-1.00] by magnetite Fe2+# (Fe2+/Fe2++Mg2+) = 0.78-1.00 and Fe3+# (Fe3+/Fe3++Al3+) = 0.98-1.00] via a coupled dissolution – reprecipitation mechanism is also preserved in the composite (i.e., zoned) crystals from the San Manuel deposit, which was additionally overprinted by an additional recrystallization event as a result of grain boundary migration recrystallization. Our results show that deformation in a fluid-assisted deformation regime has induced chemical modification of the original magnesioferrite aggregates as well as strain localization. This close physicochemical link offers new avenues of interpreting the chemical signatures of Mg-Fe oxides, utilizing their microstructurally controlled variation or lack thereof.

How to cite: González-Pérez, I., Noval-Ruiz, S., González-Jímenez, J. M., Gervilla, F., Fanlo, I., and Tornos, F.: Evaluating the effects of deformation on the chemistry of composite magnesioferrite-magnetite crystals by means of EBSD, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-10025, https://doi.org/10.5194/egusphere-egu21-10025, 2021.

EGU21-61 | vPICO presentations | GMPV5.1

Mechanisms of bastnasite formation: replacement of calcite by rare earth carbonates.

Adrienn Maria Szucs, Alexandra Stavropoulou, Claire O'Donnell, Seana Davis, and Juan Diego Rodriguez-Blanco

The interaction of rare earth bearing (La, Nd, Dy) aqueous solutions with calcite crystals at was studied at ambient and hydrothermal conditions (25-220 °C) and resulted in the solvent-mediated surface precipitation and subsequent pseudomorphic mineral replacement of calcite by rare earth carbonates. Calcite grains were replaced from their periphery inwards, and the newly formed REE-bearing carbonates follow the crystallisation sequence lanthanite [REE2(CO3)3·8H2O] → kozoite [orthorhombic REECO3(OH)] → hydroxylbastnasite [hexagonal REECO3(OH)]. The specific rare earth involved in these processes and the temperature have a significant role in the polymorph selection, crystallisation pathways and kinetics of mineral replacement. La- and Nd-bearing kozoite, grows oriented onto the calcite surface, forming an epitaxy, due to their structural similarities. This phase forms elongated crystals on [100], with the {011} and {0-11} as major forms. The epitaxial relationship is (104) [010]cc ║(001) [100]koz and is strongly dependent on the ionic radius of the rare earth in the structure of kozoite. These results have strong implications for the understanding of mineralisation reactions occurring in REE-bearing carbonatite deposits, the most important resources of rare earths in the world.

How to cite: Szucs, A. M., Stavropoulou, A., O'Donnell, C., Davis, S., and Rodriguez-Blanco, J. D.: Mechanisms of bastnasite formation: replacement of calcite by rare earth carbonates., EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-61, https://doi.org/10.5194/egusphere-egu21-61, 2021.

EGU21-11559 | vPICO presentations | GMPV5.1

Tourmalinisation in peraluminous granitic context : from experiment to thermodynamic modelling

Julien Fort, Stanislas Sizaret, Michel Pichavant, Arnault Lassin, Johann Tuduri, and Olivier Blein

Tourmaline records the physico chemical conditions during its cristallisation, as its primary chemical zonations are generally unbalanced, its occurrence as alteration product could be used to decipher the physicochemical properties of mineralizing fluids. However, the role of the tourmalinisation in hydrothermal processes remains little studied, if not poorly understood.  The complexity of its thermodynamic properties is related to the presence of four cationic sites allowing the accommodation of a wide variety of elements (Henry and Dutrow, 2018). Moreover the phenomena of deprotonation, Si-IVB and valence state, make the approach of solid solution properties complex (Hughes et al., 2001; Henry et al., 2011; Bačík, 2015; Morgan, 2016). Thus, thermodynamic properties are most often estimated  (Garofalo et al., 2000; Hinsberg and Schumacher, 2007) and only a few measurements could be carried out on a reduced number of near-endmembers crystals (Kuyunko et al., 1984; Ogorodova et al., 2012).

