Fundamentals of C-isotope geochemistry were established in the mid-1950s. Its use as a proxy in paleoceanography and paleoclimatology was long underestimated. While oxygen isotope geochemistry was identified early as a powerful tool in Ice Age history, carbon isotope geochemistry evolved only in the 1970s into a valuable instrument in paleoceanography and paleolimnology.  In 1976, Judy McKenzie was offered the chance to build the first stable isotope lab at ETH Zürich. Judy was, together with her team, among the first geoscientists searching for applications of C-isotope geochemistry in paleoceanography and limnogeology. Seasonal fluctuations in lake productivity were monitored in C-isotope composition of lake sediments and C-isotope records measured in pelagic carbonates served as a tracer of circulation and productivity in Cenozoic and Mesozoic oceans. In the eighties C-isotope geochemistry was recognized as a proxy of the global carbon cycle and its history was traced in C-isotope records measured in pelagic carbonates. The ETH Lab contributed with the several publications on C-isotopes and the carbon cycle to the seminal Chapman conference on “The Carbon Cycle and Atmospheric CO₂: Natural Variations Archean to Present” (Florida, 1984). An improved understanding of marine carbon fractionation processes allowed to use paired carbonate and organic carbon isotope analyses as a proxy for past atmospheric carbon dioxide concentrations. Today C-isotope geochemistry is established as a most valuable tool in paleoclimatology and paleoceanography, in sedimentology and geomicrobiology.

How to cite: Weissert, H.: Early days of carbon isotope geochemistry in paleoceanography and limnogeology - tales from Judy’s ETH Lab , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-3855, https://doi.org/10.5194/egusphere-egu24-3855, 2024.

The pioneering work of Judith McKenzie and her colleague Kerry Kelts identified the presence of dolomites associated with the oxidation of organic material in sediments obtained from the Deep Sea Drilling Project.  This discovery led to the wide spread recognition that dolomites form in association with microbial sulfate reduction.   Later Judy’s work proposed that the microbes were more than agents of creating a suitable geochemical environments, but actually were instrumental in precipitating dolomite.  This work stimulated the research of many, but the questions have always arisen as to what degree microbial processes are responsible for dolomite formation and other carbonate minerals in the ancient record.  Some have proposed different geochemical indices such as carbon or magnesium isotopes or the concentration of certain elements, maybe diagnostic of microbial processes.  However, these tools frequently provide equivocal evidence and therefore are not definitive. In this presentation we provide several examples of the use of a new geochemical tool, the dual clumped isotope proxy (Δ₄₇ and Δ₄₈).  Deviations from equilibrium, particular of Δ₄₈ values, provide strong evidence of the influence of different mechanisms of the precipitation of dolomite and calcite.  In this presentation we present several examples in which the dual clumped isotope proxy has been employed.  These include not only dolomites, but also meteoric LMC calcite cements, previously believed to have form without the influence of microbial processes.  While the dual clumped proxy may also yield equivocal results, it will be a welcome addition to the tools used to understand the roles of microbes during carbonate precipitation.

How to cite: Swart, P. and Lu, C.: Identification of microbial influences on carbonate precipitation using dual clumped isotopes, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-12046, https://doi.org/10.5194/egusphere-egu24-12046, 2024.

Judith McKenzie contributed pivotal studies in using lacustrine sedimentary systems as natural analogues for the much larger marine environment. In this context, she introduced marine depositional processes and concepts to lakes, and in turn, used their smaller dimensions and more controllable boundary conditions to gain more insights into the controls of lithological and geochemical signals in any sedimentary system. One example of using this approach is the study of the prograding mixed carbonate-siliciclastic shallow-water shelf of Lake Constance, that is characterized by endogenic carbonate production ('lacustrine chalk'), water currents, progradation and related drift deposits, as they also have been investigated in the marine domain. A recent bathymetric survey of Lake Constance revealed ~170 mysterious mounds composed of loosely deposited rocks aligned in a ~10-km-long chain along the southern Swiss shoreline of Lake Constance in a water depth of 3–5 m. The mounds are 10–30 m in diameter and up to 1.5 m high. Over their entire length of occurrence, the mounds are estimated to be composed of ~60 million individual boulders, with a total weight of ~78,000 t. A ground penetrating radar (GPR) survey showed that the mounds are not linked to the glacial substrate but were rather deposited artificially on the edge of a prograding shelf composed of mixed carbonate-siliciclastic Late Glacial to Holocene lake sediments. Here, we present the results of a coring campaign with four piston cores along a GPR transect across one of the mounds. The cores recovered the full postglacial sedimentary succession all the way into the basal till that is overlain by lacustrine sediments dating back to ~14,400 cal. BP. The four cores are merged into a ~12.4-m-long composite section reflecting continuous sedimentation from the siliciclastic-dominated Late Glacial to the carbonate-rich Late Holocene. The stratigraphic horizon representing the mound's construction was radiocarbon-dated to ~5,600–5,300 cal. BP, placing them in the Neolithic period. This age was confirmed by radiocarbon dating of wood samples collected during underwater excavation of the mounds. Geochemical analysis of the Holocene sedimentary succession shows generally high carbonate contents (average of 69%). The interval from 5,750 to 4,950 cal. BP, a part of the mound period, is characterized by a Holocene minimum in carbonate content (average of 57%) and by larger mean grain sizes. Comparing these values to those from a recent surface-sediment depth transect indicates that this was a period of rather low lake levels, which might have favored mound construction. Correlations to nearby archaeological sites and to the general West-Central European lake-level record indicates that the mounds likely were built during a short phase of low lake levels during a general trend of climatic cooling followed by a lake-level transgression.

