The DIC carbon isotope evolutions during CO2 bubbling: implications for ocean acidification laboratory culture

Ocean acidification increases pCO2 and decreases pH of seawater and its impact on marine organisms has emerged as a key research focus. In addition to directly measured variables such as growth or calcification rate, stable isotopic tracers such as carbon isotopes have also been used to more completely understand the physiological processes contributing to the response of organisms to ocean acidification. To simulate ocean acidification in laboratory cultures, direct bubbling of seawater with CO2 has been a preferred method because it adjusts pCO2 and pH without altering total alkalinity. Unfortunately, the carbon isotope equilibrium between seawater and CO2 gas has been largely ignored so far. Frequently, the dissolved inorganic carbon (DIC) in the initial seawater culture has a distinct 13C/12C ratio which is far from the equilibrium expected with the isotopic composition of the bubbled CO2. To evaluate the consequences of this type of experiment for isotopic work, we measured the carbon isotope evolutions in two chemostats during CO2 bubbling and composed a numerical model to simulate this process. The isotopic model can predict well the carbon isotope ratio of dissolved inorganic carbon evolutions during bubbling. With help of this model, the carbon isotope evolution during a batch and continuous culture can be traced dynamically improving the accuracy of fractionation results from laboratory culture. Our simulations show that if not properly accounted for in experimental or sampling design, many typical culture configurations involving CO2 bubbling can lead to large errors in estimated carbon isotope fractionation between seawater and biomass or biominerals, consequently affecting interpretations and hampering comparisons among different experiments. Therefore, we describe the best practices on future studies working with isotope fingerprinting in the ocean acidification background.

Complex Biomineralization Pathways of the Belemnite Rostrum Cause Biased Paleotemperature Estimates

Paleotemperatures based on δ18O values derived from belemnites are usually “too cold” compared to other archives and paleoclimate models. This temperature bias represents a significant obstacle in paleoceanographic research. Here we show geochemical evidence that belemnite calcite fibers are composed of two distinct low-Mg calcite phases (CP1, CP2). Phase-specific in situ measurement of δ18O values revealed a systematic offset of up to 2‰ (~8 °C), showing a lead–lag signal between both phases in analyses spaced less than 25 µm apart and a total fluctuation of 3.9‰ (~16 °C) within a 2 cm × 2 cm portion of a Megateuthis (Middle Jurassic) rostrum. We explain this geochemical offset and the lead–lag signal for both phases by the complex biomineralization of the belemnite rostrum. The biologically controlled formation of CP1 is approximating isotope fractionation conditions with ambient seawater to be used for temperature calculation. In contrast, CP2 indicates characteristic non-isotope equilibrium with ambient seawater due to its formation via an amorphous Ca-Mg carbonate precursor at high solid-to-liquid ratio, i.e., limited amounts of water were available during its transformation to calcite, thus suggesting lower formation temperatures. CP2 occludes syn vivo the primary pore space left after formation of CP1. Our findings support paleobiological interpretations of belemnites as shelf-dwelling, pelagic predators and call for a reassessment of paleoceanographic reconstructions based on belemnite stable isotope data.

Oxygen Isotope Equilibrium of the Shallow-Water Benthic Foraminifer Hanzawaia nipponica Asano in Tosa Bay, Southwest Japan

