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Despite being a prominent continental-scale feature, the late Mesoproterozoic North American Midcontinent Rift did not result in the break-up of Laurentia, and subsequently underwent structural inversion. The timing of inversion is critical for constraining far-field effects of orogenesis and processes associated with the rift's failure. The Keweenaw fault in northern Michigan (USA) is a major thrust structure associated with rift inversion; it places ca. 1093 Ma rift volcanic rocks atop the post-rift Jacobsville Formation, which is folded in its footwall. Previous detrital zircon (DZ) U-Pb geochronology conducted by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) assigned a ca. 950 Ma maximum age to the Jacobsville Formation and led researchers to interpret its deposition and deformation as postdating the ca. 1090–980 Ma Grenvillian Orogeny. In this study, we reproduced similar DZ dates using LA-ICP-MS and then dated 19 of the youngest DZ grains using high-precision chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS). The youngest DZ dated by CA-ID-TIMS at 992.51 ± 0.64 Ma (2σ) redefines the maximum depositional age of the Jacobsville Formation and overlaps with a U-Pb LA-ICP-MS date of 985.5 ± 35.8 Ma (2σ) for late-kinematic calcite veins within the brecciated Keweenaw fault zone. Collectively, these data are interpreted to constrain deposition of the Jacobsville Formation and final rift inversion to have occurred during the 1010–980 Ma Rigolet Phase of the Grenvillian Orogeny, following an earlier phase of Ottawan inversion. Far-field deformation propagated >500 km into the continental interior during the Ottawan and Rigolet phases of the Grenvillian Orogeny.

The stable isotopic composition of methane (CH4) is commonly used to fingerprint natural gas origins. Over the past 50 years, there have been numerous proposals that both microbial and thermogenic CH4 can form in or later attain hydrogen isotopic equilibrium with water (H2O) and carbon isotopic equilibrium with carbon dioxide (CO2). Evaluation of such proposals requires knowledge of the equilibrium fractionation factors between CH4 and H2O or CO2 at the temperatures where microbial and thermogenic CH4 form in or are found in the environment, which is generally less than 200 °C. Experimental determinations of these fractionation factors are only available above 200 °C, requiring extrapolation of these results beyond the calibrated range or the use of theoretical calculations at lower temperatures. Here, we provide a calibration of the equilibrium hydrogen isotopic fractionation factor for CH4 and hydrogen gas (H2) (DαCH4(g)–H2(g)) based on experiments using γ-Al2O3 and Ni catalysts from 3 to 200 °C. Results were regressed as a 2nd order polynomial of 1000 × lnDαCH4(g)–H2(g) vs. 1/T (K−1) yielding: 1000 × l n D α C H 4 ( g ) - H 2 ( g ) = 3.5317 × 10 7 T 2 + 2.7749 × 10 5 T - 179.48 We combine this calibration with previous experimental determinations of hydrogen isotope equilibrium between H2, H2O(g), and H2O(l) and we provide an interpolatable experimental calibration of 1000 × lnDαCH4(g)–H2O(l) from 3 to 200 °C. Our resulting 4th order polynomial is the following equation: 1000 × l n D α C H 4 ( g ) - H 2 O l = - 7.9443 × 10 12 T 4 + 8.7772 × 10 10 T 3 - 3.4973 × 10 8 T 2 + 5.4398 × 10 5 T - 382.05 At 3 °C, the value from our calibration differs by 93‰ relative to what would be calculated based on the extrapolation of the only experimental calibration currently available to temperatures below its calibrated range (lowest temperature of 200 °C; Horibe and Craig, 1995). We additionally provide new theoretical estimates of hydrogen isotopic equilibrium between CH4(g), H2(g), and H2O(g) and carbon isotopic equilibrium between CH4(g) and CO2(g) using Path Integral Monte Carlo (PIMC) calculations. Our PIMC calculations for hydrogen isotopic equilibrium between CH4 and H2 agree 1:1 with our experiments. Finally, we compile carbon and hydrogen isotopic measurements of CH4, CO2, and H2O from various environmental systems and compare observed differences between carbon and hydrogen isotopes to those expected based on isotopic equilibrium. We find that isotopic compositions of some microbial gases from marine sedimentary, coalbed, and shale environments are consistent with those expected for CH4 H2O(l) hydrogen and CH4 CO2 carbon isotopic equilibrium. In contrast, microbial terrestrial and pure culture gases are not consistent with both CH4 H2O(l) hydrogen and CH4 CO2 carbon isotopic equilibrium. These results are explained qualitatively using previously developed conceptual models that link free energy gradients available to microorganisms to the degree that their enzymes can promote isotope-exchange reactions between CH4, CO2, and H2O.

