Carbonate clumped isotope thermometry, based on the temperature-dependence of clumping of ¹³C and ¹⁸O in the carbonate molecule (Δ₄₇) is a promising tool for paleoclimate reconstruction. In the last few years many discrepancies among Δ₄₇-temperature calibrations have been resolved across the range of relevant paleoclimate temperatures (Meinicke et al., 2020; Anderson et al., 2021). However, there might be other environmental effects on biogenic carbonates from parameters such as the pCO₂ and growth rates of the organisms that are still unresolved. We provide a new assessment of the temperature dependence of clumped isotopes in laboratory grown biogenic carbonate at well-constrained experimental conditions, with results from three species of coccolithophores across a growth temperature range of 6-27°C. The three cultured species cover a range of growth rates, growth conditions and species-specific carbon and oxygen vital effects. Because variations in pCO₂ and media carbon chemistry are known to trigger vital effects in carbon and oxygen isotopes in coccoliths, we decoupled the temperature solubility effect on CO₂ by manipulating culture CO₂ independently. Three pCO₂ levels at reduced, present day and elevated levels; 200, 400 and 1000 ppm respectively, were kept constant for at least two different temperatures through a continuous culturing set-up. Our new multi-parameter comparison, using updated standardization approaches, provides a critical test of previous conclusions (Katz et al., 2017) that coccolithophore clumped isotopes show little to no vital effects and are close to abiotic equilibrium. Thus, we have performed the first calibration of coccolith calcite and clumped isotopes combining different temperature and pCO₂ conditions.

References:

Anderson, N. T., J. R. Kelson, S. Kele, M. Daëron, M. Bonifacie, J. Horita, T. J. Mackey, et al. 2021. "A Unified Clumped Isotope Thermometer Calibration (0.5–1,100°C) Using Carbonate‐Based Standardization." Geophysical Research Letters 48 (7).

Katz, A., M. Bonifacie, M. Hermoso, P. Cartigny, D. Calmels. 2017. “Laboratory-grown coccoliths exhibit no vital effect in clumped isotope (Δ47) composition on a range of geologically relevant temperatures.” Geochimica et Cosmochimica Acta 208: 335-353.

Meinicke, N., S.L. Ho, B. Hannisdal, D. Nürnberg, A. Tripati, R. Schiebel, and A.N. Meckler. 2020. "A robust calibration of the clumped isotopes to temperature relationship for foraminifers." Geochimica et Cosmochimica Acta 270: 160-183.

How to cite: Clark, A. J., Torres Romero, I., Jaggi, M., Bernasconi, S. M., and Stoll, H.: A new clumped isotope-temperature calibration of cultured coccoliths under different pCO2 and temperature conditions, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-15203, https://doi.org/10.5194/egusphere-egu23-15203, 2023.

The major climatic forcing parameters on Earth climate are temperature and the atmospheric concentrations of CO₂. Even if their evolutions covaried to the first-order, the geological record show periods with non-linear evolution between those two parameters. Such delinking requires accurate paleoclimate reconstructions with implications for the modelling studies of our future climate.

pCO₂ and Sea Surface Temperature (SST) reconstructions are usually quantified using proxies relying on both the organic matter produced by coccolithophores (UK37’ index and δ¹³C_alkenones) and calcite of foraminiferal tests (δ¹¹B, δ¹⁸O, Mg/Ca). These proxies have been very useful for a variety of paleoclimatic advances, yet present unresolved and potentially important biases. As an example, alkenone carbon isotopes are not able to register low to moderate pCO₂ levels (Badger et al., 2019). This is notoriously a major issue for paleoclimate reconstructions of the last 6 My (Plio-Pleistocene period).

