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Large isotopic variability at the micron-scale in ‘Shuram’ excursion carbonates from South Australia
Ediacaran-aged (635–541 million years ago) marine sediments contain a large negative carbon isotope (δ 13 C) excursion, in which carbonate δ 13 C values reach -12‰ (VPDB). Known as the ‘Shuram’ excursion, many workers have interpreted this δ 13 C record as an unprecedented perturbation to the global carbon cycle, leading to speculation about a causal connection to the broadly contemporaneous rise of animal life. Others have interpreted the δ 13 C signal as a product of diagenesis, thereby minimizing its relevance for understanding the evolution of metazoans. In this work, we present SEM imaging and in-situ δ 13 C and δ 18 C values measured by secondary ion mass spectrometry (SIMS) to assess these competing hypotheses in the Wonoka Formation of South Australia. Our results from the minimum of the excursion show that rounded sedimentary grains of calcite have δ 13 C values between -12.8 to -10.6‰ and δ 18 C values between 17.8 to 15.5‰ (VPDB). Euhedral dolomite that appears to have grown unimpeded in open sedimentary pore spaces also is present. These early-stage dolomites are interpreted as early authigenic in origin and have δ 13 C values that reach +5‰, requiring a formation fluid with a substantially different δ 13 C composition from basin waters or bulk sediment. Together, these results provide little evidence for the hypothesis that a late diagenetic overprint has generated the ‘Shuram’ excursion in the Wonoka. Instead, they suggest the presence of a large carbon isotopic gradient in the surface environment, with shallow waters capable of precipitating carbonates with very low δ 13 C (down to 12‰) and deeper shelf and/or marine pore waters generating carbonates with positive carbon isotope values (up to +5‰). Because negative isotope excursions of similar magnitude are found in widely dispersed Ediacaran basins, it is likely that this gradient was characteristic of shelf environments of this period and that a still-unknown global process led to the ‘Shuram’ excursion in shallow water carbonates.
Carbon kinetic isotope effect in the reaction of CH4 with HO
The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.
Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical
The reaction of the hydroxyl radical (HO) with the stable carbon isotopes of methane has been studied as a function of temperature from 273 to 353 K. The measued ratio of the rate coefficients for reaction with (C-12)H4 relative to (C-13)H4 (k12/k13) was 1.0054 (+ or - 0.0009 at the 95 percent confidence interval), independent of temperature within the precision of the measurement, over the range studied. The precision of the present value is much improved over that of previous studies, and this result provides important constraints on the current understanding of the cycling of methane through the atmosphere through the use of carbon isotope measurements.
Carbon and oxygen isotope study of carbonates from highly shocked clasts of the polymict breccia of the Haughton Crater (Canada)
It is known that the release of volatiles on impact is an important controlling factor in cratering processes in carbonate terranes and in the mobility of chemical elements. In order to assess the nature and the role of carbon- and oxygen-bearing volatiles during impact-induced metamorphism of sedimentary rocks, the C-13/C-12 and O-18/O-16 ratios and carbonate contents were determined for 30 shocked clasts from the Haughton Crater polymict breccia as well as for some unshocked carbonates from the sedimentary cover adjacent to the crater. Shock-induced CO2 loss during decarbonation of calcite is known to be a function of peak pressure and ambient partial pressure of the volatile species. In our clast samples, shocked from 20 to 60 GPa, we expect about 20 to 100 percent CO2 loss and preferential depletion in C-13 and O-18 in the residual carbonate. Rayleigh model (progressive loss of CO2) and batch model (single-step loss of CO2) curves for this depletion are shown. The magnitudes of the C-13 and O-18 depletions increase with the increase of the CO2 loss. In addition, the isotopic depletions should be correlated with an enrichment in CaO and MgO in the residual solid.
Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters
A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.