This study aims to investigate experimentally the stability field of schorl (Na-Fe) – dravite (Na-Mg) solid solution at 2 kbar total pressure between 400° and 600°C as a function of the boron content of the fluid and fO2 condition, using an internally heated gas apparatus. Those metasomatic experiments have been conducted on a mixture of naturals crystals of cordierite + albite, representing a peraluminous granite composition in a Na-Mg-Fe-Al-Si-B-O-H system, characterized by a high-Mg, low-Fe content. These experiments were performed in order to simulate a classic aluminous host of these tourmaline alterations in granitic context. The results will be studied, in terms of stability of the tourmaline species, chemistry variation and texture. They will be compared with thermodynamic models build using data from the literature (Korges et al., 2018; Pan et al., 2019 among others) . Ultimately, the objective is to characterize in a P, T, W/R space, the chemical evolution of fluids, the alteration sequence of rocks and the variations in volumes related to the successive reactions.

How to cite: Fort, J., Sizaret, S., Pichavant, M., Lassin, A., Tuduri, J., and Blein, O.: Tourmalinisation in peraluminous granitic context : from experiment to thermodynamic modelling, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-11559, https://doi.org/10.5194/egusphere-egu21-11559, 2021.

EGU21-16170 | vPICO presentations | GMPV5.1

Multi-Element Correlation Analysis of Cu-bearing Tourmaline using LA-ICP-Time-Of-Flight-MS

Hao A.O. Wang, Michael S. Krzemnicki, Susanne Büche, Sarah Degen, Leander Franz, and Rainer Schultz-Guttler

Major, minor and trace element analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been applied to a broad range of mineral samples for characterization, mineral resources prospection, tracing and provenance determination, radiometric dating and studies on mineral formation conditions. In this study, we present a state-of-the-art LA-ICP-Time-Of-Flight-MS (LA-ICP-TOF-MS) technique for multi-element analysis of gem-quality Cu-bearing tourmaline from Brazil, Mozambique and Nigeria, with a special focus on elemental correlation among and within various provenances.

A TOF-MS obtains a full mass spectrum from 7Li+ to 238U+ simultaneously with an improved mass resolving power. These advantages over other conventional ICP-MS setups allow the TOF users to apply a novel concept of “first measure, then determine” which elements are of interest for the analysis of geological samples. Since the TOF-MS technique requires no/limited a priori knowledge about the sample before measurement, this technique can be beneficial for studying elements which occur infrequently in the minerals and for analysing full elemental composition in unidentified inclusions.

Multi-element composition of more than 400 Cu-bearing tourmaline samples (majority elbaite, Na-rich) was analysed using LA-ICP-TOF-MS that cover various colors, qualities and provenances available in the gem and jewellery trade. In order to investigate the elemental correlation, a non-linear unsupervised dimension reduction was performed on the high dimensional multi-element dataset using t-distributed stochastic neighbor embedding (t-SNE) algorithm. An unsupervised calculation works solely with the elemental concentrations and without labels of data points, for example color or provenance. The clusters in the geochemical data visualization indicates elemental similarity of various samples. We found that t-SNE algorithm is better than principle component analysis (PCA) algorithm in maintaining intrinsic elemental correlation from the original high dimensional space and embedding such information onto low dimensional datasets for visualization. Therefore, the t-SNE method excels in distinguishing within-group elemental similarities from between-group similarities. The separation of subgroups achieved with t-SNE is in agreement with the confirmed geographic provenances.

Additionally, a unique type of Cu-bearing liddicoatite (Ca and REE-rich) was recently discovered near Maraca in Mozambique (Nampula area). Since they have been reported so far only from this occurrence, this type of tourmaline is especially interesting to study how elements correlated during tourmaline formation. Applying t-SNE calculation on these samples, we have found two groups (or four subgroups) of these tourmaline samples. When multi-element concentration was plotted, it can be seen that light-REEs (La to Nd) have an apparent correlation with Ca concentration, however a negative correlation was observed between mid-REEs (Sm to Ho) and Ca. A correlation of Na to Bi and Th was also observed.