Carbonate mud represents one of the most important geochemical archives for reconstructing ancient climatic, environmental, and evolutionary change from the rock record. Mud also represents a major sink in the global carbon cycle. Yet, there remains no consensus about how and where carbonate mud is formed. Here, we present stable isotope and trace-element data from carbonate constituents in the Bahamas, including ooids, corals, foraminifera, and algae. We use geochemical fingerprinting to demonstrate that carbonate mud cannot be sourced from the abrasion and mixture of any combination of these macroscopic grains. Instead, an inverse Bayesian mixing model requires the presence of an additional aragonite source. We posit that this source represents a direct seawater precipitate. We use geological and geochemical data to show that “whitings” are unlikely to be the dominant source of this precipitate and, instead, present a model for mud precipitation on the bank margins that can explain the geographical distribution, clumped-isotope thermometry, and stable isotope signature of carbonate mud. Next, we address the enigma of why mud and ooids are so abundant in the Bahamas, yet so rare in the rest of the world: Mediterranean outflow feeds the Bahamas with the most alkaline waters in the modern ocean (>99.7th-percentile). Such high alkalinity appears to be a prerequisite for the nonskeletal carbonate factory because, when Mediterranean outflow was reduced in the Miocene, Bahamian carbonate export ceased for 3-million-years. Finally, we show how shutting off and turning on the shallow carbonate factory can send ripples through the global climate system.

The hydrogen isotopic composition of methane (CH4) is used as a fingerprint of gas origins. Exchange of hydrogen isotopes between CH4 and liquid water has been proposed to occur in both low- and high-temperature settings. However, despite environmental evidence for hydrogen isotope exchange between CH4 and liquid water, there are few experimental constraints on the kinetics of this process. We present results from hydrothermal experiments conducted to constrain the kinetics of hydrogen isotope exchange between CH4 and supercritical water. Seven isothermal experiments were performed over a temperature range of 376–420 °C in which deuterium-enriched water and CH4 were reacted in flexible gold reaction cell systems. Rates of exchange were determined by measuring the change in the δD of CH4 over the time course of an experiment. Regression of derived second order rate constants (kr) vs. 1000/T (i.e., an Arrhenius plot) yields the following equation: ln(kr) = −17.32 (±4.08, 1 s.e.) × 1000/T + 3.19 (±6.01, 1 s.e.) (units of kr of sec−1 [mol/L]−1), equivalent to an activation energy of 144.0 ± 33.9 kJ/mol (1 s.e.). These results indicate that without catalysts, CH4 will not exchange hydrogen isotopes with liquid water on a timescale shorter than the age of the Earth (i.e., billions of years) at temperatures below 100–125 °C. Exchange at or below these temperatures is thought to occur due to the activity of life, and thus hydrogen isotopic equilibrium between methane and water may be a biosignature at low temperatures on Earth (in the present or the past) and on other planetary bodies. At temperatures ranging from 125 to 200 °C, hydrogen isotope exchange between CH4 and liquid water can occur on timescales of millions to hundreds of thousands of years, indicating that in thermogenic natural gas systems CH4 may isotopically equilibrate with water and achieve equilibrium isotopic compositions. Finally, the kinetics indicate that in deep-sea hydrothermal systems, the hydrogen (and thus clumped) isotopic composition of CH4 is likely set by formation and/or storage conditions isolated from the active flow regime. The determined kinetics indicate that once methane is entrained in circulating fluids, the expected time-temperature pathways are insufficient for measurable hydrogen isotope exchange between CH4 and water to occur.

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 extensi...

Circulation more than temperature Changes in continental configuration and sea level affected the ocean's oxygen levels and the rate of denitrification between 70 and 30 million years ago. That finding by Kast et al. shows a fundamental difference from the modern ocean, in which the extent of suboxia is controlled primarily by global temperature. Changes in the nitrogen isotopic composition of marine organic matter correlate with the collision of India and Asia and the circulation changes that occurred as a result. Later, isotopic composition changed further in response to a fall in sea level as global cooling caused ice sheets to grow. Science , this issue p. 386

The release of long‐stored carbon from thawed permafrost could fuel increased methanogenesis in northern lakes, but it remains unclear whether old carbon substrates released from permafrost are metabolized as rapidly by methanogenic microbial communities as recently produced organic carbon. Here, we apply methane (CH₄) clumped isotope (Δ₁₈) and ¹⁴C measurements to test whether rates of methanogenesis are related to carbon substrate age. Results from culture experiments indicate that Δ₁₈ values are negatively correlated with CH₄ production rate. Measurements of ebullition samples from thermokarst lakes in Alaska and glacial lakes in Sweden indicate strong negative correlations between CH₄ Δ₁₈ and the fraction modern carbon. These correlations imply that CH₄ derived from older carbon substrates is produced relatively slowly. Relative rates of methanogenesis, as inferred from Δ₁₈ values, are not positively correlated with CH₄ flux estimates, highlighting the likely importance of environmental variables other than CH₄ production rates in controlling ebullition fluxes.

