Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes

The isotopic composition of apatites from sedimentary phosphorite deposits has been used previously to reconstruct ancient conditions on the surface of the earth. However, questions remain as to whether these minerals retain their original isotopic composition or are modified during burial and lithification. To better understand how apatites in phosphorites form and are diagenetically modified, we present new isotopic measurements of δ^(18)O values and clumped-isotope-based (Δ_(47)) temperatures of carbonate groups in apatites from phosphorites from the past 265 million years. We compare these measurements to previously measured δ^(18)O values of phosphate groups from the same apatites. These results indicate that the isotopic composition of many of the apatites do not record environmental conditions during formation but instead diagenetic conditions. To understand these results, we construct a model that describes the consequences of diagenetic modification of phosphorites as functions of the environmental conditions (i.e., temperature and δ^(18)O values of the fluids) during initial precipitation and subsequent diagenesis. This model captures the basic features of the dataset and indicates that clumped-isotope-based temperatures provide additional quantitative constraints on both the formational environment of the apatites and subsequent diagenetic modification. Importantly, the combination of the model with the data indicates that the δ^(18)O values and clumped-isotope temperatures recorded by phosphorites do not record either formation or diagenetic temperatures, but rather represent an integrated history that includes both the formation and diagenetic modification of the apatites

Neoproterozoic to early Phanerozoic rise in island arc redox state due to deep ocean oxygenation and increased marine sulfate levels

A rise in atmospheric O_2 levels between 800 and 400 Ma is thought to have oxygenated the deep oceans, ushered in modern biogeochemical cycles, and led to the diversification of animals. Over the same time interval, marine sulfate concentrations are also thought to have increased to near-modern levels. We present compiled data that indicate Phanerozoic island arc igneous rocks are more oxidized (Fe^(3+)/ΣFe ratios are elevated by 0.12) vs. Precambrian equivalents. We propose this elevation is due to increases in deep-ocean O_2 and marine sulfate concentrations between 800 and 400 Ma, which oxidized oceanic crust on the seafloor. Once subducted, this material oxidized the subarc mantle, increasing the redox state of island arc parental melts, and thus igneous island arc rocks. We test this using independently compiled V/Sc ratios, which are also an igneous oxybarometer. Average V/Sc ratios of Phanerozoic island arc rocks are elevated (by +1.1) compared with Precambrian equivalents, consistent with our proposal for an increase in the redox state of the subarc mantle between 800 and 400 Ma based on Fe^(3+)/ΣFe ratios. This work provides evidence that the more oxidized nature of island arc vs. midocean-ridge basalts is related to the subduction of material oxidized at the Earth’s surface to the subarc mantle. It also indicates that the rise of atmospheric O_2 and marine sulfate to near-modern levels by the late Paleozoic influenced not only surface biogeochemical cycles and animal diversification but also influenced the redox state of island arc rocks, which are building blocks of continental crust

Measurement of intact methane isotopologues, including ^(13)CH_3D

Methane (CH_4) is both a significant greenhouse gas and resource. Its present and past cycling can be studied through measurements of concentration and/or bulk isotopic ratios (^(13)C/^(12)C, D/H, and ^(14)C/^(12)C). Currently, isotope ratios are measured by mass spectrometric analysis of H_2 and CO_2 produced from CH_4, or by spectroscopy of CH_4. However, the interpretation of bulk isotopic variations of CH_4 are often equivocal, necessitating additional tracers

Effects of temperature and carbon source on the isotopic fractionations associated with O_2 respiration for ^(17)O/^(16)O and ^(18)O/^(16)O ratios in E. coli

^(18)O/^(16)O and ^(17)O/^(16)O ratios of atmospheric and dissolved oceanic O_2 are used as biogeochemical tracers of photosynthesis and respiration. Critical to this approach is a quantitative understanding of the isotopic fractionations associated with production, consumption, and transport of O_2 in the ocean both at the surface and at depth. We made measurements of isotopic fractionations associated with O_2 respiration by E. coli. Our study included wild-type strains and mutants with only a single respiratory O_2 reductase in their electron transport chains (either a heme-copper oxygen reductase or a bd oxygen reductase). We tested two common assumptions made in interpretations of O_2 isotope variations and in isotope-enabled models of the O_2 cycle: (i) laboratory-measured respiratory ^(18)O/^(16)O isotopic fractionation factors (^(18)α) of microorganisms are independent of environmental and experimental conditions including temperature, carbon source, and growth rate; And (ii) the respiratory ‘mass law’ exponent, θ, between ^(18)O/^(16)O and ^(17)O/^(16)O, ^(17)α = (^(18)α)^θ, is universal for aerobic respiration. Results demonstrated that experimental temperatures have an effect on both ^(18)α and θ for aerobic respiration. Specifically, lowering temperatures from 37 to 15 °C decreased the absolute magnitude of ^(18)α by 0.0025 (2.5‰), and caused the mass law slope to decrease by 0.005. We propose a possible biochemical basis for these variations using a model of O_2 reduction that incorporates two isotopically discriminating steps: the reversible binding and unbinding of O_2 to a terminal reductase, and the irreversible reduction of that O_2 to water. Finally, we cast our results in a one-dimensional isopycnal reaction-advection-diffusion model, which demonstrates that enigmatic δ^(18)O and Δ^(17)O variations of dissolved O_2 in the dark ocean can be understood by invoking the observed temperature dependence of these isotope effects

Modeling the effects of diagenesis on carbonate clumped-isotope values in deep- and shallow-water settings

