Journal articles: 'Stable and clumped isotope'

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Demény, Attila, László Rinyu, Péter Németh, György Czuppon, Nóra Enyedi, Judit Makk, Szabolcs Leél-Őssy, Dóra Kesjár, and Ivett Kovács. "Bacterial and abiogenic carbonates formed in caves–no vital effect on clumped isotope compositions." PLOS ONE 16, no. 1 (January 25, 2021): e0245621. http://dx.doi.org/10.1371/journal.pone.0245621.

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Speleothems (dominated by cave-hosted carbonate deposits) are valuable archives of paleoclimate conditions. As such, they are potential targets of clumped isotope analyses that may yield quantified data about past temperature variations. Clumped isotope analyses of stalagmites, however, seldom provide useful temperature values due to various isotope fractionation processes. This study focuses on the determination of the microbially induced vital effect, i.e., the isotope fractionation processes related to bacterial carbonate production. A cave site with biologically mediated amorphous calcium carbonate precitation was selected as a natural laboratory. Calcite deposits were farmed under a UV lamp to prevent bacterial activity, as well as under control conditions. Microbiological analyses and morphological investigations using scanning electron microscopy showed that the UV lamp treatment effectively reduced the number of bacterial cells, and that bacterial carbonate production strongly influenced the carbonate’s morphology. Stable oxygen isotope analyses of calcite and drip waters, as well as clumped isotope measurements revealed that, although most of the studied carbonates formed close to oxygen isotope equilibrium, clumped isotope Δ47 values varied widely from equilibrium to strongly fractionated data. Site-specific kinetic fractionations played a dominant role in the distribution of Δ47 values, whereas bacterial carbonate production did not result in a detectable clumped isotope effect.

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Thiagarajan, Nivedita, Jon Halvard Pedersen, Harald Brunstad, Joachim Rinna, Aivo Lepland, and John Eiler. "Clumped isotope constraints on the origins of reservoir methane from the Barents Sea." Petroleum Geoscience 28, no. 2 (March 14, 2022): petgeo2021–037. http://dx.doi.org/10.1144/petgeo2021-037.

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The Barents Sea basin is an oil and gas province containing more than 760 million tons of oil equivalents. The reservoir geology of the Barents Sea is complex due to multiple episodes of subsidence, uplift and erosion, which opened a network of extensional and wrench related faults allowing for fluid migration. The multifaceted geological history complicates efforts to describe the source and characteristics of natural gas in the subsurface Barents Sea. Here we apply stable isotopes, including methane clumped isotope measurements, to thirteen natural gases from five (Skrugard Appraisal, Havis, Alta, Filicudi, and Svanefjell) reservoirs in the Loppa High area in the southwestern Barents Sea to estimate the origins of methane. We compare estimates of methane formation temperature based on clumped isotopes to thermal evolution models for the region. We find that the methane has diverse origins including microbial and thermogenic sources forming and equilibrating at temperatures ranging from 34–238°C. Our clumped isotope temperature estimates are consistent with thermal evolution models for the area. These temperatures can be explained by gas generation and expulsion in the oil and gas window followed by isotopic re-equilibration in some reservoirs due to microbial methanogenesis and/or anaerobic oxidation of methane. Gases from the Skrugard Appraisal, Havis and Alta have methane equilibration temperatures consistent with maximum burial temperatures, while gases from Svanefjell have methane equilibration temperatures consistent with current reservoir temperature, suggesting isotope re-equilibration in the shallow reservoir. Gases from Filicudi on the other hand are consistent with generation over multiple points over its thermal history.

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Passey, Benjamin H. "Reconstructing Terrestrial Environments Using Stable Isotopes in Fossil Teeth and Paleosol Carbonates." Paleontological Society Papers 18 (November 2012): 167–94. http://dx.doi.org/10.1017/s1089332600002606.

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Carbon isotopes in Neogene-age fossil teeth and paleosol carbonates are commonly interpreted in the context of past distributions of C3 and C4 vegetation. These two plant types have very different distributions in relation to climate and ecology, and provide a robust basis for reconstructing terrestrial paleoclimates and paleoenvironments during the Neogene. Carbon isotopes in pre-Neogene fossil teeth are usually interpreted in the context of changes in the δ13C value of atmospheric CO2, and variable climate-dependent carbon-isotope discrimination in C3 plants. Carbon isotopes in pre-Neogene soil carbonates can be used to estimate past levels of atmospheric CO2. Oxygen isotopes in fossil teeth and paleosol carbonates primarily are influenced by the oxygen isotopic compositions of ancient rainfall and surface waters. The oxygen isotopic composition of rainfall is has a complex, but tractable, relationship with climate, and variably relates to temperature, elevation, precipitation amount, and other factors. Mammal species that rely on moisture in dietary plant tissues to satisfy their water requirements (rather than surface drinking water) may have oxygen isotopic compositions that track aridity. Thus, oxygen isotopes of fossil mammals can place broad constraints on paleoaridity. Carbonate clumped isotope thermometry allows for reconstruction of soil temperatures at the time of pedogenic carbonate mineralization. The method is unique because it is the only thermodynamically based isotopic paleothermometer that does not require assumptions about the isotopic composition of the fluid in which the archive mineral formed. Soil temperature reflects a complex interplay of air temperature, solar radiative heating, latent heat effects, soil thermal diffusivity, and seasonal variations of these parameters. Because plants and most animals live in and/or near the soil, soil temperature is an important aspect of terrestrial (paleo)climate.

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Krsnik, Emilija, Katharina Methner, Marion Campani, Svetlana Botsyun, Sebastian G. Mutz, Todd A. Ehlers, Oliver Kempf, Jens Fiebig, Fritz Schlunegger, and Andreas Mulch. "Miocene high elevation in the Central Alps." Solid Earth 12, no. 11 (November 23, 2021): 2615–31. http://dx.doi.org/10.5194/se-12-2615-2021.

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Abstract. Reconstructing Oligocene–Miocene paleoelevation contributes to our understanding of the evolutionary history of the European Alps and sheds light on geodynamic and Earth surface processes involved in the development of Alpine topography. Despite being one of the most intensively explored mountain ranges worldwide, constraints on the elevation history of the European Alps remain scarce. Here we present stable and clumped isotope measurements to provide a new paleoelevation estimate for the mid-Miocene (∼14.5 Ma) European Central Alps. We apply stable isotope δ–δ paleoaltimetry to near-sea-level pedogenic carbonate oxygen isotope (δ18O) records from the Northern Alpine Foreland Basin (Swiss Molasse Basin) and high-Alpine phyllosilicate hydrogen isotope (δD) records from the Simplon Fault Zone (Swiss Alps). We further explore Miocene paleoclimate and paleoenvironmental conditions in the Swiss Molasse Basin through carbonate stable (δ18O, δ13C) and clumped (Δ47) isotope data from three foreland basin sections in different alluvial megafan settings (proximal, mid-fan, and distal). Combined pedogenic carbonate δ18O values and Δ47 temperatures (30±5 ∘C) yield a near-sea-level precipitation δ18Ow value of -5.8±1.2 ‰ and, in conjunction with the high-Alpine phyllosilicate δD value of -14.6±0.3 ‰, suggest that the region surrounding the Simplon Fault Zone attained surface elevations of >4000 m no later than the mid-Miocene. Our near-sea-level δ18Ow estimate is supported by paleoclimate (iGCM ECHAM5-wiso) modeled δ18O values, which vary between −4.2 ‰ and −7.6 ‰ for the Northern Alpine Foreland Basin.

