Calcium isotopes in deep time: Potential and limitations

Calcium is an essential element in the biogeochemical cycles that regulate the long-term climate state of Earth. The removal of CO2 from the ocean-atmosphere system is controlled by the burial of carbonate sediments (CaCO3), ultimately linking the global calcium and carbon cycles. This fundamental link has driven the development of the stable calcium isotope proxy with applica-tion to both ancient skeletal and non-skeletal bulk carbonate sediments. Calcium isotope ratios (44/40Ca) have been used to track long-term changes in seawater chemistry (e.g., aragonite vs. calcite seas) and to elucidate short-term climatic perturbations associated with mass extinction events. However, developments in the calcium isotope proxy have shown that 44/40Ca values in carbonate minerals also are sensitive to changes in precipitation rates, mineralogy and diagene-sis, thereby complicating the application of the proxy to the reconstruction of global cycles. First, inorganic carbonate precipitation experiments have demonstrated that carbonate 44/40Ca values are sensitive to precipitation rates with higher rates generally leading to larger fractiona-tion. Second, 44/40Ca values are sensitive to carbonate mineralogy with inorganic aragonite and calcite being on average ~1.5‰ and ~0.9‰ depleted relative to contemporaneous seawater, re-spectively. The effects of both changes in carbonate mineralogy and precipitation rates affect primary and secondary minerals, but are particularly pronounced during carbonate diagenesis where relatively slow rates of recrystallization and neomorphism can lead to significant changes in bulk sediment 44/40Ca values. Third, changes in faunal composition expressed in skeletal fossil archives can lead to large changes in carbonate 44/40Ca values that are decoupled from changes in global cycles. Nevertheless, when these factors are appropriately considered the ap-plication of calcium isotopes in ancient carbonate sediments becomes a powerful tool for under-standing biogeochemical processes that operate over many scales; from diagenetic changes with-in the sediment pore-space, to regional changes across ancient carbonate platforms, and to global changes in seawater chemistry through time. Importantly, the processes that contribute to varia-bility in carbonate 44/40Ca values are likely to impact other carbonate-bound proxies, highlight-ing the potential for calcium isotopes as a hint to better understand the variability of other iso-tope systems

The effect of extraction techniques on calcium concentrations and isotope ratios of marine pore water

Comparing two different techniques applied for the extraction of marine pore water samples from sediments, the well-established whole round (WR) method and the more recent Rhizon method, in terms of their effects on stable calcium isotope ratios in extracted pore waters, we recognize a systematic offset between the two sampling methods. Higher δ44/40Ca values are associated with lower Ca concentrations for the Rhizon sampling technique and lower δ44/40Ca values are associated with higher Ca concentrations for the corresponding WR-derived pore water samples. Models involving Rayleigh fractionation and mixing calculation suggest that the observed offset is most likely caused by a combined process of CaCO3 precipitation and ion exchange taking place during Rhizon sampling-induced CO2 degassing. Changing pressure, extraction time or extraction yield during WR pressing does not lead to a variation in δ44/40Ca, indicating that no Ca isotope fractionation takes place during the sampling of pore water. On the basis of analytical and modelling results, WR samples appear to provide δ44/40Ca values that are more representative of the ‘true’ pore water isotopic composition. While the difference between the sampling techniques is close to the present-day analytical precision of Ca isotope analysis, it may become more relevant with increasing analytical precision in the future

Calcium isotope fractionation and its controlling factors over authigenic carbonates in the cold seeps of the northern South China Sea

In this study, we analyzed stable calcium isotope results of authigenic carbonates from two cold seep areas of the Dongsha area and the Baiyun Sag in the northern South China Sea. The stable isotopes of carbon and oxygen as well as the mineral composition of authigenic carbonates were used to investigate control calcium isotope fractionation. The δ 44/40Ca ratios of the southwestern Dongsha area samples ranged from 1.21‰ to 1.52‰ and the ratio of the Baiyun Sag sample was 1.55‰ of the SRM915a isotope standard. X-ray diffraction analysis showed that the carbonate samples consisted of dolomite, calcite and aragonite, with small amounts of high-Mg calcite and siderite. The δ 13C values of the carbonates of the southwestern Dongsha area varied between −49.21‰ and −16.86‰ of the Vienna PeeDee Belemnite (VPDB) standard and the δ 18O values ranged from 2.25‰ to 3.72‰ VPDB. The δ 13C value of the Baiyun Sag sample was 2.36‰ VPDB and the δ 18O value was 0.44‰ VPDB. The δ 13C values of the carbonates of the southwestern Dongsha area revealed there is methane seeping into this area, with a variable contribution of methane-derived carbon. The sampled carbonates covered a range of δ 13C values suggesting a dominant methane carbon source for the light samples and mixtures of δ 13C values for the heavier samples, with possibly an organic or seawater carbon source. The δ 18O values indicated that there is enrichment in 18O, which is related to the larger oxygen isotope fractionation in dolomite compared to calcite. The results of the Baiyun Sag sample exhibited normal seawater carbon and oxygen isotopic values, indicating that this sample is not related to methane seepage but instead to precipitation from seawater. The relatively high δ 44/40Ca values indicated either precipitation at comparatively high rates in pore-water regimes with high alkalinity, or precipitation from an evolved heavy fluid with high degrees of Ca consumption (Raleigh type fractionation). The dolomite samples from the Dongsha area revealed a clear correlation between the carbon and calcium isotope composition, indicating a link between the amount and/or rate of carbonate precipitation and methane contribution to the bicarbonate source. The results of the three stable isotope systems, mineralogy and petrography, show that mineral composition, the geochemical environment of authigenic carbonates and carbon source can control the calcium isotope fractionation.This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (KZCX2-YW-GJ03-01), the National Natural Science Foundation of China (40706022, U0733003 and 41176052), the National Basic Research Program of China (2009CB219502-4) and the Knowledge Innovation Program of South China Sea Institute of Oceanology, Chinese Academy of Sciences (LYQY200806). The authors thank the University of Aveiro and Universität Münster for the facilities provided for this research. We appreciate the thoughtful and constructive comments provided by editors and reviewers, which improve the manuscript.publishe