In a rare four-color (pink, purple, blue, green) Cu-bearing tourmaline sample from Quintos mine in the state of Rio Grande do Norte, Brazil, multi-element analysis was conducted along a profile across the entire color variation, from the core of the crystal (pink) to the rim of the crystal (green) to monitor elemental variations and correlations throughout the crystal growth process of this tourmaline within the pegmatite.

How to cite: Wang, H. A. O., Krzemnicki, M. S., Büche, S., Degen, S., Franz, L., and Schultz-Guttler, R.: Multi-Element Correlation Analysis of Cu-bearing Tourmaline using LA-ICP-Time-Of-Flight-MS, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-16170, https://doi.org/10.5194/egusphere-egu21-16170, 2021.

EGU21-16379 | vPICO presentations | GMPV5.1

Magnetite (U-Th-Sm)/He dating: analytical challenges and application

Marianna Corre, Martine Lanson, Arnaud Agranier, Stephane Schwartz, Fabrice Brunet, Cécile Gautheron, and Rosella Pinna

Magnetite (U-Th-Sm)/He dating method has a strong geodynamic significance, since it provides geochronological constraints on serpentinization episodes, which are associated to important geological processes such as ophiolite obductions, subduction zones, transform faults and fluid circulations. Although helium content that range from 0.1 pmol/g to 20 pmol/g can routinely be measured, the application of this dating technique however is still limited due to major analytical obstacles. The dissolution of a single magnetite crystal and the measurement of the U, Th and Sm present at the ppb level in the corresponding solution, remains highly challenging, especially because of the absence of magnetite standard. In order to overcome these analytical issues, two strategies have been followed, and tested on magnetite from high-pressure rocks from the Western Alps (Schwartz et al., 2020). Firstly, we purified U, Th and Sm (removing Fe and other major elements) using ion exchange columns in order to analyze samples, using smaller dilution. Secondly, we performed in-situ analyzes by laser-ablation-ICPMS. Since no solid magnetite certified standard is yet available, we synthetized our own by precipitating magnetite nanocrystals. The first quantitative results obtained by LA-ICP-MS using this synthetic material along with international glass standards, are promising. The laser-ablation technique overcomes the analytical difficulties related to sample dissolution and purification. It thus opens the path to the dating of magnetite (and also spinels) in various ultramafic rocks such as mantle xenoliths or serpentinized peridotites in ophiolites.

Schwartz S., Gautheron C., Ketcham R.A., Brunet F., Corre M., Agranier A., Pinna-Jamme R., Haurine F., Monvoin G., Riel N., 2020, Unraveling the exhumation history of high-press ure ophiolites using magnetite (U-Th-Sm)/He thermochronometry. Earth and Planetary Science Letters 543 (2020) 116359.

How to cite: Corre, M., Lanson, M., Agranier, A., Schwartz, S., Brunet, F., Gautheron, C., and Pinna, R.: Magnetite (U-Th-Sm)/He dating: analytical challenges and application, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-16379, https://doi.org/10.5194/egusphere-egu21-16379, 2021.

Stability relations of the REE-bearing accessory phases and alteration processes in the cancrinite-bearing nepheline syenite from the Čistá pluton (the center of the upper-crustal Tepla–Barrandian unit, Bohemian Massif, Czech Republic) were studied. Observations of rock microtextures, quantitative analyses of minerals and compositional X-ray mapping were performed using electron probe microanalysis (EPMA). The primary REE-bearing accessory minerals assemblage includes monazite-(Ce) associated with gadolinite-group minerals (i.e. gadolinite-(Ce) and gadolinite-(Y)), which were partially replaced by britholite-(Ce), bastnäsite-(Ce), aggregates of fine-grained REE-bearing phases (possibly fluorapatite and/or britholite-(Ce)) and, rarely, cerianite. K-feldspar and albite form intergrowths or symplectites with REE-phases in the investigated reaction microtextures. Furthermore, the zircon crystals demonstrate oscillatory zoning and/or extensive patchy zoning due to alteration processes. The alteration of accessory minerals are interpreted as driven by K- and Na-bearing alkali fluids with high CO2 activity during late- to post-magmatic processes.

