scholarly journals Oxygen isotope composition of waters recorded in carbonates in strong clumped and oxygen isotopic disequilibrium

2019 ◽  
Author(s):  
Caroline Thaler ◽  
Amandine Katz ◽  
Magali Bonifacie ◽  
Bénédicte Ménez ◽  
Magali Ader
Keyword(s):  
Oxygen Isotope ◽  
Isotope Composition ◽  
Isotopic Equilibrium ◽  
Oxygen Isotopic ◽  
Vital Effects ◽  
Biogenic Carbonates ◽  
Clumped Isotope ◽  
Interstitial Waters ◽  
Isotopic Disequilibrium ◽  
Paleoenvironmental Reconstructions

Abstract. Paleoenvironmental reconstructions, which are mainly retrieved from oxygen isotope (δ18O) and clumped isotope (Δ47) compositions of carbonate minerals, are compromised when carbonate crystallization occurs in isotopic disequilibrium. To date, knowledge of these common isotopic disequilibria, known as vital effects in biogenic carbonates, remains limited and the potential information recorded by δ18O and Δ47 offsets from isotopic equilibrium values is largely overlooked. Additionally, in carbonates formed in isotopic equilibrium, the use of the carbonate δ18O signature as a paleothermometer relies on our knowledge of the paleowaters' δ18O value, which is often assumed. Here, we report the largest Δ47 offsets observed to date (as much as −0.270 ‰), measured on microbial carbonates, that are strongly linked to carbonate δ18O offsets (−25 ‰) from equilibrium. These offsets are likely both related to the microorganism metabolic activity and yield identical erroneous temperature reconstructions. Unexpectedly, we show that the δ18O value of the water in which carbonates precipitated, as well as the water-carbonate δ18O fractionation dependence to temperature at equilibrium can be retrieved from these paired δ18O and Δ47 disequilibrium values measured in carbonates. The possibility to retrieve the δ18O value of paleowaters, sediments' interstitial waters or organisms' body water at the carbonate precipitation loci, even from carbonates formed in isotopic disequilibrium, opens long-awaited research avenues for both paleoenvironmental reconstructions and biomineralization studies.

scholarly journals Oxygen isotope composition of waters recorded in carbonates in strong clumped and oxygen isotopic disequilibrium

2020 ◽  
Vol 17 (7) ◽  
pp. 1731-1744 ◽  
Author(s):  
Caroline Thaler ◽  
Amandine Katz ◽  
Magali Bonifacie ◽  
Bénédicte Ménez ◽  
Magali Ader
Keyword(s):  
Oxygen Isotope ◽  
Isotope Composition ◽  
Carbonate Precipitation ◽  
Isotopic Equilibrium ◽  
Oxygen Isotopic ◽  
Vital Effects ◽  
Biogenic Carbonates ◽  
Clumped Isotope ◽  
Isotopic Disequilibrium ◽  
Paleoenvironmental Reconstructions

Abstract. Paleoenvironmental reconstructions, which are mainly retrieved from oxygen isotope (δ18O) and clumped isotope (Δ47) compositions of carbonate minerals, are compromised when carbonate precipitation occurs in isotopic disequilibrium. To date, knowledge of these common isotopic disequilibria, known as vital effects in biogenic carbonates, remains limited, and the potential information recorded by δ18O and Δ47 offsets from isotopic equilibrium values is largely overlooked. Additionally, in carbonates formed in isotopic equilibrium, the use of the carbonate δ18O signature as a paleothermometer relies on our knowledge of the paleowaters' δ18O value, which is often assumed. Here, we report the largest Δ47 offsets observed to date (as much as −0.270 ‰), measured on microbial carbonates that are strongly linked to carbonate δ18O offsets (−25 ‰) from equilibrium. These offsets are likely both related to the microorganism metabolic activity and yield identical erroneous temperature reconstructions. Unexpectedly, we show that the δ18O value of the water in which carbonates precipitated, as well as the water–carbonate δ18O fractionation dependence on temperature at equilibrium, can be retrieved from these paired δ18O and Δ47 disequilibrium values measured in carbonates. The possibility to retrieve the δ18O value of paleowaters, sediments' interstitial waters or organisms' body water at the carbonate precipitation loci, even from carbonates formed in isotopic disequilibrium, opens long-awaited research avenues for both paleoenvironmental reconstructions and biomineralization studies.