© 2018 Elsevier Ltd Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this “water effect” also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes (‘clumped’ isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103times higher compared with dry (pure CO2) conditions in the temperature range of this study (385–450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures (“blocking temperatures”) for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150–200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external fluids. We explore the mechanism(s) by which clumped isotope reordering rates may be modestly increased under wet, high-pressure conditions, including changes in defect concentrations in the near surface environment due to reactions at the water–mineral interface, and lattice deformation resulting from pressurization of samples.

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O2) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

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.

^(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.

© 2017 Geological Society of America. Carbonates form ubiquitously throughout the history of deposition, burial, and uplift of basins. As such, they potentially record the environmental conditions at the time of formation. Carbonate clumped isotopes provide the temperature of precipitation but can be internally reordered if the host rock is exposed to elevated temperatures over geologic time scales. Here, we exploited this kinetic behavior by analyzing multiple generations of cements that capture the range of environments experienced by the El Abra Formation from eastern Mexico. From this, we developed a quantitative diagenetic history for these different phases of cementation. We observed a 70 °C range in clumped isotope temperatures from 64 °C to 134 °C for these cements, which is not compatible with their inferred precipitation environments. This suggests that bond reordering occurred during burial but did not fully reorder all cements to a common apparent temperature. We reconstructed original cement growth temperatures and the isotopic signature of the parent fluids to show that precipitation from a marine pore fluid began at 125 Ma, contemporaneous with deposition, and continued throughout burial to temperatures of at least 138 °C at 42 Ma. We show that precipitation of equant cements, which occluded 90% of the pore space, was coincident with Laramide-related burial to depths greater than 3800 m. A U-Pb age of diagenetic calcite of 77.1 ± 3.6 Ma provides independent support for our estimates of the absolute timing of precipitation of two distinct phases of the paragenesis. This is the first demonstration of the utility of integrating U-Pb age dating with reordered clumped isotope temperatures to provide quantitative constraints on the time-temperature history of cementation. Such information may ultimately lead to advances in our understanding of the formational environments and geological processes that drive diagenesis in carbonates for temperatures below the clumped isotope "blocking temperature".

© 2015 Elsevier Ltd. Sources of methane to sedimentary environments are commonly identified and quantified using the stable isotopic compositions of methane. The methane "clumped-isotope geothermometer", based on the measurement of multiply substituted methane isotopologues (13CH3D and 12CH2D2), shows promise in adding new constraints to the sources and formational environments of both biogenic and thermogenic methane. However, questions remain about how this geothermometer behaves in systems with mixtures of biogenic and thermogenic gases and different biogenic environments. We have applied the methane clumped-isotope thermometer to a mixed biogenic-thermogenic system (Antrim Shale, USA) and to biogenic gas from gas seeps (Santa Barbara and Santa Monica Basin, USA), a pond on the Caltech campus, and methanogens grown in pure culture. We demonstrate that clumped-isotope based temperatures add new quantitative constraints to the relative amounts of biogenic vs. thermogenic gases in the Antrim Shale indicating a larger proportion (~50%) of thermogenic gas in the system than previously thought. Additionally, we find that the clumped-isotope temperature of biogenic methane appears related to the environmental settings in which the gas forms. In systems where methane generation rates appear to be slow (e.g., the Antrim Shale and gas seeps), microbial methane forms in or near both internal isotopic equilibrium and hydrogen-isotope equilibrium with environmental waters. In systems where methane forms rapidly, microbial methane is neither in internal isotopic equilibrium nor hydrogen-isotope equilibrium with environmental waters. A quantitative model of microbial methanogenesis that incorporates isotopes is proposed to explain these results.