How to cite: Anselmetti, F., Perler, D., Benguerel, S., Brem, H., Gilliard, F., Hornung, J., Keiser, T., Leuzinger, U., Schaller, S., Szidat, S., Vogel, H., and Wessels, M.: Swiss lakes as model oceans: A mixed carbonate-siliciclastic shelf drift hosting a 10-km-long chain of 170 submerged Neolithic mounds, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-11488, https://doi.org/10.5194/egusphere-egu24-11488, 2024.

From 2016 to 2020, Judy McKenzie joined the community of COST Action CA15103 - Uncovering the Mediterranean salt giant (MEDSALT) to verify her hypothesis that an ongoing dolomitization front exists in the pelagic sediments overlying Messinian evaporites below the Messina Abyssal Plain, in ~4000 water depth in the Ionian Sea, central Mediterranean. Legacy scientific ocean drilling data from DSDP Leg 42A, Site 374 reveal a 25 m-thick latest Miocene dolomitic mudstone capped by 8.5 m of earliest Pliocene dolomite above gypsum/dolomitic mudstone cycles and anhydrite and salts. The Pliocene dolomite is made of dolomicrite with an unusual crystal morphology, suggesting diagenetic replacement of the original pelagic calcite ooze. The underlying latest Messinian dolomitic mudstone with minor gypsum layers contains Ca-rich dolomite with white spherules of lüneburgite. DSDP Site 374 shipboard interstitial water geochemical profiles further indicate that saline brine is diffusing upwards into the early Pliocene dolomicrite. A significant decrease in sulfate concentration suggests ongoing bacterial sulfate reduction, whereas the chloride profile remains constant.

Following discussion and brainstorming with Judy, a geophysical site investigation cruise on the RV Meteor was organized by the University of Hamburg. Cruise M-144 was conducted in 2018 with a multi-channel reflection seismic survey centered at DSDP Leg 42A, Site 374 using a 6 kjoule sparker source and a digital 144-channel streamer with an active length of 600 m. The objectives of the cruise were to:

• Obtain a detailed seismic stratigraphy in the surrounding of DSDP Leg 42A, Site 374, which was targeted as re-occupation Site within IODP Proposal 857C - The demise of a salt giant: climatic-environmental transition during the terminal Messinian Salinity Crisis (Claudia Bertoni and co-workers);
• Estimate the lateral dimensions of the combined dolomite/evaporite lithologic units in the lonian Sea.

Objective 1 was achieved, and the drilling proposal supported by the R/V Meteor Site Survey was forwarded by the Science Evaluation Panel to the JR Facility Board for scheduling. Unfortunately scheduling could not happen before the end of IODP.

Objective 2 was based on the assumption that the acoustic impedance contrasts induced by the dolomitization front could be detected in relatively high-resolution seismic reflection data. In the M-144 data, the uppermost Messinian dolomite- and gypsum-bearing sediments are characterized by a package of strong and positive reflection amplitudes (High Amplitude Reflection Package, HARP). The lateral continuity of the reflections is very low and the upper boundary is quite irregular. Based on the seismic data, the areal extent of the dolomite deposit beneath the lonian abyssal plain can be estimated in a few tens of thousands km². This would be the Rosengarten of the Ionian Sea that Judy was looking for.

This abstract will present previous and new seismic data, collected with Meteor Cruise M-199 in February-March 2024 with similar acquisition parameters to those of M-144, to further address objective 2. However, crucial sedimentological and geochemical data to validate Judy’s fascinating hypothesis can only be derived from new scientific drilling.

How to cite: Camerlenghi, A., Huebscher, C., Micallef, A., Bertoni, C., Aloisi, G., and Lofi, J.: The intriguing hypothesis of a modern “Rosengarten” in the subsurface of the deep Ionian Basin, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9689, https://doi.org/10.5194/egusphere-egu24-9689, 2024.