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de Winter, Niels J., Johan Vellekoop, Robin Vorsselmans, Asefeh Golreihan, Jeroen Soete, Sierra V. Petersen, Kyle W. Meyer, Silvio Casadio, Robert P. Speijer, and Philippe Claeys. "An assessment of latest Cretaceous Pycnodonte vesicularis (Lamarck, 1806) shells as records for palaeoseasonality: a multi-proxy investigation." Climate of the Past 14, no. 6 (June 8, 2018): 725–49. http://dx.doi.org/10.5194/cp-14-725-2018.

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Abstract. In order to assess the potential of the honeycomb oyster Pycnodonte vesicularis for the reconstruction of palaeoseasonality, several specimens recovered from late Maastrichtian strata in the Neuquén Basin (Argentina) were subject to a multi-proxy investigation, involving scanning techniques and trace element and isotopic analysis. Combined CT scanning and light microscopy reveals two calcite microstructures in P. vesicularis shells (vesicular and foliated calcite). Micro-XRF analysis and cathodoluminescence microscopy show that reducing pore fluids were able to migrate through the vesicular portions of the shells (aided by bore holes) and cause recrystallization of the vesicular calcite. This renders the vesicular portions not suitable for palaeoenvironmental reconstruction. In contrast, stable isotope and trace element compositions show that the original chemical composition of the foliated calcite is well-preserved and can be used for the reconstruction of palaeoenvironmental conditions. Stable oxygen and clumped isotope thermometry on carbonate from the dense hinge of the shell yield sea water temperatures of 11°C, while previous TEX86H palaeothermometry yielded much higher temperatures. The difference is ascribed to seasonal bias in the growth of P. vesicularis, causing warm seasons to be underrepresented from the record, while TEX86H palaeothermometry seems to be biased towards warmer surface water temperatures. The multi-proxy approach employed here enables us to differentiate between well-preserved and diagenetically altered portions of the shells and provides an improved methodology for reconstructing palaeoenvironmental conditions in deep time. While establishing a chronology for these shells was complicated by growth cessations and diagenesis, cyclicity in trace elements and stable isotopes allowed for a tentative interpretation of the seasonal cycle in late Maastrichtian palaeoenvironment of the Neuquén Basin. Attempts to independently verify the seasonality in sea water temperature by Mg ∕ Ca ratios of shell calcite are hampered by significant uncertainty due to the lack of proper transfer functions for pycnodontein oysters. Future studies of fossil ostreid bivalves should target dense, foliated calcite rather than sampling bulk or vesicular calcite. Successful application of clumped isotope thermometry on fossil bivalve calcite in this study indicates that temperature seasonality in fossil ostreid bivalves may be constrained by the sequential analysis of well-preserved foliated calcite samples using this method.

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Little, Reginald B. "Evidence of Stable Isotope 13C Causing All Cancers." European Journal of Applied Physics 4, no. 4 (August 14, 2022): 37–44. http://dx.doi.org/10.24018/ejphysics.2022.4.4.187.

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Evidence for a general mechanism of genesis of all cancers is given by presenting a puzzle and using recent results of aspartame and acesulfame-K to fit the pieces of the cancer puzzle together for proof of the mechanism of oncogenesis. Aspartame and acesulfame-K have been linked to cancer. Aspartame is a modified dipeptide (methylated phenylalanine (modified) and aspartic acid), so modified amino acids were thought to be more innocuous. The author previously noted isotopically enriched and/or clumped bond-specific amino acids and oligonucleotides have different biochemical reactions for different biology. Acesulfame-K is not a peptide or oligonucleotide but it has some similar chemical structure to oligonucleoside and reversibly decomposes to affect oligonucleosides and affect cells and bacteria cells like E Coli for producing isotopically enriched amino acids indirectly. E. Coli is present in the human digestive system and is known to accelerate stable isotope enrichment of amino acids with 13C, 15N, and/or 17O. Thereby acesulfame-K and aspartame induce isotopic enrichments and excessive 13C, 15N, and/or 17O introductions into proteins and nucleic acids. Such effects of 13C isotopes as induced by the bacteria and these chemicals like aspartame and acesulfame-K may be coupled to effects of static magnetic field(s) and radio frequency electromagnetic waves for explaining the complexity of results and inconsistent results from separating these effects. Thereby the 13C isotope enriched phenylalanine and/or aspartic acid may be the basis of malfunctioning normal cells for the genesis of cancer. Further support for this theory of 13C causing cancer by ingestion of aspartame is given by also noting the mystery and confounding results of monosodium glutamate causing cancer as the glutamate is synthesized by bacterial culture and the resulting ingested glutamic acid enriched with 13C and 15N and possibly 17O causes adverse biochemistry and enzymatics (relative to glutamate from healthy plants and animals rather than the bacterial industrial glutamate in MSG) for cancer and other diseases as explaining the observation of cancer and other diseases from acute and chronic MSG ingestion over months and years. The third case of bacterial production of insulin during the last 25 years for recent correlation to insulin causing cancer relative to less cancer from older methods of insulin production is more evidence of bacterial production of amino acids and peptides causing enriched heavy isotopes and the resulting enriched amino acids and peptides causing cancer relative to ingestion of 13C enriched carbohydrates.

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Thiagarajan, Nivedita, Antoine Crémière, Clara Blättler, Aivo Lepland, Kalle Kirsimäe, John Higgins, Harald Brunstad, and John Eiler. "Stable and clumped isotope characterization of authigenic carbonates in methane cold seep environments." Geochimica et Cosmochimica Acta 279 (June 2020): 204–19. http://dx.doi.org/10.1016/j.gca.2020.03.015.

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de Winter, Niels J., Tobias Agterhuis, and Martin Ziegler. "Optimizing sampling strategies in high-resolution paleoclimate records." Climate of the Past 17, no. 3 (June 21, 2021): 1315–40. http://dx.doi.org/10.5194/cp-17-1315-2021.

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Abstract. The aim of paleoclimate studies resolving climate variability from noisy proxy records can in essence be reduced to a statistical problem. The challenge is to extract meaningful information about climate variability from these records by reducing measurement uncertainty through combining measurements for proxies while retaining the temporal resolution needed to assess the timing and duration of variations in climate parameters. In this study, we explore the limits of this compromise by testing different methods for combining proxy data (smoothing, binning, and sample size optimization) on a particularly challenging paleoclimate problem: resolving seasonal variability in stable isotope records. We test and evaluate the effects of changes in the seasonal temperature and the hydrological cycle as well as changes in the accretion rate of the archive and parameters such as sampling resolution and age model uncertainty in the reliability of seasonality reconstructions based on clumped and oxygen isotope analyses in 33 real and virtual datasets. Our results show that strategic combinations of clumped isotope analyses can significantly improve the accuracy of seasonality reconstructions compared to conventional stable oxygen isotope analyses, especially in settings in which the isotopic composition of the water is poorly constrained. Smoothing data using a moving average often leads to an apparent dampening of the seasonal cycle, significantly reducing the accuracy of reconstructions. A statistical sample size optimization protocol yields more precise results than smoothing. However, the most accurate results are obtained through monthly binning of proxy data, especially in cases in which growth rate or water composition cycles obscure the seasonal temperature cycle. Our analysis of a wide range of natural situations reveals that the effect of temperature seasonality on oxygen isotope records almost invariably exceeds that of changes in water composition. Thus, in most cases, oxygen isotope records allow reliable identification of growth seasonality as a basis for age modeling in the absence of independent chronological markers in the record. These specific findings allow us to formulate general recommendations for sampling and combining data in paleoclimate research and have implications beyond the reconstruction of seasonality. We briefly discuss the implications of our results for solving common problems in paleoclimatology and stratigraphy.

