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A diurnal carbon engine explains 13C-enriched carbonates without increasing the global production of oxygen.

ABSTRACT: In the past 3 billion years, significant volumes of carbonate with high carbon-isotopic ([Formula: see text]C) values accumulated on shallow continental shelves. These deposits frequently are interpreted as records of elevated global organic carbon burial. However, through the stoichiometry of primary production, organic carbon burial releases a proportional amount of [Formula: see text], predicting unrealistic rises in atmospheric [Formula: see text] during the 1 to 100 million year-long positive [Formula: see text]C excursions that punctuate the geological record. This carbon-oxygen paradox assumes that the [Formula: see text]C of shallow water carbonates reflects the [Formula: see text]C of global seawater-dissolved inorganic carbon (DIC). However, the [Formula: see text]C of modern shallow-water carbonate sediment is higher than expected for calcite or aragonite precipitating from seawater. We explain elevated [Formula: see text]C in shallow carbonates with a diurnal carbon cycle engine, where daily transfer of carbon between organic and inorganic reservoirs forces coupled changes in carbonate saturation ([Formula: see text]) and [Formula: see text]C of DIC. This engine maintains a carbon-cycle hysteresis that is most amplified in shallow, sluggishly mixed waters with high rates of photosynthesis, and provides a simple mechanism for the observed [Formula: see text]C-decoupling between global seawater DIC and shallow carbonate, without burying organic matter or generating O2.

SUBMITTER: Geyman EC

PROVIDER: S-EPMC6900632 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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A diurnal carbon engine explains <sup>13</sup>C-enriched carbonates without increasing the global production of oxygen.

Geyman Emily C EC Maloof Adam C AC

Proceedings of the National Academy of Sciences of the United States of America 20191108 49

In the past 3 billion years, significant volumes of carbonate with high carbon-isotopic ([Formula: see text]C) values accumulated on shallow continental shelves. These deposits frequently are interpreted as records of elevated global organic carbon burial. However, through the stoichiometry of primary production, organic carbon burial releases a proportional amount of [Formula: see text], predicting unrealistic rises in atmospheric [Formula: see text] during the 1 to 100 million year-long positi ...[more]

PMID: 31704769

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Project description:L-1-Chloro-4-phenyl-3-tosylamido[1-13C]butan-2-one (Tos-[1-13C]Phe-CH2Cl) and Tos-[1-13C,2H2]Phe-CH2Cl were prepared and used to alkylate delta-chymotrypsin. The relaxation parameters of the 13C-n.m.r. signal resulting from the alkylation of histidine-57 in both enzyme-inhibitor complexes were determined at 1.88 T and 6.34 T as well as the spin-lattice relaxation times of the backbone alpha-carbon atoms of the unenriched Tos-Phe-CH2-delta-chymotrypsin complex. It is concluded that the species examined do not have significant internal librational motions and that the rotational correlation time of the monomeric enzyme-inhibitor complex is 16.0 +/- 3.2 ns. The signal from the 13C-enriched atom of Tos-[1-13C,2H2]Phe-CH2Cl is split into a quintet (JCD = 23 Hz) whereas in the Tos-[1-13C,2H2]Phe-CH2-delta-chymotrypsin complex the signal from the 13C-enriched inhibitor carbon atom is decoupled. This decoupled signal had linewidths of 16 +/- 3 Hz and 52 +/- 2 Hz at 1.88 T and 6.34 T respectively, whereas linewidths at 40 +/- 2 Hz and 53 +/- 4 Hz were obtained for the same signal in the Tos-[1-13C]Phe-CH2-delta-chymotrypsin complex at 1.88 T and 6.34 T respectively. Therefore whereas deuteration produces a 2.5-fold reduction in linewidth at 1.88 T there is no significant decrease in the linewidth at 6.34 T. This result is explained by using the rigid rotor model, which predicts that the quadrupolar spin-lattice relaxation rate will be faster at low field strengths, resulting in more efficient deuterium decoupling by scalar relaxation of the second kind at lower field strengths. It is also predicted that deuterium decoupling by scalar relaxation will become less efficient as rotational correlation times increase. The consequences of these predictions for the detection of 13C-enriched atomic probes of proteins are discussed. It is also shown that a spin-echo pulse sequence can be used to remove signals due to protonated carbon atoms without attenuating the signal due to deuterated carbon atoms.

Dataset Information

A diurnal carbon engine explains 13C-enriched carbonates without increasing the global production of oxygen.

Publications

A diurnal carbon engine explains <sup>13</sup>C-enriched carbonates without increasing the global production of oxygen.

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