Long-Term 13 C Uptake by 12 C-Enriched Calcite
Knowledge of the exchange of carbon isotopes between dissolved inorganic carbon and calcite minerals is of long-standing importance for the interpretation of sedimentary paleoclimate records and 14 C transport in the geosphere. To assess the mechanism and rates of carbon isotope exchange, we equilibrated 12 C-pure synthetic calcite particles in water, first in a glovebox and then in contact with atmospheric P CO 2 and 13 C/ 12 C ratio, at two different temperatures. Cavity ring-down infrared spectroscopy δ 13 C measurements of the solid revealed sustained 13C incorporation for over a period of 500 days (21 °C) and 125 days (50 °C). We developed a quantitative model for recrystallization and isotope exchange, assuming that the interfacial free energy provides a thermodynamic driving force for the growth of larger particles at the expense of smaller ones. Furthermore, this Ostwald ripening model did not reproduce the kinetics of 13C uptake and required greater coarsening than observed. Rather, the data were best explained by a mechanism involving surface exchange and solid-phase diffusion of 13C into the particles with an inferred effective diffusion constant at 21 °C of about 10 –25 m 2 /s. Although this work cannot rule out the possibility that structural or chemical aspects of the synthetic particles enabled faster 13 C uptake than could be observed in natural systems, this study adds to the body of the recent work, suggesting that fast exchange processes are possible, likely through grain boundaries and other defects.
Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes
Carbon and oxygen stable isotopic compositions of lacustrine carbonate from a southeastern Michigan marl lake display linear covariance over a range of 4.0% Peedee belemnite (PDB) in oxygen and 3.9% (PDB) in carbon. Mechanisms of delta 13 C-delta 18 O coupling conventionally attributed to lake closure in arid-region basins are inapplicable to hydrologically open lake systems. Thus, an alternative explanation of isotopic covariance in temperate region dimictic marl lakes is required. We propose that isotopic covariance is a direct record of change in regional climate. In short-residence-time temperate-region lake basins, summer meteoric precipitation is enriched in 18O relative to winter values, and summer organic productivity enriches epilimnic dissolved inorganic carbon in 13C. Thus, climate change toward longer summers and/or shorter winters could result in greater proportions of warm-month meteoric precipitation, longer durations of warm-month productivity, and net long-term enrichment in carbonate 18O and 13C. Isotopic covariance observed in the Michigan marl lake cores is interpreted to reflect postglacial warming from 10 to 3 ka followed by cooler mean annual temperature, a shift toward greater proportions of seasonal summer precipitation, a shortening of the winter season, or some combination of these three factors.
Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs
An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.
The Cretaceous-Tertiary boundary marine extinction and global primary productivity collapse
The extinction of marine phyto-and zoo-plankton across the K-T boundary has been well documented. Such an event may have resulted in decreased photosynthetic fixation of carbon in surface waters and a collapse of the food chain in the marine biosphere. Because the vertical and horizontal distribution of the carbon isotopic composition of total dissolved carton (TDC) in the modern ocean is controlled by the transfer of organic carbon from the surface to deep reservoirs, it follows that a major disruption of the marine biosphere would have had a major effect on the distribution of carbon isotopes in the ocean. Negative carbon isotope excursions have been identified at many marine K-T boundary sequences worldwide and are interpreted as a signal of decreased oceanic primary productivity. However, the magnitude, duration and consequences of this productivity crisis have been poorly constrained. On the basis of planktonic and benthic calcareous microfossil carbon isotope and other geochemical data from DSDP Site 577 located on the Shatsky Rise in the north-central Pacific, as well as other sites, researchers have been able to provide a reasonable estimate of the duration and magnitude of this event.
The carbon components in SNC meteorites of feldspathic harzburgite composition
Two meteorites collected in Antarctica, ALH A77005 and LEW 88516, have characteristics which link them to the shergottite group of SNC meteorites. Essentially, ALH A77005 and LEW 88516 are feldspathic harzburgites, being comprised of roughly equal quantities of olivine and pyroxene, with an additional few percent of feldspar which has subsequently been converted to maskelynite by shock. The meteorites represent samples of a cumulate rock which is itself composed of two different lithologies: in one, large pyroxenes poikilitically enclose olivine crystals, while the other consists of interstitial areas made up of pyroxene, olivine, maskelynite, whitlockite, troilite, ilmenite and chlorapatite. It has been proposed that meteorites such as ALH A77005 (and LEW 88516) are relict samples of the source peridotite from which the other shergottites formed. As such it should be informative to study in detail the carbon components present within these samples, in order to make comparisons with data from other shergottites. Although not plutonic in origin, and therefore not sampling a truly deep source, analyses of ALH A77005 and LEW 88516 should assist with attempts to define the bulk carbon isotopic composition of Mars. This has been assessed previously through analyses of carbon of presumed magmatic origin in other SNC meteorites, but the carbon isotopic compositions obtained seem to be at variance with what might be expected. It is important to constrain the carbon isotopic composition of Mars as well as possible so that models of atmospheric evolution, based on carbon isotopic data, can yield the most reliable results.