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Falk, E. S., W. Guo, A. N. Paukert, J. M. Matter, E. M. Mervine, and P. B. Kelemen. "Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements." Geochimica et Cosmochimica Acta 192 (November 2016): 1–28. http://dx.doi.org/10.1016/j.gca.2016.06.026.

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Vieira, Daniella S. C., Daniel Pivko, László Rinyu, László Palcsu, Gabriella I. Kiss, Hsun-Ming Hu, Chuan-Chou Shen, and Sándor Kele. "Age and Depositional Temperature of Quaternary Travertine Spring Mounds from Slovakia." Minerals 13, no. 6 (June 10, 2023): 794. http://dx.doi.org/10.3390/min13060794.

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Travertine spring mounds are common in Slovakia; however, their age and depositional temperature are still poorly known. Our study is the first multimethodological investigation involving stable carbon, oxygen, and clumped isotope (Δ47) analyses and U-Th age determination of travertine mounds from different locations in Slovakia (Santovka, Dudince, Čerin, Bešeňová, Liptovský Ján, Liptovské Sliače, Vyšné Ružbachy, Gánovce, and Sivá Brada) to provide information about their age, origin, precipitation conditions, and temperature. The positive δ13C values imply that the parent water was charged with heavy CO2 of deep origin. The δ18O values of spring waters range between −11.4‰ and −8.9‰, whereas the δ2H values vary from −80.5‰ to −58.3, indicating a meteoric origin for spring waters. Clumped isotope compositions (Δ47) correspond to a deposition temperature between 4 °C and 32 °C. The U-Th age data of the studied travertines vary from 1.2 (Liptovské Sliače) to 301 ka (Dudince). Our results can serve as a basis for further detailed geochronological and geochemical studies to reconstruct the paleoclimate and paleoenvironment during travertine deposition periods in Slovakia since the mid-Pleistocene transition.

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Bojar, A. V., A. Pelc, and C. Lécuyer. "About this title - Stable Isotope Studies of the Water Cycle and Terrestrial Environments." Geological Society, London, Special Publications 507, no. 1 (2021): NP. http://dx.doi.org/10.1144/sp507.

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This volume is devoted to Earth surface environmental reconstructions and environmental changes that may be deciphered and modelled using stable isotopes along with mineralogical/chemical, sedimentological, palaeontological/biological and climatological methodologies. The book is divided into two sections, both using stable isotopes (δD, δ18O, δ13C, d15N, δ34S, clumped isotopes Δ47) in various samples and phases as the main research tool. The first section is devoted to studies focusing on the distribution of isotopes in precipitation, groundwater, lakes, rivers, springs, tap water, mine water and their relationship with terrestrial environments at regional to continental scale. In relation to this, the second section includes case studies from a range of continental settings, investigating cave deposits (stalagmites, bat guano), animal skeletons (dinosaurs, alligators, turtles, bivalves), present and past soils (palaeosols) and limestones. The sections focus on the interaction between the surficial water cycle and underground water storage with deposits acting as archives of short- to long-term climatic and environmental changes. Examples from the Early Cretaceous to present time come from Europe, Asia, Africa, North and South America.

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Ryb, Uri, and John M. Eiler. "Oxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem." Proceedings of the National Academy of Sciences 115, no. 26 (June 11, 2018): 6602–7. http://dx.doi.org/10.1073/pnas.1719681115.

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The18O/16O of calcite fossils increased by ∼8‰ between the Cambrian and present. It has long been controversial whether this change reflects evolution in the δ18O of seawater, or a decrease in ocean temperatures, or greater extents of diagenesis of older strata. Here, we present measurements of the oxygen and ‟clumped” isotope compositions of Phanerozoic dolomites and compare these data with published oxygen isotope studies of carbonate rocks. We show that the δ18O values of dolomites and calcite fossils of similar age overlap one another, suggesting they are controlled by similar processes. Clumped isotope measurements of Cambrian to Pleistocene dolomites imply crystallization temperatures of 15–158 °C and parent waters having δ18OVSMOWvalues from −2 to +12‰. These data are consistent with dolomitization through sediment/rock reaction with seawater and diagenetically modified seawater, over timescales of 100 My, and suggest that, like dolomite, temporal variations of the calcite fossil δ18O record are largely driven by diagenetic alteration. We find no evidence that Phanerozoic seawater was significantly lower in δ18O than preglacial Cenozoic seawater. Thus, the fluxes of oxygen–isotope exchange associated with weathering and hydrothermal alteration reactions have remained stable throughout the Phanerozoic, despite major tectonic, climatic and biologic perturbations. This stability implies that a long-term feedback exists between the global rates of seafloor spreading and weathering. We note that massive dolomites have crystallized in pre-Cenozoic units at temperatures >40 °C. Since Cenozoic platforms generally have not reached such conditions, their thermal immaturity could explain their paucity of dolomites.

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Cui, Jingwei, and Yongfu Liu. "Determination of Formation Time of Calcareous Cements in Marine Sandstone and Their Influence on Hydrocarbon Accumulation: A Case Study of the Carboniferous Donghe Sandstone in the Hadexun Oilfield, Tarim Basin." Geofluids 2021 (March 9, 2021): 1–15. http://dx.doi.org/10.1155/2021/8897663.

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Based on core observations, the microheterogeneity, diagenetic features, diagenetic mineral compositions, and stable isotopes of cements in the calcareous interlayers in the Donghe sandstone were studied by polarizing microscopy, cathodoluminescence microscopy, X-ray diffractometry, isotope ratio mass spectrometry, and other techniques. By determining the proportions of cements of two phases by a statistical method and their clumped isotope values by an end-member method, the multiphase calcareous cementation was shown to be the major contributor to densification. Cluster isotopes revealed that the average formation temperatures of calcareous cements in phases II and III of cementation were 45–50°C and 80–90°C, indicating that they were products of the A and B phases during early diagenesis, respectively. According to the homogenization temperatures of coeval salt-water inclusions associated with hydrocarbon inclusions, which range from 100°C to 130°C, basin modeling revealed that the basin underwent mainly one stage of hydrocarbon charging during 8–5 Ma in the Miocene period. The cements of the two phases in the oil-free calcareous interlayers in the Donghe sandstone, which are the main controlling factor of the oil-water distribution in the reservoir at present, formed much earlier than the oil filling in the oil-bearing sandstone.

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De Vleeschouwer, David, Marion Peral, Marta Marchegiano, Angelina Füllberg, Niklas Meinicke, Heiko Pälike, Gerald Auer, et al. "Plio-Pleistocene Perth Basin water temperatures and Leeuwin Current dynamics (Indian Ocean) derived from oxygen and clumped-isotope paleothermometry." Climate of the Past 18, no. 5 (June 1, 2022): 1231–53. http://dx.doi.org/10.5194/cp-18-1231-2022.