During the Cretaceous, the Berriasian-Aptian interval witnessed a transition from a relatively cool climate with intermittent polar ice to a greenhouse state that persisted throughout the Late Cretaceous. These palaeoclimatic changes were associated with the construction of Large Igneous Provinces (LIPs), which significantly perturbed the ocean-atmosphere system by introducing large amounts of CO₂, trace metals, and micronutrients, thereby impacting the biosphere. Our study focused on the Tethyan Ocean during the Early Cretaceous, examining the resilience of planktonic and shallow-water benthic calcifying algae to environmental changes. We observed their adaptation, recovery dynamics, and the influence of palaeoCO₂ levels on their resilience. Calcification patterns of calcareous nannoplankton served as a proxy for ecological and engineering resilience. While calcareous nannoplankton as a whole showed high resistance, individual taxa exhibited varying levels of resilience. Nannoconids, particularly narrow-canal ones, were highly sensitive and had low resistance. In contrast, Watznaueria barnesiae showed the least sensitivity and highest resistance, likely due to its adaptive strategies and long lifespan. Nannoplankton calcification recovery (engineering resilience) from the Weissert Event took approximately 3 million years. After OAE1a, instead, nannoplankton did not return to pre-perturbation conditions. In shallow-water platforms, Dasycladales, aragonitic benthic calcifiers, exhibited lower resilience compared to nannofossils. They experienced a decline in species diversity across both the Weissert Event and the OAE 1a, which could indicate higher sensitivity to reduced carbonate saturation under high pCO₂ conditions. After the Valanginian Weissert Event, Dasycladales were able to recover, albeit they show a much lower engineering resilience compared to nannoconids, as it took nearly 10 million years to revert to pre-disturbance diversity. The OAE 1a represented a more intense perturbation: their decrease of species diversity was much more drastic and permanent, and Dasycladales were unable to recover, losing their dominant role as carbonate platform biocalcifiers for the remainder of the Cretaceous. Our study provides an assessment of the resilience of Tethyan phytoplanktonic and shallow-water benthic calcifying algae to disturbances during the Early Cretaceous, with implications for tipping points associated with palaeo-CO₂ levels. The differential responses in terms of timing and magnitude and the recovery dynamics contribute to the understanding of the potential impacts of current and future global changes on the resilience of marine ecosystems and the thresholds that may lead to ecological crises.

How to cite: Erba, E. and Parente, M.: The resilience of Tethyan planktonic and benthic calcifying algae to Early Cretaceous perturbations: comparison between the Valanginian Weissert Event and the early Aptian Oceanic Anoxic Event 1a, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2826, https://doi.org/10.5194/egusphere-egu24-2826, 2024.

The Nerja Cave is located in an alpine folding chain, specifically in the Inner Zone of the Betic Range (SE, Spain), and it is developed within middle Triassic dolomite marbles (Carrasco et al., 1998). Its mean annual temperature is 18.1 ± 0.1 °C (Jiménez de Cisneros et al., 2021). Moon-milk deposits, a white substance present inside caves. Samples were collected in the touristic part of the cave and were characterized using synchrotron high-resolution XRD (HR-XRD), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). We detected the presence of amorphous magnesium carbonate (AMC), huntite, and dolomite. Additionally, the AMC formation and the subsequent crystallization process were studied in laboratory conditions to gain a more comprehensive understanding of the processes occurring in the cave. We performed titration experiments using magnesium and calcium chloride solutions and potassium carbonate buffers to investigate nucleation and transformation processes at elapsed times (1, 2, 7, and 14 days). The filtered solids were characterized by XRD, SEM, FTIR, Raman, and TEM. The results of these analyses highlighted the critical role of AMC in the formation of Ca-Mg crystalline carbonates.

Acknowledgment to financial support is given by the Spanish Ministry of Science and Innovation through the research project PID2021-125305NB-I00 and the project from the Junta de Andalucía through the EMERGIA research program under the grant agreement EMERGIA20_38594.

Carrasco F, Durán JJ, Andreo B, Liñán C, Vadillo I (1998) Consideraciones sobre el karst de Nerja. Karst en Andalucía 173–181

Jiménez de Cisneros, C., Peña, A., Caballero, E., & Liñán, C. (2021). A multiparametric approach for evaluating the current carbonate precipitation and external soil of Nerja Cave (Málaga, Spain). International Journal of Environmental Research, 15, 231-243.

How to cite: Bonilla-Correa, S., Ruiz-Agudo, E., Asta Andrés, M. P., Huber, L., Jiménez de Cisneros, C., and Liñán-Baena, C.: Non-Classical Crystallization in Moon-Milk Deposits in the Nerja Cave, Spain , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-18784, https://doi.org/10.5194/egusphere-egu24-18784, 2024.

Routine methods of concrete production contribute 9% to anthropogenic CO₂ emissions and demands 2-3% energy, along with 9% water consumption. Despite these environmental costs, concrete structures frequently undergo deterioration due to unavoidable physical, chemical, and biochemical stressors, resulting in cracks that permit gas diffusion, water, and pollutants penetration, ultimately compromising its integrity and internal steel reinforcement. Microbially induced CaCO₃ precipitation has emerged as a sustainable way of concrete protection and self-healing. However, the detailed mechanisms and formation of various CaCO₃ polymorphs remain inadequately explored.

In this ongoing study, samples were prepared by inoculating a growth medium, containing urea and nutrients, with different fungi under diverse growth conditions. High-resolution Scanning Transmission X-ray Microscopy (STXM) in the Ca 2p energy range (340−360 eV) were employed to investigate the fungal-induced formation and chemical speciation of CaCO₃ at the cellular base or interface between hypha and the surrounding ions. To discriminate potential absorption saturation effects, only spectra (NEXAFS) extracted from thin regions (≈ 30 nm) of the entire sample thickness were considered for spectral analysis. Furthermore, SEM with EDS was used to reveal morphology and elemental distribution, and composition in studied sample thin sections.

