GMPV2.1 | Solving geoscience problems using mineralogy
EDI
Solving geoscience problems using mineralogy
Convener: Jannick Ingrin | Co-conveners: Mara MurriECSECS, Melanie J. SieberECSECS, Nicola CampomenosiECSECS, Julia SordylECSECS, Stylianos AspiotisECSECS, Marta Berkesi
Orals
| Mon, 15 Apr, 14:00–15:45 (CEST), 16:15–18:00 (CEST)
 
Room D3
Posters on site
| Attendance Tue, 16 Apr, 10:45–12:30 (CEST) | Display Tue, 16 Apr, 08:30–12:30
 
Hall X1
Posters virtual
| Attendance Tue, 16 Apr, 14:00–15:45 (CEST) | Display Tue, 16 Apr, 08:30–18:00
 
vHall X1
Orals |
Mon, 14:00
Tue, 10:45
Tue, 14:00
Mineralogy is the cornerstone of many disciplines and is used to solve a wide range of questions in geoscience. This broad session offers the opportunity to explore the diversity of methods and approaches used to study minerals and how minerals behave and evolve in their many contexts. Also, we will address issues that involve the use and development of spectroscopic techniques and the relevant ab initio simulations beyond current applications in metamorphic and magmatic petrology applied to the Earth and other planetary bodies.
We welcome contributions on all aspects of mineralogy, including environmental, soil science, metamorphic, plutonic, deep Earth, planetary, applied mineralogy, and so on. All approaches are welcome: analytical, experimental and theoretical."

Orals: Mon, 15 Apr | Room D3

Chairpersons: Jannick Ingrin, Mara Murri, Melanie J. Sieber
14:00–14:05
14:05–14:25
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EGU24-1725
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solicited
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Highlight
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On-site presentation
Luca Bindi

The study of iron-magnesium silicates within rocky planetary interiors has been a cornerstone of mineralogy, petrology and planetary science, offering insights into the composition and evolution of celestial bodies. The talk will present an exploration of the current understanding of these silicates and critically examines the question: Have we truly discovered them all?

Recent advancements in analytical techniques, including high-pressure experiments and computations, have challenged conventional assumptions about the ubiquity and diversity of iron-magnesium silicates. During the talk, key discoveries on Earth, Mars, and other celestial bodies will be reviewed revealing unexpected mineralogical variations and prompting a reevaluation of existing models.

How to cite: Bindi, L.: Iron-magnesium silicates in rocky planetary interiors: Have we really discovered them all?, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1725, https://doi.org/10.5194/egusphere-egu24-1725, 2024.

14:25–14:35
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EGU24-2231
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ECS
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On-site presentation
Hang yang and Jinlong Yao

Charnockite is an orthopyroxene-bearing felsic rock and an important constituent of the deep crust, thus, it holds significant importance in uncovering crustal growth and differentiation mechanisms. However, its generation and preservation remain debated. By focusing on mineral records, we here aim to provide a more detailed understanding of these issues. The Gaozhou charnockite in the Yunkai terrane of South China was chosen for extensive mineralogical studies and thermodynamic modeling. The Gaozhou charnockite contains granulitic enclaves, and mineral assemblages within charnockite can be divided into three phases, with the peak phase mainly composed of orthopyroxene, and minor biotite. Meanwhile, the charnockite and enclaves show comparable compositions of biotite and orthopyroxene. Embayed textures and high TiO2 content in biotite grains suggest high-temperature anatexis. On the other hand, the orthopyroxenes with inclusions and high Al2O3 content indicate peritectic origin. Moreover, reaction intergrowths of biotite with orthopyroxene grains have also been observed, suggesting that these grains were generated by the consumption of biotite. The Gaozhou charnockite has much lower zircon water content (135 ppm, median) as compared to that of the contemporary Opx-free granites (202-643 ppm, medians) in the Yunkai terrane, indicating dry primary parental melts. In addition, phase equilibria modeling constraints peak anatexis conditions at 860-870 ℃/6.2-7.0 kbar. Peritectic orthopyroxenes must have been generated by the incongruent melting of biotite under high-temperature granulitic facies in the lower crust. Subsequently, these grains were entrained and migrated by low water content melts to the upper crust. Therefore, overall observations favor a model of selective entrainment of source materials at a low magma water environment for the generation of the Gaozhou charnockite.

How to cite: yang, H. and Yao, J.: Generation of the charnockite by residua entrainment in water-deficient melts: insights from minerals composition and H2O-in-zircon, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2231, https://doi.org/10.5194/egusphere-egu24-2231, 2024.

14:35–14:45
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EGU24-20603
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On-site presentation
Donna Whitney, Sara Hanel, Max Wilke, and Angelika Rosa

A fundamental observation regarding oceanic subduction systems is that the starting material of subduction (MORB) is less oxidized than a major end-product (primitive magma in arcs), likely as a result of infiltration of mantle source regions by oxidized components from the subducted slab. Important redox-sensitive elements in slabs are S, C, H, and transition elements such as Fe and Mn. Fe is important because it is volumetrically significant, and release of other redox agents by dehydration reactions in subducted altered oceanic crust is controlled in part by Fe3+/∑Fe. Lawsonite (Lws) and epidote-group minerals (EGMs) are hydrous Ca-Al silicates that are key phases in subduction-zone H2O and element cycling owing to their composition and abundance, and the Lws-EGM transition has been linked to significant changes in fluid composition. Fe is a major component in most EGMs and a more minor but common component in Lws. Fe in Lws and metamorphic EGMs is generally assumed to be entirely Fe3+ that substitutes for Al in octahedral sites. However, results of Fe-XANES analyses for Lws and EGMs in blueschist and eclogite were acquired at the European Synchrotron Radiation Facility and show a wide range of Fe3+/∑Fe. Results for Lws appear robust because there are no signs of beam damage during analysis and there does not appear to be a strong orientation effect (linear dichroism). EGMs similarly show no beam damage effects but, in contrast to Lws, show significant variation in XANES spectra and resulting calculated Fe3+/∑Fe as a function of orientation. Although Fe in some Lws analyzed is entirely Fe3+, Lws and EGMs from New Caledonia blueschists contain substantial Fe2+. Work is in progress to determine what controls Fe3+/∑Fe in Lws and EGMs, but a preliminary conclusion is that Fe2+ in these phases in subducted oceanic crust may be greater than currently known, with implications for phase equilibria calculations and understanding of subduction redox conditions and processes.

How to cite: Whitney, D., Hanel, S., Wilke, M., and Rosa, A.: Variation in Fe2+ / Fe3+ in hydrous silicates in subducted oceanic crust, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-20603, https://doi.org/10.5194/egusphere-egu24-20603, 2024.

14:45–14:55
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EGU24-4694
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On-site presentation
Luca Terribili and Juan Diego Rodriguez-Blanco

Fluocerite is a rare earth element (REE) fluoride mineral with chemical formula (REE)F3. It is found in nature as an accessory mineral in magmatic-hydrothermal REE ore deposits, including alkaline complexes and carbonatites, where is associated with REE fluorocarbonates (i.e. bastnasite, parisite, synchysite), REE-bearing fluorite, cerianite, monazite and xenotime. Due to its relatively scarcity in these deposits, fluocerite kinetics and mechanisms of crystallisation, its role in REE fractionation and as phase for the evolution of magmatic-hydrothermal REE mineralizing systems have not received a lot of attention in the past years. Recently instead, fluocerite is gaining interest as it was suggested to be a precursor phase of bastnasite. Bastnasite is one of the most important minerals for the extraction of REE, indispensable in modern world because of their wide range of hi-tech industry and in clean energy applications. For this reason, illuminating the mechanisms of fluocerite crystallization and its role in the evolution of REE deposits could significantly enhance our understanding of the genesis of REE fluorocarbonates. 
The present study has two main objectives: 1) To study the kinetics and mechanisms of the fluocerite formation at temperatures ranging from ambient to low hydrothermal (up to 200 °C) 2) To demonstrate in situ that fluocerite reacting in the presence of a CO3-rich solution can transform into REE fluorocarbonates in hydrothermal conditions. 
For the first purpose, fluocerite was synthesized by reacting pure fluorite (CaF2) powder with REE-bearing solutions at different temperatures. To achieve the second objective, synthetic fluocerite was reacted with Na2CO3 solutions at hydrothermal conditions up to 200 °C. Samples of solids were taken at specific time intervals to follow the ongoing of the crystallisation reactions. The nature of crystallising solids, their quantification and growth morphology were determined with a combination of powder X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive microscopy (SEM-EDS).
Our results showed that the fluocerite crystallisation rate decreases proportionally with the REE atomic number and increases with increasing T. The activation energy of crystallisation is similar irrespective of the REE used in the synthesis (~75 KJ/mol) while the activation energy of nucleation increases with the REE atomic number (80 - 96 KJ/mol). All fluocerites reacted with the CO3-bearing solutions transformed into bastnasite at all temperature, also forming cerianite in the Ce-bearing experiments. 

How to cite: Terribili, L. and Rodriguez-Blanco, J. D.: Mechanistic insights into the fluorite-fluocerite-bastnasite transformation, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4694, https://doi.org/10.5194/egusphere-egu24-4694, 2024.

14:55–15:05
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EGU24-2301
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ECS
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On-site presentation
Giulia Mingardi, Julien Gasc, Matteo Ardit, Matteo Alvaro, and Alexandre Schubnel

Quartz, the most common mineral constituent of the Earth’s continental crust, undergoes the displacive α-β transformation at pressures and temperatures of the lower crustal conditions. This transition is associated with important variations in the thermodynamic properties (such as thermal expansion and isothermal bulk modulus) and is therefore thought to cause important seismic velocity contrasts that are distinguished by seismic tomography. The α-β transition is characterized by a non-linear increase in volume with temperature and an abrupt variation in bulk modulus, which, at the transition, drops from about 70 GPa to nearly zero within 10-15 K. Although well-known at room pressure, the behavior of quartz across the transition at high pressure, i.e., at Earth-relevant conditions, remains largely unexplored.

In this work, we have characterized this transition at high P-T conditions by means of X-ray diffraction and acoustic measurements. The experiments were performed at the European Synchrotron Radiation Facility (ESRF, beamline ID06) using a multi anvil press up to 3 GPa and 1400 °C. The measured velocities show a strong decrease of Vp toward the phase transition, followed by a steep increase in the β-field, reaching values higher than those in the α-field. In our data, this increase is not as large as that predicted by thermodynamic models using the known elastic properties of quartz (e.g., Abers and Hacker 2016). As anticipated, Vs is rather constant throughout the transition, resulting in major variations in the Vp/Vs ratio. The unit cell volume was calculated from the collected diffraction patterns. Contrary to the well-documented negative thermal expansion of quartz in the β-field at room pressure, the unit cell volumes obtained at high-pressure show a slight continuous volume increase during heating after the phase transition.

In conclusion, we document here that the behaviour of quartz across the α-β transition at high P-T is different from what has been previously predicted, which is likely a consequence of the poor knowledge of β-quartz thermo-elastic properties at high P-T. This could affect the interpretation of seismic data in the deep crust, which is currently based on extrapolations of the room-pressure behavior of the α-β quartz transition.

How to cite: Mingardi, G., Gasc, J., Ardit, M., Alvaro, M., and Schubnel, A.: What can we learn from X-ray diffraction and seismic velocities across the alpha-beta quartz transition at lower crust conditions? , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2301, https://doi.org/10.5194/egusphere-egu24-2301, 2024.

15:05–15:15
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EGU24-8290
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ECS
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On-site presentation
Kacper Staszel and Maciej Manecki

Constant development of high and green technologies makes rare earth elements (REE) more viable than ever. Relative scarcity of REE and lack of proper substitutes increase the demand for inexpensive and efficient methods of their recovery. Some new methods and technologies have been already proposed but their effectiveness leaves much to be desired. Most recently, precipitation in form of lead apatite has been proven to provide with very high levels of REE removal from aqueous solutions.

Substitution of REE in apatites has been broadly studied for calcium–phosphate apatite specimens, while lead–phosphates have been usually omitted. Recent studies suggested that precipitation of Pb and individual REE, induced by the presence of phosphates and Cl ions, results in near complete removal of cations from solutions in the form of REE-containing pyromorphite Pb5(PO4)3Cl. The goal of this study was to optimize the procedure. 

Pyromorphite (Pym) was precipitated from a solution of phosphoric acid (1:1) containing REE (each element at the concentration of 15 ppm) by addition of NaCl and Pb(NO3)2 (powder). The addition was conducted 5 times with very small amount of Pb relative to phosphates: 1/200, 1/100, 1/50, 1/20 and 1/10 of Pb needed for complete reaction with phosphoric acid. The amount of Cl was used in 1.5 times excess with respect to stoichiometric Pb. Each time solids and solutions were separated and sampled for the analysis.

The synthesis was carried out under atmospheric pressure, at an ambient temperature of about 21°C and at pH=3. Powder X-ray diffraction (XRPD) was used to identify the obtained phases, scanning electron microscopy (SEM) to examine the morphology of the crystals, energy-dispersive X-ray spectroscopy (EDS) for analysis of the elemental composition of solids, while solutions were analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-OES).

Most REE are removed already at the first, lowest dose of Pb: more than 99% of La, Ce, Pr, Nd, Sm, Eu, and Gd; between 90 and 96% of Tb, Dy, Ho, and Er; between 80 and 50% of Tm, Yb, and Lu; 46% of Sc, 86% of Y, and 98% of Th disappear from the solution. After the third addition, REE are removed completely (except for Sc, which required 5 amendments). All these elements were removed from solution by precipitation of REE-containing Pym. An admixture of "phosphoschultenite" PbHPO4 also appears in the precipitate, which most likely does not contain REE (or contains much less than Pym).

These preliminary results indicate strong affinity of REE with Pym structure. In contrast to previous findings (Sordyl et al., 2023), a fractionation of REE was observed. Further analyses are in demand for better understanding of the mechanism of these processes which will allow for optimization of industrial applications.

This research was funded by National Science Centre research grant no. 2021/43/O/ST10/01282.

 

References:

Sordyl, J., Staszel, K., Leś, M., & Manecki, M. (2023). Removal of REE and Th from solution by co-precipitation with Pb-phosphates. Applied Geochemistry, 158, 105780. https://doi.org/10.1016/j.apgeochem.2023.105780

How to cite: Staszel, K. and Manecki, M.: First evidence of strong REE compatibility with pyromorphite Pb5(PO4)3Cl, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-8290, https://doi.org/10.5194/egusphere-egu24-8290, 2024.