Acknowledgements: This work was supported by the National Science Centre research grant no. 2017/27/B/ST10/00813.

How to cite: Jaranowski, M., Budzyń, B., Kozub-Budzyń, G. A., Sláma, J., and Klomínský, J.: Stability relations of monazite-(Ce), gadolinite-(Ce), gadolinite-(Y), britholite-(Ce) and bastnäsite-(Ce) during late- to post-magmatic processes in nepheline syenite (Čistá pluton, Czech Republic), EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-820, https://doi.org/10.5194/egusphere-egu21-820, 2021.

The pressure-temperature conditions are transient in time and space during tectonic processes. To understand the complete P-T history of crustal domains examining the mineral paragenetic sequences and zoning profiles of minerals from diverse lithologies in the domain is necessary. But in highly tectonised crustal domains establishing time equivalence between far-spaced samples is difficult. To overcome this, a mylonite sample with closely spaced layers of different mineralogy collected from the South Maharashtra Shear Zone located along the north of Western Dharwar Craton (Rekha and Bhattacharya, 2014) was studied. The mylonite has four mineralogically distinct layers of few millimeters width containing garnet porphyroblasts of distinct zoning pattern separated by quartz layers. Layer-1 has two domains on the basis of the relative abundance of quartz; Layer-1A with more quartz and less flaky minerals and Layer-1B with less quartz and more flaky minerals. Layer-1A is composed of quartz>biotite>plagioclase>chlorite>K-feldspar with syn- to post-tectonic garnet porphyroblasts and the fabric is defined by shape preferred biotite-chlorite aggregates, recrystallized plagioclase and quartz ribbons.Layer-1B is relatively quartz poor and plagioclase>biotite>chlorite>K-feldspar aggregates rich domain as compared to L1A with biotite-chlorite aggregates and recrystallized plagioclase defined fabric.Prehnite elongated parallel to schistosity present but not very common. Layer-2 is very thin with amphibole-biotite±chlorite defined foliation and consists of plagioclase-K-feldspar-quartz with large garnet porphyroblast ofsyn to post-tectonic origin. Chlorites are mainly present near to garnet. Layer-3 is composed of biotite-calcite-plagioclase-chlorite-quartz with syn/post-tectonic garnet porphyroblast and the foliation is defined by biotite-chlorite aggregates, recrystallize plagioclase, calcite grains aligned parallel to the foliation and elongated quartz grains.Layer-3 is separated from the quartz layers on both sides by the formation of thin hornblende layers arranged parallel to the foliation. Very few hornblende grains found within the layer aligned parallel with the fabric defining minerals. Large pre-tectonic muscovite grains are preserved in Layer-3 and are altered to epidote along the margins of the grain. Layer-4 consists of hornblende, calcite, quartz with few plagioclase, K-feldspar and post tectonic garnet porphyroblast. The fabric is defined by the long axis of amphibole and calcite grains aligned parallel to it. Later biotite-prehnite grains formed at high angle to the fabric defining minerals. Conventional geothermobarometers were used for P-T estimation and it varies from 450-560°C and 6 kbar for Layer-1A, 445-550°C and 7 kbar for Layer-1B, 475-570°C and 6 kbar for Layer-2, 450-575°C and 7-8 kbar for Layer-3 and 450-5500°C and 7-9 kbar for Layer-4 at reference temperature of 500°C and pressure of 6kbar. Though different layers have distinctly different mineral assemblages there is hardly any variation in the P-T conditions which implies the original bulk rock composition was different for different layers not the P-T conditions of deformation.

Keywords: Mylonite, Western Dharwar Craton, Geothermobarometry

How to cite: Praharaj, P. and Rekha, S.: Role of P-T conditions and bulk rock composition in the mineralogical variations in millimeter scale: a study from South Maharashtra Shear Zone, western India , EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-9966, https://doi.org/10.5194/egusphere-egu21-9966, 2021.