The preliminary results suggest that the samples spectra resembled those of pure calcite and aragonite, according to reference spectra. These are the most stable CaCO₃ biomaterials. Notably, the intensity of weak peaks preceding each main resonance peak of the Ca L3 and Ca L2 edges were relatively smaller for aragonite-dominated spots than in calcite-dominated spots. As revealed by the spectral analysis, some fungi showed the ability to form CaCO₃, predominantly in the form of either calcite or aragonite. Other fungal strains demonstrated a more heterogeneous precipitation behavior by forming both phases, albeit in distinct nano spots within the same sample. Furthermore, a few fungal species exhibited the ability to precipitate other crystalline Ca minerals, most likely CaPO₄, as shown by SEM/EDS analyses.

In conclusion, the results of this ongoing investigation provided not only valuable insight on distinctive fungal behaviors in the biomineralization process, but also revealed spatial nanoscale heterogeneity in CaCO₃ speciation under the same fungal conditions.

How to cite: Tuyishime, J. R. M., Hammer, E., Pla i Ferriol, M., Thånell, K., Alwmark, C., and Zou, H.: Nanoscale insights: unraveling fungal-induced precipitation of CaCO3 polymorphs for self-healing concrete, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-22168, https://doi.org/10.5194/egusphere-egu24-22168, 2024.

The formation of leaf compressions is dependent on the type of sediment in which the leaves are buried and on burial depth because greater burial depth leads to a more anoxic environment conducive to fossilization. Recent research has hypothesized that the presence of a microbial biofilm on leaf surfaces in the early stages of decay also enhances preservation. In decaying leaves, the biofilm community is likely influenced by the same factors: sediment type and burial depth. Here we investigate experimentally the microbial community composition of microbial biofilms formed on floating and buried leaves of living Ginkgo in four sediment types—montmorillonite clay, kaolin clay, quartz sand, and pond mud. Leaves were placed in aquariums with pond water under identical light conditions and room temperatures for three months. The leaves, sediments, and pond water were then evaluated with 16S and ITS sequencing to identify the bacterial and fungal communities. We found that the biofilms on the floating and buried leaves differed in their basic microbial community composition. The leaves buried in the kaolin clay showed the most distinctive microbial communities, while the montmorillonite clay buried leaves contained several genera noted for biomineralization. In general, the buried leaves had microbial communities that were more diverse than those on the floating leaves and richer in anaerobic microbes and biomineralizers. These results suggest that biofilms form best in very fine-grained sediments with low organic content, such as kaolin and montmorillonite clays, and under burial conditions fostering anaerobic environments and the incorporation of minerals that enhance biomineralization on leaf surfaces. Our results provide new insights into the role of microbial biofilms and microbe–sediment interactions in the early stages of leaf fossilization.

How to cite: Palmer, B., Karacic, S., Bierbaum, G., and Gee, C.: Deciphering Fossilization Pathways: Sediment Composition Impacts Biofilm-Forming and Biomineralizing Microbial Communities in Early Stages of Leaf Taphonomy, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-14998, https://doi.org/10.5194/egusphere-egu24-14998, 2024.

Ferruginous conditions prevailed in the oceans through much of Earth’s history. However, past biogeochemical cycling inferred from mineral components in ancient iron formations remain poorly constrained in terms of microbial processes prior to lithification. In Lake Towuti, Indonesia, ferruginous sediments are deposited under stratified conditions that mimic the Earth’s early oceans. Over geologic time, Lake Towuti experienced dynamic redox conditions, resulting in variable ferric and organic matter fluxes feeding microbial life at the lake floor. Although environmental conditions exert control over microbial assemblages at the time of deposition, geochemical evolution of these substrates select for specific groups of microorganisms capable of maintaining metabolic activity during entombment.

The 100 m long core retrieved by the ICDP Towuti Drilling Project allowed for investigations of the subsurface biosphere, pore water geochemistry and diagenesis of iron minerals. We established the abundance and phylogenetic distribution of microorganisms along the 1 Ma stratigraphic record, and created integrated environmental and geochemical datasets in order to identify the main taxa and metabolic features involved in sediment mineralization. Ferruginous conditions predominantly selected for Bathyarchaeia. Relevant metabolisms identified from metagenome-assembled genomes indicated sulfur transformation and (homo)acetogenesis, suggesting that heterotrophic dark carbon fixation and cryptic sulfur cycling linked to iron minerals may be prominent features of microbial life in this ferruginous system.

Changes in environmental processes and conditions lead to variability in metal and organic substrate concentrations with depth, while sustaining different microbial processes in various depth intervals. Geochemical profiles reflect microbial activity after deposition and demonstrated mineral precipitation induced by microbial mineralization. Precipitation of magnetite (Fe₃O₄), millerite (NiS), siderite (FeCO₃), and vivianite (Fe₃[PO₄]₂ · 8H₂O) from pore water constitute biosignatures of microbial iron and sulfate reduction, fermentation and methanogenesis. For example, oxygen, iron, and carbon isotopes measured on siderites enabled us to differentiate between depositional and diagenetic signals. Siderite δ¹⁸O signatures reflected in-lake hydrological fluctuations. Low negative δ⁵⁶Fe values recorded periods of water column stratification and oxygenation events, with minor diagenetic redistribution. Negative δ¹³C signatures reflected incorporation of biogenic HCO₃^- during organic matter fermentation, whereas positive δ¹³C excursions indicated mass balance due to increased production of biogenic methane.