Carbonate clumped-isotope geothermometry is a tool used to reconstruct formation or (re)equilibration temperatures of carbonate bearing minerals, including carbonate groups substituted into apatite. It is based on the preference for isotopologues with multiple heavy isotopes (for example, ^(13)C^(16)O_2^(18)O^(2−) groups) to be more abundant at equilibrium than would be expected if all isotopes were randomly distributed amongst all carbonate groups. Because this preference is only a function of temperature, excesses of multiply substituted species can be used to calculate formation temperatures without knowledge of the isotopic composition of water from which the mineral precipitated or other phases with which it may have equilibrated. However, the measured temperature could be modified after mineral growth if exchange of isotopes amongst carbonate groups within the mineral has occurred through internal isotope-exchange reactions. Because these exchange reactions occur through thermally activated processes, their rates depend on temperature and increase at higher temperatures. Thus internal isotope-exchange reactions could lead to effective re-equilibration at high temperatures, overprinting the original temperatures recorded during mineral growth. We measured clumped-isotope temperatures in carbonate bearing minerals (including apatites) from several carbonatites to constrain the kinetics of these internal isotope-exchange reactions. We observe two key trends for clumped-isotope temperatures in carbonatites: (i) clumped-isotope temperatures of apatites and carbonate-bearing minerals decrease with increasing intrusion depth and (ii) apatites record lower clumped-isotope temperatures than carbonate minerals from the same intrusion. We additionally conducted heating experiments at different temperatures to derive the temperature dependence for the rate constants that describe the alteration of clumped-isotope temperatures with time in calcites and apatites. We find that calcites exhibit complex kinetics as has been seen in previous studies. To quantify these results, we constructed a model that incorporates both diffusion of isotopes through the crystal lattice and isotope-exchange reactions between adjacent carbonate groups. We tested this model through comparison to previous measurements of optical calcites and brachiopods and to samples with known cooling histories and find that the model is able to reasonably capture kinetic data from previous experiments and the observed clumped-isotope temperatures of calcites assuming geologically reasonable cooling rates. A similar model for apatite over-predicts the observed clumped-isotope temperatures found in natural samples; we hypothesize this discrepancy is the result of annealing of radiation damage in our experiments, which lowers the diffusivity and rate of isotope exchange of carbonate groups compared to damaged natural samples. Finally, we constructed models to explore how heating can alter recorded clumped-isotope temperatures. Our model predicts that samples change in clumped-isotope temperatures in two stages. The first stage changes the recorded clumped isotope temperatures by

International audience; Recent measurements of methane (CH4) by the Mars Science Laboratory (MSL) now confront us with robust data that demand interpretation. Thus far, the MSL data have revealed a baseline level of CH4 (*0.4 parts per billion by volume [ppbv]), with seasonal variations, as well as greatly enhanced spikes of CH4 with peak abundances of *7 ppbv. What do these CH4 revelations with drastically different abundances and temporal signatures represent in terms of interior geochemical processes, or is martian CH4 a biosignature? Discerning how CH4 generation occurs on Mars may shed light on the potential habitability of Mars. There is no evidence of life on the surface of Mars today, but microbes might reside beneath the surface. In this case, the carbon flux represented by CH4 would serve as a link between a putative subterranean biosphere on Mars and what we can measure above the surface. Alternatively, CH4 records modern geochemical activity. Here we ask the fundamental question: how active is Mars, geochemically and/or biologically? In this article, we examine geological, geochemical, and biogeo- chemical processes related to our overarching question. The martian atmosphere and surface are an over- whelmingly oxidizing environment, and life requires pairing of electron donors and electron acceptors, that is, redox gradients, as an essential source of energy. Therefore, a fundamental and critical question regarding the possibility of life on Mars is, ‘‘Where can we find redox gradients as energy sources for life on Mars?’’ Hence, regardless of the pathway that generates CH4 on Mars, the presence of CH4, a reduced species in an oxidant-rich environment, suggests the possibility of redox gradients supporting life and habitability on Mars. Recent missions such as ExoMars Trace Gas Orbiter may provide mapping of the global distribution of CH4. To discriminate between abiotic and biotic sources of CH4 on Mars, future studies should use a series of diagnostic geochemical analyses, preferably performed below the ground or at the ground/atmosphere interface, including measurements of CH4 isotopes, methane/ethane ratios, H2 gas concentration, and species such as acetic acid. Advances in the fields of Mars exploration and instrumentation will be driven, augmented, and supported by an improved un- derstanding of atmospheric chemistry and dynamics, deep subsurface biogeochemistry, astrobiology, planetary geology, and geophysics. Future Mars exploration programs will have to expand the integration of complementary areas of expertise to generate synergistic and innovative ideas to realize breakthroughs in advancing our under- standing of the potential of life and habitable conditions having existed on Mars. In this spirit, we conducted a set of interdisciplinary workshops. From this series has emerged a vision of technological, theoretical, and meth- odological innovations to explore the martian subsurface and to enhance spatial tracking of key volatiles, such as CH4.

