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Daniel P Schrag

Publications and source records attributed to Daniel P Schrag.

9 recordsLinked to original sources

Permanent carbon dioxide storage in deep-sea sediments.

Stabilizing the concentration of atmospheric CO(2) may require storing enormous quantities of captured anthropogenic CO(2) in near-permanent geologic reservoirs. Because of the subsurface temperature profile of terrestrial storage sites, CO(2) stored in these reservoirs is buoyant. As a result, a portion of the injected CO(2) can escape if the reservoir is not appropriately sealed. We show that injecting CO(2) into deep-sea sediments below [corrected] 3,000-m water depth and a few hundred meters of sediment provides permanent geologic storage even with large geomechanical perturbations. At the high pressures and low temperatures common in deep-sea sediments, CO(2) resides in its liquid phase and can be denser than the overlying pore fluid, causing the injected CO(2) to be gravitationally stable. Additionally, CO(2) hydrate formation will impede the flow of CO(2)(l) and serve as a second cap on the system. The evolution of the CO(2) plume is described qualitatively from the injection to the formation of CO(2) hydrates and finally to the dilution of the CO(2)(aq) solution by diffusion. If calcareous sediments are chosen, then the dissolution of carbonate host rock by the CO(2)(aq) solution will slightly increase porosity, which may cause large increases in permeability. Karst formation, however, is unlikely because total dissolution is limited to only a few percent of the rock volume. The total CO(2) storage capacity within the 200-mile economic zone of the U.S. coastline is enormous, capable of storing thousands of years of current U.S. CO(2) emissions.

Animals↗

Heterotrophic Archaea dominate sedimentary subsurface ecosystems off Peru.

Studies of deeply buried, sedimentary microbial communities and associated biogeochemical processes during Ocean Drilling Program Leg 201 showed elevated prokaryotic cell numbers in sediment layers where methane is consumed anaerobically at the expense of sulfate. Here, we show that extractable archaeal rRNA, selecting only for active community members in these ecosystems, is dominated by sequences of uncultivated Archaea affiliated with the Marine Benthic Group B and the Miscellaneous Crenarchaeotal Group, whereas known methanotrophic Archaea are not detectable. Carbon flow reconstructions based on stable isotopic compositions of whole archaeal cells, intact archaeal membrane lipids, and other sedimentary carbon pools indicate that these Archaea assimilate sedimentary organic compounds other than methane even though methanotrophy accounts for a major fraction of carbon cycled in these ecosystems. Oxidation of methane by members of Marine Benthic Group B and the Miscellaneous Crenarchaeotal Group without assimilation of methane-carbon provides a plausible explanation. Maintenance energies of these subsurface communities appear to be orders of magnitude lower than minimum values known from laboratory observations, and ecosystem-level carbon budgets suggest that community turnover times are on the order of 100-2,000 years. Our study provides clues about the metabolic functionality of two cosmopolitan groups of uncultured Archaea.

Anaerobiosis↗

Biogeochemistry of carbonates: recorders of past oceans and climate.

Trace metal proxies bound within the calcium carbonate tests of oceanic organisms provide a unique insight into how the climate system works on timescales which span eight orders of magnitude, from annual to hundreds of millions of years. Whilst the motivation for developing these proxies was the idea that thermodynamic equilibria control the chemistry during precipitation, in reality the application of trace metal proxies relies upon empirical calibration. Such calibration can be applied to a wide range of environmental reconstructions, but more accurate application of proxies requires a mechanistic understanding of the biomineralization process. The partitioning of trace metals into biogenic carbonates reflects to some extent the same pattern as an inorganic crystal, but there is an additional selectivity and differing environmental sensitivity to, e.g., temperature, which confirms that biochemical processes also play a role in the uptake and assembly of ions into a crystal. Different organisms display differing degrees of biological control on their carbonate chemistry. Aragonitic coral chemistry is most similar to inorganic precipitation from seawater whilst coccolithophores are most different, and these contrasts correlate with the degree of control of the organism over its biomineralization. Selectivity between Ca and trace metals during biomineralization arises during transport by pumps, channels, or nucleation upon an organic matrix. The biological selectivity of the transporters and matrix is strikingly similar in its base chemistry to the selective assembly of ions into a crystal. In each case, the selectivity between Ca2+ and trace metals derives from the balance between the energy required for dehydration of the hexaaqua complex of the cation, and the energy released from the new coordination geometry of binding with either carbonyl oxygen from polysaccharides or amino acids, or carbonate oxygen in the crystal. This is a speculative idea, but with some careful chemical calculations based on the energy of binding of Ca2+ or the trace metal ions to these macromolecular structures, it provides an alternative thermodynamic framework within which to consider the application of trace metal proxies.