How to cite: Kallmeyer, J., Ruiz-Blas, F., Henny, C., Russell, J., Vogel, H., and Vuillemin, A.: Subsurface biosphere, pore water geochemistry and mineral biosignatures along the 1 Ma sediment archive of ferruginous Lake Towuti, Indonesia, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-11076, https://doi.org/10.5194/egusphere-egu24-11076, 2024.

The hydration structure at the mineral-water interface is decisive for understanding fundamental reactions taking place at mineral surfaces, including mineral dissolution, growth and weathering. Recent advancements in three-dimensional atomic force microscopy (3D AFM) have opened the potential to directly image the hydration structure above a surface, providing unparalleled structural insights into mineral−water interfaces [1].

Here, the hydration structures at the calcite-water [2] and dolomite-water [3] interface will be presented with an emphasis on discussing the differences that arise from the presence of magnesium in dolomite as compared to calcium in calcite. Analysing site-specific vertical positions of hydration layers and comparing them with molecular dynamics simulations unambiguously unravels the minute but decisive difference in ion hydration and provides a clear means for telling calcium and magnesium ions apart.

[1]         T. Fukuma, Y. Ueda, S. Yoshioka, H. Asakawa, Phys. Rev. Lett. 2010, 104, 016101

[2]         H. Söngen, M. Nalbach, H. Adam, A. Kühnle, Rev. Sci. Instrum. 2016, 87, 063704

[3]         H. Söngen, C. Marutschke, P. Spijker, E. Holmgren, I. Hermes, R. Bechstein, S. Klassen, J. Tracey, A. S. Foster, A. Kühnle, Langmuir 2017, 33, 125

How to cite: Kühnle, A.: Hydration structure on dolomite: Telling calcium and magnesium apart, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1334, https://doi.org/10.5194/egusphere-egu24-1334, 2024.

The formation of dolomite in the sediments of the Sabkha of Abu Dhabi was the subject of Judy’s PhD thesis and the question of the origin of dolomite remained at the center of her scientific interests throughout her career. The main focus was on the influence of microbial activity on dolomite formation, both in the field and through laboratory experiments. Over the years, Judy’s contributions particularly advanced our understanding of the role of microbes in the formation of dolomite.

With the development of clumped isotope geochemistry, a new tool is now available to better characterize the conditions leading to the formation of dolomite in the geological record. This tool exploits the preference of¹³C-¹⁸O bonds in carbonate molecules to form with decreasing temperature and provides a thermometer that can be used to constrain the formation temperature and the oxygen isotope composition of the fluids involved in the precipitation of dolomite. The interpretation of dolomite clumped isotopes in the geological record, however, is complicated by the fact that early-diagenetic dolomite is generally poorly ordered and non-stoichiometric, and it converts to a more stable form during diagenesis. In this contribution we will present case studies from the Alps to show how the original clumped isotope compositions of dolomite are modified during diagenesis under different thermal regimes, and we will discuss the preservation of clumped isotope signatures in dolomite.

How to cite: Bernasconi, S., Rosskopf, R., Looser, N., and Hemingway, J.: Understanding the origin of dolomite in the sedimentary record: the contribution of clumped isotope thermometry., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-8190, https://doi.org/10.5194/egusphere-egu24-8190, 2024.

Early lithification of carbonate mud during the subaerial exposure stage, under semiarid conditions, has been proposed to facilitate dolomite formation. However, how the biogeochemical processes during subaerial diagenesis promote dolomite formation remains unclear. Here, we employ a multiproxy approach to investigate the process of dolomite formation by analyzing modern dolomite crusts forming in lagoon Brejo do Espinho (LBE). Petrological analysis reveals that the crusts comprise coexisting high-Mg calcite (HMC) and dolomite. Low Fe and Mn concentrations indicate the formation of dolomite under oxic conditions, while a higher Sr concentration in well-lithified crust suggests primary bacterial-induced dolomite precipitation. The Mg isotopic composition of the crusts exhibits a lighter value compared to that of modern sabkha dolomite, suggesting different dolomitization processes and Mg sources. More negative δ¹³C values of the crusts than unlithified carbonate mud in LBE, indicating the incorporation of ¹³C depleted organic carbon. The biogeochemical processes related to decaying organic matter during subaerial diagenesis generate partially oxidized organic matter that promotes Mg²⁺ dehydration and enhances the dissolution of primary HMC, ultimately triggering the transition of HMC to dolomite or/and direct dolomite precipitation. The ancient "dolomite factory" operated through cyclic deposition of carbonate sediments and penecontemporaneous subaerial diagenesis.

How to cite: Ning, M., McKenzie, J. A., Vasconcelos, C., and Shen, B.: Dolomite formation during penecontemporaneous subaerial diagenesis: Evidence from modern dolomite crusts forming in lagoon Brejo do Espinho, Brazil, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-3489, https://doi.org/10.5194/egusphere-egu24-3489, 2024.