15:15–15:25
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EGU24-565
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ECS
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On-site presentation
Anna Musolino, Bertrand Devouard, Pierre Rochette, Pierrick Roperch, Pierre-Marie Zanetta, Anne-Magali Seydoux-Guillaume, Daniel Ferry, and Andrea Campos

When exposed to high-temperature conditions (~1670°C), zircon crystals (ZrSiO4) decompose according to the reaction: ZrSiO4→ZrO2+SiO2 [2,8]. Under optical and electron microscopes, decomposed zircons are easily identified by the presence of bright rims of baddeleyite (ZrO2) surrounding the unaltered primary crystal core (ZrSiO4). Due to the high temperatures needed for this reaction to occur (i.e., exceeding the highest temperatures normally reached by magmatic processes or wildfires on the Earth’s surface), finding decomposed zircons in natural glass has become a handy unequivocal way to relate natural glass to extreme processes like meteoritical impacts [1], airbursts [6], or lightning [3]. If recognizing fulgurites (i.e., products of lightning) is more easily done because of their morphology, the identification of impact glasses can be problematic, especially when they are not associated with a known impact crater. This work aims to demonstrate the reliability of zircon decomposition as a geothermometer, used to identify impact (or airbursts) glasses.

Through high-temperature experiments, we show that the decomposition of zircons can occur in natural systems at lower temperatures than the ones predicted by models. At T=900-1000°C (P=1 bar, exposed to air), in the presence of Ca-sulfates and NaCl-rich soil called ‘caliche’ (from the Atacama Desert, chosen for its relation with one of the most recent debated case, that of Pica glass – [4,5,6,7]), zircons decomposed forming the typical bright rims. Using FEG-SEM-EDS, Raman spectroscopy, and TEM (on thin foils prepared using FIB), however, we show that the Zr-rich rim mineralogy in our experiments differs from previous petrographic descriptions, with assemblages of baddeleyite, baddeleyite + Ca-Zr-oxide, or only Ca-Zr-oxide.

In conclusion, we demonstrate that decomposed zircons could also result from lower temperature processes than impacts or airbursts and should be used more carefully in assessing the origin of glasses. Also, we suggest that a more detailed mineralogical characterization of decomposed zircons (rarely done after their detection) is needed to correctly assess the formation conditions of samples containing such rims.  

References

[1] El Goresy A., 1965. Baddeleyite and its significance in impact glasses. Journal of Geophysical Research, 70:3453-3456.

[2] Kaiser A., et al., 2008. Thermal stability of zircon (ZrSiO4). Journal of the European Ceramic Society, 28:2199-2211.

[3] Kenny G.G. and Pasek M.A., 2021. The response of zircon to the extreme pressures and temperatures of a lightning strike. Scientific Reports, 11:1560.

[4] Roperch P., et al., 2017. Surface vitrification caused by natural fires in Late Pleistocene wetlands of the Atacama Desert. Earth and Planetary Science Letters, 469:15-26.

[5] Roperch P., et al., 2022. Widespread glasses generated by cometary fireballs during the late Pleistocene in the Atacama Desert, Chile: COMMENT. Geology, 50.5:e550.

[6] Schultz P.H., et al., 2022. Widespread glasses generated by cometary fireballs during the late Pleistocene in the Atacama Desert, Chile. Geology, 50.2:205-209.

[7] Schultz P.H., et al., 2022. Widespread glasses generated by cometary fireballs during the late Pleistocene in the Atacama Desert, Chile: REPLY. Geology, 50:e551.

[8] Timms N.E., et al., 2017. A pressure-temperature phase diagram for zircon at extreme conditions. Earth-Science Reviews, 165:185-202.

How to cite: Musolino, A., Devouard, B., Rochette, P., Roperch, P., Zanetta, P.-M., Seydoux-Guillaume, A.-M., Ferry, D., and Campos, A.: Decomposed zircons: A reliable geothermometer to identify impact and airburst glasses?, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-565, https://doi.org/10.5194/egusphere-egu24-565, 2024.

15:25–15:35
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EGU24-2878
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On-site presentation
Sebastian Ritterbex and Oliver Plümper

Serpentines are among the most abundant hydrous minerals in oceanic lithospheres formed by hydrothermal alteration of ultramafic mantle rocks (i.e. peridotites). Antigorite – the high temperature and pressure variety of serpentine – is considered to be the dominant water carrier within down-going oceanic slabs. The successive dehydration of antigorite during subduction of partially serpentinized oceanic lithospheres is strongly associated with the water cycle in the upper mantle and is expected to play an important role in the generation of arc magmatism (Ulmer & Trommsdorff, 1995; Schmidt & Poli, 1998), and influence rheological properties of oceanic slabs by processes such as dehydration embrittlement which is thought to trigger intermediate-to-deep focus earthquakes (Jung et al., 2004; Ferrand et al., 2017).

Antigorite is a hydrous phyllosilicate known for its polysomatism: The number of SiO4 tetrahedra m along its a-cell periodicity. Previous electron microscopy studies reported the existence of antigorite within a wide range of m values (~13-23) depending on the pressure (P) and temperature (T) conditions (Mellini et al., 1987; Wunder et al., 2001). However, there is a lack of the combined structural and thermodynamic evidence about the stability of the different antigorite polysomes along the P,T-paths of subducting oceanic lithospheres.

We use a theoretical mineral physics approach based on first principles density functional theory calculations to quantify the phase diagrams of the terminal dehydration reactions of antigorite with different m-values between 13-19 under subarc depth P,T conditions. Our results elucidate the significance of the compositional variations of antigorite on the dehydration of serpentinized oceanic slabs during the progressive stages of subduction.

How to cite: Ritterbex, S. and Plümper, O.: First principles investigation of the effect of compositional variations on the terminal breakdown of antigorite in subduction zones, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2878, https://doi.org/10.5194/egusphere-egu24-2878, 2024.

15:35–15:45
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EGU24-14196
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ECS
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On-site presentation
Shaunna Morrison, Anirudh Prabhu, Robert Hazen, Michael Wong, Donato Giovannelli, and Ahmed Eleish

Determining the habitability of planets remains a fundamental question in science and society. In this study, we harness network theory to explore the unique patterns exhibited by minerals and their mineralizing environments in both biotic and abiotic contexts throughout the evolution of Earth and other terrestrial bodies in our solar system [1-. By examining mineralogical networks across diverse planetary systems, including early solar system bodies, the early Hadean Earth (closely related to modern-day Mars), plate tectonics, and modern Earth, we gain valuable insights into Earth's history and the factors that have shaped the development and sustainability of life. Our investigation reveals distinct characteristics within biotic networks, setting them apart from their abiotic counterparts.

This research significantly advances our understanding of the intricate interplay between Earth and life. Network analysis offers deeper insights into the connections between minerals and living systems, providing invaluable perspectives on the emergence and co-evolution of life on our planet. Moreover, our findings contribute to identifying and characterizing planetary biosignatures, essential for the search for extraterrestrial life. Recognizing these unique patterns within biotic networks lays the groundwork for developing targeted exploration strategies for detecting potential biosignatures and interpreting the complexities of planetary environments.

Our innovative network analysis of minerals and mineralizing environments sheds new light on the relationships between Earth and life. By delving into the intricate connections within biotic and abiotic systems, we deepen our understanding of Earth's dynamic history and enhance our knowledge of potential habitats for life beyond our planet.

How to cite: Morrison, S., Prabhu, A., Hazen, R., Wong, M., Giovannelli, D., and Eleish, A.: Characterizing life influence on Earth's mineralogy via mineral network analysis, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-14196, https://doi.org/10.5194/egusphere-egu24-14196, 2024.

Coffee break
16:15–16:20
16:20–16:30
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EGU24-8479
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solicited
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Highlight
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On-site presentation
Olivier Beyssac

The NASA Perseverance rover is exploring Jezero crater on Mars since february 2021 [1]. Perseverance’s main goal is to investigate the past geologic and environmental conditions of Jezero crater and seek evidence of past life. For this, the rover has characterized the local geology of the crater floor and is presently working in an ancient river delta. Then, Perseverance will explore the crater rim, and possibly some regions outside of the crater. In addition, the rover selects and collects the most compelling samples that will be retrieved and brought back to Earth by a future mission (NASA/ESA Mars Sample Return project) for more detailed study.

Perseverance uses a panel of spectroscopic tools based on the analysis of sunlight reflectance in the visible and near-infrared domains (MastcamZ, SuperCam), deep-UV (SHERLOC) and time-resolved (SuperCam) Raman, Laser Induced Breakdown Spectroscopy - LIBS (SuperCam) and X-ray fluorescence (PIXL). Some instruments can analyze the chemistry and mineralogy of rocks remotely up to several meters [2-3] while others work close to the rock for higher spatial resolution (~100 mm) and better textural control [4-5]. The rover is operated nearly every day and sends data almost immediately to Earth.

On the crater floor, Perseverance found igneous rocks: basaltic lava or pyroclastic flows [6] covering an olivine-rich cumulate [4,7]. The magmatic mineral assemblage, including the textural relationships, was carefully described: mostly Fe-rich pyroxenes in the basaltic flows, and a cumulate composed of dominant olivine with augite and pigeonite, as well as some phosphates and (Cr-)Ti-Fe-oxides in both units. The bulk of these rocks is weakly altered but Fe-Mg carbonates [8], sulfates [5] and various phyllosilicates [9] were detected showing that fluid-rock interactions locally occurred. After the crater floor, Perseverance began exploring the sedimentary rocks in the Jezero western fan, which is still in progress. On the fan, some float rocks show intense alteration to kaolinite followed by metamorphism [10].

Perseverance instruments which have an original design optimized for lightness, resistance to extreme conditions and performance will be introduced. Doing spectroscopy on Mars is challenging but these instruments have worked perfectly so far. A large amount of data, including some first-time achievements on Mars, have been collected and will be summarized with special emphasis on spectroscopic data.

[1] Farley et al., Science, 2022 ; [2] Bell et al., Science Advances, 2022 ; [3] Wiens et al., Sciences Advances, 2022 ; [4] Liu et al., Science, 2022 ; [5] Scheller et al., Science, 2022 ; [6] Udry et al., JGR Planets, 2023 ; [7] Beyssac et al., JGR Planets, 2023 ; [8] Clavé et al., JGR Planets, 2023 ; [9] Mandon et al., JGR Planets, 2023 ; [10] Royer et al., LPSC 2024.

How to cite: Beyssac, O.: Spectroscopy on Mars with NASA Perseverance rover, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-8479, https://doi.org/10.5194/egusphere-egu24-8479, 2024.

16:30–16:40
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EGU24-5885
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ECS
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On-site presentation
Lisa Baratelli, Boriana Mihailova, Mauro Prencipe, Fernando Cámara, and Matteo Alvaro

Omphacitic clinopyroxenes exhibit widespread occurrence in various geological settings and rock types, making them promising candidates for Raman elastic geothermobarometry applications. Raman elastic geobarometry uses the deformation recorded by mineral inclusions to determine the pressure and temperature conditions under which they were entrapped. Raman scattering, which is highly sensitive to structural deformations, provides valuable insights into the variations in crystal structure that occur due to heating or compression. While several host-inclusion systems have been investigated, clinopyroxene inclusions have not been extensively studied. Therefore, the application of Raman elastic geobarometry to omphacites in different mineral hosts necessitates an accurate calibration of Raman-peak positions against hydrostatic pressure.

Natural omphacite crystals can exhibit cationic ordering associated with crystallization temperature, which affects their elastic behaviour. To address these aspects, we conducted a study on natural ordered (P2/n) and experimentally disordered (C2/c) omphacite crystals from Münchberg Massif (Germany). In situ high-pressure Raman spectroscopy measurements were performed using a diamond anvil cell. As expected, the frequencies of the modes increased with increasing pressure. By examining omphacite crystals with varying degrees of order obtained through isothermal annealing experiments, we observed that progressive cationic disorder primarily led to peak broadening, while changes in Raman peak positions were predominantly influenced by pressure variations.

Additionally, the chemical composition of omphacites influences the Raman-peak positions and their pressure evolution. Therefore, we analysed Fe3+-rich omphacites from Lugros and Camarate (Bétic Cordilleras, SE Spain), and Voltri (Italy) along with synthetic iron-free omphacites. This analysis is an initial step towards the chemical calibration of omphacites using Raman spectroscopy.

To gain a deeper understanding of the elastic behaviour of modes suitable for elastic geobarometry, we simulated the Raman spectrum of a fully ordered omphacite (Jd50Di50 composition) at different pressures using ab initio Hartree-Fock/Density Functional Theory simulations. The simulated data exhibited excellent agreement with experimental spectra, enabling us to comprehend the pressure dependence of specific modes. Leveraging these findings, we can calculate the entrapment pressure of omphacite inclusions still confined within their host rocks by determining Raman shifts of the main peaks alongside changes in cation order.

Our results provide valuable insights into the calibration and application of Raman elastic geobarometry for omphacitic clinopyroxenes. By considering the influence of chemical composition and cationic ordering, we have enhanced our understanding of the elastic behaviour of omphacite and its potential for geobarometric calculations. These findings offer a valuable tool for determining the pressure and temperature conditions of geological processes involving omphacitic clinopyroxenes.

How to cite: Baratelli, L., Mihailova, B., Prencipe, M., Cámara, F., and Alvaro, M.: Raman elastic geobarometry: investigating cation order in omphacitic clinopyroxenes, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-5885, https://doi.org/10.5194/egusphere-egu24-5885, 2024.

16:40–16:50
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EGU24-14692
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ECS
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On-site presentation
Javier Garcia-Toloza, Camilo Betancur, Holman Alvarado, and Carlos Julio Cedeño

Gemological reports have gained a crucial role in today’s gemstone trading because they provide buyers and sellers with information regarding gem features, which in turn can be translated to monetary value. Although there is information about technics to separate Colombian emeralds from other countries, not much information is available about how to differentiate emeralds from the Western Belt (COC), and those from the Eastern Belt (COR), two main produced zones in Colombia, those districts more recognized are, Muzo and Chivor, respectively. This work aims to show the advances made in one of the techniques used in a gemological laboratory to determine the origin of emeralds.
The analysis of fluid inclusions via Raman spectroscopy can yield beneficial information regarding the chemical properties of mineral systems. Primary fluid inclusions trapped by emerald permit us to know the chemistry and the thermobarometric conditions of the mineralizing fluids. Fluid inclusions are usually three-phase inclusions with contain three or more phases including liquids, gases, and salt (halite). Sometimes they are multiphase with solids such as calcite. The gas phases are typically CO2, N2, and CH4 (Cheilletz et al., 1994; Giuliani et al., 1993; Giuliani et al., 1995; Romero & Hernandez, 1999; García-Toloza et al., 2017). Raman spectra of CO2 exhibit two bands near 1285 cm-1 and 1385 cm-1, this feature is well-known as the Fermi doublet (Fernandez, 1983; Howard-Locke, 1971); the distance between these bands is proportional to the fluid density (Rosso & Bodnar, 1995; Song Y. et al., 2003). 
The data of ∆ Fermi doublet suggest that values below 103.1 are exclusive from the COR, whereas there is an overlap from 103.1 to 103.4. Additionally, the position of the two main CO2 bands varies significantly between the two Colombian belts. The location of peaks from the COR are found at lower energy levels. Thus, this method may be used to estimate the provenance of some populations, the Fermi doublet is not only helpful to differentiate between the Colombian emerald belts but also between Colombian emeralds from samples from Brazil and Afghanistan.