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Abstract. The Pliocene sedimentary record provides a window into Earth's climate dynamics under warmer-than-present boundary conditions. However, the Pliocene cannot be considered a stable warm climate that constitutes a solid baseline for middle-of-the-road future climate projections. The increasing availability of time-continuous sedimentary archives (e.g., marine sediment cores) reveals complex temporal and spatial patterns of Pliocene ocean and climate variability on astronomical timescales. The Perth Basin is particularly interesting in that respect because it remains unclear if and how the Leeuwin Current sustained the comparably wet Pliocene climate in Western Australia, as well as how it influenced Southern Hemisphere paleoclimate variability. To constrain Leeuwin Current dynamics in time and space, this project obtained eight clumped-isotope Δ47 paleotemperatures and constructed a new orbitally resolved planktonic foraminifera (Trilobatus sacculifer) stable isotope record (δ18O) for the Plio-Pleistocene (4–2 Ma) interval of International Ocean Discovery Program (IODP) Site U1459. These new data complement an existing TEX86 record from the same site and similar planktonic isotope records from the Northern Carnarvon Basin (Ocean Drilling Program (ODP) Site 763 and IODP Site U1463). The comparison of TEX86 and Δ47 paleothermometers reveals that TEX86 likely reflects sea surface temperatures (SSTs) with a seasonal warm bias (23.8–28.9 ∘C), whereas T. sacculifer Δ47 calcification temperatures probably echo mixed-layer temperatures at the studied Site U1459 (18.9–23.2 ∘C). The isotopic δ18O gradient along a 19–29∘ S latitudinal transect, between 3.9 and 2.2 Ma, displays large variability, ranging between 0.5 ‰ and 2.0 ‰. We use the latitudinal δ18O gradient as a proxy for Leeuwin Current strength, with an inverse relationship between both. The new results challenge the interpretation that suggested a tectonic event in the Indonesian Throughflow as the cause for the rapid steepening of the isotopic gradient (0.9 ‰ to 1.5 ‰) around 3.7 Ma. The tectonic interpretation appears obsolete as it is now clear that the 3.7 Ma steepening of the isotopic gradient is intermittent, with flat latitudinal gradients (∼0.5 ‰) restored in the latest Pliocene (2.9–2.6 Ma). Still, the new analysis affirms that a combination of astronomical forcing of wind patterns and eustatic sea level controlled Leeuwin Current intensity. On secular timescales, a period of relatively weak Leeuwin Current is observed between 3.7 and 3.1 Ma. Notably, this interval is marked by cooler conditions throughout the Southern Hemisphere. In conclusion, the intensity of the Leeuwin Current and the latitudinal position of the subtropical front are both long-range effects of the same forcing: heat transport through the Indonesian Throughflow (ITF) valve and its propagation through Indian Ocean poleward heat transport. The common ITF forcing explains the observed coherence of Southern Hemisphere ocean and climate records.

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Quesnel, Benoît, Philippe Boulvais, Pierre Gautier, Michel Cathelineau, Cédric M. John, Malorie Dierick, Pierre Agrinier, and Maxime Drouillet. "Paired stable isotopes (O, C) and clumped isotope thermometry of magnesite and silica veins in the New Caledonia Peridotite Nappe." Geochimica et Cosmochimica Acta 183 (June 2016): 234–49. http://dx.doi.org/10.1016/j.gca.2016.03.021.

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Letulle, Thomas, Danièle Gaspard, Mathieu Daëron, Florent Arnaud-Godet, Arnauld Vinçon-Laugier, Guillaume Suan, and Christophe Lécuyer. "Multi-proxy assessment of brachiopod shell calcite as a potential archive of seawater temperature and oxygen isotope composition." Biogeosciences 20, no. 7 (April 12, 2023): 1381–403. http://dx.doi.org/10.5194/bg-20-1381-2023.

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Abstract. Most of our knowledge of past seawater temperature history is based on δ18O values of calcium carbonate fossil shells. However, the determination of past temperatures using this proxy requires the knowledge of past seawater δ18O values, which is generally poorly constrained. Other paleothermometers using carbonate archives, such as Mg/Ca ratios and clumped isotopes (Δ47), have been developed to allow for paleotemperatures to be estimated independently and to allow past ocean δ18O values to be calculated using various groups of calcifying organisms. Articulated brachiopod shells are some of the most commonly used archives in studies of past oceanic geochemistry and temperature. They are abundant in the fossil record since the Cambrian, and for decades, their low Mg–calcite mineralogy has been considered relatively resistant to diagenetic alteration. Here, we investigate the potential of brachiopod shells as recorders of seawater temperatures and seawater δ18O values using new brachiopod shell geochemical data by testing multiple well-established or suggested paleothermometers applied to carbonate archives. Modern articulated brachiopod shells covering a wide range of temperatures (−1.9 to 25.5 ∘C), depths (5 to 3431 m) and salinities (33.4 to 37.0 PSU) were analysed for their stable isotope compositions (δ13C, δ18O and Δ47) and their elemental ratios (Mg/Ca, Sr/Ca, Na/Ca and Li/Ca). Our data allowed us to propose a revised oxygen isotope fractionation equation between modern-brachiopod shell calcite and seawater: (1) T = - 5.0 ( ± 0.2 ) ( δ 18 O c - δ 18 O sw ) + 19.4 ( ± 0.4 ) , where δ18Oc is in ‰ VPDB, δ18Osw is in ‰ VSMOW, and T is in ∘C. Our results strongly support the use of clumped isotopes as an alternative temperature proxy but confirm significant offsets relative to the canonical relationship established for other biogenic and abiogenic calcium carbonate minerals. Brachiopod shell Mg/Ca ratios show no relationship with seawater temperatures, indicating that this ratio is a poor recorder of past changes in temperatures, an observation at variance with several previous studies. Despite significant correlations with brachiopod living temperature, brachiopod shell Sr/Ca, Na/Ca and Li/Ca values indicate the influence of environmental and biological factors unrelated to temperature, which undermines their potential as alternative temperature proxies. Kinetic effects (growth rates) could explain most of the deviation of brachiopod shell calcite from expected isotopic equilibrium with seawater and part of the distribution of Sr/Ca, Na/Ca and Li/Ca ratios.

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Van Plantinga, Alexander A., and Ethan L. Grossman. "Stable and clumped isotope sclerochronologies of mussels from the Brazos River, Texas (USA): Environmental and ecologic proxy." Chemical Geology 502 (December 2018): 55–65. http://dx.doi.org/10.1016/j.chemgeo.2018.10.012.

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Zhang, Hongrui, Chuanlian Liu, Luz María Mejía, and Heather Stoll. "Technical note: Accelerate coccolith size separation via repeated centrifugation." Biogeosciences 18, no. 5 (March 18, 2021): 1909–16. http://dx.doi.org/10.5194/bg-18-1909-2021.

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Abstract. Coccolithophores play a key role in the marine carbon cycle and ecosystem. The carbonate shells produced by coccolithophore, named as coccolith, could be well preserved in the marine sediment for millions of years and become an excellent archive for paleoclimate studies. The micro-filtering and sinking–decanting methods have been successfully designed for coccolith separation and promoted the development of geochemistry studies on coccolith, such as the stable isotopes and Sr / Ca ratio. However, these two methods are still not efficient enough for the sample-consuming methods. In this study, the trajectory of coccolith movement during a centrifugation process was calculated in theory and carefully tested by separations in practice. We offer a MATLAB code to estimate the appropriate parameter, angular velocity at a fixed centrifugation duration, for separating certain coccolith size fractions from bulk sediment. This work could improve the efficiency of coccolith separation, especially for the finest size fraction, and make it possible to carry out the clumped isotope and radio carbon analyses on coccoliths in sediment.

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Matera, Paola Francesca, Gennaro Ventruti, Martina Zucchi, Andrea Brogi, Enrico Capezzuoli, Domenico Liotta, Tsai-Luen Yu, et al. "Geothermal Fluid Variation Recorded by Banded Ca-Carbonate Veins in a Fault-Related, Fissure Ridge-Type Travertine Depositional System (Iano, southern Tuscany, Italy)." Geofluids 2021 (January 30, 2021): 1–28. http://dx.doi.org/10.1155/2021/8817487.