Our approach is to use a unique archive – the coccoliths – for determination of coeval SST and pCO₂. Coccoliths are small calcite plates produced by unicellular photosynthetic algae called coccolithophores. They are a very promising substrate to analyse for paleoclimate studies because they calcify in the uppermost water column and because their isotopic ratios are sensitive to both photosynthesis and calcification (Hermoso et al. 2020). Therefore, these isotopic ratios provide physiological and metabolic information about coccolithophores of the past. In order to infer paleoclimates from the sedimentary archives, we have to deconvolve the isotopic biological imprint (vital effect) from the environment signal. For the evaluation of the vital effects, we have undertaken a large-scaled culture experiments with various strains of coccolithophore grown under various CO₂ concentrations and pH (Le Guevel et al. in prep). Even if we have managed culture until 1400ppm and 7.55 unit of pH, we were particularly interested in low pCO₂ and high pH conditions because the bibliography is lacking of vital effect for Plio-Pleistocène applications. All the selected strains produce coccoliths within the size range of the one we find predominantly in the marine sediments throughout geological times.

We document a large decrease of the carbon differential vital effect with the CO₂ concentration increase between Gephyrocapsa oceanica and Coccolithus braarudii. This is consistent with previous studies but the absolute values are slightly different and we provide a more precise dataset at low to moderate pCO₂ than the previous ones (Rickaby et al., 2010; Hermoso et al., 2016). We propose the first study of the oxygen and carbon vital effect of the Helicosphaera carteri group with combined CO₂/pH changes. Taken together, the culture data and measurements of the isotopic composition of the calcite biominerals allows better paleoreconstructions of SST and aqueous CO₂.

How to cite: Le Guevel, G., Minoletti, F., Geisen, C., and Hermoso, M.: Developing a robust biogeochemical framework of the coccolith vital effects for more reliable paleoclimatic reconstructions, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-5544, https://doi.org/10.5194/egusphere-egu23-5544, 2023.

Organo-sedimentary structures built by benthic microbial communities, known as microbialites, dominated the fossil record for the first 3 billion years of Earth’s history. Various microbial metabolisms contribute to microbialite lithification, each of which can be based on biogeochemical cycling of elements capable of supporting life. Arsenic (As), a common element on the surface of Precambrian Earth, has been proposed to have supported the development of early life associated with the construction of primitive microbial carbonates. These As-based metabolisms have left evidence of their existence within the 2.7 Ga old Tumbiana stromatolites, showing the potential of this metalloid to serve as an archive of the dynamic interplay between microbes, minerals, and their environment of deposition throughout Earth’s history. However, significant changes in the geochemical composition of microbialites likely occur during early taphonomic modification and later diagenetic alteration. Therefore, establishing the mechanisms driving the arsenic geochemistry of ancient microbialites can be challenging.

Motivated by these challenges, our objective was to evaluate the mechanisms controlling the initial incorporation of arsenic into actively accreting microbialites, as well as the preservation of the [As] signal during early taphonomic alteration of the structure. Hamelin Pool (Western Australia) is one of the few modern systems that host As-based metabolisms in the microbial communities involved in microbialite accretion. Conventional terminology recognizes four types of microbial mats that produce recognizable internal microfabrics in Hamelin Pool microbialites: pustular, smooth, colloform, and transitional mat types. Over time, these initial microfabrics all follow a similar evolution subdivided into two successive stages: (1) precipitation of micrite along laminations and around clots and; (2) precipitation of aragonitic marine cement. Therefore, Hamelin Pool microbialite fabrics provide a unique and step-wise window into the processes that form ancient microfabrics, particularly highlighting the importance of their early taphonomic evolution in the fate of the As biosignal originally incorporated during initial accretion of the structure.