How to cite: Garcia-Toloza, J., Betancur, C., Alvarado, H., and Cedeño, C. J.: Raman spectroscopy analysis of fluid inclusions as a tool in determination of origin of Colombian emeralds., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-14692, https://doi.org/10.5194/egusphere-egu24-14692, 2024.

16:50–17:00
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EGU24-5906
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ECS
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On-site presentation
Nisha Bhattarai and Ruth H. Ellerbrock

Abstract

Functional groups (e.g. alcohol, hydroxyl, carboxyl etc.) of soil organic matter are responsible for soil properties like cation exchange capacity or wettability. Functional groups can be characterized by spectroscopic procedures like Fourier transform infrared (FTIR) spectroscopy since the infrared light can introduce vibration modes within the groups. Only the light of an energy similar to the bonding energy of the C=O bond, for example, causes the absorption bands of the functional groups to show up at typical wavenumber (WN) regions in FTIR spectra. However, when the C=O group interacts with cations, the bonding energy may change thereby affecting the WN region of the absorption band. This change in WN (following organic matter (OM)-cation interaction) may limit procedures of automated spectral interpretation, which are mostly based on fixed ranges -determined from textbooks, or sets of single wave numbers determined by statistical approaches.

Our study aims to quantify the effect of OM-cation interactions on the spectral features (intensity and WN region of C=O absorption bands) in FTIR spectra. To quantify the effect of OM-cation interactions on defined functional groups as far as possible, we study mixtures of polygalacturonic acid (PGA; as a model substance for soil organic matter) with different polyvalent cations (Ca2+, Fe³+, Al³+) at different concentrations.

PGA-cation mixtures with different cation concentrations were prepared, freeze dried, and characterized using FTIR spectroscopy (KBr technique). A proton-cation exchange at the carboxylic acid groups during PGA-Cation interaction gives rise to a COO- band in FTIR. Since the cation effect is found in an earlier study to be stronger for the COO- band (1620-1550 cm-1) as compared to the C=O band, the interpretation of the FTIR spectra focuses on the COO- band. Compared to spectra of pure PGA, the spectra of all PGA-cation mixtures show a significant positive correlation between COO- band intensity and cation concentration. Additionally, a shift in the maximum of COO- band towards lower WN was observed for all cations, which depends on the kind of cations and increased with cation concentration.

Increase in intensity of the COO- band and the shift in WN region of COO- band maxima confirms changes in FTIR spectral features with cation addition and that those changes depend on the type of cation. The results suggest that type and concentration of cation should be considered when interpreting FTIR spectra of organic matter since both, change in intensity and shift in the WN of the band maxima, could restrict procedures of automated spectral interpretation, which mostly rely on fixed ranges (from textbooks), or sets of single wave numbers determined by statistical approaches. For a deeper understanding on the relation between OM-cation interactions, organic matter with increasing heterogeneity and complexity need to be studied.

How to cite: Bhattarai, N. and Ellerbrock, R. H.: Spectral characterization of organic matter is affected by polyvalent cations interaction, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-5906, https://doi.org/10.5194/egusphere-egu24-5906, 2024.

17:00–17:10
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EGU24-12774
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ECS
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On-site presentation
Michele Cassetta, Francesco D'Amico, Barbara Rossi, Emanuele De Bona, Alessia Sambugaro, Mattia Biesuz, Renat Almeev, Francesco Vetere, Daniele Giordano, Francesco Enrichi, Nicola Daldosso, and Gino Mariotto

The understanding of the vitrification processes encompasses all the fields between geo- and material- sciences. Glass represents a non-equilibrium picture of its parental super-cooled liquid (SCL) and the last melt fraction quenched after a volcanic eruption. The SCL is usually read as a system that moves away from equilibrium without having enough time to explore the phase-space. In these conditions it is unable to find new configurations, causing a drop of the thermodynamic equilibrium and a glass is formed. This system is named non-ergodic and at eruptive temperatures represent a key component that may experiences fragmentation [1]. This particular state is generally referred to the thermal interval preceding the glass transition temperature (Tg, T at which the viscosity is 1012 Pa s) and the monitoring of its micro-structural evolution requires the less invasive experimental technique. With this regard we have used the deep UV-Raman spectroscopy to investigate a set of silicate model-glasses, loaded with different iron contents. This spectroscopic approach allows for the acquisition of fluorescence-free spectra with a maximized signal in the high-wavenumber region (between 850-1300 cm-1) thus providing the finest conditions for the assessment of the tetrahedral arrangement through the Qn deconvolution analysis (n represents the number of bridging oxygens) [2]. Here we correlate the trend of each Qn unit with temperature across the Tg-interval. Our results display a clear T-dependent rearrangement of the Qn distribution in function of iron content. Our finding, supported by differential scanning calorimetry, thermal dilatometry, Mössbauer, FTIR and ATR measurements, may deliver helpful insights into the thermal-dependent microstructural evolution through the Tg-interval and the viscous behavior of silicate SCLs.

  • [1] D. B. Dingwell, Science 273, 1054 (1996).
  • [2] M. Cassetta, B. Rossi, S. Mazzocato, F. Vetere, G. Iezzi, A. Pisello, M. Zanatta, N. Daldosso, M. Giarola, and G. Mariotto, Chem. Geol. 644, 121867 (2024).

How to cite: Cassetta, M., D'Amico, F., Rossi, B., De Bona, E., Sambugaro, A., Biesuz, M., Almeev, R., Vetere, F., Giordano, D., Enrichi, F., Daldosso, N., and Mariotto, G.: In-situ structural analysis of silicate supercooled liquids through deep-UV Raman spectroscopy , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-12774, https://doi.org/10.5194/egusphere-egu24-12774, 2024.

17:10–17:20
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EGU24-11495
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ECS
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On-site presentation
Bartosz Puzio and Maciej Manecki

Similar to Ca-apatites, carbonate substitutions are also possible in Pb-apatites although they are still not fully characterized [1,2]. Therefore, for the first time, a comprehensive comparison of the IR spectra of synthetic Pb-apatite analogs has been carried out with a detailed examination of the rather often ignored carbonate substitutions. CO32- ions can be substituted in the apatite structure in two different positions: by substitution of an anion located in the X-position in the channel, such as OH- or halogen (A-type substitution), or by substitution of an anion in the tetrahedral position, such as PO43- or AsO43- (B-type carbonate substitution). This can be illustrated by the following chemical formula: Pb10-y(Na,K)y[(PO4)6-y(CO3)y][(X)2-2x(CO3)x], where x≈y. IR studies have shown that in apatites prepared at high temperature, most of the carbonates are located in the channel. Under low-temperature environmental conditions, the formation of AB-carbonated Pb apatites is much more plausible [3]. Some Pb apatites, such as fluoride apatites e.g. Pb10(AsO4)6F2, do not tend to incorporate carbonate at all, at least not during precipitation from solutions with CO32- concentrations similar to environmental (pCO2=10-3.5 atm). This is likely due to the greater ordering in apatite channels, where the fluoride anion occupies the mirror plane.

In the present work, various Pb-apatites containing As and V were prepared by precipitation from an aqueous solution in the presence of Na+ cations at room temperature and open to the air. The type of A- or B- carbonate substitution was determined in IR spectra collected at room temperature based on asymmetric stretching of the carbonate (ν3) and out-of-plane bending (ν2) modes. The high-frequency component of the ν3 region of the A-type carbonate for Pb apatites showed the greatest variability with chemical composition. For example, in Pb10(AsO4)6OH0.86(CO3)0.07 hydroxylmimetite, the bands at 1462 and 1421 cm-1 are attributed to A-type carbonate substitution, while the bands occurring at 1385 and 1348 cm-1 are associated with B-type. Compared to lead phosphates and vanadates, carbonate bending oscillations ν2 at 870 cm-1 are not apparent in arsenate Pb apatites due to overlap with the As-O stretching mode. In situ IR measurements were also carried out during temperature rise to 500 °C to determine the thermal stability of individual carbonate substitutions in the Pb-apatite structure. In general, most Pb-apatites begin to release carbonates around 300 °C. As the temperature increases, bands in the ν2 and ν3 carbonate regions begin to disappear until the apatite structure completely disintegrates.

 

References

[1] Yoder, C. H., Bollmeyer, M. M., Stepien, K. R., & Dudrick, R. N. (2019). The effect of incorporated carbonate and sodium on the IR spectra of A-and AB-type carbonated apatites. American Mineralogist: Journal of Earth and Planetary Materials, 104(6), 869-877.

[2] Kwaśniak-Kominek, M., Manecki, M., Matusik, J., & Lempart, M. (2017). Carbonate substitution in lead hydroxyapatite Pb5(PO4)3OH. Journal of Molecular Structure, 1147, 594-602.

[3] Lempart, M., Manecki, M., Kwaśniak-Kominek, M., Matusik, J., & Bajda, T. (2019). Accommodation of the carbonate ion in lead hydroxyl arsenate (hydroxylmimetite) Pb5(AsO4)3OH. Polyhedron, 161, 330-337.

How to cite: Puzio, B. and Manecki, M.: Carbonates substitution in lead apatites – IR spectroscopic study, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-11495, https://doi.org/10.5194/egusphere-egu24-11495, 2024.

17:20–17:30
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EGU24-16793
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On-site presentation
Mattia Gilio, Marta Morana, Ross J. Angel, Boriana Mihailova, and Matteo Alvaro

Earthquakes result from the brittle failure of rocks at depths and are primarily induced by far-field tectonic stresses. Despite this general understanding, the atomic-scale mechanisms triggering brittle failure in dry ductile crustal rocks remain elusive. Quartz, a widespread mineral in the lower crust, undergoes an instantaneous polymorphic transformation from the α to β phase under pressure and temperature conditions aligning with estimates for several lower-crustal paleo-earthquakes, recorded as pseudotachylytes. The α–β quartz transition is characterized by displacive reversibility. As α–quartz approaches the transition temperature (Tc = 847 K for a free quartz crystal at atmospheric pressure) under constant pressure, its volume increases nonlinearly without abrupt jumps. However, near the phase-transition temperature, the bulk modulus of quartz exhibits a notable drop from approximately 30 GPa to nearly zero, followed by an abrupt rise to over 70 GPa within 10 K temperature range (Lakshtanov et al., 2007).

Near the α–β transition, quartz inclusions within garnet hosts should develop substantial differential strain, thereby imposing strong differential stresses on the surrounding host crystal. We used in situ high-temperature Raman spectroscopy on quartz inclusions in garnet to monitor the structural deformation and atomic dynamics across the phase transition. The temperature-dependent behaviour of the phonon wavenumbers (ω) in quartz inclusions, particularly the hardening and disappearance of a minimum in ω(T) for A modes near 208 and 464 cm-1 (related to the α–β phase transition), along with the persistence of Raman activity at ~128 cm-1 and ~355 cm-1 above Tc, confirms the accumulation of abnormally high strain in confined quartz grains near the anticipated phase transition. The stored elastic energy in the inclusion is subsequently released through the inclusion-host boundary into the host during the α–β transition. This release causes the garnet around the quartz inclusion to fracture or, in some instances, shatter due to the significant differential stresses forming within the inclusion at its transition. Notably, inclusions of apatite and zircon within the same garnets remain unchanged under the same conditions, thereby excluding the possibility of fracturing being caused by the host garnet itself.

Our experiments show that the α–β transition of a single quartz inclusion in garnet is sufficient to fracture the host phase in a laboratory environment. This process can be upscaled to quartz-bearing rocks at lower crustal conditions and might provide the initial mechanical instabilities necessary to trigger ductile and/or brittle deformation in quartz-bearing rocks, eventually leading to earthquakes.

 

References

Lakshtanov, D.L., Sinogeikin, S.V., Bass, J.D., 2007. High-temperature phase transitions and elasticity of silica polymorphs. Physics and Chemistry of Minerals 34, 11-22.

How to cite: Gilio, M., Morana, M., Angel, R. J., Mihailova, B., and Alvaro, M.: High-temperature Raman spectroscopy of quartz inclusions in garnet: a tool to investigate lower crustal rheology, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-16793, https://doi.org/10.5194/egusphere-egu24-16793, 2024.

17:30–17:40
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EGU24-19040
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On-site presentation
Krzysztof Gaidzik, Filip Šarc, Justyna Ciesielczuk, Andrea Martín Pérez, Adrijan Košir, Bojan Otoničar, Tomasz Powolny, Andrzej Tyc, Vanessa Johnston, and Beata Gebus-Czupyt

Dedolomitization is a geological process where dolomite undergoes transformation into calcite via the influx of aggressive Ca-rich solutions derived from various sources (e.g., evaporite dissolution). This conversion can take place in diverse environments. Our study focuses on a unique occurrence of dedolomite within a cave environment in the Mravljetovo brezno v Gošarjevih rupah cave located in central Slovenia. The cave walls exhibit distinctive yellowish and reddish crusts and covers that originated from dedolomitization process developed within this cave system.

Macro- and microscopic observations reveal that yellowish lithologies are of sedimentary origin, where dominating dedolomite (i.e., replacive calcite) is associated by mainly detrital particles with a high content of quartz, muscovite, clay minerals, and lithoclasts. In contrast, red lithologies are associated with the transitional zone between sedimentary layers and the host rock dolomite, featuring peculiar calcite crystals with abundant pore space and intercrystalline iron oxides and clay. The transitional zone itself consists of a calcite mosaic with smaller dolomite remnant embedded within the calcite structure.

The primary objective of this study is to conduct a comprehensive mineralogical analysis (XRD, SEM-EDS, EMPA, μXRF, CL, and Raman spectroscopy), aiming to recognize their interrelationships and utilize them as proxies for understanding the processes leading to dedolomitization.

Dedolomitization is evidenced by the abundance of corroded dolomite rhombs infilled with calcite, coupled with the development of moldic (dissolution-related) porosity, and subsequent crystallization of vein calcite. Detrital quartz reveals embayed crystal boundaries, as well as rounded lithoclasts enriched in clay-group species (e.g., illite). Subordinate detrital apatite, rutile, and zircon were also recognized. Besides, some mineral phases of authigenic origin were detected based on their habits and textural relationships. These include clay-group species (i.e., kaolinite, illite, and/or possible mixed-layer clays), as well as S- and Na-rich apatite, and fluorite. The formation of dedolomite was followed by the decrease of Mg and increase of Fe as evidenced by elemental mapping. These changes can reflect oxidizing conditions and subsequent precipitation of Fe3+ in hematite or goethite/lepidocrocite mineral phases that stained dedolomitized regions red to yellow.