scholarly journals Advances and Challenges in Palaeoenvironmental Studies Based on Oxygen Isotope Composition of Skeletal Carbonates and Phosphates

Geosciences ◽  
2021 ◽  
Vol 11 (10) ◽  
pp. 419
Author(s):  
Hubert Wierzbowski
Keyword(s):  
Oxygen Isotope ◽  
Oxygen Isotopes ◽  
Isotope Composition ◽  
Sedimentary Basins ◽  
Sea Level Changes ◽  
Temperature Trends ◽  
Isotope Record ◽  
Vital Effects ◽  
Reliable Temperature ◽  
Clumped Isotope

Oxygen isotopes are widely used in palaeoenvironmental and palaeoclimatic studies as they record variations in the precipitation temperature of biogenic carbonates and phosphates. Problems associated with the preservation state of fossils, selection of the proper temperature equation, vital effects occurring during biomineralization, habitat effects of organisms as well as salinity, bathymetry and water circulation changes limit, however, the applicability of oxygen isotopes to reconstruction of ancient environmental settings. The progress of oxygen isotope studies, temperature calculations and ambiguities of the isotope record are discussed in this paper. The same applies to the methods of retrieving reliable temperature signals and the record of water chemistry changes based on well-preserved calcareous and phosphatic fossils. Sometimes neglected importance of sedimentological and faunistic data associated with sea-level changes and salinity variations is emphasised as an important tool for refinement of the temperature trends of epeiric sedimentary basins. In addition, published case datasets and new laboratory techniques, including micro-area and clumped isotope analyses, are presented to demonstrate examples and prospective ways of extension of the scope of palaeoenvironmental research. The provided information may be used in discussion and a critical review of published oxygen isotope data and their palaeoenvironmental interpretations.

scholarly journals Oxygen isotope equilibrium in brachiopod shell fibres in the context of biological control

2008 ◽  
Vol 72 (1) ◽  
pp. 239-242 ◽  
Author(s):  
M. Cusack ◽  
A. Pérez-Huerta ◽  
P. Chung ◽  
D. Parkinson ◽  
Y. Dauphin ◽  
...  
Keyword(s):  
Oxygen Isotope ◽  
Isotope Composition ◽  
Seawater Temperature ◽  
Environmental Data ◽  
Ambient Seawater ◽  
Secondary Layer ◽  
Vital Effect ◽  
Vital Effects ◽  
Stable Oxygen ◽  
Isotope Equilibrium

With their long geological history and stable low-Mg calcite shells, Rhynchonelliform brachiopods are attractive sources of environmental data such as past seawater temperature (Buening and Spero, 1996; Auclair et al., 2003; Brand et al., 2003; Parkinson et al., 2005). Concerns about the influence of vital effects on the stable isotope composition of brachiopod shells (Popp et al., 1986), led to isotope analyses of different parts of brachiopod shells in order to identify those parts of the shell that are influenced by any vital effect and those parts that may be suitable recorders of seawater temperature via stable oxygen isotope composition (Carpenter and Lohmann, 1995; Parkinson et al., 2005). Such detailed studies demonstrated that the outer primary layer of acicularcalcite is isotopically light in both δ18O and δ13C while the secondary layer, composed of calcite fibres, is in oxygen-isotope equilibrium with ambient seawater(Fig. 1) (Parkinson et al., 2005).