As a metastable precursor to crystalline carbonate minerals, amorphous calcium-magnesium carbonate (ACMC) has been implicated in the formation of enigmatic fabrics and minerals, such as calcite microspar, fibrous cements and fabric-retentive dolomite, that characterise both modern and ancient carbonate systems (e.g. Wang et al., 2012). The detection of nanocrystals within ancient dolomicrite, using high-resolution transmission electron microscopy, strengthens this hypothesis (Meister & Frisia, 2019).

However, it has remained unclear whether natural, abiotic processes could produce ACMC, because of a requirement for extreme carbonate supersaturation. This study tests the hypothesis that – in the presence of micromolar concentrations of aqueous phosphate, which can inhibit aragonite precipitation (Roest-Ellis et al., 2021) – the evaporation of Neoproterozoic seawater may have increased alkalinity, pH, and carbonate saturation enough to precipitate ACMC in shallow-water settings.

We conducted evaporation experiments using phosphate-free and phosphate-bearing ([PO₄]_Total = 50 μmol/kg) synthetic seawater with Tonian composition. Solution samples, pH and alkalinity measurements were collected at regular intervals over 9-14 days. Final solids were collected and analysed using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy.

Experimental data show that phosphate-bearing seawater undergoing evaporative concentration reaches increasingly high alkalinity, pH and carbonate saturation until the first solid phase forms. Analytical data indicate that ACMC precipitated during evaporation of phosphate-bearing seawater, whereas aragonite dominated in phosphate-free systems. When evaporating the water more slowly, the ACMC is observed to recrystallise into other metastable carbonate minerals – either fibrous monohydrocalcite or needles of hydromagnesite, depending on the solution’s initial Mg/Ca ratio.

These results suggest that low concentrations of species which inhibit crystalline carbonate precipitation allow extreme carbonate supersaturation to be reached upon evaporation. We speculate that this pathway may have facilitated platform-scale production of metastable precursors to syndepositional and early diagenetic dolomite in shallow-water late Proterozoic carbonate sediments, consistent with sedimentological and stratigraphic evidence for evaporation.

How to cite: Methley, P., Jiang, C., Strauss, J., and Tosca, N.: Evaporation of seawater produces amorphous calcium-magnesium carbonate when aragonite precipitation is inhibited, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-17981, https://doi.org/10.5194/egusphere-egu24-17981, 2024.

At Schoenmakerskop on the coast near Gqeberha (Port Elizabeth), modern microbialite deposits are forming where CaCO₃-supersaturated groundwater emerges at the contact between Pleistocene aeolianites and the underlying Cape Supergroup bedrock (Edwards et al. 2017). Two different systems were investigated: well-laminated spring line tufa deposits above intertidal beachrocks, and a series of barrage pools with active and remnant rimstone deposits showing thrombolitic and laminated mesofabrics. Petrographic light-microscopy and scanning electron microscopy (SEM) were used to investigate the relative contributions of biotic and abiotic processes in the formation of these microbialites.

Light-microscopy identified isopachous light-brown sparry crusts consisting of tabular or platy carbonate, interpreted to have formed predominantly by chemical precipitation. Hybrid crusts were also found comprising alternating organic-rich layers and sparry crusts, along with colloform and micritic microtextures. Fossilised algal filaments were identified and SEM observations revealed both densely and loosely packed layers of hollow, unbranched filaments encrusted by microcrystalline carbonate. Exceptionally well-preserved draping biofilms were also found in some samples. Evidence for trapping and binding of clastic material was very limited, with only occasional diatom fragments. Taken together our observations point to a system dominated by chemical precipitation of carbonate with rapid precipitation leading to exceptional preservation of biofilms in submerged samples, and entombment of algal and sometimes microbial filaments. Evidence for biologically induced extracellular mineralisation of the algal filaments and microbial biofilms is recorded in these microbialites. The potential of these deposits to serve as analogues for chemical stromatolites in the fossil record is explored.

Edwards et al. (2017). Macro- and Meso-fabric structures of peritidal tufa stromatolites along the Eastern Cape coast of South Africa. Sedimentary Geology 359: 62-75.

How to cite: McLoughlin, N. and Mahlapha, K.: Microtextures of modern tufa stromatolites from the peritidal zone near Schoenmakerskop, Eastern Cape, South Africa: investigating the relative contributions of microbes, algae and chemical precipitation to microbialite growth   , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-3371, https://doi.org/10.5194/egusphere-egu24-3371, 2024.

Hamelin Pool in Shark Bay, Western Australia, is a natural laboratory to study in situ stromatolitic carbonate formation in a hypersaline lagoon. Stromatolitic carbonates sampled at three different tidal environments (supratidal, intertidal and subtidal; cf. Martin et al., 2023) show a gradual increase in Ba isotopic compositions (d¹³⁸Ba) from -0.12 ‰ to modern open ocean values (up to 0.6 ‰) with decreasing Ba concentrations following classic Rayleigh pattern. Declining Ba/Ca ratios (0.93 to 0.32) follow conservative mixing trends with increasing Co, Li, Sr and Ni concentrations from the shore to subtidal environments. Due to the lack of riverine influx into Shark Bay, groundwater discharge is the likeliest source for two end-members mixing with seawater. We observe fingerprints of the groundwater end-member in a supratidal sample showing particular low, stable Ba isotope values (-0.12 ‰), which further corresponds with elevated Mn/Sr ratios and the lowest O isotope compositions (2.9 ‰) as an indicator for a meteoric origin. This end-member likely reflects carbonate precipitation near shore under the influence of groundwater discharge and reaction with high alkalinity fluids derived from the local Tamala Limestone aquifer (d¹³⁸Ba = 0.09 to 0.24 ‰ at 0.3 to 19 PSU; cf., Mayfield et al., 2021). In contrast, the stromatolitic carbonates that form in equilibrium with a saline end-member show heavy Ba isotope compositions (0.57‰).