© 2018 The Author(s). Methane clumped-isotope compositions provide a new approach to understanding the formational conditions of methane from both biogenic and thermogenic sources. Under some conditions, these compositions can be used to reconstruct the formational temperatures of the gas, and this capability can be applied to common subsets of both biogenic and thermogenic systems. Additionally, there are examples in which clumped-isotope compositions do not reflect gas-formation temperatures but instead mixing effects and kinetic phenomena; such kinetic effects also occur in common and recognizable subtypes of biogenic and thermogenic gases. Here we review the use of methane clumped-isotope measurements for understanding the origin of methane in the subsurface. We review methane clumped-isotope measurements from numerous biogenic and thermogenic natural gas reservoirs.We then place these measurements in the context of common frameworks for identifying the formational conditions of methane including the use of methane δ13C and δD values and C1/C2-3ratios. Finally, we propose a framework for how methane clumped isotopes can be used to identify the origin of methane accumulations.

© 2017 Elsevier Ltd The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism.

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O

Exhumation and accompanying retrograde metamorphism alter the compositions and textures of metamorphic rocks through deformation, mineral–mineral reactions, water–rock reactions, and diffusion-controlled intra- and inter-mineral atomic mobility. Here, we demonstrate that these processes are recorded in the clumped- and single-isotope (δ^(13)C and δ^(18)O) compositions of marbles, which can be used to constrain retrograde metamorphic histories. We collected 27 calcite and dolomite marbles along a transect from the rim to the center of the metamorphic core-complex of Naxos (Greece), and analyzed their carbonate single- and clumped-isotope compositions. The majority of Δ_(47) values of whole-rock samples are consistent with exhumation- controlled cooling of the metamorphic complex. However, the data also reveal that water–rock interaction, deformation driven recrystallization and thermal shock associated with hydrothermal alteration may considerably impact the overall distribution of Δ_(47) values. We analyzed specific carbonate fabrics influenced by deformation and fluid–rock reaction to study how these processes register in the carbonate clumped-isotope system. Δ_(47) values of domains drilled from a calcite marble show a bimodal distribution. Low Δ_(47_ values correspond to an apparent temperature of 260 °C and are common in static fabrics; high Δ_(47) values correspond to an apparent temperature of 200 °C and are common in dynamically recrystallized fabrics. We suggest that the low Δ_(47) values reflect diffusion-controlled isotopic reordering during cooling, whereas high Δ_(47) values reflect isotopic reordering driven by dynamic recrystallization. We further studied the mechanism by which dynamic recrystallization may alter Δ_(47) values by controlled heating experiments. Results show no significant difference between laboratory reactions rates in the static and dynamic fabrics, consistent with a mineral-extrinsic mechanism, in which slip along crystal planes was associated with atomic-scale isotopic reordering in the calcite lattice. An intrinsic mechanism (enhanced isotopic reordering rate in deformed minerals) is contraindicated by these experiments. We suggest that Δ_(47) values of dynamically recrystallized fabrics that form below the diffusion-controlled blocking-temperature for calcite constrain the temperature of deformation. We find that Δ_(47)-based temperatures of static fabrics from Naxos marbles are ∼60–80 °C higher than commonly observed in slowly cooled metamorphic rocks, and would suggest cooling rates of ∼10^5°C Myr^(−1). A similar thermal history is inferred for dolomite marbles from the core vicinity, which preserve apparent temperatures up to 200 °C higher than a typical blocking temperature (∼300 °C). This finding could be explained by a hydrothermal event driving a brief thermal pulse and locally resetting Δ_(47) values. Rapid cooling of the core-complex region is consistent with a compilation of published cooling ages and a new apatite U–Th/He age, associating the thermal event with the emplacement of a granodiorite pluton at ∼12 Ma.

Isotope geochemistry is in the midst of a remarkable period of innovation and discovery; the last decade (or so) has seen the emergence of ‘nontraditional’ stable isotopes of metals (i.e., variations in isotopic compositions of Mg, Fe, Cu, etc.), a great expansion of mass-independent isotope geochemistry, the invention of clumped isotope geochemistry, and new capabilities for measurements of position-specific isotope effects in organic compounds. These advances stem from the emergence of multi-collector plasma mass spectrometry, innovations in gas source mass spectrometry, infrared absorption spectroscopy, and nuclear magnetic resonance techniques. These new observations demand new connections between isotope geochemistry and the chemical physics that underlie isotopic variations, including experimental study and modeling of vibrational isotope effects, photochemical isotope effects, and various nuclear volume and magnetic effects. Importantly, such collaborations also have something to offer chemists and physicists because the novel observations of emerging branches of stable isotope geochemistry hold the potential to reveal new insights into the nature of chemical bonds and reactions. This review looks broadly across the frontiers of new methods and discoveries of stable isotope geochemistry and the fundamental chemical–physics problems they pose, focusing in particular on the most pressing problems in: kinetic isotope effects in complex systems; mass independent isotope geochemistry (both the strong effects in photochemical reactions and the subtle variations of more conventional reactions); clumped isotope geochemistry; and the position-specific isotopic anatomies of organic molecules.

Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542 Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (delta Cr-53 up to +5.0 parts per thousand.) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (Fe-HR) to total iron (Fe-tot) which indicate a predominance of anoxic water columns (Fe-HR/Fe-tot>0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd T-DM model ages=2.1-2.2 Ga) provenance typical of the Rio de la Plata Craton. The association of positive delta Cr-53-ferruginous (Fe-HR/Fe-tot>0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian-Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian-Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic. (C) 2012 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved. Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (δ 53Cr up to +5.0%) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (Fe HR) to total iron (Fe tot) which indicate a predominance of anoxic water columns (Fe HR/Fe tot>0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd T DM model ages=2.1-2.2Ga) provenance typical of the Rio de la Plata Craton. The association of positive δ 53Cr-ferruginous (Fe HR/Fe tot>0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian-Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian-Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic.

We describe a new high-resolution, multi-collector gas source mass spectrometer designed for isotopic analysis of volatile and semi-volatile molecules: the Thermo Scientific MAT253-Ultra, a prototype double-focusing isotope ratio mass spectrometer installed in the Caltech laboratories for stable isotope geochemistry. This instrument achieves mass resolving power of up to ∼27,000 (M/ΔM) and can analyze diverse gases and semi-volatile compounds using a conventional dual inlet and/or a carrier gas. It has a multi-collector array comprised of 7 detector positions with adjustable spacing, all of which can register ions through an SEM or Faraday cup and spanning up to a 10^(13) range in signal strength. Abundance sensitivity in the He mass range is as good as 10^(−12), and precision commonly approaches the counting statistics limit down to 0.1‰ (SEM) or 0.01‰ (Faraday) for a range of analytes. This instrument permits resolution of isobaric interferences arising from both contaminants and multiple isotopologues of an analyte that share a cardinal mass, enabling direct isotopic analysis of molecules with complex mass spectra such as hydrocarbons. This ability should enable the measurement of position-specific isotopic compositions, including multiple substitutions, by comparing isotope ratios of molecular ions with those of daughter fragment ions (assuming products of recombination and other source reactions are recognized and corrected for). The combination of high mass resolution with stable multicollection will provide a wide range of potential new tools for isotope geochemistry, including (but not limited to): singly and multiply substituted methane and larger hydrocarbons; position-specific ^(13)C analysis of propane and larger hydrocarbons; precise analysis of ^(17)O/^(16)O and ^(18)O/^(16)O on fragment ions from CO_2 and other molecules; analysis of a variety of N_2O isotopologues (including ^(18)O, ^(17)O, position-specific ^(15)N, and various ‘clumped’ species); and high precision and abundance sensitivity noble gas analyses. These capabilities greatly extend the scope of stable isotope variations that can be utilized for problems in forensics, environmental geochemistry, biochemistry, and Earth and planetary sciences.

© 2016 Elsevier Ltd. Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium δ18values spanning a range of more than 5‰.

© 2017 John Wiley & Sons Ltd The Athel silicilyte is an enigmatic, hundreds of meters thick, finely laminated quartz deposit, in which silica precipitated in deep water (>~100–200 m) at the Ediacaran–Cambrian boundary in the South Oman Salt Basin. In contrast, Meso-Neoproterozoic sinks for marine silica were dominantly restricted to peritidal settings. The silicilyte is known to contain sterane biomarkers for demosponges, which today are benthic, obligately aerobic organisms. However, the basin has previously been described as permanently sulfidic and time-equivalent shallow-water carbonate platform and evaporitic facies lack silica. The Athel silicilyte thus represents a unique and poorly understood depositional system with implications for late Ediacaran marine chemistry and paleoecology. To address these issues, we made petrographic observations, analyzed biomarkers in the solvent-extractable bitumen, and measured whole-rock iron speciation and oxygen and silicon isotopes. These data indicate that the silicilyte is a distinct rock type both in its sedimentology and geochemistry and in the original biology present as compared to other facies from the same time period in Oman. The depositional environment of the silicilyte, as compared to the bounding shales, appears to have been more reducing at depth in sediments and possibly bottom waters with a significantly different biological community contributing to the preserved biomarkers. We propose a conceptual model for this system in which deeper, nutrient-rich waters mixed with surface seawater via episodic mixing, which stimulated primary production. The silica nucleated on this organic matter and then sank to the seafloor, forming the silicilyte in a sediment-starved system. We propose that the silicilyte may represent a type of environment that existed elsewhere during the Neoproterozoic. These environments may have represented an important locus for silica removal from the oceans.