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Banded Ca-carbonate veins in travertine deposits are efficient recorders of the compositional fluctuations of geothermal fluids flowing (or flowed) from deep reservoirs up to the surface, within fault zones. In this view, these veins represent key tools for decoding those factors that influenced the geochemical variations. We have analyzed veins developed in fractures channeling geothermal fluids forming travertine deposits. The studied veins cut a fossil travertine fissure ridge, near the Larderello geothermal area (Iano area, southern Tuscany) where geothermal fluid circulation is favored by NE-trending strike-to-oblique-slip faults and their intersections with NW-trending normal ones. U-Th dating indicates that fluid circulation occurred from (at least) 172 ka to 21 ka. In this time span, the geothermal fluid changed in composition, and the banded Ca-carbonate veins recorded these variations in terms of mineralogical and stable isotope composition and temperature ( T ) of deposition. We also documented for the first time the occurrence of Mn-rich black tree-shaped structures within the veins. Mineralogy coupled with stable and clumped isotope measurements allows the reconstruction of some features (i.e., crystal texture, temperature, and CO2 origin) and the inference of the processes (i.e., pH, T, and pCO2 variations) that have controlled the fluid evolution through time. Multiple-stage and one-stage deposition processes have played an important role in modifying the stable isotope composition of banded Ca-carbonate veins; temperature coupled with pCO2 also influenced their mineralogical composition. Interpreted in the context of the tectonic setting, the data show that the NW-trending faults have mainly controlled travertine deposition. Their intersection with NE-trending faults, interpreted as transfer faults, highlights the important role of transfer zones in channeling the geothermal fluids.

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Al-Ramadan, Khalid, Ardiansyah Koeshidayatullah, Dave Cantrell, and Peter K. Swart. "Impact of basin architecture on diagenesis and dolomitization in a fault-bounded carbonate platform: outcrop analogue of a pre-salt carbonate reservoir, Red Sea rift, NW Saudi Arabia." Petroleum Geoscience 26, no. 3 (September 11, 2019): 448–61. http://dx.doi.org/10.1144/petgeo2018-125.

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The early Miocene Wadi Waqb carbonate in the Midyan Peninsula, NE Red Sea is of great interest not only because of its importance as an archive of one of the few pre-salt synrift carbonate platforms in the world, but also as a major hydrocarbon reservoir. Despite this importance, little is known about the diagenesis and heterogeneity of this succession. This study uses petrographical, elemental chemistry, stable isotope (δ13C and δ18O) and clumped isotope (Δ47) analyses to decipher the controlling processes behind the formation of various diagenetic products, especially dolomite, from two locations (Wadi Waqb and Ad-Dubaybah) that have experienced different diagenetic histories. Petrographically, the dolomites in both locations are similar, and characterized by euhedral to subhedral crystals (50–200 µm) and fabric-preserving dolomite textures. Clumped isotope analysis suggests that slightly elevated temperatures were recorded in the Ad-Dubaybah location (up to 49°C), whereas the Wadi Waqb location shows a sea-surface temperature of c. 30°C. These temperature differences, coupled with distinct δ18OVPDB values, can be used to infer the chemistry of the fluids involved in the dolomitization processes, with fluids at the Wadi Waqb location displaying much higher δ18OSMOW values (up to +4‰) compared to those at the Ad Dubaybah location (up to −3‰). Two different dolomitization models are proposed for the two sites: a seepage reflux, evaporative seawater mechanism at the Wadi Waqb location; and a fault-controlled, modified seawater mechanism at the Ad-Dubaybah location. At Ad-Dubaybah, seawater was modified through interaction with the immature basal sandstone aquifer, the Al-Wajh Formation. The spatial distribution of the dolostone bodies formed at these two locations also supports the models proposed here: with the Wadi Waqb location exhibiting massive dolostone bodies, while the dolostone bodies in the Ad-Dubaybah location are mostly clustered along the slope and platform margin. Porosity is highest in the slope sediments due to the interplay between higher precursor porosity, the grain size of the original limestone and dolomitization. Ultimately, this study provides insights into the prediction of carbonate diagenesis in an active tectonic basin and the resultant porosity distribution of a pre-salt carbonate reservoir system.

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Tyne, R. L., P. H. Barry, M. Lawson, D. J. Byrne, O. Warr, H. Xie, D. J. Hillegonds, et al. "Rapid microbial methanogenesis during CO2 storage in hydrocarbon reservoirs." Nature 600, no. 7890 (December 22, 2021): 670–74. http://dx.doi.org/10.1038/s41586-021-04153-3.

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AbstractCarbon capture and storage (CCS) is a key technology to mitigate the environmental impact of carbon dioxide (CO2) emissions. An understanding of the potential trapping and storage mechanisms is required to provide confidence in safe and secure CO2 geological sequestration1,2. Depleted hydrocarbon reservoirs have substantial CO2 storage potential1,3, and numerous hydrocarbon reservoirs have undergone CO2 injection as a means of enhanced oil recovery (CO2-EOR), providing an opportunity to evaluate the (bio)geochemical behaviour of injected carbon. Here we present noble gas, stable isotope, clumped isotope and gene-sequencing analyses from a CO2-EOR project in the Olla Field (Louisiana, USA). We show that microbial methanogenesis converted as much as 13–19% of the injected CO2 to methane (CH4) and up to an additional 74% of CO2 was dissolved in the groundwater. We calculate an in situ microbial methanogenesis rate from within a natural system of 73–109 millimoles of CH4 per cubic metre (standard temperature and pressure) per year for the Olla Field. Similar geochemical trends in both injected and natural CO2 fields suggest that microbial methanogenesis may be an important subsurface sink of CO2 globally. For CO2 sequestration sites within the environmental window for microbial methanogenesis, conversion to CH4 should be considered in site selection.

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Lüdecke, Tina, Ottmar Kullmer, Ulrike Wacker, Oliver Sandrock, Jens Fiebig, Friedemann Schrenk, and Andreas Mulch. "Dietary versatility of Early Pleistocene hominins." Proceedings of the National Academy of Sciences 115, no. 52 (December 10, 2018): 13330–35. http://dx.doi.org/10.1073/pnas.1809439115.

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New geochemical data from the Malawi Rift (Chiwondo Beds, Karonga Basin) fill a major spatial gap in our knowledge of hominin adaptations on a continental scale. Oxygen (δ18O), carbon (δ13C), and clumped (Δ47) isotope data on paleosols, hominins, and selected fauna elucidate an unexpected diversity in the Pleistocene hominin diet in the various habitats of the East African Rift System (EARS). Food sources of early Homo and Paranthropus thriving in relatively cool and wet wooded savanna ecosystems along the western shore of paleolake Malawi contained a large fraction of C3 plant material. Complementary water consumption reconstructions suggest that ca. 2.4 Ma, early Homo (Homo rudolfensis) and Paranthropus (Paranthropus boisei) remained rather stationary near freshwater sources along the lake margins. Time-equivalent Paranthropus aethiopicus from the Eastern Rift further north in the EARS consumed a higher fraction of C4 resources, an adaptation that grew more pronounced with increasing openness of the savanna setting after 2 Ma, while Homo maintained a high versatility. However, southern African Paranthropus robustus had, similar to the Malawi Rift individuals, C3-dominated feeding strategies throughout the Early Pleistocene. Collectively, the stable isotope and faunal data presented here document that early Homo and Paranthropus were dietary opportunists and able to cope with a wide range of paleohabitats, which clearly demonstrates their high behavioral flexibility in the African Early Pleistocene.

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Webb, Michael A., and Thomas F. Miller. "Position-Specific and Clumped Stable Isotope Studies: Comparison of the Urey and Path-Integral Approaches for Carbon Dioxide, Nitrous Oxide, Methane, and Propane." Journal of Physical Chemistry A 118, no. 2 (January 3, 2014): 467–74. http://dx.doi.org/10.1021/jp411134v.