EGU21-4392 | vPICO presentations | GMPV5.1

Monitoring mineral precipitation sequence of Lake Magadi soda lake: A multi-technical approach

Melese Getenet, Juan Manuel García-Ruiz, Franziska Emmerling, Dominik Al-Sabbagh, Fermín Otálora, and Cristóbal Verdugo-Escamilla

Lake Magadi is a saline soda lake in East African Rift Valley, occupying the axial trough of Southern Kenyan Rift. Its fed by perennial saline hot/warm springs, which evolve into the soda and saline chemistry of the lake. The main processes thought to cause the enrichment of the lake in Na+, CO32-, Cl-, HCO3- and SO42- are evaporative concentration, mineral precipitation and fractional dissolution [1]. Lake Magadi is considered an analogous environment to the early Earth [2]. The high pH, silica and carbonate content of Lake Magadi allows the formation of silica and carbonate induced self-assembled mineral structures [3,4]. Revealing the mineral precipitation sequence of Lake Magadi have implications in understanding the geochemistry of evaporative rift settings and soda oceans. We have experimentally investigated the mineral precipitation sequence during evaporation at 25 °C. The sequence of mineral precipitation was recorded by using in-situ video microscopy. The mineral patterns observed in video microscopies were identified by spectroscopic, diffraction and electron microscopy techniques. The mineralogy and elemental composition of the precipitates were determined by using Raman spectroscopy, powder X-ray diffractions and scanning electron microscopy coupled with energy dispersive X-ray analyser. The results of the ex-situ analyses were compared with the in-situ X-ray diffraction. In-situ X-ray diffractions were performed on acoustically levitated droplets in the μSpot beamline at BESSY II synchrotron (Berlin, Germany). Finally, thermodynamic evaporation simulation was performed by using PHREEQC code with Pitzer database. Ex-situ and in-situ experiments revealed that mineral precipitation begins with trona, followed by halite and finally thermonatrite. In PHREEQC simulations, natron was observed instead of thermonatrite, suggesting the role of kinetics in the mineral assemblages. This multi-technical approach of in-situ monitoring and ex-situ characterization is a powerful approach to unveil mineral precipitation patterns and the resulting geochemical evolution in evaporative rift settings.

Acknowledgments: We acknowledge funding from the European Research Council under grant agreement no. 340863, from the Ministerio de Economía y Competitividad of Spain through the project CGL2016-78971-P and Junta de Andalucía for financing the project P18-FR-5008. M.G. acknowledges Grant No. BES-2017-081105 of the Ministerio de Ciencia, Innovacion y Universidades of the Spanish government.

References:

[1] Eugster, H.P. (1970). Chemistry and origin of the brines of Lake Magadi, Kenya. Mineralogical Society of America Special Papers, 3, 213–235.

[2] Kempe, S.; Degens, E.T. (1985). An early soda ocean?. Chem. Geol.  53, 95–108

[3] Getenet, M.; García-Ruiz, J.M.; Verdugo-Escamilla, C.; Guerra-Tschuschke, I (2020). Mineral Vesicles and Chemical Gardens from Carbonate-Rich Alkaline Brines of Lake Magadi, Kenya, Crystals, 10, 467.

[4] García-Ruiz J.M., van Zuilen M.A., Bach W. (2020) Mineral self-organization on a lifeless planet. Phys Life Rev, 34–35,62–82

How to cite: Getenet, M., García-Ruiz, J. M., Emmerling, F., Al-Sabbagh, D., Otálora, F., and Verdugo-Escamilla, C.: Monitoring mineral precipitation sequence of Lake Magadi soda lake: A multi-technical approach, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-4392, https://doi.org/10.5194/egusphere-egu21-4392, 2021.

