“…), thus significantly lower than the measured experimental fluid temperature. This result is in good agreement with the observations of Staudigel & Swart () who performed dry heating experiments both under vacuum and under a CO 2 atmosphere. These authors observed rapid decrease of the Δ 47 of aragonite after 2·5 h heating at 125°C, but also found that none of the aragonites heated at temperatures lower than 375°C reached the equilibrium value within the three day duration of the experiments.…”
For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different 18O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ47 which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ18O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ18O and Δ47 signatures reveal exchange with the aqueous fluid, whereas δ13C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.
“…), thus significantly lower than the measured experimental fluid temperature. This result is in good agreement with the observations of Staudigel & Swart () who performed dry heating experiments both under vacuum and under a CO 2 atmosphere. These authors observed rapid decrease of the Δ 47 of aragonite after 2·5 h heating at 125°C, but also found that none of the aragonites heated at temperatures lower than 375°C reached the equilibrium value within the three day duration of the experiments.…”
For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different 18O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ47 which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ18O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ18O and Δ47 signatures reveal exchange with the aqueous fluid, whereas δ13C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.
“…Although carbon and oxygen isotope analyses based on samples obtained by micromilling devices (similar to those used in this study) have been shown to slightly alter the δ 18 O values of some carbonate material due to the transformation of aragonite induced by heat generated in the milling process (Waite & Swart, ), the speed with which the samples were drilled here (50 g ) was below the threshold at which a change would be expected to occur (Staudigel & Swart, ). The two isotope systems analysed here can be controlled by both depositional and diagenetic processes.…”
Marine carbonates are among the most important archives of environmental information in both modern and past environments. Widely used but particularly sensitive archives are the aragonitic skeletons of scleractinian corals. However, due to the metastable nature of aragonite, a multitude of chemical, mineralogical, and (micro)biological processes can lead to diagenetic alteration of these archives and their proxy information can be altered or lost. Here, hydrothermal alteration experiments were performed to create a better understanding of the diagenesis of an often‐utilized genus, Porites. Same‐specimen subsamples were heated in two fluid types and at two temperatures and durations, and their resulting alteration features were assessed to allow insight to the mechanisms and drivers of diagenetic modification. Experiments with fluid temperatures of 130°C induced remobilization and darkening of organic matrices, with no other evidence for alteration observed. In contrast, specimens exposed to a temperature of 160°C underwent significant diagenetic alteration dependent on fluid type. Fluid chemistry, particularly Mg/Ca ratios, was found to regulate the type of alteration (e.g. neomorphism or reprecipitation). Reaction with meteoric water resulted in almost complete neomorphism of the aragonite skeleton to blocky calcite, as well as significant exchange with the experimental fluid. In comparison, samples altered in the experimental burial fluids record no mineralogic or significant isotopic change, but instead, small‐scale dissolution–reprecipitation of the primary skeleton, along with the precipitation of pore‐filling aragonitic needle cements was observed. The δ18Ocarbonate data indicate transformation via dissolution–reprecipitation mechanisms depending on the degree and mechanism of diagenesis, and are strongly dependent on fluid chemistry. The main outcome of this work is that a multi‐proxy approach has the best potential to shed light on the interpretation of processes and pathways of aragonitic coral alteration. This study has implications for early alteration of carbonate archives within varying diagenetic fluids, with results aiding in the identification of past burial conditions.
“…Scale bars represent 1.0 cm.Figure 2Alteration of mineralogy and geochemical proxies in modern Mercenaria campechiensis shells by simulated prehistoric cooking methods: Untreated (grey triangles and grey striped areas), boiled (blue triangles), roasted (green circles), and burned shells (orange diamonds). ( a ) Conversion of primary aragonite into secondary calcite with the predicted aragonite-calcite conversion based on the Arrhenius model for biogenic aragonite of Staudigel & Swart 29 (solid lines). ( b ) Clumped-isotopic composition (Δ 47 ) reported in the absolute reference frame (ARF) defined by Dennis et al .…”
Section: Resultsmentioning
confidence: 99%
“…( a ) Conversion of primary aragonite into secondary calcite with the predicted aragonite-calcite conversion based on the Arrhenius model for biogenic aragonite of Staudigel & Swart 29 (solid lines). ( b ) Clumped-isotopic composition (Δ 47 ) reported in the absolute reference frame (ARF) defined by Dennis et al .…”
The reconstruction of pre-depositional cooking treatments used by prehistoric coastal populations for processing aquatic faunal resources is often difficult in archaeological shell midden assemblages. Besides limiting our knowledge of various social, cultural, economic and technological aspects of shell midden formation, unknown pre-depositional cooking techniques can also introduce large errors in palaeoclimate reconstructions as they can considerably alter the geochemical proxy signatures in calcareous skeletal structures such as bivalve shells or fish otoliths. Based on experimental and archaeological data, we show that carbonate clumped-isotope thermometry can be used to detect and reconstruct prehistoric processing methods in skeletal aragonite from archaeological shell midden assemblages. Given the temperature-dependent re-equilibration of clumped isotopes in aragonitic carbonates, this allows specific processing, cooking or trash dispersal strategies such as boiling, roasting, or burning to be differentiated. Besides permitting the detailed reconstruction of cultural or technological aspects of shell midden formation, this also allows erroneous palaeoclimate reconstructions to be avoided as all aragonitic shells subjected to pre-historic cooking methods show a clear alteration of their initial oxygen isotopic composition.
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