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Dong, Jibao, John Eiler, Zhisheng An, Naiqin Wu, Weiguo Liu, Xiangzhong Li, Nami Kitchen, and Fengyan Lu. "Clumped and stable isotopes of land snail shells on the Chinese Loess Plateau and their climatic implications." Chemical Geology 533 (February 2020): 119414. http://dx.doi.org/10.1016/j.chemgeo.2019.119414.

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Wichern, Nina M. A., Niels J. de Winter, Andrew L. A. Johnson, Stijn Goolaerts, Frank Wesselingh, Maartje F. Hamers, Pim Kaskes, Philippe Claeys, and Martin Ziegler. "The fossil bivalve Angulus benedeni benedeni: a potential seasonally resolved stable-isotope-based climate archive to investigate Pliocene temperatures in the southern North Sea basin." Biogeosciences 20, no. 12 (June 21, 2023): 2317–45. http://dx.doi.org/10.5194/bg-20-2317-2023.

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Abstract. Bivalves record seasonal environmental changes in their shells, making them excellent climate archives. However, not every bivalve can be used for this end. The shells have to grow fast enough so that micrometre- to millimetre-sampling can resolve sub-annual changes. Here, we investigate whether the bivalve Angulus benedeni benedeni is suitable as a climate archive. For this, we use ca. 3-million-year-old specimens from the Piacenzian collected from a temporary outcrop in the Port of Antwerp area (Belgium). The subspecies is common in Pliocene North Sea basin deposits, but its lineage dates back to the late Oligocene and has therefore great potential as a high-resolution archive. A detailed assessment of the preservation of the shell material by micro-X-ray fluorescence, X-ray diffraction, and electron backscatter diffraction reveals that it is pristine and not affected by diagenetic processes. Oxygen isotope analysis and microscopy indicate that the species had a longevity of up to a decade or more and, importantly, that it grew fast and large enough so that seasonally resolved records across multiple years were obtainable from it. Clumped isotope analysis revealed a mean annual temperature of 13.5 ± 3.8 ∘C. The subspecies likely experienced slower growth during winter and thus may not have recorded temperatures year-round. This reconstructed mean annual temperature is 3.5 ∘C warmer than the pre-industrial North Sea and in line with proxy and modelling data for this stratigraphic interval, further solidifying A. benedeni benedeni's use as a climate recorder. Our exploratory study thus reveals that Angulus benedeni benedeni fossils are indeed excellent climate archives, holding the potential to provide insight into the seasonality of several major climate events of the past ∼ 25 million years in northwestern Europe.

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Zheng, Jianfeng, Yongjin Zhu, Lili Huang, Guo Yang, and Fangjie Hu. "Geochemical Characteristics and Their Geological Significance of Lower Cambrian Xiaoerblak Formation in Northwestern Tarim Basin, China." Minerals 12, no. 6 (June 20, 2022): 781. http://dx.doi.org/10.3390/min12060781.

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Lower Cambrian Xiaoerblak Formation is one of the major exploration targets in Cambrian pre-salt Tarim Basin; however, the exploration breakthrough is restricted by insufficient understanding of its sedimentary evolution and reservoir genesis. In this paper, based on a systematic description of the outcrop in the Xiaoerblak section, northwestern Tarim Basin, some samples were selected for tests of stable carbon and oxygen isotopic compositions, strontium isotopic composition, order degree, trace and rare earth elements, U-Pb isotopic age and clumped isotope. It is found that the Xiaoerblak Formation mainly develops nine types of dolomites, i.e., laminated microbial dolomite, thrombolite dolomite, stromatolite dolomite, foamy microbial dolomite, grain dolomite, etc. According to the lithofacies associations, it can be divided into three members: Xi 1, Xi 2, and Xi 3, of which member Xi 2 is subdivided into three submembers. The characteristics of lithofacies assemblage formed bottom to top indicate that it can be described as a third-order sequence. The Xiaoerblak Formation was deposited in a nearshore shallow seawater environment characterized by high water salinity and temperature under a warm and humid climate during the Early Cambrian, giving rise to the sedimentary sequence of inner ramp lagoon, subtidal microbial mound shoal and tidal flat in the carbonate ramp setting from bottom to top. Its dolomitization occurred in the penecontemporaneous–shallow burial period when the temperature was relatively low and high-salinity seawater acted as the main dolomitizaiton fluid. The reservoir space mainly comprises primary microbial framework pores and vugs formed by the atmospheric freshwater dissolution. Reservoirs were controlled by lithofacies, high-frequency sequence boundary and early dolomitization. The research results are of great significance for presalt Cambrian lithofacies paleogeographic mapping and reservoir prediction.

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Yang, Wei, Rusi Zuo, Xu Wang, Yan Song, Zhenxue Jiang, Qun Luo, Jixuan Zhai, Qianyou Wang, Chen Zhang, and Ziya Zhang. "Sensitivity of lacustrine stromatolites to Cenozoic tectonic and climatic forcing in the southern Junggar Basin, NW China: New insights from mineralogical, stable and clumped isotope compositions." Palaeogeography, Palaeoclimatology, Palaeoecology 514 (January 2019): 109–23. http://dx.doi.org/10.1016/j.palaeo.2018.10.011.

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Matthews, A., H. P. Affek, A. Ayalon, H. B. Vonhof, and M. Bar-Matthews. "Eastern Mediterranean climate change deduced from the Soreq Cave fluid inclusion stable isotopes and carbonate clumped isotopes record of the last 160 ka." Quaternary Science Reviews 272 (November 2021): 107223. http://dx.doi.org/10.1016/j.quascirev.2021.107223.

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DeFelipe, I., D. Pedreira, J. A. Pulgar, E. Iriarte, and M. Mendia. "Mantle exhumation and metamorphism in the Basque-Cantabrian Basin (NSpain): Stable and clumped isotope analysis in carbonates and comparison with ophicalcites in the North-Pyrenean Zone (Urdach and Lherz)." Geochemistry, Geophysics, Geosystems 18, no. 2 (February 2017): 631–52. http://dx.doi.org/10.1002/2016gc006690.

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Hudson, Adam M., Jay Quade, Guleed Ali, Douglas Boyle, Scott Bassett, Katharine W. Huntington, Marie G. De los Santos, Andrew S. Cohen, Ke Lin, and Xiangfeng Wang. "Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates." Geochimica et Cosmochimica Acta 212 (September 2017): 274–302. http://dx.doi.org/10.1016/j.gca.2017.06.024.

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Li, Lin, Majie Fan, Nathaniel Davila, Greg Jesmok, Bryce Mitsunaga, Aradhna Tripati, and Devon Orme. "Carbonate stable and clumped isotopic evidence for late Eocene moderate to high elevation of the east-central Tibetan Plateau and its geodynamic implications." GSA Bulletin 131, no. 5-6 (November 28, 2018): 831–44. http://dx.doi.org/10.1130/b32060.1.

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Bonde, Joshua W., Peter A. Druschke, Richard P. Hilton, Amy C. Henrici, and Stephen M. Rowland. "Preservation of latest Cretaceous (Maastrichtian)—Paleocene frogs (Eorubeta nevadensis) of the Sheep Pass Formation of east-central Nevada and implications for paleogeography of the Nevadaplano." PeerJ 8 (July 3, 2020): e9455. http://dx.doi.org/10.7717/peerj.9455.