Injection of alkaline groundwaters into the hypersaline waters of Hamelin Pool likely contributed to an enhanced rate of carbonate precipitation, possibly catalysed by nucleation within or onto extra-polymeric substances of diverse microbial mats. Interaction of benthic microbes, especially cyanobacteria, in alkaline waters may offer promising carbon sequestration pathways in the modern high pCO₂ atmosphere and small-scale mitigation to the harmful impacts of the current climate crisis.

References: Martin et al., 2023, GCA; Mayfield et al., 2021, Nature Communications

How to cite: Hohl, S. V., Lin, Y., Viehmann, S., and Martin, A.: Conservative mixing of highly alkaline groundwater with hypersaline seawater at Shark Bay recorded by Ba isotopic compositions in stromatolitic carbonates, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4713, https://doi.org/10.5194/egusphere-egu24-4713, 2024.

Ferromanganese concretions, ubiquitous both in deep ocean environments and shallow-water coastal regions worldwide, are the subject of renewed scientific interest due to their multifaceted importance as underwater habitats, critical raw material sources, and invaluable repositories of paleoceanographic information. The magnetic properties of ferrimagnetic minerals within concretions, as well as the origins of their natural remanent magnetization, represent areas of study that are still in their early stages of exploration. Recent findings have unveiled the role of biogenic magnetite in the development of biogeochemical remanent magnetization within deep ocean crusts and nodules, pointing to the influence of microbial catalysis in their precipitation. While extensive research on magnetic properties of deep ocean Fe-Mn deposits has been conducted, similar investigations in fast-growing shallow-water concretions have remained notably absent. Furthermore, the specific mechanisms governing the formation and (bio)mineralization of diverse concretion morphotypes (crust-like, discoidal and spheroidal) in shallow-water setting remain enigmatic.

Our work focuses on ferromanganese concretions in shelf areas and seas, with samples from the the Baltic Sea. We report here the magnetic characteristics, microstructure, and origin of Baltic Sea concretions, which sheds light on their formation processes and environmental implications. To achieve this, we combined nano- and micro-computed tomography imaging, electron microscopy, micro-X-ray fluorescence spectroscopy, and a suite of detailed magnetic property investigations. Spheroidal concretions are prevalent in many parts of the coastal Baltic Sea and contain a higher proportion of fine-grained magnetite with evidence of bullet-shaped magnetofossils produced by magnetotactic bacteria. Bullet-shaped magnetofossils are usually produced in eutrophic and less oxic environments, as supported by the possible presence of rhodochrosite, which indicates diagenetic Mn release from surrounding sediments, especially in deeper water settings. In contrast, crust and discoidal concretions in shallower waters contain higher proportions of detrital (including magnetically hard) minerals, which reflects an increased continental influence. Microstructural analysis of the concretions reveals multiple growth stages, with laminated, columnar, and dendritic structures indicating varying hydrodynamic and depositional conditions. In general, spheroidal concretions seem to form in more tranquil settings compared to discoidal and crust concretions.

Our results provide insights into the complex interplay of environmental conditions, biogenic processes, and mineralogical composition that influence ferromanganese concretion growth and magnetic properties in the Baltic Sea. We further argue that biogenic magnetite contributes globally to the remanent magnetization of shallow and deep-sea ferromanganese concretions.  

This work was supported by the Research Council of Finland (Fermaid project, grant 332249).

How to cite: Wasiljeff, J., Salminen, J., Roberts, A., Hu, P., Brown, M., Kuva, J., Lukkari, S., Jolis, E., Heinsalu, A., Hong, W.-L., Lepland, A., Suuroja, S., Parkkonen, J., and Virtasalo, J.: Morphology-Driven Magnetic Characteristics of Shallow-Water Ferromanganese Concretions, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-16540, https://doi.org/10.5194/egusphere-egu24-16540, 2024.

The transition to renewable energy and the acceleration of technology demand vast amounts of hi-tech metals that are critical in green energy technology. Due to increasing demand for hi-tech metals, rising interest in mining from more unconventional sources, such as the seafloor, is inevitable. Ferromanganese concretions, which are centimeter-scale accumulations of iron and manganese oxides, are common in the Baltic Sea. In addition to iron and manganese, concretions contain hi-tech metals, such as cobalt. The Fe-Mn concretions are important reaction surfaces for diverse microbial communities, and they regulate metal and nutrient cycling in the concretions. Extraction of Fe-Mn concretions from the Baltic Sea could impact the seafloor ecosystem, biogeochemical cycling of elements, concretion growth, and recovery. This study provides information on Baltic Sea Fe-Mn concretion growth rates and conditions in laboratory experiments.