Oxygen isotopic compositions (δ18O) of benthic foraminifer tests are widely used for reconstructing paleoceanographic changes, such as global ice volumes during glacial–interglacial cycles. Although deep-sea benthic foraminifers have been well characterized and are considered reliable indicators, little attention has been paid to the geochemistry of shallow-water benthic foraminifers. In this study we evaluated δ18O in the shallow-water benthic foraminifer Hanzawaia nipponica Asano, which lives in surface sediments on continental shelves and upper slopes under the influence of two warm currents, the Kuroshio and Tsushima currents, in the East China Sea, northwest Pacific, and southwestern Japan Sea. To evaluate oxygen isotope equilibrium, we analyzed δ18O of H. nipponica and ambient seawater on the continental shelf in Tosa Bay, southwest Japan. Seawater δ18O and salinity in Tosa Bay are similar to those of surface and subsurface waters in the Kuroshio region in the Okinawa Trough and the northwest Pacific. Vertical profiles of seawater δ18O show no variation with water depth (0–200 m) in Tosa Bay. However, tests of living H. nipponica (as determined by staining with Rose Bengal) and fossil (non-stained) H. nipponica, picked from samples of the top centimeter of seafloor sediment, yielded carbonate δ18O values that clearly increase with water depth, suggesting a temperature-dependent relationship. A comparison of carbonate δ18O values in living H. nipponica and those predicted on the basis of seawater δ18O and annual mean bottom temperature shows that H. nipponica tests are in oxygen isotopic equilibrium with ambient seawater. We determined the linear equations of δ18O–temperature relationship, and the slope of −5.26 (0.19‰°C−1) for living and −4.50 (0.22‰°C−1) for the fossil H. nipponica, respectively. The carbon isotopic compositions (δ13C) of H. nipponica also closely match seawater δ13C. Thus, we propose that the carbonate δ18O and δ13C of H. nipponica are useful proxies to reconstruct shallow-water paleoenvironmental changes in the northwest Pacific and its marginal seas.

Neotropical Ostracode Oxygen and Carbon Isotope Signatures - Implications for Calcification Conditions

Calcitic valves of non-marine ostracodes are important geochemical archives. Investigations of the relationship between the isotopic ranges of modern ostracode populations and their host water provide important information on local or regional conditions and influences. Here we present the first δ18Oostracode and δ13Costracode dataset of the freshwater ostracode species Cytheridella ilosvayi along with characterization of the precipitating water - chemical composition, δDwater, δ18Owater, δ13CDIC values - covering a large geographical range (Florida to Brazil). With this data we extended a newly developed approach based on the estimation of δ18O values of monthly equilibrium calcites as references for the interpretation of δ18Oostracode values.The expected apparent oxygen isotope fractionation between CaCO3 - and H2O is correlated with temperature with smaller values occurring at higher temperatures as valid at isotope equilibrium (δ18Ocalcite_eq). Additional to a species-specific offset, unusual high deviations of δ18Oostracode vs. δ18Owater values most likely reflect the time lag between valve calcification and sampling. Coincidence between δ18Oostracode and δ18Ocalcite_eq is restricted to few months indicating a seasonal calcification of Cytheridella. There is a characteristic pattern in its difference between mean δ18Oostracode and δ18Ocalcite_eq which implies that Cytheridella provides a synchronous life cycle in its geographical range with two calcification periods in spring (May, June) and autumn (October). This ubiquitous life cycle of Cytheridella in the entire study area is considered to be phylogenetically inherited. It might have originally been adapted to environmental conditions but has been conserved during the migration and radiation of the group over the Neotropical realm.

The Garies Wollastonite Deposit, Namaqualand, South Africa: High-Temperature Metamorphism of a Low-δ18O Skarn?

ABSTRACT The Garies wollastonite deposit is located in the Bushmanland terrane of the Namaqualand Metamorphic Province and is part of a discontinuous calc-silicate unit bounded by granulite facies gneiss that experienced peak metamorphic temperatures above 800 °C. In bulk, the deposit is dominated by wollastonite, but varied proportions of garnet, diopside, quartz, calcite, and vesuvianite are also present. Mineral chemistry variations across the deposit are minor, and the absence of inclusions indicates textural and chemical equilibrium. The wollastonite-bearing rocks have unusually low mineral δ18O values: –0.6 to +2.2‰ for garnet, –0.2 to +2. 6‰ for clinopyroxene, and –0.2 to +0.4‰ for wollastonite. Calcite δ18O values range from 6.8 to 11. 8‰ and δ13C values from –6.4 to –3.2‰. Calcite δ18O values are unusually low for calc-silicate rocks, but Δcalcite-garnet values from 3 to 12‰ indicate O-isotope disequilibrium between calcite and the silicate minerals. Garnet-biotite metapelitic and diopside gneisses have unexpectedly low δ18O values (<7‰). The approach to O-isotope equilibrium displayed by coexisting silicate minerals, and low mineral δ18O values in calc-silicate and metapelite and metapsammite gneisses, is consistent with low δ18O values being acquired before peak metamorphism. Low δ18O values in the minerals of the calc-silicate rocks require interaction with external fluid at high water/rock ratio. We suggest that the deposit represents a metamorphosed skarn that developed at the contact between the original carbonate rocks and intruding felsic magmas.