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Here we report on exceptional preservation of remains of the frog Eorubeta nevadensis in deposits of the Sheep Pass Formation, ranging from Late Cretaceous to Eocene, in the south Egan Range, Nevada. This formation represents a lacustrine basin within the Sevier retroarc hinterland. The formation is subdivided into six members (A–F); of interest here are members B and C. The base of member B is ?uppermost Cretaceous-Paleocene, while member C is Paleocene. Member B frogs are preserved in three taphonomic modes. Mode 1 frogs are nearly complete and accumulated under attritional processes, with frogs settling on microbial mats, as evidenced by crenulated fabric of entombing limestone. Mode 2 involves accumulation of frogs as a result of attritional processes. These frogs are mostly complete with some showing evidence of invertebrate scavenging. Possible scavengers are gastropods, ostracods, and decapods. Mode 3 is represented by isolated, reworked remains of frogs as a result of storm activity, supported by the association of elements with disarticulated bivalves and mud rip-up clasts. Member C preserves frogs in two taphonomic modes. Mode 4 are nearly complete frogs that accumulated during discrete mass mortality events. Numerous individuals are preserved along bedding planes in identical preservational states. Mode 5 is beds of frog bone hash, which represent increased energy to the depositional system (likely tempestites) and reworking of previously buried frog remains. Taphonomy of the frogs, along with the associated fauna and flora, are consistent with preservation in a cool, temperate lake basin, supporting previous interpretations that the Nevadaplano was an elevated plateau during the late Cretaceous through the Eocene. This is a period of time coincident with a climatic thermal optimum, thus the most parsimonious explanation for a temperate lake at the latitude of east-central Nevada is to invoke high elevation, which is consistent with independent structural and clumped stable isotope studies.

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Wang, Xu, Linlin Cui, Jixuan Zhai, and Zhongli Ding. "Stable and clumped isotopes in shell carbonates of land snails Cathaica sp. and Bradybaena sp. in north China and implications for ecophysiological characteristics and paleoclimate studies." Geochemistry, Geophysics, Geosystems 17, no. 1 (January 2016): 219–31. http://dx.doi.org/10.1002/2015gc006182.

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Eiler, J. M. "‘Clumped’ isotope geochemistry." Geochimica et Cosmochimica Acta 70, no. 18 (August 2006): A156. http://dx.doi.org/10.1016/j.gca.2006.06.1379.

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Harper, Dustin T., Marina B. Suarez, Jessica Uglesich, Hailu You, Daqing Li, and Peter Dodson. "Aptian–Albian clumped isotopes from northwest China: cool temperatures, variable atmospheric pCO2 and regional shifts in the hydrologic cycle." Climate of the Past 17, no. 4 (August 3, 2021): 1607–25. http://dx.doi.org/10.5194/cp-17-1607-2021.

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Abstract. The Early Cretaceous is characterized by warm background temperatures (i.e., greenhouse climate) and carbon cycle perturbations that are often marked by ocean anoxic events (OAEs) and associated shifts in the hydrologic cycle. Higher-resolution records of terrestrial and marine δ13C and δ18O (both carbonates and organics) suggest climate shifts during the Aptian–Albian, including a warm period associated with OAE 1a in the early Aptian and a subsequent “cold snap” near the Aptian–Albian boundary prior to the Kilian and OAE 1b. Understanding the continental system is an important factor in determining the triggers and feedbacks to these events. Here, we present new paleosol carbonate stable isotopic (δ13C, δ18O and Δ47) and CALMAG weathering parameter results from the Xiagou and Zhonggou formations (part of the Xinminpu Group in the Yujingzi Basin of NW China) spanning the Aptian–Albian. Published mean annual air temperature (MAAT) records of the Barremian–Albian from Asia are relatively cool with respect to the Early Cretaceous. However, these records are largely based on coupled δ18O measurements of dinosaur apatite phosphate (δ18Op) and carbonate (δ18Ocarb) and therefore rely on estimates of meteoric water δ18O (δ18Omw) from δ18Op. Significant shifts in the hydrologic cycle likely influenced δ18Omw in the region, complicating these MAAT estimates. Thus, temperature records independent of δ18Omw (e.g., clumped isotopes or Δ47) are desirable and required to confirm temperatures estimated with δ18Op and δ18Oc and to reliably determine regional shifts in δ18Omw. Primary carbonate material was identified using traditional petrography, cathodoluminescence inspection, and δ13C and δ18O subsampling. Our preliminary Δ47-based temperature reconstructions (record mean of 14.9 ∘C), which we interpret as likely being representative of MAAT, match prior estimates from similar paleolatitudes of Asian MAAT (average ∼ 15 ∘C) across the Aptian–Albian. This, supported by our estimated mean atmospheric paleo-pCO2 concentration of 396 ppmv, indicates relatively cooler midlatitude terrestrial climate. Additionally, our coupled δ18O and Δ47 records suggest shifts in the regional hydrologic cycle (i.e., ΔMAP, mean annual precipitation, and Δδ18Omw) that may track Aptian–Albian climate perturbations (i.e., a drying of Asian continental climate associated with the cool interval).

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Holdsworth, Chris, John MacDonald, and Cedric John. "Non-Linear Clumped Isotopes from DIC Endmember Mixing and Kinetic Isotope Fractionation in High pH Anthropogenic Tufa." Minerals 12, no. 12 (December 14, 2022): 1611. http://dx.doi.org/10.3390/min12121611.

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Clumped isotope values (Δ47) of carbonates forming in high pH conditions do not correspond to mineral precipitation temperatures due to certain effects including kinetic isotope fractionation and dissolved inorganic carbon (DIC) endmember mixing. Field-based archives of these carbonate environments are needed to evaluate and quantity these effects accurately. In this study, we measure the clumped isotope values of anthropogenic carbonates for the first time. Tufa layers were analyzed from samples precipitating in a high pH (>10) stream that drains a major slag heap in north east England. Δ47 values are 0.044‰–0.183‰ higher than expected equilibrium values. Non-linear distribution of clumped isotope data is diagnostic of DIC endmember mixing, rather than partial equilibration of DIC. Episodic dilution of hydroxide-rich stream waters by equilibrated rainfall surface runoff provides the mechanism by which mixing occurs. Δ47 values are ~0.010‰–0.145‰ higher than linear clumped isotope mixing profiles, suggesting that the majority of Δ47 increase results from a combination of endmember non-linear mixing effects and an atmosphere-hydroxide sourcing of DIC. The diagnostic trends and variation in clumped isotope values present in these results demonstrates the potential of anthropogenic carbonate systems as a useful archive for studying and quantifying kinetic effects in clumped isotopes.

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Affek, Hagit P. "Clumped Isotope Paleothermometry: Principles, Applications, and Challenges." Paleontological Society Papers 18 (November 2012): 101–14. http://dx.doi.org/10.1017/s1089332600002576.

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Clumped isotopes geochemistry measures the thermodynamic preference of two heavy, rare, isotopes to bind with each other. This preference is temperature dependent, and is more pronounced at low temperatures. Carbonate clumped isotope values are independent of the carbonate δ13C and δ18O, making them independent of the carbon or oxygen composition of the solution from which the carbonate precipitated. At equilibrium, it is therefore a direct proxy for the temperature in which the carbonate mineral formed. In most cases, carbonate clumped isotopes record the temperature of carbonate formation, irrespective of the mineral form (calcite, aragonite, or bioapatite) or the organism making it. The carbonate formation temperatures obtained from carbonate clumped isotope analysis can be used in conjunction with the δ18O of the same carbonate, to constrain the oxygen isotope composition of the water from which the carbonate has precipitated. There are, however, cases of deviation from thermodynamic equilibrium, where both clumped and oxygen isotopes are offset from the expected values. Such carbonates must be characterized and calibrated separately. For deep-time applications, special care must be paid to the preservation of the original signal, in particular with respect to diagenetic alteration associated with atomic scale diffusion that may be undetectable by common tests for diagenesis.

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Winkelstern, Ian Z., Stephen E. Kaczmarek, Kyger C. Lohmann, and John D. Humphrey. "Calibration of dolomite clumped isotope thermometry." Chemical Geology 443 (December 2016): 32–38. http://dx.doi.org/10.1016/j.chemgeo.2016.09.021.