Calcium isotope (δ^44/40Ca ) variations of Neogene planktonic foraminifera

Measurements of the calcium isotopic composition (δ44/40Ca) of planktonic foraminifera from the western equatorial Pacific and the Indian sector of the Southern Ocean show variations of about 0.6‰ over the past 24 Myr. The stacked δ44/40Ca record of Globigerinoides trilobus and Globigerina bulloides indicates a minimum in δ44/40Casw (seawater calcium) at 15 to 16 Ma and a subsequent general increase toward the present, interrupted by a second minimum at 3 to 5 Ma. Applying a coupled calcium/carbon cycle model, we find two scenarios that can explain a large portion of the observed δ44/40Casw variations. In both cases, variations in the Ca input flux to the ocean without proportional changes in the carbonate flux are invoked. The first scenario increases the riverine calcium input to the ocean without a proportional increase of the carbonate flux. The second scenario generates an additional calcium flux from the exchange of Ca by Mg during dolomitization. In both cases the calcium flux variations lead to drastic changes in the seawater Ca concentrations on million year timescales. Our δ44/40Casw record therefore indicates that the global calcium cycle may be much more dynamic than previously assumed

Simulations of precipitation kinetics in Ti2AlNb-based multiphase alloys synthesized by laser powder bed fusion

High-temperature Ti2AlNb-based alloys are structural candidate materials for weight reduction in engines and aircraft. The precipitation kinetics underlying the complex microstructure observed in Ti2AlNb-based alloys was investigated using computational tools for simulating diffusion controlled precipitation processes. The microstructure of alloys processed by laser powder bed fusion (LPBF) was investigated using electron microscopy. The phase fractions were determined by high-energy X-ray diffraction during in situ annealing of the samples. Precipitation reaction models were used as implemented in the Thermo-Calc PRISMA software in combination with a well-developed thermodynamic database, Thermo-Calc Software TCTI/Ti-alloys database version 3. In particular the volume fractions of strengthening phases were quantified during the simulations and final phase fractions tailored as a function of temperature and alloy composition. Different nucleation and growth mechanisms were simulated and correlated with experimental observations at relative early stages of the precipitation process. Moreover, we identify models’ limitations and key model parameters through a sensitivity analysis of the adjustable parameters using the parametric optimization software Optislang

Ancient Nursery Area for the Extinct Giant Shark Megalodon from the Miocene of Panama

BACKGROUND: As we know from modern species, nursery areas are essential shark habitats for vulnerable young. Nurseries are typically highly productive, shallow-water habitats that are characterized by the presence of juveniles and neonates. It has been suggested that in these areas, sharks can find ample food resources and protection from predators. Based on the fossil record, we know that the extinct Carcharocles megalodon was the biggest shark that ever lived. Previous proposed paleo-nursery areas for this species were based on the anecdotal presence of juvenile fossil teeth accompanied by fossil marine mammals. We now present the first definitive evidence of ancient nurseries for C. megalodon from the late Miocene of Panama, about 10 million years ago. METHODOLOGY/PRINCIPAL FINDINGS: We collected and measured fossil shark teeth of C. megalodon, within the highly productive, shallow marine Gatun Formation from the Miocene of Panama. Surprisingly, and in contrast to other fossil accumulations, the majority of the teeth from Gatun are very small. Here we compare the tooth sizes from the Gatun with specimens from different, but analogous localities. In addition we calculate the total length of the individuals found in Gatun. These comparisons and estimates suggest that the small size of Gatun's C. megalodon is neither related to a small population of this species nor the tooth position within the jaw. Thus, the individuals from Gatun were mostly juveniles and neonates, with estimated body lengths between 2 and 10.5 meters. CONCLUSIONS/SIGNIFICANCE: We propose that the Miocene Gatun Formation represents the first documented paleo-nursery area for C. megalodon from the Neotropics, and one of the few recorded in the fossil record for an extinct selachian. We therefore show that sharks have used nursery areas at least for 10 millions of years as an adaptive strategy during their life histories

Investigating crystal orientation patterns of foraminiferal tests by electron backscatter diffraction analysis

We studied the crystallographic orientation of calcite crystals in benthic foraminifers by electron backscatter diffraction (EBSD). Individuals of two species, Gyroidinoides soldanii and Cibicidoides grimsdalei, featuring different test structures, were investigated for a time span covering 43&thinsp;Myr. The aims of this study are to visualize test structure differences in foraminifers and to reveal potential changes in crystal orientation and grain size over time caused by diagenetic reactions such as recrystallization. Such recrystallization effects over time may aid in the interpretation of time-resolved geochemical data obtained on foraminiferal samples for paleo-environmental reconstructions. The EBSD patterns clearly resolve the different test structures of the two species. Cibicidoides grimsdalei has the c axes perpendicular to the test surface. An apparent shift in the preferred crystal orientation can most likely be attributed to a mismatch between the equatorial plane and cutting plane of the foraminiferal test, highlighting the importance of reproducible preparation techniques. In Gyroidinoides soldanii, the c axes of the calcite crystals show a broader distribution of the crystals with no preferred orientation. The specimens show no change in crystal sizes over time, with a frequency maximum corresponding to the spot size of the electron beam. Overall, the differences between the two species demonstrate that EBSD is a powerful tool to visualize and differentiate between foraminiferal test structures.</p