No ion is an island: Multiple ions involved during boron incorporation into CaCO3

2021 ◽  
Author(s):  
Michael Henehan ◽  
Christa Klein-Gebbinck ◽  
Gavin Foster ◽  
Jill Wyman ◽  
Mathis Hain ◽  
...  
Keyword(s):  
Calcium Carbonate ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Boron Isotope ◽  
Minor Role ◽  
Growth Mechanisms ◽  
Minor Elements ◽  
Vital Effects ◽  
Biogenic Carbonates ◽  
Trace And Minor Elements

<p>Boron isotope ratios, as measured in marine calcium carbonate, are a proven tracer of past seawater and calcifying fluid pH and thus a powerful tool for the reconstruction of past atmospheric CO<sub>2</sub> and monitoring of coral physiology. For such applications, understanding the inorganic baseline upon which foraminiferal vital effects or coral pH upregulation are superimposed should be an important prerequisite. Yet, investigations into boron isotope fractionation in synthetic CaCO<sub>3 </sub>polymorphs have often reported variable and even conflicting results, implying that we may not fully understand pathways of boron incorporation into calcium carbonate.  Here we address this topic with experimental data from calcite and aragonite precipitated across a range of pH in the presence of both Mg and Ca. We confirm the results of previous studies that the boron isotope composition of inorganic aragonite precipitates closely reflects that of aqueous borate ion, but that calcites display a higher degree of scatter, and diverge from the boron isotope composition of borate ion at low pH. We discuss these findings with reference to the simultaneous incorporation of other trace and minor elements, and highlight a number of mechanisms by which crystal growth mechanisms may influence the concentration and isotope composition of boron in CaCO<sub>3</sub>. In particular, we highlight the potential importance of surface electrostatics in driving variability in published synthetic carbonate datasets. Importantly for palaeo-reconstruction, however, these electrostatic effects are likely to play a much more minor role during natural precipitation of biogenic carbonates.</p>

scholarly journals Oxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem

2018 ◽  
Vol 115 (26) ◽  
pp. 6602-6607 ◽  
Author(s):  
Uri Ryb ◽  
John M. Eiler
Keyword(s):  
Oxygen Isotope ◽  
Isotope Exchange ◽  
Isotope Composition ◽  
Temporal Variations ◽  
Oxygen Isotope Exchange ◽  
Diagenetic Alteration ◽  
Isotope Studies ◽  
Dolomite Problem ◽  
Clumped Isotope

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.

scholarly journals Identifying vital effects in <i>Halimeda</i> algae with Ca isotopes

2014 ◽  
Vol 11 (24) ◽  
pp. 7207-7217 ◽  
Author(s):  
C. L. Blättler ◽  
S. M. Stanley ◽  
G. M. Henderson ◽  
H. C. Jenkyns
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Test Organism ◽  
Isotope Ratios ◽  
First Order ◽  
Geological Past ◽  
Rayleigh Distillation ◽  
Vital Effects ◽  
Specific Factors ◽  
Biogenic Carbonates

Abstract. Geochemical records of biogenic carbonates provide some of the most valuable records of the geological past, but are often difficult to interpret without a mechanistic understanding of growth processes. In this experimental study, Halimeda algae are used as a test organism to untangle some of the specific factors that influence their skeletal composition, in particular their Ca-isotope composition. Algae were stimulated to precipitate both calcite and aragonite by growth in artificial Cretaceous seawater, resulting in experimental samples with somewhat malformed skeletons. The Ca-isotope fractionation of the algal calcite (−0.6‰) appears to be much smaller than that for the algal aragonite (−1.4‰), similar to the behaviour observed in inorganic precipitates. However, the carbonate from Halimeda has higher Ca-isotope ratios than inorganic forms by approximately 0.25‰, likely because of Rayleigh distillation within the algal intercellular space. In identifying specific vital effects and the magnitude of their influence on Ca-isotope ratios, this study suggests that mineralogy has a first-order control on the marine Ca-isotope cycle.