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Herlambang, Adhipa, Cédric M. John, and Henrik Drake. "Physicochemical Conditions of the Devonian-Jurassic Continental Deep Biosphere Tracked by Carbonate Clumped Isotope Temperatures of Granite-Hosted Carbonate Veins." Geofluids 2023 (March 15, 2023): 1–10. http://dx.doi.org/10.1155/2023/8445328.

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Previous studies have shown that microorganisms thrive in oligotrophic fracture systems, and metabolisms include consumption and production of methane. In the Laxemar, Götemar, and Forsmark areas of Sweden, ancient microbial activity has previously been demonstrated by large δ13CVPDB variability of carbonate vein infillings within granitic host rocks. Here, we apply carbonate clumped isotope thermometry to reconstruct the temperature of precipitation of the carbonate within these veins. The carbonate clumped isotope temperatures indicate that mineralization took place between 46°C and 108°C, in line with previously published fluid inclusion data (<50°C to 113°C). The new carbonate clumped isotope data more accurately narrows temperatures at the lower end of this range as fluid inclusions are not easily applicable below 80°C, a temperature regime of high importance for paleobiological reconstructions. Our results demonstrate that large volumes of biogenic carbonate cement were formed from low-temperature microbial processes in low-salinity water, succeeding calcite of deep brine origin. The known burial and thermal history of the region combined with our carbonate clumped isotope data place the microbial activity at the end of the Variscan orogeny and later events (e.g., Jurassic). Thus, carbonate clumped isotope thermometry reduces uncertainties in deep biosphere studies by providing more accurate temperature constraints in the low-temperature regime, the biogenic processes, and the origin of the diagenetic fluids.

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Mering, John A., Shaun L. L. Barker, Katharine W. Huntington, Stuart Simmons, Gregory Dipple, Benjamin Andrew, and Andrew Schauer. "Taking the Temperature of Hydrothermal Ore Deposits Using Clumped Isotope Thermometry." Economic Geology 113, no. 8 (December 1, 2018): 1671–78. http://dx.doi.org/10.5382/econgeo.2018.4608.

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Abstract Better tools are needed to map the thermal structure of ore deposits. Here, carbonate clumped isotope thermometry is applied for the first time in epithermal, skarn, and carbonate-hosted deposits to identify the conditions involved in metal transport and deposition. Clumped isotope temperature calibrations were tested by measurement of carbonates from three geothermal fields in the Taupo volcanic zone, New Zealand, that record growth temperatures between 130° and 310°C. Results for modern Taupo volcanic zone calcites were paired with known fluid δ18O values and these indicate precipitation in equilibrium with produced geothermal waters. Measurements carried out at the Waihi low sulfidation deposit in New Zealand, the Antamina polymetallic skarn in Peru, and the Mount Isa sediment hosted Pb-Zn and Cu deposit in Queensland, Australia, demonstrate that clumped isotope values are sensitive to temperature gradients defined using other methods. At Waihi, an andesite-hosted deposit, temperature controls the majority of variation in carbonate mineral δ18O. At Mount Isa, ~300° to 400°C temperatures were recorded in a 1.5 Ga orebody, which are consistent with fluid inclusion values, highlighting the longevity of clumped isotope archives in dolomite minerals. Collectively, these results demonstrate the potential for clumped isotopes to delineate the heat footprint around deposits that contain carbonates, and to more effectively disentangle magmatic and meteoric fluid δ18O signals.

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Wang, D. T., D. S. Gruen, B. S. Lollar, K. U. Hinrichs, L. C. Stewart, J. F. Holden, A. N. Hristov, et al. "Nonequilibrium clumped isotope signals in microbial methane." Science 348, no. 6233 (March 5, 2015): 428–31. http://dx.doi.org/10.1126/science.aaa4326.

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Eiler, John M. "Paleoclimate reconstruction using carbonate clumped isotope thermometry." Quaternary Science Reviews 30, no. 25-26 (December 2011): 3575–88. http://dx.doi.org/10.1016/j.quascirev.2011.09.001.

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Eiler, J. M. "A practical guide to clumped isotope geochemistry." Geochimica et Cosmochimica Acta 70, no. 18 (August 2006): A157. http://dx.doi.org/10.1016/j.gca.2006.06.1380.

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Came, Rosemarie E., Uwe Brand, and Hagit P. Affek. "Clumped isotope signatures in modern brachiopod carbonate." Chemical Geology 377 (June 2014): 20–30. http://dx.doi.org/10.1016/j.chemgeo.2014.04.004.

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Huntington, Katharine W., and Alex R. Lechler. "Carbonate clumped isotope thermometry in continental tectonics." Tectonophysics 647-648 (April 2015): 1–20. http://dx.doi.org/10.1016/j.tecto.2015.02.019.

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Passey, Benjamin H., and Gregory A. Henkes. "Carbonate clumped isotope bond reordering and geospeedometry." Earth and Planetary Science Letters 351-352 (October 2012): 223–36. http://dx.doi.org/10.1016/j.epsl.2012.07.021.

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Kluge, Tobias, Hagit P. Affek, Yi Ge Zhang, Yuri Dublyansky, Christoph Spötl, Adrian Immenhauser, and Detlev K. Richter. "Clumped isotope thermometry of cryogenic cave carbonates." Geochimica et Cosmochimica Acta 126 (February 2014): 541–54. http://dx.doi.org/10.1016/j.gca.2013.11.011.

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Davies, Amelia J., and Cédric M. John. "The clumped (13C18O) isotope composition of echinoid calcite: Further evidence for “vital effects” in the clumped isotope proxy." Geochimica et Cosmochimica Acta 245 (January 2019): 172–89. http://dx.doi.org/10.1016/j.gca.2018.07.038.

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Jautzy, Josué J., Martine M. Savard, Denis Lavoie, Omid H. Ardakani, Ryan S. Dhillon, William F. Defliese, and Ariane Castagner. "Clumped isotope geothermometry of an Ordovician carbonate mound, Hudson Bay Basin." Journal of the Geological Society 178, no. 1 (September 15, 2020): jgs2020–102. http://dx.doi.org/10.1144/jgs2020-102.

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The Hudson Bay sedimentary basin was overlooked geologically until two decades ago. Recent efforts to understand the palaeogeothermal history of this basin have led to the evaluation of fluid inclusion microthermometry, apatite fission track, organic matter reflectance and Rock–Eval analyses. Although apatite fission track and organic maturity indicators tend to show relatively low maximum burial temperatures (60–80°C), evidence of potential oil slicks on the sea surface and oil and gas shows in offshore wells have been reported across Hudson Bay. Fluid inclusion microthermometry in a carbonate mound sequence suggests homogenization temperatures of 118 ± 25 and 93 ± 10°C for recrystallized synsedimentary marine calcite and late pore-filling burial calcite, respectively. This sequence provides an interesting geological framework to test the application of clumped isotope thermometry against independent geothermometers. Here, we present clumped isotope data acquired on the late calcite cements and diagenetically altered early marine phases. The integration of clumped isotopic data with other thermal indicators allows the reconstruction and refinement of the thermal–diagenetic history of these carbonates by confirming an episode of heating, probably of hydrothermal origin and prior to normal burial diagenesis, that reset both fluid inclusions and the clumped isotope indicators without recrystallization.

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Kimball, Justine, Robert Eagle, and Robert Dunbar. "Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals." Biogeosciences 13, no. 23 (December 12, 2016): 6487–505. http://dx.doi.org/10.5194/bg-13-6487-2016.

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Abstract. Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures, and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

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Journal articles on the topic 'Stable and clumped isotope'

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