An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation
Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.
Global geochemical cycles of carbon, sulfur and oxygen
Time resolved data on the carbon isotopic composition of carbonate minerals and the sulfur isotopic composition or sulfate minerals show a strong negative correlation during the Cretaceous. Carbonate minerals are isotopically heavy during this period while sulfate minerals are isotopically light. The implication is that carbon is being transferred from the oxidized, carbonate reservoir to the reservoir of isotopically light reduced organic carbon in sedimentary rocks while sulfur is being transferred from the reservoir of isotopically light sedimentary sulfide to the oxidized, sulfate reservoir. These apparently oppositely directed changes in the oxidation state of average sedimentary carbon and sulfur are surprising because of a well-established and easy to understand correlation between the concentrations of reduced organic carbon and sulfide minerals in sedimentary rocks. Rocks rich in reduced carbon are also rich in reduced sulfur. The isotopic and concentration data can be reconciled by a model which invokes a significant flux of hydrothermal sulfide to the deep sea, at least during the Cretaceous.
The relation between isotopic composition of argon and carbon in natural gases
The methods and results of determination of the argon and carbon isotope compositions of hydrocarbon gases of Mezozoic complexes of Western Siberia are presented. Based on the Ar-36, Ar-40, C-12, C-13 content of the various deposits and on the presumed mechanisms of entry of these isotopes into the deposits, it is concluded that formation of natural gas in some deposits included vertical migration from a lower complex.
The submillimeter wave astronomy satellite
The Submillimeter Wave Astronomy Satellite (SWAS) selected for flight as part of the Small Explorer Program is described. SWAS consists of a 55 by 71 cm near optical quality off axis primary mirror, two heteorodyne radiometers with Schottky barrier diode mixers, and a single broadband (1.4 GHz) Acousto Optical Spectrometer (AOS). SWAS primary objective is to conduct a high spectral resolution survey of galactic molecular clouds in low lying transitions of water, molecular oxygen, atomic carbon and isotopic carbon monoxide. These species are crucial in gaining a better understanding of the chemistry and cooling of dense molecular clouds.
Boron isotopes in blue diamond record seawater-derived fluids in the lower mantle
Boron is a quintessential crustal element but its conspicuous presence in diamond – a mantle mineral – raises questions about potential subduction pathways for boron and other volatiles. It has been a long-standing goal to characterize the isotopic composition of boron in blue, boron-bearing (Type IIb) diamonds to reveal its origin. Mineral inclusions indicate that Type IIb diamonds crystallize at transition zone to lower mantle depths, meaning that if the boron is subducted it would trace a pathway of volatile elements into the deep mantle. Here, using off-line laser ablation sampling, we present the first boron isotope compositions, along with trace element contents and carbon isotope compositions, of a suite of blue diamonds mainly sourced from the Cullinan diamond mine in South Africa. The ten analyzed blue diamonds have a wide range in δ 11 B, between -9.2 ± 2‰ and -0.5 ± 2‰, compared to the more restricted range for mid-ocean ridge basalts (-7.1 ± 0.9‰). Carbon isotope values for the blue diamonds range between -20.6 and -1.8‰, with a mode at -17‰, significantly more negative than the main mantle mode at -5‰. Combined, the boron and carbon isotope compositions require fluid input from subducted oceanic lithosphere down into deep mantle source regions of blue diamonds. This finding highlights a deep subduction pathway for volatiles to stoke the source regions of deeply-derived magmas.
Early Fluid Activity on Ryugu Inferred By Oxygen, Carbon, and 53Mn-53Cr Isotopic Analyses of Carbonates and Magnetite
Samples from asteroid Ryugu returned by the Hayabusa2 mission contain evidence of extensive alteration by aqueous fluids and appear related to the CI chondrites. To understand the sources of the fluid and the timing of chemical reactions occurring during the alteration processes, we investigated the oxygen, carbon, and 53Mn-53Cr systematics of carbonate and magnetite in two Ryugu particles. We find that the fluid was initially between 0−20 °C and enriched in 13C, and 17O and 18O, and subsequently evolved towards lighter carbon and oxygen isotopic compositions as alteration proceeded. Carbonate ages show that this fluid-rock interaction took place within the first ~1.8 million years of solar system history, requiring early accretion either in a planetesimal less than ~20 km in diameter or within a larger body which was disrupted and reassembled.