EGU21-12619 | vPICO presentations | GMPV5.1

Comparison of Microporous Minerals for Potential Contaminant Uptake

Marvin Osorio, Christopher Oze, and Aaron Celestian

Microporous minerals have many industrial applications, from filtration to contaminant immobilization. Natural and synthetic minerals, including zeolites, clays, and silica aerogel, represent a few examples of microporous minerals with distinctive structures, surface charges, and porosity. Analysis and comparison of their crystal structures are necessary to determine how each mineral may be suited for contaminant uptake. Here we assessed the structure of microporous minerals, specifically rowleyite, clinoptilolite, vermiculite, and silica aerogel.  Raman spectroscopy, X-ray fluorescence, and X-ray powder diffraction were used to create and model atomic mineral structures to visualize atomic and macroscope features. Taking into account pore size and surface charge each mineral was reviewed to find the best fit with regards to heavy metal uptake, mainly Pb (lead). Overall, we provide a comparative framework to assess microporous minerals that will inform future flow-through experiments for heavy metal uptake.

How to cite: Osorio, M., Oze, C., and Celestian, A.: Comparison of Microporous Minerals for Potential Contaminant Uptake, EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-12619, https://doi.org/10.5194/egusphere-egu21-12619, 2021.

EGU21-870 | vPICO presentations | GMPV5.1

Reach of pollution and sediment correlation with the tailings in Šibenik Bay (Croatia)

Laura Huljek, Hana Fajković, and Željko Kwokal

To determine the influence of the historic factory of electrodes and ferroalloys on the Šibenik bay sediments, XRPD analysis were carried out. The factory was established in the city of Šibenik, on the coast of the Krka River estuary, and produced calcium carbide, and later electrodes and ferroalloys. It was active from 1900 until 1995 [1]. During that time, a large amount of produced tailings were stored nearby and on the shore of the estuary. Due to the presence of the strong winds (bora and sirocco), which can reach up to 130 km/h, the tailings material could be transported to long distances [2].

Samples of tailing were collected at the location of the former factory, which is a tailing hill today, samples of dust were collected from the rooftop of the factory in the 1980s. Other samples were taken on a 1 km distant beach in the Šibenik bay  (Beach A) and a 19 km distant beach on the island in the outer Šibenik archipelago (Beach B). Both beaches are located south-west of the factory. The samples from the beaches were taken with a corer at different depths: 0 – 3 cm, 3 – 5 cm, around 5 cm. The sample from 3 – 5 cm depth was not analysed.

Bulk sample and a fraction <63 µm were analysed on X-Ray Diffractometer. The XRPD analysis of the sediments from Beach B in the outer Šibenik archipelago shows that calcite and quartz are the most abundant phases. This mineral composition shows that distant islands were not affected by aeolian transportation of the factory dust and tailing. In the bulk samples from Beach A, in the uppermost part (0 – 3 cm depth) mineral components are calcite, aragonite, calcium manganite, bustamite ferroan and carbon, while calcite, quartz, aragonite, calcium manganite and manganosite are present in the fraction <63 µm. The sample from the depth of 5 cm at the same beach, shows calcite, aragonite and Mn-oxide, while fraction <63 µm lacks in Mn-oxide.

A bulk sample of tailings shows mineral components: calcite, quartz, calcium manganite, bustamite ferroan and gypsum which corresponds to the previous research [3], and there is also manganese silicon, manganese silicide, carbon and amorphous phase [4]. A fraction <63 µm of the tailing, shows the following mineral phases: calcite, quartz, calcium manganite and bustamite ferroan, as presented in previous research [3]. Analysis of the rooftop dust shows three phases: carbon, bustamite ferroan and manganosite, which does not correspond to the data given from the factory [3].

From the presented results, it could be concluded that the historic factory influenced sediments in the Šibenik bay, however, its influence was not detected on the Beach B 19 km to the SW, which opens the question of reach and distance to which tailings can be transported by sea and/or wind.

This work has been supported in part (samples collection) by Croatian Science Foundation under the project lP-2019-04-5832.

How to cite: Huljek, L., Fajković, H., and Kwokal, Ž.: Reach of pollution and sediment correlation with the tailings in Šibenik Bay (Croatia), EGU General Assembly 2021, online, 19–30 Apr 2021, EGU21-870, https://doi.org/10.5194/egusphere-egu21-870, 2021.