Furthermore, we seek to investigate the potential influence of these mineralogical dynamics on cave formation and speleogenesis. All these findings can contribute to a better understanding of geological and geochemical mechanisms governing dedolomitization processes within cave environments.

This work is funded by the Slovenian and Polish research agencies (ARRS and NCN) through the bilateral Polish-Slovenian research project CEUS (project code in Slovenia: N1-0226; project code in Poland: 2020/39/I/ST10/02357).

How to cite: Gaidzik, K., Šarc, F., Ciesielczuk, J., Martín Pérez, A., Košir, A., Otoničar, B., Powolny, T., Tyc, A., Johnston, V., and Gebus-Czupyt, B.: Mineralogical study of dedolomitization in cave environments –the Mravljetovo brezno v Gošarjevih rupah cave, central Slovenia, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-19040, https://doi.org/10.5194/egusphere-egu24-19040, 2024.

17:40–17:50
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EGU24-2915
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ECS
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On-site presentation
Rémi Rateau, Kerstin Drost, Melanie Maddin, Adrienn Szucs, Luca Terribili, Paul Guyett, and Juan Diego Rodriguez-Blanco

In November 2023, the European Union reached a provisional agreement on an European Critical Raw Materials Act, which encourages the local production, processing, and recycling of critical elements, notably the rare earth elements (REE). While indispensable for the green energy transition, their production is notoriously environmentally damaging, and efforts are being made to reduce this environmental footprint, for example via the use of secondary REE sources from waste or by the application of green chemistry and circular economy principles.

In this study, we investigated the potential of hen eggshell calcite waste to be recycled for the uptake of REE from industrial and waste streams. We interacted commercial eggshells with 50 mM multi-REE (La, Nd, Dy) solutions at 25 to 205 °C between three hours and three months. The resulting products were characterized by powder XRD and Rietveld refinement for quantitative phase identification; SEM electron imaging for structural characterization; SEM energy dispersive spectroscopy for elemental mapping and quantification of major and minor elements; and laser ablation ICP-MS for trace element mapping.

We observe a pervasive diffusion of the REE inside the eggshell calcite, along pathways formed by the intracrystalline organic matrix and calcite crystal boundaries, and without any partitioning of La, Nd and Dy. At 90 °C, calcite is observed dissolving and being replaced by kozoite spherulites, reminiscent of natural kozoite crystals. At 165 °C and 205 °C, an interface coupled dissolution-precipitation mechanism is observed, resulting in the complete dissolution of the calcite and its pseudomorphic replacement by polycrystalline kozoite. At 205 °C, kozoite itself is slowly replaced by hydroxylbastnäsite, the stable form of rare earth hydroxycarbonate, following a crystallization pathway previously established with inorganic calcite. Minor REE zoning at the eggshell grain scale is also observed, hinting at a potential use for REE separation.

Our results demonstrate two potential applications of eggshell waste for the sustainable recovery of REE from aqueous solutions: at low temperatures, as a mixed organic-inorganic adsorbent and absorbent; and at higher temperatures as an efficient sacrificial template for the precipitation of rare earth hydroxycarbonates.

How to cite: Rateau, R., Drost, K., Maddin, M., Szucs, A., Terribili, L., Guyett, P., and Rodriguez-Blanco, J. D.: Sustainable recovery of rare earth elements with eggshell waste calcite, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2915, https://doi.org/10.5194/egusphere-egu24-2915, 2024.

17:50–18:00
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EGU24-9462
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ECS
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Virtual presentation
Oral Sarıkaya and Şenel Özdamar

In this study, investigated the geology, mineralogy, petrography and geochemistry of metavolcanic rocks in northern Ilgın (Konya). There are two Paleozoic and Mesozoic metamorphic rock groups in the study area. Alluvium and Neogene sediments are unconformably layered over these rocks. Paleozoic metamorphic group include metasediments and metacarbonates. This metamorphic group consist of metaconglomerate at their base and continue upward as metasandstone, metaquartzite, phyllite, schist, metachert, and metacarbonate at the top. Mesozoic metamorphic group consists of metasediments, metacarbonates, and metavolcanic rocks. There is metaconglomerate at the base and continue upward shale, metasandstone, and metacarbonate at the top. The main difference between the two groups is that the Mesozoic metamorphic group contains metavolcanic rocks. These metavolcanic rocks, which are the main subject of this study, occur at five different locations within the study area. These are Dereköy – Kurtlukaya Hill, Küçüktokmak Hill, Kocatokmak Hill, Göleç Hill, and Avdan Village. Metavolcanic rocks are commonly observed as massive metalavas, but in some areas they exhibit a significant degree of foliation. These rocks include quartz, feldspar, and muscovite. In some areas, quartz veins cut the rocks, and in others, iron oxides are observed. The metavolcanic rocks that are the main target of this study are metariolitic - alkaline metariolitic rocks. The rocks have undergone slight metamorphism, and foliation is clearly visible in some samples. The rocks consist of an average of 40-50% matrix and 50-60% quartz, alkali feldspar, muscovite and plagioclase minerals and exhibit a hemicrystalline porphyritic texture. The matrix of the rocks consists of fine-grained quartz, alkali feldspar and sericite minerals. These rocks’ SiO2 contents vary between 63.60-71.97%; K2O contents vary between 3.4-10.52%; Al2O3 contents vary between 15.78-18.56%; Fe2O3 contents vary between 0.94-4.26% and TiO2 contents vary between 0.02-0.57%. The rocks are calc-alkaline and shoshonitic in character. In addition, the rocks are peraluminous and silica-saturated. Trace element analysis shows that Ba is present in high concentrations (88–391 ppm) in  the rocks. Samples from Avdan and Dereköy have high Zr values (424–597 ppm) and Rb values (190–360 ppm). Eu values ​​(0.06–0.55) are low in all samples. Low Eu and high Ba are state that crustal contamination. The spider diagrams shows a decrease in Sr, Hf, and Ti elements, especially Eu, and an increase in other elements in the rocks. The negative anomalies observed in Sr and Eu elements indicate that fractional crystallization of feldspars. Enrichment of elements such as Th, Nb, and Zr indicate that crustal contamination. These rocks exhibit a relatively LREE-rich, HREE-poor composition, and show fractionation from LREEs to HREEs in normalized distribution pattern according to chondrite. The formation of the rocks includes fractional crystallization, assimilation-fractional crystallization, magma mixing and crustal contamination events. Ilgın metavolcanic rocks were formed as a result of magmatic activity that developed simultaneously with the collision after orogeny in the within plate environment.

Keywords: Geochemistry, Ilgın/Konya, metavolcanic rocks, petrography, Turkey.

How to cite: Sarıkaya, O. and Özdamar, Ş.: Petrography and Geochemistry of the North of Ilgin (Konya) Metavolcanic Rocks, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9462, https://doi.org/10.5194/egusphere-egu24-9462, 2024.

Posters on site: Tue, 16 Apr, 10:45–12:30 | Hall X1

Display time: Tue, 16 Apr 08:30–Tue, 16 Apr 12:30
Chairpersons: Nicola Campomenosi, Julia Sordyl, Marta Berkesi
X1.150
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EGU24-4623
Pierre Beck and the Supercam and M2020 team members

Introduction:  Hydrated silica has been detected from orbit in Jezero crater [Tarnas et al., 2019] and holds great promise for the astrobiology science goals of the M2020 mission and the MSR Program. Early entombment within an hydrated silica matrix has been shown to minimize the molecular degradation of microorganisms during advanced diagenesis [Alleon et al., 2016a,b; Alleon et al., 2018].

On sol 0910, a float rock was automatically selected by the AEGIS system after a rover drive when entering the margin unit from the Jezero delta top. The target is a light-toned partially buried float with lustrous appearance.

LIBS: The chemistry of 9/10 points reveal a homogeneous composition, enriched in SiO2. The average SiO2 for these 9 points is 75.0 wt.% while the average total of quantified oxides is 83.5 wt. %.  

VISIR reflectance: The reflectance spectra share an overall blue slope, and exhibit absorptions at 1.9 µm (H2O), 2.2 µm (X-OH) and 1.4 µm (OH & H2O). The chemistry derived from LIBS (mean Al2O3< 2 wt.%) leads to the attribution of the 2.2 µm band to Si-OH. All such absorptions are present within spectra of terrestrial hydrated silica.

What type of hydrated silica? The reflectance spectra show that this target contains both Si-OH and molecular water. The position of absorption bands departs from what is typically observed for opals and chalcedony is at present the closest spectral analogue in term of band depths and position.

What origin? A 2.2 µm band has been observed in the IR spectra from the fan top and the margin unit, together with carbonate signatures. The LIBS derived chemistry of the targets suggest that this 2.2 band is related to hydrated silica. This suggests that the formation of the hydrated silica is associated with carbonate formation (locally or in the catchment) and that AEGIS_0910A may have the same origin. One possible scenario that is being investigated is that this silica material could represent the precipitates from a fluid that dissolved the ubiquitous olivine found in Jezero floor and delta, and concomitantly precipitated carbonates that are abundant in delta-rocks and the marginal unit ([Calvé et al., LPSC 2024; Wiens et al., LPSC 2024]).

Here, IR spectroscopy reveals that this hydrated silica-rich material is more crystalline that the hydrated silica deposits previously reported on Mars from orbit and in situ at Marias Pass, Gale crater [Pan et al., 2021; Gabriel et al., 2022; Ruff et al., 2011; Rapin et al., 2018].

Summary: Two independent lines of evidence, IR and LIBS, reveal that the float rock analyzed on sol 910 is made of hydrated silica. This target is unique so far in the SuperCam dataset (> 500 targets), but may be linked to high SiO2 points observed in the carbonate-rich delta bedrock units. Based on IR, this rock seems more akin to a micro-crystalline type silica, in contrast to previous observations of silica from the ground. Such a target may have trapped and preserved biosignatures, together with unique information on the paleoenvironmental conditions of the Jezero crater.

How to cite: Beck, P. and the Supercam and M2020 team members: Multi-spectroscopic detections of hydrated-silica in the Jezero crater   , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4623, https://doi.org/10.5194/egusphere-egu24-4623, 2024.

X1.151
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EGU24-10421
Zoltán Szalai, Mate Karlik, Gergely Jakab, Anna Vancsik, István Gábor Hatvani, Dóra Cseresznyés, and Csilla Király

Diffuse Reflectance Infrared Fourier Transform Spectroscopy (FTIR DRIFT) is a widely used method for investigating soil organic materials. The existing literature suggests variations in sample preparation techniques for soil analysis. Notably, the powdering and drying method may influence the presence of organic materials, clay minerals, and carbonates. These minerals are occasionally found as coatings on different mineral surfaces and sometimes as part of the matrix within soil aggregates. This study examined four topsoils of distinct types from Hungary: Arenosol, Leptosol, Gleysol, and Phaeozem (WRB2022). The samples were pulverized both to < 250 µm and < 63 µmAnd also various procedures for drying were used: 1-hour drying sessions at 50 °C, 100 °C, 150 °C, 200 °C, and 250 °C, as well as overnight drying at 50 °C, 100 °C, and 150 °C. Additionally, samples were measured without undergoing extra drying at room temperature. This study aimed to focus on significant organic material bands.

Pulverization has a more pronounced effect on FTIR DRIFT spectra in soils with aggregates, furthermore, when the original soils contain a higher proportion of sand fraction. The drying method affects the measured absorbance values at the highlighted wavenumbers with an underlined influence on the aliphatic components range. Support of the National Research, Development, and Innovation Office (Hungary) under contract K142865, and Eötvös Loránd Research Network SA41/2021 are gratefully acknowledged.

How to cite: Szalai, Z., Karlik, M., Jakab, G., Vancsik, A., Hatvani, I. G., Cseresznyés, D., and Király, C.: Effect of sample preparation on the FTIR DRIFT spectra in the case of soils with different organic material content, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-10421, https://doi.org/10.5194/egusphere-egu24-10421, 2024.

X1.152
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EGU24-3365
Optical probing of glass transition at high pressure allows whole-mantle silicate melt viscosity models
(withdrawn)
Sergey S. Lobanov and Sergio Speziale
X1.153
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EGU24-17632
Sabrina Nazzareni, Gabriele Giuli, and Henrik Skogby

The Dellen impact structure is located in a ca. 20 km wide basin filled by two lakes in the east central Sweden. The complex structure is covered by a thick moraine deposit, and most impact melted material can be found as loose blocks and boulders scattered throughout the moraine. Geophysical measurements show the presence of a coherent impact melt body about 9 km wide and 200-500 m thick for which impact ages  between 90, 110, to 140 Ma were determined [1]-[2]. 

The impact melt glass (commonly referred as dellenite) consisting of phenocrysts of subhedral orthopyroxene (Wo4En63Fs33), skeletal plagioclase (average An59Ab38Or3), and euhedral magnetite within a glassy matrix of rhyolitic composition. MicroFTIR measurements performed in the glass matrix and euhedral glass blebs within the skeletal plagioclase show the presence of 1.4 wt% water in the rhyolitic glass. We estimated that the dellenite vitrified at ca. P=200-300 bar by comparing the glass water content  with the water solubility of a similar composition silicate melt following  Papale's model [3].

Dellenite orthopyroxene was studied by polarized FTIR spectroscopy, Mössbauer spectroscopy, single crystal X-ray diffraction and EMPA. They are iron rich enstatite (Wo4 En63 Fs33) with a Fe3+/Fetot ratio of 1.6%. They have very weak to absent OH vibrational bands in the IR spectra, corresponding to H2O contents ranging from 0 to 39 ppm H2O, a variability suggesting H loss during post-formation processes, which may occur via the relatively fast redox reaction Fe2+ +OH- =Fe3+ +O2- +½H2. 

In volcanic pyroxenes H loss may be a common process occurring at different moments from crystallization to post-eruption. However, H incorporation in pyroxene is associated with point defects governed by slow kinetics diffusion rates, which are retained in the structure when H is lost. By reversing the redox reaction the original H content of pyroxene can thus be recovered by thermal annealing experiments under reducing conditions [4]-[5].

In order to restore H that was possibly lost, dellenite pyroxenes were thermally annealed under hydrogen atmosphere (at 1 Atm) in a horizontal glass-tube furnace by thermal annealing experiments at 700°C for 17 hours. FTIR spectra were recorded after each heating step. All the samples increased their hydrogen content and the final average water content is 77 ppm. 