© 2016 Elsevier Ltd. 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 δ18O values and clumped-isotope-based (δ47) temperatures of carbonate groups in apatites from phosphorites from the past 265 million years. We compare these measurements to previously measured δ18O 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 δ18O 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 δ18O 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.

Molecular oxygen (O2) is the second most abundant gas in the Earth’s atmosphere, but in many natural environments, its concentration is reduced to low or even undetectable levels. Although low-oxygen-adapted organisms define the ecology of low-oxygen environments, their capabilities are not fully known. These capabilities also provide a framework for reconstructing a critical period in the history of life, because low, but not negligible, atmospheric oxygen levels could have persisted before the “Great Oxidation” of the Earth’s surface about 2.3 to 2.4 billion years ago. Here, we show that Escherichia coli K-12, chosen for its well-understood biochemistry, rapid growth rate, and low-oxygen-affinity terminal oxidase, grows at oxygen levels of ≤ 3 nM, two to three orders of magnitude lower than previously observed for aerobes. Our study expands both the environmental range and temporal history of aerobic organisms. Molecular oxygen (O2) is the second most abundant gas in the Earth’s atmosphere, but in many natural environments, its concentration is reduced to low or even undetectable levels. Although low-oxygen-adapted organisms define the ecology of low-oxygen environments, their capabilities are not fully known. These capabilities also provide a framework for reconstructing a critical period in the history of life, because low, but not negligible, atmospheric oxygen levels could have persisted before the “Great Oxidation” of the Earth’s surface about 2.3 to 2.4 billion years ago. Here, we show that Escherichia coli K-12, chosen for its well-understood biochemistry, rapid growth rate, and low-oxygen-affinity terminal oxidase, grows at oxygen levels of ≤ 3 nM, two to three orders of magnitude lower than previously observed for aerobes. Our study expands both the environmental range and temporal history of aerobic organisms.

The history of atmospheric O2 partial pressures (Po2) is inextricably linked to the coevolution of life and Earth's biogeochemical cycles. Reconstructions of past Po2 rely on models and proxies but often markedly disagree. We present a record of Po2 reconstructed using O2/N2 ratios from ancient air trapped in ice. This record indicates that Po2 declined by 7 per mil (0.7%) over the past 800,000 years, requiring that O2 sinks were ~2% larger than sources. This decline is consistent with changes in burial and weathering fluxes of organic carbon and pyrite driven by either Neogene cooling or increasing Pleistocene erosion rates. The 800,000-year record of steady average carbon dioxide partial pressures (Pco2) but declining Po2 provides distinctive evidence that a silicate weathering feedback stabilizes Pco2 on million-year time scales.

The analysis of mass 47 isotopologues of CO_2 (mainly ^(13)C^(18)O^(16)O) is established as a constraint on sources and sinks of environmental CO_2, complementary to δ^(13)C and δ^(18)O constraints, and forms the basis of the carbonate clumped isotope thermometer. This measurement is commonly reported using the Δ_(47) value — a measure of the enrichment of doubly substituted CO_2 relative to a stochastic isotopic distribution. Values of Δ_(47) for thermodynamically equilibrated CO_2 approach 0 (a random distribution) at high temperatures (≥ several hundred degrees C), and increase with decreasing temperature, to ≈ 0.9% at 25 °C. While the thermodynamic properties of doubly substituted isotopologues of CO_2 (and, similarly, carbonate species) are relatively well understood, there are few published constraints on their kinetics of isotopic exchange. This issue is relevant to understanding both natural processes (e.g., photosynthesis, respiration, air–sea or air–groundwater exchange, CO_2 degassing from aqueous solutions, and possibly gas–sorbate exchange on cold planetary surfaces like Mars), and laboratory handling of CO_2 samples for Δ_(47) analysis (e.g., re-equilibration in the presence of liquid water, water ice or water adsorbed on glass or metal surfaces). We present the results of an experimental study of the kinetics of isotopic exchange, including changes in Δ_(47) value, of CO_2 exposed to liquid water between 5 and 37 °C. Aliquots of CO_2 gas were first heated to reach a nearly random distribution of its isotopologues and then exposed at low pressure for controlled periods of time to large excesses of liquid water in sealed glass containers. Containers were held at 5, 25 and 37 °C and durations of exchange ranging from 5 min to 7 days. To avoid the formation of a boundary layer that might slow exchange, the tubes were vigorously shaken during the period of exchange. At the end of each experiment, reaction vessels were flash frozen in liquid nitrogen. CO_2 gas was then recovered from the head space of the reaction vessel, purified and analyzed for its Δ_(47), δ^(13)C and δ^(18)O by gas source isotope ratio mass spectrometry. Equilibrium was reached for both δ^(18)O and Δ_(47) after durations of a few hours to tens of hours. Δ^(18)O values at equilibrium were consistent with known fractionation factors for the CO_2–H_2O system. The evolution of δ^(18)O and Δ_(47) with experiment duration were consistent with first-order reactions, with rate constants equal to each other (within error), averaging 0.19 h^(−1) at 5 °C, 0.38 h^(−1) at 25 °C and 0.65 h^(−1) at 37 °C. We calculate an activation energy for this isotopic exchange reaction of 26.2 kJ/mol. By comparison, Mills and Urey (1940) measured the rate of ^(18)O exchange between CO_2(aq) and water to have a rate of 11 h^(−1) at 25 °C and an activation energy of 71.7 kJ/mol. Our finding of a slower rate and lower activation energy is consistent with the rate limiting step of our experiment being the CO_2(g)–CO_2(aq) exchange, even when samples are shaken during the partial equilibration. Our results broadly resemble those from the study of (Affek, 2013), though this prior study found a lower rate constant for Δ_(47). We propose that the difference is due to analytical uncertainties and explore the theoretical consequences of unequal reaction rates between ^(12)C^(18)O^(16)O and ^(13)C^(18)O^(16)O with a forward model.