Ore Genesis of the Takatori Tungsten–Quartz Vein Deposit, Japan: Chemical and Isotopic Evidence

The Takatori hypothermal tin–tungsten vein deposit is composed of wolframite-bearing quartz veins with minor cassiterite, chalcopyrite, pyrite, and lithium-bearing muscovite and sericite. Several wolframite rims show replacement textures, which are assumed to form by iron replacement with manganese postdating the wolframite precipitation. Lithium isotope ratios (δ7Li) of Li-bearing muscovite from the Takatori veins range from −3.1‰ to −2.1‰, and such Li-bearing muscovites are proven to occur at the early stage of mineralization. Fine-grained sericite with lower Li content shows relatively higher δ7Li values, and might have precipitated after the main ore forming event. The maximum oxygen isotope equilibrium temperature of quartz–muscovite pairs is 460 °C, and it is inferred that the fluids might be in equilibrium with ilmenite series granitic rocks. Oxygen isotope ratios (δ18O) of the Takatori ore-forming fluid range from +10‰ to +8‰. The δ18O values of the fluid decreased with decreasing temperature probably because the fluid was mixed with surrounding pore water and meteoric water. The formation pressure for the Takatori deposit is calculated to be 160 MPa on the basis of the difference between the pressure-independent oxygen isotope equilibrium temperature and pressure-dependent homogenization fluid inclusions temperature. The ore-formation depth is calculated to be around 6 km. These lines of evidence suggest that a granitic magma beneath the deposit played a crucial role in the Takatori deposit formation.

Isotopic carbon turnover in pig hoof and rib

The objective of this study was to evaluate the behavior of carbon incorporation and turnover in hoof and ribs of pigs at different periods of development in the search for tissues that reflect longer the former diet. We used 132 commercial hybrids (barrows and females), weaned at an average age of 21 days, distributed in a completely randomized design with four treatments on different days of substitution of corn (C4 cycle plant grain) diets with broken rice (C3 cycle plant grain) at 21, 42, 63 and 110 days of age to change the carbon-13 isotope signal. By means of isotopic dilution curves, we observed that animals whose C4 diet was replaced with C3 diet at 21, 42, 63 and 110 days of age, for hoof and rib, reached a new level of isotope equilibrium. Bone samples are better choices to reflect the former diet, due to conservation of the isotopic signal for longer.

Temperatures of Late Cretaceous (Campanian) methane-derived authigenic carbonates from the Western Interior Seaway, South Dakota, USA, using clumped isotopes

Methane seep deposits, comprising large, carbonate-rich mounds formed from hydrocarbon seepage, were widely distributed in the Late Cretaceous Western Interior Seaway (WIS) of North America. Well-preserved, methane-derived authigenic carbonates (MDACs) from these deposits have been shown to retain petrological, paleontological, and geochemical imprints of their ancient depositional setting, all of which are important for understanding the dynamics and evolution of the shallow, epeiric WIS. To better characterize the environmental conditions of WIS seeps, we applied clumped isotope paleothermometry to magnesium calcite MDAC samples from five seep localities in the upper Campanian Pierre Shale, South Dakota, USA. We measured 21 subsamples, including 18 micritic carbonates and demonstrated apparent clumped isotope equilibrium between MDACs and WIS bottom waters. Extreme 13C depletion in most samples (δ13C ranging to −45.44‰) indicates they were precipitated with oxidized methane as a major source of dissolved inorganic carbon, which itself implies a close association with ancient methanotrophic metabolism. The average clumped isotope paleotemperature from the micritic carbonates is 23 ± 7 °C (1σ standard deviation), which agrees with bottom water paleotemperatures inferred from δ18O measurements of MDACs and well-preserved mollusk shells at similar localities in the WIS. The calculated average δ18Ow value for these samples is −0.5 ± 1.7‰ (1σ SD), which is indistinguishable from previously reported calculation on Campanian seawater δ18Ow from fossil mollusk shells, but elevated above younger fossils collected from other locations in the WIS. Our conclusions are inconsistent with previously hypothesized disequilibrium for WIS MDAC clumped isotope and therefore we propose that fossil MDAC deposits may be used as paleotemperature archives.