Cation partition as derived by the SC-XRD and EMPA were used to calculate the orthopyroxene closure temperature (Tc) which is expression of the cooling rate for the cpx-host rock. Preliminary results point to a high Tc (833°C) due to a quite fast host-rock cooling rate. 

A tentative model for the evolution of the rhyolitic portion of the Dellen impact melt is under development merging geophysical data with our experimental data on water content of pyroxene and glass, and pyroxene geospeedometry.  

References:

[1]Henkel H (1992) Tectonophysics 216, 31-40

[2]Mark DF Lindgren P Fallick AE (2014) Geological Society of London Special Publication 378, 349-366

[3]Papale P (1999) Am Mineral 84, 477-792

[4]Weis FA Skogby H Stalder R (2016)  Am Mineral 101(10): 2233-2247

[5]Nazzareni S Barbarossa V Skogby H Zanon V Petrelli M (2020)  CMP 175:87

How to cite: Nazzareni, S., Giuli, G., and Skogby, H.: Dellen crater impact melt rock: pyroxenes as a proxy for melt thermal history and water content, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-17632, https://doi.org/10.5194/egusphere-egu24-17632, 2024.

X1.154
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EGU24-16706
|
ECS
Justine L. Myovela, László E. Aradi, Tamás Spránitz, Máté Hegedűs, Patrik Konečný, János Kovács, and Márta Berkesi

The Styrian Basin, situated in the transition zone between the Pannonian Basin and the Eastern Alps, is believed to have formed above a lithospheric wedge, which have been affected by a subduction. The Late Miocene-Pliocene alkali basalts sampled the subcontinental lithospheric mantle beneath the area, bringing mantle xenoliths to the surface (e.g., [1] [2]). These xenoliths are amphibole-rich, indicating extensive modal metasomatism at mantle depth. Our goal is to better understand the possible fluid and melt-related processes in these xenoliths by studying fluid and melt inclusions in them. In the studied samples, one category of xenoliths contains both fluid and melt inclusions (co-entrapped), while the other contains only fluid inclusions. We carried out 3D confocal Raman mapping, Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM), Electron Microprobe Analysis (EMPA), and Scanning Electron Microscope with Energy Dispersive Spectroscopy (SEM-EDS). Our primary objectives are to 1) gain insights into the nature of metasomatic agents based on fluid and melt inclusions and 2) test the applicability of 3D Raman mapping on inclusions. The studied inclusions are primary (fluid inclusions) and pseudosecondary (fluid and melt inclusions), occurring in orthopyroxene, clinopyroxene, and amphibole. The fluid inclusions are irregular to negative crystal-shaped (3-100 μm), whereas melt inclusions are glass-rich with rounded to negative crystal shapes (4-15 μm).

A series of 3D Raman mapping on these fluid inclusions has revealed complex phase assemblages comprising fluid and solid phases (magnesite, silicate glass, pyrite, talc, anhydrite, and nahcolite). The fluid is dominated by CO2 (up to 99.3 mol%) and H2O (up to 8.7 mol%). EMPA indicates that the trapped silicate glass in the melt inclusions is H2O-bearing (up to 3.3 wt%) and exhibits an evolved composition (i.e., trachyandesitic composition with SiO2 between 54.31-60.65 wt%) relative to the host basalt of the studied xenoliths.

We discovered pargasitic amphiboles within SiO2-rich glass in the melt inclusion that co-entrapped with the CO2-H2O-rich fluid phase (where H2O content is likely high relative to mantle fluids). This strongly suggests that amphiboles were likely crystallized from an immiscible SiO2-rich melt and CO2-H2O-rich fluid that could have been circulating in the mantle wedge above a subducted slab. This immiscible component is suggested to be a metasomatic agent that modified this mantle portion beneath the Styrian Basin.  Furthermore, this study revealed that the laser-induced heating effect could overestimate sulfides in the 3D Raman models, while silicate glass could be underrepresented due to its low Raman scattering properties. However, complementary FIB-SEM serial slicing provides a clear outline of silicate glass in fluid inclusions. Despite these limitations, 3D Raman mapping has proven to be a powerful tool for unravelling complex phase assemblages in inclusions.

This research was supported by the NKFIH_FK research fund nr. 132418 to M. Berkesi. Part of this research was funded by the Doctoral School of Earth Sciences of the University of Pécs.

 

References:

[1]. Aradi et al., 2019; Földtani Közlöny, 149 (1). pp. 35-49.

[2]. Aradi et al., 2017; Tectonics, 36, 2987–3011.

Keywords: 3D Raman mapping, complex inclusions, mantle metasomatism, subduction zone, Styrian Basin.

 

How to cite: Myovela, J. L., Aradi, L. E., Spránitz, T., Hegedűs, M., Konečný, P., Kovács, J., and Berkesi, M.: Unravelling metasomatic agent in amphibole-rich upper mantle xenoliths from the Styrian Basin (W-Carpathian Pannonian Region): Insights from 3D Raman mapping of complex inclusions, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-16706, https://doi.org/10.5194/egusphere-egu24-16706, 2024.

X1.155
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EGU24-12017
Simon Bushmaker, William Nachlas, and Chloë Bonamici

Jarosite, a hydrous K-rich sulfate mineral, was found in fine-grain quantities on the Martian surface by the Opportunity rover in 2004. Jarosite found in some terrestrial settings can form a complete solid solution with ammoniojarosite through substitution of the ammonium ion (NH4+) which replaces K+ within its crystal structure. Requiring water and acidic conditions to form, jarosite stands as a potential indicator of ancient N-bearing environments on the Martian surface. The Mars Perseverance rover is currently exploring the Martian surface with analytical instrumentation that may be capable of detecting N-rich jarosite, including the SHERLOC (Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals) and the PIXL (Planetary Instrument for X-ray Lithochemistry) detectors. To investigate the detection of N in jarosite with Raman and X-ray spectroscopy, we analyzed several terrestrial samples of jarosite and ammoniojarosite using laser Raman spectroscopy and electron-excited Wavelength Dispersive X-ray Spectroscopy (WDS). Comparison of high wavenumber regions of Raman spectra with WDS spectra of N K-α X-rays on the same samples will be used to investigate detection and quantification of N as ammonium in jarosite.

How to cite: Bushmaker, S., Nachlas, W., and Bonamici, C.: X-ray and Raman spectroscopy of jarosite and ammoniojarosite from several terrestrial localities, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-12017, https://doi.org/10.5194/egusphere-egu24-12017, 2024.

X1.156
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EGU24-12281
Helen E. King and Aleks Živković

Exploring the Raman oxygen isotope signatures of calcite and vaterite

Oxygen isotope tracers have been increasingly used to differentiate between solid-state and fluid-mediated mineral transformation pathways (e.g., Julia et al. 2023). When 18O enrichment within oxyanion bearing minerals is analysed using Raman spectroscopy, the kinetically hindered formation of different isotopologues can also provide an in-situ timer for these processes (King et al. 2014). However, at present we assume that each isotopologue band in the vibrational spectrum has an equivalent intensity when present at the same concentration within the crystal structure. Here we test this hypothesis by exploring the vibrational spectra of two important oxyanion-bearing minerals, calcite and vaterite. These are polymorphs of CaCO3 and reflect a metastable, transition phase and the thermodynamically most stable mineral expected in many natural systems found at the Earth’s surface.

Here we have used a joint experimental and theoretical approach to demonstrate that isotopic substitution changes both band positions and band intensities to different extents, depending on the vibrational spectroscopy method used and the bands examined. Density functional theory simulations (King et al. 2022) show that for calcite, the most intense Raman bands, the υ1 symmetrical stretching, related to individual isotopologues are found to have very similar intensities and are not affected by changes in isotopologue distribution within the material. Splitting of some bands due to changes in symmetry correlate to observed effects in experimentally produced 18O enriched calcite.In contrast, vaterite vibrational bands were found to change more extensively upon isotope substitution, thus they can only be used to evaluate relative changes in the 18O concentration within the material. These results are expected to contribute to a deeper und less ambiguous understanding of evaluating isotopic enrichment effects in the vibrational spectra of calcium carbonates.

Julia et al. 2023 Chemical Geology, 621, 121364.

King et al. 2014 Crystal Growth & Design, 14, pp. 3910.

King et al. 2022 Crystals, 13, 48.

How to cite: King, H. E. and Živković, A.: Exploring the Raman oxygen isotope signatures of calcite and vaterite, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-12281, https://doi.org/10.5194/egusphere-egu24-12281, 2024.

X1.157
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EGU24-1209
|
ECS
Patrícia Jones, Alberto Caracciolo, Edward W Marshall, and Elisa Johanna Piispa

The volcanic landscapes of Iceland's Westfjords are marked by the intriguing presence of Plagioclase Ultraphyric Basalts (PUBs), distinctive lava formations that are a focal point of this research. Characterized by plagioclase contents so high (up to 50-60%) that they approach the crystallinity of a crystal mush, these formations offer a unique opportunity to explore the extreme end of lava crystallinity and the influence of abundant large plagioclase crystals on lava viscosity and flow. The main aim of this research is to understand how the abundance of large plagioclase crystals influences the viscosity and flow of lavas at the extreme end of lava crystallinity, as well as better understand the origin of the crystal cargo. The interplay between the crystals and the magma is crucial for better understanding the origins and flow characteristics of these volcanic formations. This is achieved through an interdisciplinary approach, combining petrographical and geochemical analyses, including Inductively Coupled Plasma (ICP) for major element trace element analysis, with Anisotropy of Magnetic Susceptibility (AMS) to determine the flow direction within the lava. This comprehensive method provides insights into the crystallization conditions of magmas and minerals, as well as the textural and compositional characteristics of the plagioclase crystals. The outcomes of this research are not only crucial for understanding the unique aspects of the Westfjords’ volcanic regions but also have significant implications for predicting volcanic hazards and refining magma dynamics models, thereby enhancing our ability to mitigate the impacts of volcanic activity.

 

How to cite: Jones, P., Caracciolo, A., Marshall, E. W., and Piispa, E. J.: Understanding the flow dynamics of a Plagioclase Ultraphyric Basalt- a case study from the Westfjords, Iceland, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1209, https://doi.org/10.5194/egusphere-egu24-1209, 2024.

X1.158
|
EGU24-764
|
ECS
Karolina Mil, Bożena Gołębiowska, Adam Włodek, and Adam Pieczka

The Karkonosze granite (~320–312 Ma) is interpreted as a syn-collisional to magmatic arc intrusion. It is known for distinct symptoms of post-magmatic activity, including formation of intragranitic pegmatites observed in Szklarska Poręba quarry with overprinted W–Sn–Mo–Bi hydrothermal mineralization (e.g., Kozłowski et al., 1978; Pieczka & Gołębiowska, 2012).

Tin mineralization in the granite quarry at Szklarska Poreba is represented by cassiterite (Karwowski et al., 1972), Sn-rich titanite, malayaite, stokesite, and rare tin sorosilicates – kristiansenite, kozłowskiite and silesiaite (Evans et al., 2008;  Pieczka et al., 2022, 2023) The presence of all the above-mentioned mineral phases was confirmed by chemical microanalysis using the electron probe microanalyzer JEOL SuperProbe JXA-8230 and structure refinement. Cassiterite was recognized in an association mainly with scheelite, molybdenite, wolframite, chalcopyrite, and pyrite. These minerals crystallized from high-temperature aqueous fluids, subsequently followed by sulphide-rich stage (Karwowski et al., 1973). Sn-rich titanite, forming an isomorphic series with malayaite, CaTi[SiO4]O–CaSn[SiO4]O, shows chemical heterogeneity, with a maximum SnO2 content up to 15.88 wt% (32 mol% Sn end-member), and elevated Nb2O5 (up to 9.85 wt%), Ta2O5 (up to 7.88 wt%), and Sc2O3 (up to 1.90 wt%). Malayaite is close to the pure Sn end-member, it contains up to 97 mol% Sn end-member with minor Fe, Nb, Ta contents. Stokesite, CaSnSi3O9·2H2O, occurs as a rim grown around the outermost parts of Sn-rich titanite crystals, veinlets cutting cassiterite, and in direct contact with fluorite. Its crystals were also observed on surfaces or within fractures in bismuthinite.

The initial source of Sn was related to the final stage of pneumatolytic processes, in the granitic complex with successive development during hydrothermal activity. Fluid inclusion studies indicate that cassiterite crystalized at temperatures of 515–470ºC (Kozłowski et al., 2002).

The precipitation of Sn-rich titanite was likely initiated under elevated metal activities at slightly lower temperatures and high oxygen fugacity.

Stokesite, representing the final stage of the Sn assemblage, slowly crystallized in free spaces, was found in a direct contact with fluorite, which homogenization temperature in the Szklarska Poręba assemblage was estimated at 159-172 oC (Kozłowski & Matyszczak, 2022). Therefore, stokesite and fluorite may have formed during the same stage of hydrothermal processes. Since no alterations had been observed on the cassiterite grains, a secondary source of tin for later Sn-rich minerals was excluded.

 

How to cite: Mil, K., Gołębiowska, B., Włodek, A., and Pieczka, A.: Tin mineralization in post-magmatic processes: a case of post-magmatic activity in the Szklarska Poręba Huta quarry, Lower Silesia, SW Poland , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-764, https://doi.org/10.5194/egusphere-egu24-764, 2024.

X1.159
|
EGU24-17688
|
ECS
|
Rabindranath Mondal, Gaurav Shukla, and Swastika Chatterjee

The mantle transition zone (MTZ) is known to be potentially hydrated as laboratory
experiments have shown that the two major mineral phases namely wadsleyite (β-M2SiO4 ;
M: Mg, Fe) and ringwoodite (γ-M2SiO4; M: Mg, Fe) can accommodate significant amounts of
water in the form of hydroxyl ions in their crystal structure. Direct in-situ evidence of the
MTZ being (at least locally) hydrated has been derived from natural diamonds containing
hydrous ringwoodite inclusions (Pearson 2014, Nature). Hence, in this study, we have
investigated the crystal structure and the thermoelastic properties of Fe-bearing ringwoodite
as a function of temperature, pressure, and water content (0 wt%, 1.56 wt%, 3.3 wt%) using a
combination of first-principles density functional theory (DFT) and quasi-harmonic
approximation (QHA). Our calculation reveals that hydration in general causes a reduction in
the sound wave velocity of ringwoodite. However, the ‘reduction’ brought in by hydration is
significantly suppressed at pressures corresponding to the lower part of the MTZ.
Consequently, the sound wave velocities for the 1.56 wt% water-containing ringwoodite
model is found to become very similar to the sound wave velocities of the anhydrous
ringwoodite. However, when the water concentration is increased further to ~3.3 wt%, the pressure-induced
suppression at lower MTZ pressures though present is not significant. These findings indicate that though seismic
waves may not be able to precisely decipher the state of hydration of the lower part of MTZ
when the water concentration is less than 1.56 wt%, it is still robust enough to locate regions
of very high water concentration ~ 3.3 wt%.