Making of methane deep underground Technologies such as hydraulic fracturing, or “fracking,” can now extract natural gas from underground reservoirs. Within the gas, the ratio of certain isotopes holds clues to its origins. Stolper et al. analyzed a wide range of natural gas, including samples from some of the most active fracking sites in the United States. Using a “clumped isotope” technique, the authors could estimate the high temperatures at which methane formed deep underground, as well as the lower temperatures at which ancient microbes produced methane. The approach can help to distinguish the degree of mixing of gas from both sources. Science , this issue p. 1500

The zinc finger protein EVI1 is causally associated with acute myeloid leukemogenesis, and inhibition of its function with a small molecule therapeutic may provide effective therapy for EVI1-expressing leukemias. In this paper we describe the development of a pyrrole–imidazole polyamide to specifically block EVI1 binding to DNA. We first identify essential domains for leukemogenesis through structure–function studies on both EVI1 and the t(3;21)(q26;q22)-derived RUNX1-MDS1-EVI1 (RME) protein, which revealed that DNA binding to the cognate motif GACAAGATA via the first of two zinc finger domains (ZF1, encompassing fingers 1–7) is essential transforming activity. To inhibit DNA binding via ZF1, we synthesized a pyrrole–imidazole polyamide 1, designed to bind to a subsite within the GACAAGATA motif and thereby block EVI1 binding. DNase I footprinting and electromobility shift assays revealed a specific and high affinity interaction between polyamide 1 and the GACAAGATA motif. In an in vivo CAT reporter assay using NIH-3T3-derived cell line with a chromosome-embedded tet-inducible EVI1-VP16 as well as an EVI1-responsive reporter, polyamide 1 completely blocked EVI1-responsive reporter activity. Growth of a leukemic cell line bearing overexpressed EVI1 was also inhibited by treatment with polyamide 1, while a control cell line lacking EVI1 was not. Finally, colony formation by RME was attenuated by polyamide 1 in a serial replating assay. These studies provide evidence that a cell permeable small molecule may effectively block the activity of a leukemogenic transcription factor and provide a valuable tool to dissect critical functions of EVI1 in leukemogenesis.

The Microscopic Imager (MI) on the Mars Exploration Rover Opportunity has returned images of Mars with higher resolution than any previous camera system, allowing detailed petrographic and sedimentological studies of the rocks and soils at the Meridiani Planum landing site. Designed to simulate a geologist's hand lens, the MI is mounted on Opportunity's instrument arm and can resolve objects 0.1 mm across or larger. This paper provides an overview of MI operations, data calibration, and analysis of MI data returned during the first 900 sols (Mars days) of the Opportunity landed mission. Analyses of Opportunity MI data have helped to resolve major questions about the origin of observed textures and features. These studies support eolian sediment transport, rather than impact surge processes, as the dominant depositional mechanism for Burns formation strata. MI stereo observations of a rock outcrop near the rim of Erebus Crater support the previous interpretation of similar sedimentary structures in Eagle Crater as being formed by surficial flow of liquid water. Well-sorted spherules dominate ripple surfaces on the Meridiani plains, and the size of spherules between ripples decreases by about 1 mm from north to south along Opportunity's traverse between Endurance and Erebus craters.