Solution to an enigma: Explaining the slope of carbon vs. oxygen isotopic disequilibrium in biogenic and inorganic carbonates

2020 ◽  
Author(s):  
Richard Zeebe ◽  
Lauren Yumol ◽  
Joji Uchikawa
Keyword(s):  
Oxygen Isotopes ◽  
Underlying Mechanism ◽  
Ph Control ◽  
Solution Ph ◽  
Fractionation Factor ◽  
Oxygen Isotopic ◽  
Vital Effects ◽  
Widespread Phenomenon ◽  
Kinetic Effects ◽  
Isotopic Disequilibrium

&lt;p&gt;A widespread phenomenon in biogenic and inorganic carbonates that are formed out of isotopic equilibrium is a nearly ubiquitous co-variation (slope) of carbon vs. oxygen isotopes, in e.g., speleothem and cryogenic carbonates, shells and skeletons of foraminifera, corals etc. For proxy calibrations, it is critical to understand such isotope variations (often labeled kinetic or vital effects) in proxies widely used for paleo-reconstructions. Given that this phenomenon is observed in inorganic carbonates and biogenic carbonates across different phyla suggest a common underlying mechanism, possibly independent of biological controls, that is, likely of inorganic origin. Here we present results from laboratory experiments on synthetic carbonate precipitation to constrain the kinetic isotope fractionation factor (KFF) of carbon and oxygen during CO2 hydration. We used an experimental setup similar to that of an earlier study but with important modifications and tight temperature and pH control. The average d13C and d18O values of our carbonate samples (BaCO3) produced at 25 deg C and pH = 8.0 (NBS) are -29.7 +- 0.71 per mil (VPDB) and 18.8 +- 0.56 per mil (VSMOW), respectively. From the isotope data, we calculate our experimental 13KFF and 18KFF, which refer to the 13C/12C and 18O/16O fractionation between CO2(g) and BaCO3, where the d13C and d18O values of CO2(g) were calculated using known equilibrium fractionation factors. Our results show that our KFFs are the largest values compared to previously reported experimental KFFs (except for one study), suggesting that our values are closest to the full isotopic disequilibrium during CO2 hydration. Based on our KFFs, we will present the expected slope of carbon vs. oxygen isotopic disequilibrium from kinetic effects during CO2 hydration. We will also discuss the expected slope from equilibrium effects of solution pH on oxygen isotopes. Comparison with field and culture data will reveal the origin of the slope of carbon vs. oxygen isotopic disequilibrium in biogenic and inorganic carbonates.&lt;/p&gt;

Relationship between δ18O and minor element composition of Terebratalia transversa

2007 ◽  
Vol 98 (3-4) ◽  
pp. 443-449 ◽  
Author(s):  
Maggie Cusack ◽  
David Parkinson ◽  
Alberto Pérez-Huerta ◽  
Jennifer England ◽  
Gordon B. Curry ◽  
...  
Keyword(s):  
Oxygen Isotope ◽  
Isotope Composition ◽  
Seawater Temperature ◽  
Minor Element ◽  
Oxygen Isotope Composition ◽  
Secondary Layer ◽  
Vital Effects ◽  
Stable Oxygen ◽  
Temperature Proxy ◽  
Isotope Equilibrium

ABSTRACTWith their extensive fossil record and shells of stable low-Mg calcite, rhynchonelliform brachiopods are attractive sources of climate information via seawater temperature proxies such as stable oxygen isotope composition. In Terebratalia transversa (Sowerby) there is a progression towards oxygen isotope equilibrium in the calcite of the innermost secondary layer. This study confirms the lack of any vital effects influencing oxygen isotope composition of T. transversa, even in specialised areas of the innermost secondary layer. Calcite Mg/Ca ratio is another potential seawater temperature proxy, that has the advantage of not being influenced by salinity. Mg concentrations measured by electron microprobe analyses indicate that there is no concomitant decrease in Mg concentration towards the inner secondary layer, associated with the progressive shift towards oxygen isotope equilibrium. Mg distribution is heterogeneous throughout the shell and correlates with that of sulphur, which may be a proxy for organic components, suggesting that some of the Mg may not be in the calcite lattice. It is essential therefore, to determine the chemical environment of the magnesium ions to avoid any erroneous temperature extrapolations in brachiopods or any other calcite biomineral.

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