Based on microbialites collected from Hamelin Pool that have been characterized petrographically, we evaluated the evolution of [As] recorded in the Hamelin Pool microbialites at all stages of deposition and early taphonomic modifications. Results were interpreted in relation to the distinct microbial mats and their metabolisms, as well as the physicochemical and geological variability of the depositional environment. To accomplish this, we conducted a sequential leaching experiment to chemically isolate the organic matter and carbonate fractions, and measured As concentrations on a triple-quadrupole inductively coupled mass spectrometer (Agilent 8900 ICP-QQQ). Preliminary results show that elevated As concentrations are initially incorporated into microbial organic matter before being transferred to the carbonate fraction through successive stages of early taphonomic alteration. Because the carbonate fraction is diagenetically more resistant than the organic matter, this discovery could have major implications for the preservation of geochemical biosignatures in the geological record of microbialites. Our results serve as a first step towards improving the utility of [As] as an indicator of biogenicity in the fossil record of early Earth and, possibly, other planets such as Mars.

How to cite: Pollier, C. G. L., Koschik, C. H., Vitek, B. E., Wu, Z., Suosaari, E. P., Reid, R. P., and Oehlert, A. M.: The fate of Arsenic during early microbialite taphonomy: Implications for chemical biosignature preservation, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-10717, https://doi.org/10.5194/egusphere-egu23-10717, 2023.

Climate warming is expected to lead to a reduction in the body size of marine organisms, a trend already observed in commercial fishes, but the effects of temperature rise on size distribution in exploited populations are difficult to separate from the impact of overfishing and other anthropogenic stressors. We aim to test the hypothesis that fish body sizes, as well as growth rates changed during the late Holocene and Anthropocene in the northern Adriatic Sea due to environmental perturbations caused by climate warming. We perform sclerochronological analysis on modern otoliths from fish sampled alive, as well as radiocarbon-dated fossil otoliths of non-commercial, demersal gobies (Gobius niger Linnaeus, 1758) sampled from a sediment core taken off Piran (Slovenia) to quantify changes in body size and growth parameters throughout the Holocene. Otoliths are the aragonitic structures of the fish’ inner ear with species-specific morphology, and thanks to their incremental growth, they serve as unique environmental and life-history archive. Moreover, otolith size correlates with fish size. We use otoliths cut in half to perform both sclerochronology and radiocarbon dating, obtaining a high-resolution time series of changes in fish body size, growth dynamics and life history parameters. We employ backscatter electron (BSE) imaging and electron probe microanalysis (EPMA) to identify body sizes and growth dynamics, as well as to correlate their growth increments with climatic and other environmental parameters. The reconstructed changes in body size and growth rates of very common, non-commercial fish species over the last 7.000 years, can serve as an ecological baseline for evaluating the magnitude of ongoing temperature rise and future shifts in fish populations in response to global warming.

How to cite: Leonhard, I., Agiadi, K., Nawrot, R., Jarochowska, E., and Zuschin, M.: Reconstructing Holocene body size changes of Adriatic gobies using radiocarbon dating and sclerochronological analyses of modern and fossil otoliths, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-6697, https://doi.org/10.5194/egusphere-egu23-6697, 2023.

Crustose coralline algae (CCA) form Coralligenous build-ups, which are ranked among the most important ecosystems in the Mediterranean shelf. Their skeletal framework hosts a variety of epi- and infaunal communities, which compete for space, contributing to the reef growth, or weaken the structure throughout bio-erosive activities. Investigating the relationship between the algal framework and these hosted communities is of extreme importance for ecological and palaeoecological purposes and monitoring goals. 

In this frame, the Italian project “CRESCIBLUREEF - Grown in the blue: new technologies for the knowledge and conservation of the Mediterranean reefs”, is aimed at investigating coralligenous reefs present in the  area off the Marzamemi village (South-East Sicily). 