How to cite: Mondal, R., Shukla, G., and Chatterjee, S.: Are seismic waves robust enough to detect the presence of water in the lower part of the mantle transition zone?, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-17688, https://doi.org/10.5194/egusphere-egu24-17688, 2024.

X1.160
|
EGU24-20076
|
ECS
Exploring boron isotope fractionation during interaction of silicate melts and hydrous fluids: an experimental approach concerning ore formation
(withdrawn)
Jakob Rauscher, Bernd Wunder, Max Wilke, Robert Trumbull, Sandro Jahn, Melanie J. Sieber, Julie Michaud, Florian Pohl, Maria Rosa Scicchitano, Michael Fechtelkord, and Oona Appelt
X1.161
|
EGU24-18335
|
ECS
David Heuser, Renelle Dubosq, Ge Bian, Elena Petrishcheva, Gerlinde Habler, Baptiste Gault, Christian Leopold Lengauer, Christian Rentenberger, and Rainer Abart

At high temperatures, alkali feldspar consists of a continuous solid-solution between the Na (albite) and K (K-feldspar) end members. Below about 600°C, a miscibility gap opens, the limits of which are determined by the so-called solvus. Alkali feldspar of intermediate composition tends to exsolve when cooled from temperatures of magmatic or metamorphic crystallization, forming an intergrowth of Na- and K-rich lamellae, a microstructure referred to as perthite. Initially, coherency is maintained across the lamellar interfaces and it may be preserved over geological times. Since the lattice parameters of alkali feldspars strongly depend on composition, the exsolution lamellae must be strained to maintain coherency at the interfaces. The elastic energy required to strain the lamellae counteracts exsolution and equilibrium compositions of coexisting coherent exsolution lamellae define a coherent solvus which lies below the solvus for strain-free phase equilibria. Segregation of Na and K and subsequent lamellar coarsening is achieved by thermally activated Na-K interdiffusion. Therefore, compositions and widths of the exsolution lamellae could be used to reconstruct cooling histories. Knowing the shape and position of the coherent solvus is key for the corresponding geo-speedometry applications.

To determine the coherent solvus, initially homogeneous disordered, gem-quality alkali feldspar was annealed at temperatures between 440°C and 560°C and at atmospheric pressure, which caused it to exsolve into coherently intergrown 10 to 20 nm wide lamellae, the compositions of which were directly determined with atom probe tomography.

The application of different annealing times showed that thermodynamic equilibrium was reached during the experiments. The obtained lamellar composition define points on the coherent solvus, which were for the first time measured directly for alkali feldspars.

Additionally, equilibrium Na-K partitioning experiments between NaCl-KCl melt and the same alkali feldspars as used for the exsolution experiments were performed at atmospheric pressure and at temperatures between 800°C and 1000°C to calibrate a thermodynamic mixing model supplemented by a model for the elastic energy required for coherent exsolution. The coherent solvus calculated from the thermodynamic model and the directly measured coherent solvus are in excellent agreement. This indicates that the developed models provide an adequate description of phase equilibria in coherent lamellar intergrowth. The directly measured coherent solvus and the models form a solid base for potential applications of geo-speedometry in coherently exsolved alkali feldspars.

How to cite: Heuser, D., Dubosq, R., Bian, G., Petrishcheva, E., Habler, G., Gault, B., Lengauer, C. L., Rentenberger, C., and Abart, R.: The coherent solvus of disordered alkali feldspar determined with atom probe tomography, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-18335, https://doi.org/10.5194/egusphere-egu24-18335, 2024.

X1.162
|
EGU24-2001
|
ECS
Melanie Maddin, Remi Rateau, Adrienn Marie Szucs, Luca Terribli, and Juan Diego Rodriguez-Blanco

Rare earth elements (REE) are essential in many green, modern technologies and play a critical role in a more sustainable future [1]. However, there is a substantial risk to their supply as the availability of REE deposits with minable concentrations are limited [2]. A better understanding of the mechanisms controlling REE concentration in minerals would have applications in more efficient practices as well as REE separation techniques and recycling.

Our study investigated the reaction of multi-component REE (La, Ce, Pr, Nd, and Dy) aqueous solutions with carbonate grains of dolomite, aragonite and calcite at hydrothermal conditions (21-210 °C). Two different solutions were prepared (i) a solution with equal concentrations of each of the five REE: (ii) a solution with the concentrations of the five REEs normalized to a Post Archean Shale standard (PAAS), to mimic the rare earth element concentrations in continental crust and natural fluids.

The interaction between the REE bearing fluids with each of the carbonate grains resulted in the replacement of the host carbonate grain with a series of REE minerals following a complex crystallization sequence (lanthanite → kozoite → bastnasite → cerianite). We have found that for most of the experiments at 165 °C, when using the equal concentration solutions, the crystallization of kozoite was promoted and the REE ratio in the newly formed solids was similar to the REE ratio in solution. In contrast, when PAAS solutions were used, REE-bearing crystals were zoned or had a heterogenous distribution of REEs, often coupled with the formation of discreet REE phases (e.g., cerianite). In addition, chemical signatures indicating the presence of metastable REE-bearing phases that transformed to more thermodynamically stable polymorphs were found in multiple samples as well as symplectite textures formed by the reaction of adjacent phases. Overall, our experiments demonstrate that the polymorph selection, crystallization pathway, the kinetics of mineral formation and the chemical texture of the newly formed rock during the mineral-fluid interaction process are dependent on the REE concentrations in solution, their ionic radii, temperature, time, and solubility of the host grains.

 

References

[1] Sinding-Larsen, R., Wellmer, F.W.,. Non-renewable resource issues: Geoscientific and societal challenges, Non-Renewable Resource Issues: Geoscientific and Societal Challenges 2012.

[2] Jordens, A., Cheng, Y.P., Waters, K.E.,. A review of the beneficiation of rare earth element bearing minerals. Miner. 2013 Eng. 41, 97-114.

How to cite: Maddin, M., Rateau, R., Szucs, A. M., Terribli, L., and Rodriguez-Blanco, J. D.: Complex Multi-Stage Replacement Reactions in the REE-CaCO3 System, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2001, https://doi.org/10.5194/egusphere-egu24-2001, 2024.

X1.163
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EGU24-3030
|
ECS
Tongxu Zhao, Shang Xu, and Qiyang Gou

The interactions between clay minerals and organic matter, specifically adsorption, are widely recognized as a crucial mechanism for promoting the preservation of organic matter within sedimentary environments. This paper discusses the genesis and adsorption of clay minerals, especially their influence on the process of organic matter enrichment in sedimentary environments. The composition of clay minerals found in sediments serves as an indicator of both the climatic and lithological characteristics of the provenance area. Smectite formation is favored in mafic provenance, while the coexistence of illite and chlorite suggests cold and arid conditions. Additionally, an abundance of kaolinite indicates intense chemical weathering of the provenance area. The physical and chemical properties of clay minerals and organic matter significantly influence adsorption. Smectite is thought to adsorb more organic matter due to its greater surface area. Selective adsorption of high molecular weight, aromatic, and aliphatic compounds dissolved organic matter onto mineral surfaces may have played a role in kerogen formation. Moreover, the preservation of organic matter via clay mineral adsorption is intricately linked to the sedimentary environment. Disparities in nutrient elements during the clay minerals synsedimentary period can impact biological productivity. Furthermore, the pH and solution metal ions of the water column influence the quantity and type of organic matter adsorbed. The contribution of adsorption to organic matter preservation is influenced by redox conditions, and this contribution can be observed through density separations. Additionally, we present several recommendations for future research. Firstly, diagenesis alters the clay mineral assemblage in sedimentary rocks. However, it may be possible to reconstruct the clay mineral assemblage based on morphological, mineralogical, and chemical composition characteristics. Secondly, studies have indicated that clay minerals can facilitate the precipitation of carbonate minerals, providing insights into the formation of abiotic carbonate minerals. Finally, the practical applications of clay minerals in shale oil and gas exploration are underscored, such as their ability to predict sweet-spot areas and control reservoir properties.

How to cite: Zhao, T., Xu, S., and Gou, Q.: Differential adsorption of clay minerals: Implications for organic matter enrichment, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-3030, https://doi.org/10.5194/egusphere-egu24-3030, 2024.

X1.164
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EGU24-4776
Juan Rodriguez-Blanco, Adrienn Maria Szucs, Remi Rateau, Melanie Maddin, and Luca Terribili

Mineral replacement reactions are essential for the understanding of the genesis and chemistry of REE-bearing carbonatite deposits. Many of these reactions involve interaction of Ca-Mg and REE carbonate phases, leading to the formation of minerals with complex compositions and structures.

This study explores the oriented surface precipitation of REE carbonates during the interaction of individual and multiple REE-bearing aqueous solutions with calcite and aragonite (CaCO3) at low hydrothermal conditions (25-220 °C). This mineral-fluid interaction is translated into a temperature-dependent solvent-mediated surface precipitation and subsequent pseudomorphic mineral replacement of the CaCO3 seeds by newly formed REE carbonates. This complex replacement sequence includes the crystallisation of metastable kozoite (orthorhombic REECO3OH) via the formation of individual spindle-shaped crystals following a transient non-random orientation on the surface of the host grains, gradually covering their full surfaces.

Our experiments show that the likelihood of formation of the oriented overgrowth and its stability are controlled by structural constraints which in turn depend on four factors: temperature, ionic radii and ionic potential of the REE in the system, and dissolution rate of the host CaCO3 minerals. Also, we demonstrate that REE elements can be rapidly immobilized as REE hydroxicarbonates, even at low hydrothermal conditions. An explanation of the epitaxial overgrowth’s configuration and the atomic arrangement of the structures of the CaCO3 polymorphs and REE-kozoite will be discussed. 


[1] Szucs AM et al. Reaction Pathways toward the Formation of Bastnäsite: Replacement of Calcite by Rare Earth Carbonates. Crystal Growth & Design, 2021;21(1):512–527.
[2] Szucs AM et al. Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions. Global Challenges. 2022;2200085.

How to cite: Rodriguez-Blanco, J., Szucs, A. M., Rateau, R., Maddin, M., and Terribili, L.: Temporal growth of epitaxial layers in the CaCO3-REECO3OH system during mineral replacement processes, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4776, https://doi.org/10.5194/egusphere-egu24-4776, 2024.

X1.165
|
EGU24-4492
|
ECS
Petrography and mineralogy control the nm-μm-scale pore structure of  lacustrine carbonate-rich shales of  China
(withdrawn)
Qiyang Gou and Yangbo Lu
X1.166
|
EGU24-5725
Exploring the diversity of methods in the study of minerals: a case study on organic-rich shale in the Shahejie Formation, Bohai Bay Basin
(withdrawn)
Bo Gao, Shang Xu, Zhiyao Zhang, and Tongxu Zhao
X1.167
|
EGU24-9600
|
ECS
Anna Jędras, Jakub Matusik, Esakkinaveen Dhanaraman, Yen-Pei Fu, and Grzegorz Cempura

Photocatalysis is a promising water purification technology, that harnesses the power of light-induced reactions to degrade contaminants. Utilizing visible light in the reactions is imperative, as it comprises a significant portion of the solar spectrum, which aligns with sustainable practices. Graphitic carbon nitride (g-C3N4) is a photocatalyst active in visible light, characterized by high chemical and thermal stability, ease of synthesis, and relatively low cost. However, its performance is limited by charge carrier mobility and charge recombination. These limitations might be addressed by synthesizing heterostructures, i.e. composites containing two or more semiconductors. Heterojunctions between g-C3N4 and layered double hydroxides (LDH) have shown increased photocatalytic efficiency. LDH are crystalline, hydrotalcite-like materials that enhance the charge separation and light absorption by the heterostructure. These materials can be obtained through various synthesis methods, including coprecipitation and hydrothermal treatment, influencing their properties. Thus, this study aimed to compare heterostructures obtained by different synthesis routes and asses their photocatalytic efficiency.

Three synthesis methods were used to obtain Zn-Cr LDH/g-C3N4 heterostructures: coprecipitation, adsorption/coprecipitation, and hydrothermal treatment. For g-C3N4 preparation, melamine was heated at 550°C for 5 h. The coprecipitation method involved dissolving zinc and chromium nitrates in DI water, then adding it to a suspension of g-C3N4, while simultaneously adding a solution of NaOH and Na2CO3. The adsorption/coprecipitation method was based on adding zinc and chromium nitrates to a g-C3N4 suspension, then after 30 minutes adding a solution of NaOH and Na2CO3. The hydrothermal method included dissolving zinc and chromium nitrates in the g-C3N4 suspension, adding NaOH and Na2CO3, then placing the suspension in an oven for 24 h at 100°C. The obtained materials were characterized by XRD, SEM/TEM, XPS, TRFL, N2 adsorption/desorption, and photoelectrochemical measurements. The photocatalytic activity of heterostructures was assessed in batch experiments in aqueous solutions containing 1 ppm of estrone, with a 150 W LED lamp as a source of visible light.

The XRD patterns of obtained materials confirmed the formation of layered phases. The hydrothermal heterostructure was characterized by sharper reflections, which suggested higher structural order and/or larger crystallites. The average specific surface values (SBET) showed that the hydrothermal composite was characterized by the highest SBET - 124 m2/g. This indicated its higher porosity, compared to the materials obtained by other methods. The TRFL studies proved that the heterojunctions have lower recombination rates and longer lifetimes of charge carriers. The results of photochemical measurements suggested superior electronic conductivity and charge transfer efficiency for the hydrothermal heterostructure. The determined photoelectrochemical properties agreed well with the photocatalytic activity of heterostructures, which was the highest for the hydrothermal composite. This material led to a 99.5% estrone concentration loss after 60 minutes of reaction, in comparison to 49.9% and 75.8% loss assessed for the materials obtained by coprecipitation and adsorption/coprecipitation, respectively. The results of this study demonstrated the advantage of using the hydrothermal method to obtain LDH/g-C3N4 heterostructures with a high efficiency of pollutant photodegradation from aqueous solutions.

This research was funded by the AGH University of Science (Krakow, Poland), grant number 16.16.140.315.

How to cite: Jędras, A., Matusik, J., Dhanaraman, E., Fu, Y.-P., and Cempura, G.: Zn-Cr LDH/g-C3N4 heterostructure for estrone photodegradation: what is the effect of synthesis methods on materials’ properties and degradation efficiency?, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9600, https://doi.org/10.5194/egusphere-egu24-9600, 2024.