The measurement of multiply isotopically substituted (‘clumped isotope’) carbonate groups provides a way to reconstruct past mineral formation temperatures. However, dissolution-reprecipitation (i.e., recrystallization) reactions, which commonly occur during sedimentary burial, can alter a sample’s clumped-isotope composition such that it partially or wholly reflects deeper burial temperatures. Here we derive a quantitative model of diagenesis to explore how diagenesis alters carbonate clumped-isotope values. We apply the model to a new dataset from deep-sea sediments taken from Ocean Drilling Project site 807 in the equatorial Pacific. This dataset is used to ground truth the model. We demonstrate that the use of the model with accompanying carbonate clumped-isotope and carbonate δ^(18)O values provides new constraints on both the diagenetic history of deep-sea settings as well as past equatorial sea-surface temperatures. Specifically, the combination of the diagenetic model and data support previous work that indicates equatorial sea-surface temperatures were warmer in the Paleogene as compared to today. We then explore whether the model is applicable to shallow-water settings commonly preserved in the rock record. Using a previously published dataset from the Bahamas, we demonstrate that the model captures the main trends of the data as a function of burial depth and thus appears applicable to a range of depositional settings

Comparison of Experimental vs Theoretical Abundances of ¹³CH₃D and ¹²CH₂D₂ for Isotopically Equilibrated Systems from 1 to 500 °C

Methane is produced and consumed via numerous microbial and chemical reactions in atmospheric, hydrothermal, and magmatic reactions. The stable isotopic composition of methane has been used extensively for decades to constrain the source of methane in the environment. A recently introduced isotopic parameter used to study the formation temperature and formational conditions of methane is the measurement of molecules of methane with multiple rare, heavy isotopes (‘clumped’) such as ¹³CH₃D and ¹²CH₂D₂. In order to place methane clumped-isotope measurements into a thermodynamic reference frame that allows calculations of clumped-isotope based temperatures (geothermometry) and comparison between laboratories, all past studies have calibrated their measurements using a combination of experiment and theory based on the temperature dependence of clumped isotopologue distributions for isotopically equilibrated systems. These have previously been performed at relatively high temperatures (>150˚C). Given that many natural occurrences of methane form below these temperatures, previous calibrations require extrapolation when calculating clumped-isotope based temperatures outside of this calibration range. We provide a new experimental calibration of the relative equilibrium abundances of ¹³CH₃D and ¹²CH₂D₂ from 1–500˚C using a combination of γ-Al₂O₃ and Ni-based catalysts and compare them to new theoretical computations using Path Integral Monte Carlo (PIMC) methods and find 1:1 agreement (within ± 1 standard error) for the observed temperature dependence of clumping between experiment and theory over this range. This demonstrates that measurements, experiments, and theory agree from 1–500°C providing confidence in the overall approaches. Polynomial fits to PIMC computations, which are considered the most rigorous theoretical approach available, are given as follows (valid T ≥ 270 K): ∆¹³CH₃D≅1000×ln(K¹³CH₃D)= 1.47348×10¹⁹/T⁷ - 2.08648×10¹⁷/T⁶ + 1.19810×10¹⁵/T⁵ - 3.54757×10¹²/T⁴ +5.54476×10⁹/T³ – 3.49294×10⁶/T² + 8.89370×10₂/T ∆¹²CH₂D₂≅1000×ln(8/3×K¹²CH₂D₂)= -9.67634×10¹⁵/T⁶ + 1.71917×10¹⁴/T⁵ - 1.24819×10¹²/T⁴ + 4.30283×10⁹/T3 -4.48660×10⁶/T² + 1.86258×10³/T. We additionally compare PIMC computations to those performed utilizing traditional approaches that are the basis of most previous calibrations (Bigeleisen, Mayer, and Urey model, BMU) and discuss the potential sources of error in the BMU model relative to PIMC computations

Nitrogen isotope evidence for expanded ocean suboxia in the early Cenozoic

The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the ^(15)N/^(14)N ratio (δ^(15)N) of foraminifera shell-bound organic matter from three sediment cores was high, indicating expanded water column suboxia and denitrification. Between 57 and 50 Ma ago, δ^(15)N declined by 13 to 16 per mil in the North Pacific and by 3 to 8 per mil in the Atlantic. The decline preceded global cooling and appears to have coincided with the early stages of the Asia-India collision. Warm, salty intermediate-depth water forming along the Tethys Sea margins may have caused the expanded suboxia, ending with the collision. From 50 to 35 Ma ago, δ^(15)N was lower than modern values, suggesting widespread sedimentary denitrification on broad continental shelves. Δ^(15)N rose at 35 Ma ago, as ice sheets grew, sea level fell, and continental shelves narrowed

Nitrogen isotope evidence for expanded ocean suboxia in the early Cenozoic

The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the ^(15)N/^(14)N ratio (δ^(15)N) of foraminifera shell-bound organic matter from three sediment cores was high, indicating expanded water column suboxia and denitrification. Between 57 and 50 Ma ago, δ^(15)N declined by 13 to 16 per mil in the North Pacific and by 3 to 8 per mil in the Atlantic. The decline preceded global cooling and appears to have coincided with the early stages of the Asia-India collision. Warm, salty intermediate-depth water forming along the Tethys Sea margins may have caused the expanded suboxia, ending with the collision. From 50 to 35 Ma ago, δ^(15)N was lower than modern values, suggesting widespread sedimentary denitrification on broad continental shelves. Δ^(15)N rose at 35 Ma ago, as ice sheets grew, sea level fell, and continental shelves narrowed