scholarly journals Technical Note: A simple method for vaterite precipitation for isotopic studies: implications for bulk and clumped isotope analysis

2015 ◽  
Vol 12 (11) ◽  
pp. 3289-3299 ◽  
Author(s):  
T. Kluge ◽  
C. M. John

Abstract. Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as an additive in food, chemicals and medical products. Anhydrous CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on the characterization of vaterite under equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~0.007 mol L−1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.4 mol L−1). Vaterite precipitated as single phase or major phase (≥94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield per experiment of up to 235 mg relative to the initially dissolved CaCO3 amount of on average 360 mg enables an investigation of the oxygen isotope fractionation between the mineral and water, and the determination of clumped isotope values in vaterite.

2014 ◽  
Vol 11 (12) ◽  
pp. 17361-17390 ◽  
Author(s):  
T. Kluge ◽  
C. M. John

Abstract. Calcium carbonate (CaCO3) plays an important role in the natural environment as a major constituent of the skeleton and supporting structure of marine life and has high economic importance as additive in food, chemicals and medical products. Pure CaCO3 occurs in the three different polymorphs calcite, aragonite and vaterite, whereof calcite is the most abundant and best characterized mineral. In contrast, little is known about the rare polymorph vaterite, in particular with regard to the oxygen isotope fractionation between H2O and the mineral. Synthetic precipitation of vaterite in the laboratory typically involves rapid processes and isotopic non-equilibrium, which excludes isotope studies focused on characterization of vaterite at equilibrium conditions. Here, we used a new experimental approach that enables vaterite mineral formation from an isotopically equilibrated solution. The solution consists of a ~ 0.007 mol L-1 CaCO3 solution that is saturated with NaCl at room temperature (up to 6.5 mol L-1). Vaterite precipitated as single phase or major phase (≥ 94%) in experiments performed between 23 and 91 °C. Only at 80 °C was vaterite a minor phase with a relative abundance of 27%. The high mineral yield of up to 235 mg relative to a total dissolved CaCO3 amount of 370 mg enables an investigation of the oxygen isotope fractionation between mineral and water, and the determination of clumped isotope values in vaterite.


2020 ◽  
Author(s):  
Madeleine Vickers ◽  
Stefano Bernasconi ◽  
Clemens Ullmann ◽  
Stephen Hesselbo ◽  
Gregory Price ◽  
...  

<p>Belemnite calcite has been used extensively for Jurassic and Cretaceous stable oxygen isotope temperature reconstructions since the 1950s. However, with the advent of clumped isotope thermometry, a consistent offset between reconstructed δ<sup>18</sup>O temperatures vs Δ<sub>47</sub> temperatures from the same belemnites has been observed. We investigate the causes of this offset by analyzing samples from the aragonitic phragmacone and calcitic rostrum from the same Cylindroteuthis belemnites, along with other aragonitic benthos, from the Callovian-aged Christian Malford Lagerstätte, U.K. Our new clumped isotope data suggest that the water-calcite <sup>18</sup>O-fractionation factor in belemnite calcite was larger than that of the commonly used δ<sup>18</sup>O thermometry equations (e.g. Kim and O’Neil, 1997), and which is currently observed in other marine calcifiers. Our reconstructions suggest that the oxygen isotope fractionation is compatible with that observed in slow-forming abiotic calcites (e.g. Coplen, 2007) and in rapidly precipitating Travertines (Kele et al. 2015). The application of more established δ<sup>18</sup>O thermometry equations (Kim and O’Neil, 1997) to belemnite calcite for temperature reconstructions has resulted in a consistent underestimation of belemnite calcification temperatures, which has led to erroneous conclusions about belemnite life habits, and underestimation of global temperatures during these greenhouse times. We therefore advocate the use of calcite equations based on low precipitation rate experiments (e.g. Coplen, 2007; Kele et al., 2015) for belemnite rostra temperature reconstructions.</p>


Science ◽  
1970 ◽  
Vol 167 (3918) ◽  
pp. 536-538 ◽  
Author(s):  
N. Onuma ◽  
R. N. Clayton ◽  
T. K. Mayeda

2016 ◽  
Vol 13 (4) ◽  
pp. 1129-1144 ◽  
Author(s):  
Dominika Lewicka-Szczebak ◽  
Jens Dyckmans ◽  
Jan Kaiser ◽  
Alina Marca ◽  
Jürgen Augustin ◽  
...  

Abstract. The isotopic composition of soil-derived N2O can help differentiate between N2O production pathways and estimate the fraction of N2O reduced to N2. Until now, δ18O of N2O has been rarely used in the interpretation of N2O isotopic signatures because of the rather complex oxygen isotope fractionations during N2O production by denitrification. The latter process involves nitrate reduction mediated through the following three enzymes: nitrate reductase (NAR), nitrite reductase (NIR) and nitric oxide reductase (NOR). Each step removes one oxygen atom as water (H2O), which gives rise to a branching isotope effect. Moreover, denitrification intermediates may partially or fully exchange oxygen isotopes with ambient water, which is associated with an exchange isotope effect. The main objective of this study was to decipher the mechanism of oxygen isotope fractionation during N2O production by soil denitrification and, in particular, to investigate the relationship between the extent of oxygen isotope exchange with soil water and the δ18O values of the produced N2O. In our soil incubation experiments Δ17O isotope tracing was applied for the first time to simultaneously determine the extent of oxygen isotope exchange and any associated oxygen isotope effect. We found that N2O formation in static anoxic incubation experiments was typically associated with oxygen isotope exchange close to 100 % and a stable difference between the 18O ∕ 16O ratio of soil water and the N2O product of δ18O(N2O ∕ H2O)  =  (17.5 ± 1.2) ‰. However, flow-through experiments gave lower oxygen isotope exchange down to 56 % and a higher δ18O(N2O ∕ H2O) of up to 37 ‰. The extent of isotope exchange and δ18O(N2O ∕ H2O) showed a significant correlation (R2 = 0.70, p <  0.00001). We hypothesize that this observation was due to the contribution of N2O from another production process, most probably fungal denitrification. An oxygen isotope fractionation model was used to test various scenarios with different magnitudes of branching isotope effects at different steps in the reduction process. The results suggest that during denitrification, isotope exchange occurs prior to isotope branching and that this exchange is mostly associated with the enzymatic nitrite reduction mediated by NIR. For bacterial denitrification, the branching isotope effect can be surprisingly low, about (0.0 ± 0.9) ‰, in contrast to fungal denitrification where higher values of up to 30 ‰ have been reported previously. This suggests that δ18O might be used as a tracer for differentiation between bacterial and fungal denitrification, due to their different magnitudes of branching isotope effects.


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