Animals↗

Large perturbations of the carbon cycle during recovery from the end-permian extinction.

High-resolution carbon isotope measurements of multiple stratigraphic sections in south China demonstrate that the pronounced carbon isotopic excursion at the Permian-Triassic boundary was not an isolated event but the first in a series of large fluctuations that continued throughout the Early Triassic before ending abruptly early in the Middle Triassic. The unusual behavior of the carbon cycle coincides with the delayed recovery from end-Permian extinction recorded by fossils, suggesting a direct relationship between Earth system function and biological rediversification in the aftermath of Earth's most devastating mass extinction.

Animals↗

Oxygen isotope constraints on the sulfur cycle over the past 10 million years.

Oxygen isotopes in marine sulfate (delta18O(SO4)) measured in marine barite show variability over the past 10 million years, including a 5 per mil decrease during the Plio-Pleistocene, with near-constant values during the Miocene that are slightly enriched over the modern ocean. A numerical model suggests that sea level fluctuations during Plio-Pleistocene glacial cycles affected the sulfur cycle by reducing the area of continental shelves and increasing the oxidative weathering of pyrite. The data also require that sulfate concentrations were 10 to 20% lower in the late Miocene than today.

Bacteria↗

Influence of form IA RubisCO and environmental dissolved inorganic carbon on the delta13C of the clam-chemoautotroph symbiosis Solemya velum.

Many nutritive symbioses between chemoautotrophic bacteria and invertebrates, such as Solemya velum, have delta(13)C values of approximately -30 to -35%, considerably more depleted than phytoplankton. Most of the chemoautotrophic symbionts fix carbon with a form IA ribulose 1,5-bisphosphate carboxylase (RubisCO). We hypothesized that this form of RubisCO discriminates against (13)CO(2) to a greater extent than other forms. Solemya velum symbiont RubisCO was cloned and expressed in Escherichia coli, purified and characterized. Enzyme from this recombinant system fixed carbon most rapidly at pH 7.5 and 20-25 degrees C. Surprisingly, this RubisCO had an epsilon-value (proportional to the degree to which the enzyme discriminates against (13)CO(2)) of 24.4 per thousand, similar to form IB RubisCOs, and higher than form II RubisCOs. Samples of interstitial water from S. velum's habitat were collected to determine whether the dissolved inorganic carbon (DIC) could contribute to the negative delta(13)C values. Solemya velum habitat DIC was present at high concentrations (up to approximately 5 mM) and isotopically depleted, with delta(13)C values as low as approximately -6%. Thus environmental DIC, coupled with a high degree of isotopic fractionation by symbiont RubisCO likely contribute to the isotopically depleted delta(13)C values of S. velum biomass, highlighting the necessity of considering factors at all levels (from environmental to enzymatic) in interpreting stable isotope ratios.

Animals↗

The salinity, temperature, and delta18O of the glacial deep ocean.

We use pore fluid measurements of the chloride concentration and the oxygen isotopic composition from Ocean Drilling Program cores to reconstruct salinity and temperature of the deep ocean during the Last Glacial Maximum (LGM). Our data show that the temperatures of the deep Pacific, Southern, and Atlantic oceans during the LGM were relatively homogeneous and within error of the freezing point of seawater at the ocean's surface. Our chloride data show that the glacial stratification was dominated by salinity variations, in contrast with the modern ocean, for which temperature plays a primary role. During the LGM the Southern Ocean contained the saltiest water in the deep ocean. This reversal of the modern salinity contrast between the North and South Atlantic implies that the freshwater budget at the poles must have been quite different. A strict conversion of mean salinity at the LGM to equivalent sea-level change yields a value in excess of 140 meters. However, the storage of fresh water in ice shelves and/or groundwater reserves implies that glacial salinity is a poor predictor of mean sea level.

Journal Article↗