Two build-ups have been collected: the first one at 37 m depth, from an area rich in coralligenous cover, and the second one at 36 m depth, from a submarine channel with sparsely distributed build-ups. We present here two new investigative techniques, so far seldom applied for the characterization of the Coralligenous. The first approach involved the quantification of the surficial cover, with the use of an image analysis software, both before and after the removal of their ephemeral canopy of unmineralized organisms.These models were then analysed using Object-Based Image Analysis (OBIA) algorithms that allowed the quantification of the surficial cover. Moreover, the analysis allowed the identification and categorisation of the organisms and materials on the external part of the build-ups, confirming the primary role of CCA as the major component of the samples. Afterwards, a Computed-Tomography (CT) scan was used - for the first time with Coralligenous - to reconstruct the inner structure of the build-ups and, together with radiocarbon dating, to infer the build-ups age and growth rate. CT analysis divided the framework into four main categories based on their density (Low, Medium, High and Ultra High). The structure’s cavities, either primary or developed through taphonomic processes, have been measured as porosity. The overall highly-resolved analysis points to a complex and nonlinear growth of the build-ups. The understanding of the structural density, porosity, growth rate, and surficial cover of the build-ups is shedding some light on the Coralligenous inception and growth. 

How to cite: Bazzicalupo, P., Bracchi, V. A., Varzi, A. G., Fallati, L., Savini, A., Rosso, A., Sanfilippo, R., Guido, A., Cipriani, M., and Basso, D. M.: Novel investigative techniques on calcareous red algae build-ups: photogrammetry and CT-scan on Coralligenous from Marzamemi (Sicily), EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-12307, https://doi.org/10.5194/egusphere-egu23-12307, 2023.

To evaluate the preservation pattern of pteropods and their relationship with climatic and oceanographic history in the Laccadive Sea, a temporal variation analysis of pteropod abundance was done. For that, we employed preservation indices from calcite (Globigerina bulloides%, Globorotalia menardii abundance), as well as aragonite (e.g., total pteropod abundance, Limacina Dissolution Index (LDX), fragmentation ratio). To determine if pteropod shells have been preserved over time, we used estimated pteropod abundance. The pteropod preservation record displays excellent preservation during cold stadials, evidenced by the lower values of aragonite dissolution proxies than during the interglacials/interstadials, similar to the preservation records from other northern Indian Ocean cores evidenced by the lower values of aragonite dissolution proxies than during the interglacials/interstadials. The shallow aragonite compensation depth (ACD), weaker oxygen minimum zone (OMZ), and the lower southwest monsoon (SWM)-induced productivity are thought to be the cause of the basin-wide pteropod preservation events during the cold stadials (ACD). Additionally, during an intense northeast monsoon (NEM), the advection of cold, low-saline waters from the Bay of Bengal to the Laccadive Sea, as well as the intrusion of southern-sourced intermediate water ventilation, may have caused a deep vertical mixing of oxygen-rich surface waters, raised the pH of thermocline waters and deepened the ACD. However, the local fluctuations in the water mass properties, such as the increased productivity maxima, the intense OMZ, and shallow ACD, as well as changes in the aragonite, are responsible for the poor pteropod abundance, poor preservation and strong dissolution during the Holocene, Bølling-Allerød (B/A) and interstadial periods.

The calcification proxy indicates that the aragonite undersaturation and reduced calcification occurred during 19-16.5 kyr, preferably due to the depletion in the oceanic alkalinity caused by enhanced upwelling-induced carbonate ion exchange between the intermediate and deep water. In contrast, the preferential dissolution of smaller shells in the sediments (marked by increased average shell size and higher values of Limacina dissolution index (LDX) corresponds to strengthened OMZ and shallower ACD, pointing towards the post-depositional dissolution of aragonite shells. Therefore, the overall decrease of pteropod content of the deposits in the stadial/interstadials suggests a combination of monsoon-associated changes in water column properties, variability in aragonite saturation, intermediate water ventilation and sediment rate.

How to cite: Edayiliam, S., Adukkam Veedu, S. K., and Bejugam, N. N.: Late quaternary carbonate (pteropod) preservation in the Indian Ocean sediments: inferences on the paleoclimate and paleoceanography, EGU General Assembly 2023, Vienna, Austria, 23–28 Apr 2023, EGU23-274, https://doi.org/10.5194/egusphere-egu23-274, 2023.