Clumped isotope thermometry techniques and their application to fossil teeth and pedogenic carbonates

This Ph.D. thesis demonstrates i) the highly precise performance of refined and new analytical setups for clumped isotope analysis (Δ47 and Δ48) and ii) the applicability of clumped isotope analyses to biogenic and abiogenic carbonated apatite (Δ47) and abiogenic carbonates (Δ47 and Δ48) for research related to paleothermophysiology and paleoclimatology, whereas the overall analytical precision has been increased. A comprehensive Δ47 dataset with 122 replicate analyses is provided from which the temperature dependence of Δ47 for (bio)apatite (Δ47-1/T2) is calculated between 1 °C and 80 °C. The temperature dependence of oxygen isotope equilibrium fractionation between carbonated synthetic apatite and water (1,000ln(αCHAP-H2O)) is experimentally determined. When applied to tooth enameloid from a modern Greenland shark (Somniosus microcephalus), a Late Miocene megatooth shark (Carcharodon megalodon), and an Upper Cretaceous Tyrannosaurus rex, reconstructed Δ47-based temperatures and δ18OH2O are in line with previously published data. An analytical setup for highly precise clumped isotope analysis is described that allows for the simultaneous measurement of ∆47 and ∆48 in CO2 with external reproducibilities close to the respective shot-noise limits. The analyte gases originate from pure carbonates that were digested in hypersaturated orthophosphoric acid and purified using a fully automated device. Δ47 data sets with 117 replicate analyses in total on 22 pedogenic carbonate nodules from two Spanish Middle Miocene sections reveal the continental Southern European thermal structure during the end of the Middle Miocene Climatic Optimum (MCO) and the complete Middle Miocene Climatic Transition (MMCT; from 15.33 to 12.98 Ma).

Using Carbon Isotope Equilibrium to Screen Pedogenic Carbonate Oxygen Isotopes: Implications for Paleoaltimetry and Paleotectonic Studies

Stable isotope compositions of pedogenic carbonates (δ13Ccarb, δ18Ocarb) are widely used in paleoenvironmental and paleoaltimetry studies. At the same time, both in vertical stratigraphic sections and in horizontal transects of single paleosols, significant variability in δ18Ocarb values is observed well in excess of what could reasonably be attributed to elevation changes. Herein, a new screening tool is proposed to establish which pedogenic carbonate δ18Ocarb compositions reflect formation in isotopic equilibrium with environmental conditions through the use of the co-occurring δ13Corg composition of carbonate-occluded or in profile organic matter, where Δ13C = δ13Ccarb – δ13Corg. Based upon 51 modern soils from monsoonal, continental, and Mediterranean moisture regimes, Δ13C = +15.6 ± 1.1‰ (1σ), which closely matches theoretical predictions for carbonates formed at carbon isotope equilibrium through Fickian diffusion. Examples from both disequilibrium and equilibrium cases in the geologic record are examined, and it is shown that previous δ18Ocarb records used to infer Cenozoic uplift in southwestern Montana do not provide any constraint on paleoelevation because >90% of the pedogenic carbonate isotopic compositions are out of equilibrium. Guidelines for future paleoaltimetry studies include collection of both vertical stratigraphic sections and lateral transects, of at least three nodules per horizon, petrographic screening of nodules for diagenesis, collection of at least one independent proxy for paleoclimate or paleovegetation, and screening δ18Ocarb values using Δ13C measured for each paleosol.