X1.168
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EGU24-9623
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ECS
Klaudia Dziewiątka, Jakub Matusik, and Grzegorz Cempura

The widespread occurrence of zearalenone (ZEN) in a variety of grain products and animal feed, coupled with its capacity to accumulate in the food chain, poses a significant health risk for both humans and animals. Its ability to induce estrogen-like effects may disrupt the body's estrogen levels, thereby contributing to reproductive system diseases, even at very low concentrations. The removal of ZEN from aqueous environment is predominantly challenging due to its weakly polar nature, compounded by its high thermal stability. Photodegradation, especially when applying mineral-based photocatalysts, stands out as a promising strategy for environmentally friendly mycotoxin removal. It not only demonstrates cost-effectiveness but also entails the production of negligible secondary pollutants.

Our research employed platy kaolinite (M), synthetic calcined kaolinite nanotubes (MNC), and halloysite purchased from Sigma-Aldrich (HS) as supports for TiO2, g-C3N4, or combination of TiO2/g-C3N4 semiconductors. Each synthesis was designed to consistently yield ~20 wt% of the semiconductor or its mixture in the samples, maintaining a TiO2 to g-C3N4 ratio of 1:1. The sol-gel method was used for TiO2 synthesis [1], while porous g-C3N4 nanosheets were prepared by heating melamine at 550°C, with the addition of ammonium chloride in a 1:1 ratio. The structural, textural, morphological, and light absorption properties of the obtained samples were characterized through XRD, N2 adsorption/desorption, UV-Vis DRS spectroscopy, Raman spectroscopy, SEM, and TEM..

The UV-induced photodegradation kinetics experiments (365 nm, 10 mW/cm2) were carried out at a consistent initial ZEN concentration of ~10 ppm. ZEN concentrations were determined with high-pressure liquid chromatography (HPLC). The TiO2-loaded photocatalysts exhibited the slowest photodegradation kinetics, resulting in the final removal of ~41.9% by the M-based sample, ~63.4% by the HS-based sample, and ~86.9% by the MNC-based sample. Conversely, the impregnation with g-C3N4 and TiO2/g-C3N4 led to materials exhibiting the fastest kinetics, effectively removing over ~99.9% of the initial ZEN concentration. Notably, the nanotubular-based photocatalysts demonstrated slightly faster kinetics than those observed for the M-based materials and were comparable to those noted for the pure g-C3N4. Analogous experiments under visible light irradiation highlighted the synergistic effect for the combination of  both semiconductors, characteristic of Z-scheme heterojunction structures. Among the MNC-based samples, the least efficient photodegradation was demonstrated by the g-C3N4-containing sample (~13.7%), slightly higher for the TiO2-containing sample (~20.3%), and the most efficient removal was observed for the sample containing both semiconductors (~36.6%).

The conducted experiments revealed a significant potential of kaolinite and halloysite nanotubes as carriers for semiconductors in the effective removal of ZEN from aqueous solutions. Future aspects of our research will involve detailed investigations into the degradation pathways of ZEN and the electrochemical characterization of the materials used.

This project was supported by the National Science Centre Poland, under a research project awarded by Decision No. 2021/43/B/ST10/00868.

References:
[1] Dziewiątka K., Matusik J., Trenczek-Zając A., Cempura G. (2023). TiO2-loaded nanotubular kaolin group minerals: The effect of mineral support on photodegradation of dyes as model pollutants. Applied Clay Science, Elsevier, volume 245, 107123. 

How to cite: Dziewiątka, K., Matusik, J., and Cempura, G.: Efficient photodegradation of zearalenone: Unraveling the potential of photocatalysts based on kaolin group minerals, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9623, https://doi.org/10.5194/egusphere-egu24-9623, 2024.

X1.169
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EGU24-11168
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ECS
Authigenic minerals development and differential diagenetic evolution of lacustrine shale: implications on formation of reservoirs and diagenetic effects of long-term CO2 sequestration
(withdrawn)
Liu Wang, Bo Liu, and Longhui Bai
X1.170
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EGU24-12115
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ECS
Seppo Karvinen, Christoph Beier, and Aku Heinonen

Apatite is a ubiquitous mineral in plutonic carbonatites (magmatic carbonate-rich rocks) and associated rock types (Chakhmouradian et al., 2017). Carbonatites are enriched in incompatible elements such as P and rare earth elements (REE), which are accommodated into apatite structure among many other elements (e.g., Hughes and Rakovan, 2015), making apatite a suitable tracer for changes in magmatic-hydrothermal geochemistry.

Sokli carbonatite complex, located in eastern Lapland, Finland, is the westernmost intrusion of the Kola Alkaline Province (Vartiainen, 1980 and references therein). The Sokli complex encompasses multiple generations of carbonatite magmatism, which compositionally span from calcite carbonatite to dolomite carbonatite to late-stage Ba, Sr, REE-enriched dolomite-rich veins. Carbonatites are associated with several generations of phoscorites, exotic magnetite-apatite cumulates typically found in carbonatite complexes. Apatite is present in most rock types in the complex, from an accessory to a rock-forming mineral.

The Sokli complex has been studied for decades (O’Brien and Hyvönen, 2015), but the composition and role of magmatic apatite has not been discussed in detail outside of phosphorous mineralization studies. Previous studies indicate that with progressive fractionation the concentrations of Ba, Sr, REE, and F increase in whole-rock and mineral compositions (O’Brien and Hyvönen, 2015 and references therein). Questions that still remain open include whether apatite has recorded the proposed different magmatic and metasomatic stages and if apatite chemistry could provide arguments for the proposed liquid immiscibility relationship between carbonatites and phoscorites (Lee et al., 2004).

A variety of apatite-bearing rock types from the Sokli complex were sampled. The composition of apatite will be studied in situ for major and trace elements with electron microprobe analyzer (EPMA) and laser ablation inductively coupled mass spectrometry (LA-ICP-MS), respectively.

References cited:

Chakhmouradian, A.R., Reguir, E.P., Zaitsev, A.N., Couëslan, C., Xu, C., Kynický, J., Mumin, A.H., Yang, P., 2017. Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance. Lithos 274–275, 188–213.

Hughes, J. M., Rakovan, J. F. 2015. Structurally robust, chemically diverse: apatite and apatite supergroup minerals. Elements 11, 165–170.

Vartiainen, H., 1980. The petrography, mineralogy and petrochemistry of the Sokli carbonatite massif northern Finland. Geological Survey of Finland, Bulletin 313.

O’Brien, H., E. Hyvönen. 2015. The Sokli carbonatite complex in Maier, W.D., Lahtinen, R., O’Brien, Hugh (Eds.), Mineral Deposits of Finland. Elsevier. 305–325.

Lee, M.J., Garcia, D., Moutte, J., et al., 2004. Carbonatites and phoscorites from the Sokli complex, Finland. In: Wall, F., Zaitsev, A.N. (Eds.), Phoscorites and Carbonatites from Mantle to Mine: The Key Example of the Kola Alkaline Province. The Mineralogical Society of Britain and Ireland, London, 133–162.

How to cite: Karvinen, S., Beier, C., and Heinonen, A.: Apatite in the Sokli carbonatite complex, Finland, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-12115, https://doi.org/10.5194/egusphere-egu24-12115, 2024.

X1.171
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EGU24-14330
Maciej Manecki, Patrycja Wrona, Aleksandra Brzoska, and Kacper Staszel

There is a constant search for materials that could be used as geochemical barriers and fillers for radioactive waste storage containers. One of effective methods of immobilizing toxic elements is their precipitation in the form of sparingly soluble crystalline phases. The purpose of this study was to test the effectiveness of co-precipitation of Th from aqueous solutions in the form of crystalline lead phosphates. Such phases have high stability and low solubility and the presence of Pb has an additional effect on reducing the radiation.

Three sets of experiments were carried out by adding reagents into a solution containing non-radioactive Th at a concentration of 400 ppm:

(A) a solution containing PO43- ions (at a concentration of 1 g/L);

(B) a solution containing Pb2+ and a solution containing PO43- ions (at concentrations of 3.5 g/L and 1 g/L, respectively) added dropwise simultaneously;

(C) solutions containing Pb2+, PO43-, and Cl- ions (at concentrations of 3.5 g/L, 1.0 g/L, and 0.12 g/L, respectively) added dropwise simultaneously.

All experiments were repeated at pH = 3, 5 and 7. No reaction occurred in experiment (A), while in experiments (B) and (C) the solid phases crystallized, and the Th concentration dropped from 400 to about 0.05 ppm. In the absence of Cl (experiment B), the reaction at pH=3 led to the formation of "phosphoschultenite" PbHPO4 while at pH = 5 and 7 Th-bearing hydroxylpyromorphite Pb5(PO4)3OH was formed. In the presence of Cl ions (experiments C), Th-bearing pyromorphite Pb5(PO4)3Cl was formed over the entire pH range. Th was removed from solution by coprecipitation with Pb and incorporation of Th into lead phosphate structure.

The results showed that Pb must be present for Th to be effectively immobilized from solution in the form of phosphate phases. The presence of Cl is not as important as the presence of Pb in terms of removal efficiency, but it may be crucial for the long-term stability of the precipitated phases, since Pb5(PO4)3Cl has higher stability and lower solubility than Pb5(PO4)3OH. These findings pave the way for development of potential innovative techniques for immobilizing Th from waste and contaminated solutions, which could have implications for the safety and long-term viability of various nuclear waste disposal programs. This research was funded by National Science Center research grant no. 2021/43/O/ST10/01282.

How to cite: Manecki, M., Wrona, P., Brzoska, A., and Staszel, K.: Immobilization of radioactive Th by coprecipitation with lead apatites, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-14330, https://doi.org/10.5194/egusphere-egu24-14330, 2024.

X1.172
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EGU24-17099
Andrzej Tyc, Justyna Ciesielczuk, Krzysztof Gaidzik, and Tomasz Powolny

Sulfuric acid speleogenesis (SAS) is a general cave formation process in carbonate rocks in the presence of sulfuric acid. Such caves are mainly formed at and above the water table by abiotic or/and biotic oxidation of hydrogen sulfide (H2S). One possible source of H2S may be volcanic activity. The oxidation of H2S produces sulfuric acid that immediately reacts with carbonate host rock, producing replacement gypsum and CO2.

The Western Cordillera in the Peruvian Andes, characterized by volcanic and tectonic activity, features substantial travertine deposits. Among the most interesting and, at the same time, less known are the Mulapampa travertines located in the vicinity of the active Ampato-Sabancaya Volcanic Complex (ASVC). There are numerous collapse sinkholes in the travertine cover, and within three of them, caves have been found. discovered in three of them. Particularly interesting is the Gruta con lago cave, the bottom of which is located at the level of the current water table (ca. 40 m below ground level). It does not have the characteristic morphology of active SAS caves, but several speleogenetic by-products – mainly thick gypsum deposits – are typical of such features.

Mineralogical studies of sediment samples from the lake at the bottom of Gruta con lago corroborated the sulfuric acid genesis of the cave. Native sulfur was detected in those samples, among others. Microscopic examination of native sulfur crystals reveals traces of substantial corrosion attributable to the activity of sulfur bacteria. In the same cave lake's bottom sediments, framboidal pyrites formed inside the biofilms (presumably of sulfate-reducing bacteria) were found. Common secondary minerals in SAS caves, such as barite or celestine, are present on the cave bottom and walls.

This research was funded by the National Science Centre (Poland), grant No 2020/39/B/ST10/00042, and the Institute of Earth Sciences, University of Silesia, Poland.

How to cite: Tyc, A., Ciesielczuk, J., Gaidzik, K., and Powolny, T.: Sulfuric acid speleogenetic by-products and secondary minerals in caves of the Mulapampa travertines (Western Cordillera, Andes, Peru), EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-17099, https://doi.org/10.5194/egusphere-egu24-17099, 2024.

X1.173
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EGU24-14683
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ECS
Donjá Aßbichler, Natalie Weichselgartner, Natalie Diesner, Melvin Kayalar, Carolin Otte, Soraya Heuss-Aßbichler, Saskia Tautenhahn, and Anke M. Friedrich

Arsenic is a world-wide serious health problem occurring in various types of rocks, soil, and contaminated water resources. However, it is not always an acute health problem, as concentrations are often comparably low. But recently, it gained increasing attention with the introduction of new laws in Germany (and the EU) regarding the deposition of excavated sediments, e.g., in the context of the construction of tunnels or the mining of gravel and sand etc. The decision on whether excavated material can be used as backfill or needs landfilling depends on the analysis and classification relative to specified limit values. In the latter scenario, this can result in a significant increase in costs. It is mandatory to determine the heavy metals and arsenic (among other parameters) in the solid sample and to produce and analyze an eluate of the sample to identify soluble harmful elements that could potentially contaminate the groundwater.

At a first glance, arsenic contents in solid and in eluate often show erratic patterns, which could not be explained. In clastic sediments, an often observed (weak) correlation between arsenic and iron in solid analyses led to the assumption that arsenic is bound in iron-hydroxides. However, a comprehensive examination of the chemistry and mineralogy of a large number of samples did not reveal any clear correlations. Therefore, we studied drill-core samples and sediment profiles of poorly consolidated Miocene clastic sediments, including gravel, sands, clay and silt from different areas of the Northern Alpine foreland basin (mostly from the Munich and Ingolstadt areas).

Based on geochemical analyses, we found different “arsenic-types”: Some samples show the expected correlation pattern for arsenic in the solid and the eluate. Some samples, however, show high arsenic in the solid and low arsenic concentrations in the eluate. Also, remarkably, samples with rather low arsenic contents in the solid and high arsenic in the eluate were observed. No systematic correlation with other chemical elements or with macroscopic characteristics, e.g. grain size, could be identified. Our detailed mineralogical investigation of more than 30 samples showed that XRD analysis, which is usually used to identify the mineralogy in the finest fraction, is not sufficient to explain this behavior. Therefore, we separated all mineral phases (also in the clay fraction) and analyzed their mineral chemistry (in particular their arsenic content) with SEM, their texture with high-resolution Keyence microscopy (2000x), and combined the results with extensive leaching experiments.

Our results imply that mineralogy is the key to understanding the elution behavior of arsenic. Regarding the binding characteristics of arsenic, three different mineral types can be distinguished: 1) Fe-, Si- and Al-Hydroxides (minor tourmaline, apatite and zircon) can bind arsenic relatively well (no arsenic in the eluate), 2) chlorite and mica can adsorb high amounts of arsenate but with a weak bond (high As in eluate) and 3) smectite which releases its arsenate step-by-step with the increasing degree of swelling. The study showed that only with a detailed mineralogical and mineral-chemical analysis profound predictions on the elution behavior of arsenic can be made.

How to cite: Aßbichler, D., Weichselgartner, N., Diesner, N., Kayalar, M., Otte, C., Heuss-Aßbichler, S., Tautenhahn, S., and Friedrich, A. M.: Mineralogy – the key to understanding and predicting the elution behavior of arsenic , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-14683, https://doi.org/10.5194/egusphere-egu24-14683, 2024.

