Uncovering the Neoproterozoic carbon cycle.

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10-100 million years) characterized by δ(13)C in carbonate (δ(13)C(carb)) enriched to more than +5 per mil. Classically, δ(13)C(carb) is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ(13)C(carb) and δ(13)C in organic carbon (δ(13)C(org)) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ(13)C(carb) excursions that are decoupled from δ(13)C(org), however, indicates that other mechanisms may account for these excursions. Here we present δ(13)C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ(13)C(carb) excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ(13)C(carb) anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.

Decadal sea surface temperature variability in the subtropical South Pacific from 1726 to 1997 A.D.

We present a 271-year record of Sr/Ca variability in a coral from Rarotonga in the South Pacific gyre. Calibration with monthly sea surface temperature (SST) from satellite and ship measurements made in a grid measuring 1 degrees by 1 degrees over the period from 1981 to 1997 indicates that this Sr/Ca record is an excellent proxy for SST. Comparison with SST from ship measurements made since 1950 in a grid measuring 5 degrees by 5 degrees also shows that the Sr/Ca data accurately record decadal changes in SST. The entire Sr/Ca record back to 1726 shows a distinct pattern of decadal variability, with repeated decadal and interdecadal SST regime shifts greater than 0. 75 degrees C. Comparison with decadal climate variability in the North Pacific, as represented by the Pacific Decadal Oscillation index (1900-1997), indicates that several of the largest decadal-scale SST variations at Rarotonga are coherent with SST regime shifts in the North Pacific. This hemispheric symmetry suggests that tropical forcing may be an important factor in at least some of the decadal variability observed in the Pacific Ocean.

A theory of atmospheric oxygen.

Geological records of atmospheric oxygen suggest that pO2 was less than 0.001% of present atmospheric levels (PAL) during the Archean, increasing abruptly to a Proterozoic value between 0.1% and 10% PAL, and rising quickly to modern levels in the Phanerozoic. Using a simple model of the biogeochemical cycles of carbon, oxygen, sulfur, hydrogen, iron, and phosphorous, we demonstrate that there are three stable states for atmospheric oxygen, roughly corresponding to levels observed in the geological record. These stable states arise from a series of specific positive and negative feedbacks, requiring a large geochemical perturbation to the redox state to transition from one to another. In particular, we show that a very low oxygen level in the Archean (i.e., 10-7 PAL) is consistent with the presence of oxygenic photosynthesis and a robust organic carbon cycle. We show that the Snowball Earth glaciations, which immediately precede both transitions, provide an appropriate transient increase in atmospheric oxygen to drive the atmosphere either from its Archean state to its Proterozoic state, or from its Proterozoic state to its Phanerozoic state. This hypothesis provides a mechanistic explanation for the apparent synchronicity of the Proterozoic Snowball Earth events with both the Great Oxidation Event, and the Neoproterozoic oxidation.

Modeling the carbon cycle in Lake Matano.

Lake Matano, Indonesia, is a stratified anoxic lake with iron-rich waters that has been used as an analogue for the Archean and early Proterozoic oceans. Past studies of Lake Matano report large amounts of methane production, with as much as 80% of primary production degraded via methanogenesis. Low δ(13)C values of DIC in the lake are difficult to reconcile with this notion, as fractionation during methanogenesis produces isotopically heavy CO2. To help reconcile these observations, we develop a box model of the carbon cycle in ferruginous Lake Matano, Indonesia, that satisfies the constraints of CH4 and DIC isotopic profiles, sediment composition, and alkalinity. We estimate methane fluxes smaller than originally proposed, with about 9% of organic carbon export to the deep waters degraded via methanogenesis. In addition, despite the abundance of Fe within the waters, anoxic ferric iron respiration of organic matter degrades <3% of organic carbon export, leaving methanogenesis as the largest contributor to anaerobic organic matter remineralization, while indicating a relatively minor role for iron as an electron acceptor. As the majority of carbon exported is buried in the sediments, we suggest that the role of methane in the Archean and early Proterozoic oceans is less significant than presumed in other studies.

Subsurface characterization of methane production and oxidation from a New Hampshire wetland.

We measured the carbon isotopic composition of pore water carbon dioxide from Sallie's Fen, a New Hampshire poor fen. The isotope profiles are used in combination with a one-dimensional diffusion-reaction model to calculate rates of methane production, oxidation and transport over an annual cycle. We show how the rates vary with depth over a seasonal cycle, with methane produced deeper during the winter months and at progressively shallower depths into the summer season. The rates of methane production, constrained by the measured delta(13)C(dic) profiles, cannot explain high methane emission during the summer. We suggest that much of the methane produced during this time comes either from the unsaturated peat, or from the top 1-3 cm of saturated peat where episodic exchange with the atmosphere makes it invisible to our method.