The ferromanganese concretions were collected from the Baltic Sea during May and June 2022 for a 12-week laboratory incubation and metal tracer experiments. Triplicate concretion samples and one abiotic control sample were collected into bottles containing artificial brackish seawater and incubated in the dark at +5 °C in an orbital shaker at 100 rpm to imitate seafloor conditions. Bottles were sampled at the beginning and the end of the 12-week incubation experiment. We assessed the concretion growth with X-ray computed tomography and freshly formed concretion material with a scanning electron microscope. We analyzed the headspace methane concentrations and pH of the incubation solution. We measured phosphorus and metal (Mn, Fe, Co, V, Ni, Zn, Mo) concentrations of the incubation solution with triple quadrupole ICP-MS.

The results provide new information on the growth rates and conditions of Fe-Mn concretions. It was confirmed that concretions grew in laboratory conditions, and new growth was as much as 10 µm in 12 weeks. Headspace methane concentrations decreased in all samples during incubation, but least in abiotic controls, where the microbial activity was eliminated. The microbes living on the surface of concretions utilized methane, indicating that concretions have methanotrophic communities. Incubation solutions’ metal analysis showed that metal concentrations increased more in the abiotic controls than in biotic triplicates after a 12-week incubation, thus metals dissolved from concretions into the incubation solution faster without the activity of microbial communities. We suggest that microbes occupying the concretions have an important role in the concretions’ growth and the factors affecting the accumulation and release processes of metals.

This work was supported by the Finnish Natural Resources Research Foundation and the Research Council of Finland (Fermaid project, grant 332249).

How to cite: Majamäki, R., Purkamo, L., Hultman, J., Wasiljeff, J., Asmala, E., Yli-Hemminki, P., Jorgensen, K., Koho, K., Kuva, J., and Virtasalo, J.: Baltic Sea ferromanganese concretion growth rates and conditions, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9000, https://doi.org/10.5194/egusphere-egu24-9000, 2024.

Modern to Cenozoic hydrogenetic FeMn nodules and crusts are reliable geochemical archives of past seawater chemistry. In this study, we report the first petrographic and geochemical data of Jurassic FeMn nodules and crusts from the Calcaereous Alps of the Pyhrntal area (Austria) that were formed ca. 170 million years ago and, thus, ~ 10 million years after the Toarcian extinction event. The combined approach of petrographic data, including XRD and SEM+BSE, with major and trace element signatures and stable U-Mo isotopes of individual FeMn nodule and crust layers obtained by tandem ICP-MS and MC-ICP-MS, respectively, is used to extend the geochemical record of marine FeMn deposits roughly 100 million years back in time and evaluate their reliability as archives for Jurassic seawater. Trace elements and redox-sensitive U-Mo isotopes aid in reconstructing the origin of the FeMn nodules and redox conditions of Tethian seawater in the aftermath of the Toarcian extinction event.

The FeMn deposits of the Pyhrntal area can be subdivided into four types: Type I nodules rich in carbonates (< 90wt %; calcite, rhodochrosite) with minor Fe-oxides (10 wt%; hematite, goethite) and clays (< 20 wt %). Manganese-rich type II nodules (< 75 %; todorokite, ranceite) contain fewer carbonates (< 47 wt %), Fe oxides (<40 wt %), and clays (< 10 wt %). Type III nodules and crusts rich in Fe oxides (< 60 wt %) and carbonates (< 60 wt %) with minor Mn oxides and type IV nodules with Fe- (< 50 wt %) and Mn- oxides (10 wt %), carbonates (< 30 wt %) and < 12 wt % of clay. Despite their different mineralogy, all four FeMn deposit types show sub-parallel shale-normalized rare earth elements and yttrium (REY_SN) patterns that are typical of (modern) hydrogenetic FeMn deep-sea nodules and crusts, suggesting a seawater-derived origin. Typical REY_SN features include strong positive Ce_SN anomalies due to the oxidation of Ce³⁺ to Ce⁴⁺ on (hydr)oxide surfaces and a negative Y_SN anomaly related to higher complex stability of Y in seawater relative to neighboring REY. Furthermore, stable U and Mo isotope compositions of all four types show a narrow range in δ^98/95Mo (-0.97 to -0.56 ‰) and δ^238/235U (-0.75 to -0.47 ‰), consistent with isotopic values observed in modern and Cenozoic FeMn deposits, suggesting an overall oxic water column at latest 18 Ma after the Toarcian extinction event.

The approach using petrography with major and trace element systematics in combination with stable U-Mo isotope signatures highlights the Tethian FeMn deposits as unique geochemical archives of Jurassic seawater that enable a reliable reconstruction of the origin of the Alpine FeMn deposits and the ambient redox conditions in Tethian paleo-environments. 

How to cite: Viehmann, S., Klamt, V., Kraemer, D., Horn, I., Rüscher, C., Hohl, S. V., Fernandez, O., and Weyer, S.: The origin of Jurassic FeMn deposits and their reliability as geochemical archives for Tethian seawater, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2796, https://doi.org/10.5194/egusphere-egu24-2796, 2024.