X1.174
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EGU24-18687
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ECS
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Yike Bai, Stephen Covey-crump, Nicholas Bojdo, Merren Jones, and Alison Pawley

In the drive to develop more fuel-efficient aircraft engines to reduce the environmental impact of flying, engines are being designed to run much hotter. This is leading to a greater range of damaging interactions between the engine components and mineral dusts ingested into the engine during flight. To mitigate the effects of these interactions there is a critical need to understand mineral transformations (e.g., polymorphic changes, melting, glass transition), reactions, and mineral properties under much more extreme rates of heating and cooling than have been examined previously. Recent technological advances allow differential scanning calorimetry (Flash DSC) measurements to be made on small samples at temperatures of up to 1000 ℃, at heating/cooling rates of up to 50000 K/s, rates which comparable to those experienced by mineral dust particles inside a jet engine. Here we present two case studies, relevant in the engine context, that illustrate the capabilities of Flash DSC measurements.

A number of minerals ingested into aircraft engines undergo polymorphic transformations as they are rapidly heated inside the engine and these can have a profound effect on the accumulation rate of dust deposits on engine components. In our first case study we show the effect of heating/cooling-rate on the α - β-quartz transformation at rates between 10 to 10000 K/s (ambient pressures). During heating the temperature of the transformation increases from 573 to 608 ℃ over this heating-rate range, and the kinetics of the transformation are significantly modified.

Dust deposits may undergo melting inside an engine and infiltrate the porous coatings that are applied to engine components for thermal protection. This prevents the coatings expanding and contracting in response to temperature changes which, in turn, leads to their failure. Hence a knowledge of the viscosity of the melts (and hence infiltration-rate) and how this varies with temperature is important. Conventional methods of measuring viscosity are unable to access a considerable temperature range in which changes occur within the sample (e.g., crystallization) over the timescale of the measurement. The temperature dependence of viscosity may, however, be obtained from the heating-rate dependence of the glass transition temperature, and this is a measurement that can be made extremely rapidly by Flash DSC. In the second case study we show the temperature-dependence of viscosity over a temperature range previously inaccessible, for two CMAS melts that have compositions representative of those that are found in aircraft engines.

How to cite: Bai, Y., Covey-crump, S., Bojdo, N., Jones, M., and Pawley, A.: Differential scanning calorimetry measurements of mineral transformations at the extreme heating and cooling-rates experienced by mineral dusts ingested into aircraft engines, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-18687, https://doi.org/10.5194/egusphere-egu24-18687, 2024.

X1.175
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EGU24-176
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ECS
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Andrea Cotellucci, Fermín Otálora, Àngels Canals, Joaquín Criado-Reyes, Luca Pellegrino, Marco Bruno, Dino Aquilano, Juan Manuel Garcia-Ruiz, Francesco Dela Pierre, and Linda Pastero

Identifying the impurities that promote the selection of specific twin laws of gypsum has relevant implications for the geological studies aimed at interpreting the gypsum depositional environments both in ancient and modern deposits, and overall, on Mars surface, where “swallowtail” gypsum twin habit has been recently observed. However, because of the limited knowledge of morphological, crystallographic, and optical characteristics of the five twin laws of gypsum, relatively little has been done to understand which impurities exert a critical role in the selection of different twin laws and how this may impact our awareness about their occurrence in nature. Typically, the 100-contact twin law has been the only twin law of gypsum known so far in nature. However, some sedimentological-stratigraphic studies suggested this might not be the only widespread one. In this work, we firstly provide a geometric-crystallographic background of the five twin laws of gypsum, allowing researchers to recognize the twin laws only by the measurement of i) their re-entrant angle value and ii) the extinction angle formed between the two individuals using crossed polarizers in optical microscopy. Moreover, we show specific crystal growth laboratory experiments designed to improve our understanding of different habits and twin laws of gypsum occurring with and without the addition of carbonate ions in solution. The main results suggest that the different orientation of primary fluid inclusions with respect to the twin plane, and the main elongation of the sub-crystals making the twin, are a useful tool to distinguish between 100 and -101 twin laws, whose geometry is otherwise very hard to distinguish, especially in rock samples. Moreover, gypsum twins obtained by crystal growth laboratory experiments are compared with those detected in natural environments and the occurrence of the -101 twin law is suggested occurring in evaporitic-sedimentary environments. These results provide new insights into the mineralogical implications of twinned gypsum crystals and their potential use as a tool for a deeper comprehension of the natural gypsum deposits.

How to cite: Cotellucci, A., Otálora, F., Canals, À., Criado-Reyes, J., Pellegrino, L., Bruno, M., Aquilano, D., Garcia-Ruiz, J. M., Dela Pierre, F., and Pastero, L.: New insights on gypsum twinned crystals: mineralogical implications for natural gypsum deposits, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-176, https://doi.org/10.5194/egusphere-egu24-176, 2024.

X1.176
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EGU24-8723
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ECS
Claire Aupart, Catherine Lerouge, Philippe Lach, Florian Trichard, Manon Boulay, Magali Rizza, Pierre Valla, Pierre Voinchet, Gilles Rixhon, and Hélène Tissoux

Quartz is ubiquitous within continental crust and can virtually be found within all rock types (plutonic, metamorphic and sedimentary). During erosion, weathering and sedimentation processes, it has a very high preservation potential and is often used to trace sediments production and transport dynamics. The QUARTZ project (Multi-methods characterization of quartz for source-to-sink tracing in alluvial sediment and dosimetry approaches – French ANR) aims to use quartz as a tracer for sediment sourcing river dynamics by combining conventional characterization method such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), Laser Induced Breakdown Spectroscopy (LIBS), and Cathodo-Luminescence (CL), with dosimetric methods, such as Electronic Spin Resonance (ESR) and Optically Stimulated Luminescence (OSL) which are more classically used for Quaternary sediment dating. To this end, one must define a robust quartz chemico-structural and dosimetric signature that can be compared from one sample to the other. We also aim to better understand ESR, OSL, and CL signals controlled by structural quartz defects. These can be either intrinsic (e.g. dislocations, missing/supplementary O or Si), or extrinsic (foreign atoms), each technique being more or less sensitive to these different defects.

In this study, we apply this multi-method approach to the various bedrock lithologies of the Strengbach catchment (ca.40 km²) draining a low mountain range located in the easternmost France (Vosges). These are largely dominated by crystalline metamorphic and plutonic rocks, with secondary Triassic sandstones (Buntsandstein). Bedrock samples have been treated mechanically and chemically to extract quartz grains. These grains have been analyzed using ESR and OSL techniques and mounted on thick sections (100 µm) for CL, LA-ICP-MS, and LIBS analyses. 100-µm thick-sections were used to prevent quartz tearing apart under LA-ICP-MS laser beam. Quartz characterization was completed by the study of whole-rock bedrock thick sections, analyzed with CL, LA-ICP-MS and LIBS approaches.

Preliminary results allow identifying specific quartz chemico-structural signatures not only depending on rock type (gneiss, granite, sandstone) but also on formation process (magmatic, recrystallized, metamorphic or sedimentary). Further comparison between quartz analysis in whole rock and in separated grains samples permit to assess the impact of the chemical treatment on the quartz signatures and to identify quartz populations likely to be more represented in the alluvial sediments produced by the different lithologies. Finally, ongoing analyses point out the complex contribution of trace elements to OSL, ESR and CL signals.

How to cite: Aupart, C., Lerouge, C., Lach, P., Trichard, F., Boulay, M., Rizza, M., Valla, P., Voinchet, P., Rixhon, G., and Tissoux, H.: Quartz chemico-structural characterization: a tool for sediment source tracing, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-8723, https://doi.org/10.5194/egusphere-egu24-8723, 2024.

X1.177
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EGU24-4169
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ECS
Bruno Titon, Josée Duchesne, and Benoît Fournier

Concrete is one of the most sought-after materials in our time, second only to water in importance to developed and emerging nations alike. It has been a crucial component of major infrastructure projects for thousands of years. In the year 2022 alone, China, the largest producer of concrete, manufactured approximately 2.1 million metric tons of cement, a key ingredient in modern concrete formulations. Various concrete mixes, tailored for specific applications, have been perfected and are widely used in the industry. In broad terms, concrete consists of about three-fifths sand and rock fragments (aggregates), one-fifth cement, and one-fifth water. This combination makes it the world's most widely used building material, particularly for large structures which are reinforced with steel rods. Aggregates can be sourced from crushed rock or naturally occurring sand and gravel, but the type of aggregate used significantly influences the overall properties and robustness of the final product. The mineralogical composition of the rock itself is closely related to the quality and resilience of the concrete. Understanding the mineralogy and chemistry of the lithotypes used allows for predicting their interaction with other concrete constituents, preventing undesirable chemical reactions. Such reactions can compromise the safety and resilience of the finished product, and ultimately prevent the use of materials that would otherwise perform poorly. Among the many concrete pathologies that may arise from the use of inadequate raw materials, internal sulfate attack (ISA) mainly occurs when sulfide-bearing aggregates are used. This leads to complex chemical reactions resulting in the oxidation of sulfide phases and the release of sulfur into the cement paste. Consequently, severe cracking and internal swelling significantly compromise concrete integrity. The European standard (EN 12620:2008) is a widely used guideline that recommends a total sulfur content in aggregates not exceeding 1.0 wt.%. This threshold is reduced to 0.1 wt.% when pyrrhotite is detected in the lithotype to be used as an aggregate. Given that pyrrhotite is the second most common sulfide found in nature, it is crucial to identify and quantify the various sulfide minerals that may be present and to understand how they can affect finished concrete structures. The use of automated mineralogy, represented by software systems such as QEMSCAN, emerges as a powerful solution for identifying and quantifying pyrrhotite and any other sulfide phases in aggregates for concrete. It is a scanning electron microscope (SEM)-based system that uses backscattered electron (BSE) image segmentation and simultaneous acquisition of energy-dispersive X-ray (EDS) spectra to classify mineral phases using a pre-defined list of mineral spectra. Preliminary results from QEMSCAN analysis of both thin sections and mounts comprised of ground rock of different grain sizes have been promising. This SEM-based system can analyze whole rock samples and crushed aggregates, providing accurate results over different size intervals. Despite the expected negative correlation between sample grain size and pyrrhotite content, the results vary from 2.71 to 5.59 wt.% for total pyrrhotite content in the analyzed samples. Moreover, when averaged over all grain sizes, these results align with those obtained through traditional optical petrography.

How to cite: Titon, B., Duchesne, J., and Fournier, B.: Use of automated mineralogy for the quantification of pyrrhotite in concrete aggregates, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4169, https://doi.org/10.5194/egusphere-egu24-4169, 2024.

X1.178
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EGU24-4658
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ECS
Andrea Pierozzi, Remi Rateau, Andrea Orlando, Daniele Borrini, and Juan Diego Rodriguez Blanco

Greenhouse gases, especially CO2, have been increasing worldwide. To address this issue, carbon capture and storage (CCS) technology has been researched and developed to decrease atmospheric CO2 concentrations. Among the various methods studied, mineral carbonation is an emerging technique that involves the reaction between Ca-Mg-Fe bearing basaltic rocks and CO2 to store it in the rocks through the formation of carbonate minerals. The CarbFix project in Iceland is an example of this method. However, there is still much to learn about the physicochemical relationships between water, dissolved ions, and growing crystals in complex multicomponent systems at the atomic and nanoscale, which are essential for the successful implementation of CCS in basaltic reservoirs.

One of the methods being explored in this study involves the utilization of supercritical CO2, which is achieved above the critical temperature and pressure of 30.97 °C and 73.773 bar, respectively. Under these conditions, CO2 exhibits both liquid and gaseous properties. This work shows the results of an experiment conducted in basaltic crystals and basaltic glasses at the temperature and pressure range of 100 and 200 ºC, and 64 to 79 bar, to investigate the reaction between CO2(sc), water, natural forsterite and basaltic glass, which have demonstrated that under these conditions we have the partial dissolution of the previous mineralogical phases, and the subsequent formation of new alteration phases, but also the precipitation of carbonates with Ca, Mg and Fe. We will compare our results with studies of carbonation of synthetic forsterite.  

How to cite: Pierozzi, A., Rateau, R., Orlando, A., Borrini, D., and Rodriguez Blanco, J. D.: Carbonation experiment of basaltic crystals and glasses using supercritical CO2 under different PT conditions, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4658, https://doi.org/10.5194/egusphere-egu24-4658, 2024.

Posters virtual: Tue, 16 Apr, 14:00–15:45 | vHall X1

Display time: Tue, 16 Apr 08:30–Tue, 16 Apr 18:00
Chairperson: Stylianos Aspiotis
vX1.20
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EGU24-2730
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ECS
Hongdong Wang and Liqiang Zhang

In order to explore the favorable reservoir characteristics and diagenetic evolution laws of the Cretaceous Kukebai Formation in the Kekeya area of the southwestern Tarim Basin, and provide theoretical basis for oil and gas exploration and development in the study area, comprehensive data such as core, cast thin sections, and carbon and oxygen isotopes were used to carry out the classification of diagenetic facies types and the study of diagenetic evolution models. The results indicate that the reservoir of the Kukebai Formation in the study area is mainly composed of feldspar lithic sandstone and lithic feldspar sandstone, with mainly developed diagenetic processes such as compaction, cementation, and dissolution. The diagenetic stage is in the middle diagenetic stage A. The Kukebai Formation reservoir mainly develops four types of diagenetic facies: moderately compacted dissolution facies, moderately compacted cementation facies, strongly compacted compaction facies, and strongly cemented facies. Among them, the strong compacted phase becomes a dense reservoir due to mechanical compaction in the early stage of diagenesis, and is mainly distributed in the sand mud interbedded layers of sedimentary microfacies between river channels and estuarine dams; The strongly cemented phase is densified in the early diagenetic stage due to the precipitation of a large amount of carbonate cement, mainly developed in the sand mud interbedded layers near the mud end of underwater distributary channels and the sedimentary microfacies of estuarine dams; The dissolution effect of medium compacted dissolution phase sandstone is strong, and the reservoir properties are the best, mostly appearing in the upper part of distributary channel sand bodies with strong sedimentation and water accumulation dynamics; The medium compacted and cemented sandstone has moderate compaction, and the reservoir properties are relatively good. It mainly develops in the lower part of distributary channel sand bodies with strong hydrodynamics. There are two types of favorable reservoirs in the study area, namely the medium compacted cementation phase and the medium compacted dissolution phase sandstone.

How to cite: Wang, H. and Zhang, L.: Reservoir characteristics and diagenetic evolution of Kukebai Formation in Kekeya area, Southwest Depression of Tarim Basin, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2730, https://doi.org/10.5194/egusphere-egu24-2730, 2024.