Energy transition needs new materials.

The decreasing cost of electricity worldwide from wind and solar energy, as well as that of end-use technologies such as electric vehicles, reflect substantial progress made toward replacing fossil fuels with alternative energy sources. But a full transition to clean energy can only be realized if numerous challenges are overcome. Many problems can be addressed through the discovery of new materials that improve the efficiency of energy production and consumption; reduce the need for scarce mineral resources; and support the production of green hydrogen, clean ammonia, and carbon-neutral hydrocarbon fuels. However, research and development of new energy materials are not as aggressive as they should be to meet the demands of climate change.

Alkalinity Concentration Swing for Direct Air Capture of Carbon Dioxide.

The alkalinity concentration swing (ACS) is a new process for direct air capture of carbon dioxide driven by concentrating an alkaline solution that has been exposed to the atmosphere and loaded with dissolved inorganic carbon. Upon concentration, the partial pressure of CO2 increases, allowing for extraction and compression. Higher concentration factors result in proportionally higher outgassing pressure, and higher initial alkalinity concentrations at the same concentration factor outgas a higher concentration of CO2 . Two desalination technologies, reverse osmosis and capacitive deionization, are examined as possible ACS implementations, and two corresponding energy models are evaluated. The ACS is compared to incumbent technologies and estimates for water, land, and energy requirements for capturing one million tonnes of CO2 per year are made. Estimates for the lower end of the energy range for both approaches compare favorably to other approaches, such as solid sorbent and calcining methods.

Isotopically anomalous organic carbon in the aftermath of the Marinoan snowball Earth.

Throughout most of the sedimentary record, the marine carbon cycle is interpreted as being in isotopic steady state. This is most commonly inferred via isotopic reconstructions, where two export fluxes (organic carbon and carbonate) are offset by a constant isotopic fractionation of ~25 (termed εorg-carb ). Sedimentary deposits immediately overlying the Marinoan snowball Earth diamictites, however, stray from this prediction. In stratigraphic sections from the Ol Formation (Mongolia) and Sheepbed Formation (Canada), we observe a temporary excursion where the organic matter has anomalously heavy δ13 C and is grossly decoupled from the carbonate δ13 C. This signal may reflect the unique biogeochemical conditions that persisted in the aftermath of snowball Earth. For example, physical oceanographic modeling suggests that a strong density gradient caused the ocean to remain stratified for about 50,000 years after termination of the Marinoan snowball event, during which time the surface ocean and continental weathering consumed the large atmospheric CO2 reservoir. Further, we now better understand how δ13 C records of carbonate can be post-depostionally altered and thus be misleading. In an attempt to explain the observed carbon isotope record, we developed a model that tracks the fluxes and isotopic values of carbon between the surface ocean, deep ocean, and atmosphere. By comparing the model output to the sedimentary data, stratification alone cannot generate the anomalous observed isotopic signal. Reproducing the heavy δ13 C in organic matter requires the progressively diminishing contribution of an additional anomalous source of organic matter. The exact source of this organic matter is unclear.

A small marine biosphere in the Proterozoic.

The riverine supply of the globally limiting nutrient, phosphorus, to the ocean accounts for only a few percent of nutrient supply to photosynthetic organisms in surface waters. Recycling of marine organic matter by heterotrophic organisms provides almost all of the phosphorus that drives net primary production in the modern ocean. In the low-oxygen environments of the Proterozoic, the lack of free oxygen would have limited rates of oxic respiration, slowing the recycling of nutrients and thus limiting global rates of photosynthesis. A series of steady-state mass balance calculations suggest that the rate of net primary production in the ocean was no more than 10% of its modern value during the Proterozoic eon, and possibly less than 1%. The supply of nutrients in such a world would be dominated by river input, rather than recycling within the water column, leading to a small marine biosphere found primarily within estuarine environments.

Clumped isotope measurements of small carbonate samples using a high-efficiency dual-reservoir technique.

RATIONALE: The measurement of multiply substituted isotopologues of CO2 derived from carbonate has allowed the reconstruction of paleotemperatures from a single phase (CaCO3 ), circumventing uncertainty inherent in other isotopic paleothermometers. Traditional analytical techniques require relatively large amounts of carbonate (3-8 mg per replicate), which limits the applicability of the clumped isotope proxy to certain geological materials such as marine microfossils, commonly used for paleoclimate reconstructions. METHODS: Clumped isotope ratio measurements of small samples were made on a new, high-efficiency, dual-reservoir sample-preparation inlet system attached to a Thermo-Finnigan MAT 253 mass spectrometer. Sample gas produced on the inlet is introduced from a 10 mL reservoir directly into the source via a capillary. Reference gas fills an identical 10 mL reservoir installed between the reference bellows and the capillary. The gas pressures in the two reservoirs are initially balanced, and are allowed to decrease together over the run. RESULTS: Carbonate samples from 1 mg to 2.6 mg produced Δ47 values equivalent to those from the traditional two-bellows method with identical single-sample precision (1 SE = 0.005-0.015‰) and external standard error (SE = 0.006-0.015‰, n = 4-6). The size of sample needed to achieve good precision is controlled by the sensitivity of the mass spectrometer and the size of the fixed reservoirs and adjacent U-trap installed on our inlet. CONCLUSIONS: The high-precision clumped isotope measurements of small aliquots of carbonate obtained in this method allows for the application of this proxy to a wider range of geological sample materials, such as marine microfossils, that until now have been nearly impossible to analyze given sample size limitation.

Regional water implications of reducing oil imports with liquid transportation fuel alternatives in the United States.

The Renewable Fuel Standard (RFS) is among the cornerstone policies created to increase U.S. energy independence by using biofuels. Although greenhouse gas emissions have played a role in shaping the RFS, water implications are less understood. We demonstrate a spatial, life cycle approach to estimate water consumption of transportation fuel scenarios, including a comparison to current water withdrawals and drought incidence by state. The water consumption and land footprint of six scenarios are compared to the RFS, including shale oil, coal-to-liquids, shale gas-to-liquids, corn ethanol, and cellulosic ethanol from switchgrass. The corn scenario is the most water and land intense option and is weighted toward drought-prone states. Fossil options and cellulosic ethanol require significantly less water and are weighted toward less drought-prone states. Coal-to-liquids is an exception, where water consumption is partially weighted toward drought-prone states. Results suggest that there may be considerable water and land impacts associated with meeting energy security goals through using only biofuels. Ultimately, water and land requirements may constrain energy security goals without careful planning, indicating that there is a need to better balance trade-offs. Our approach provides policymakers with a method to integrate federal policies with regional planning over various temporal and spatial scales.

Dynamics of a Snowball Earth ocean.

Geological evidence suggests that marine ice extended to the Equator at least twice during the Neoproterozoic era (about 750 to 635 million years ago), inspiring the Snowball Earth hypothesis that the Earth was globally ice-covered. In a possible Snowball Earth climate, ocean circulation and mixing processes would have set the melting and freezing rates that determine ice thickness, would have influenced the survival of photosynthetic life, and may provide important constraints for the interpretation of geochemical and sedimentological observations. Here we show that in a Snowball Earth, the ocean would have been well mixed and characterized by a dynamic circulation, with vigorous equatorial meridional overturning circulation, zonal equatorial jets, a well developed eddy field, strong coastal upwelling and convective mixing. This is in contrast to the sluggish ocean often expected in a Snowball Earth scenario owing to the insulation of the ocean from atmospheric forcing by the thick ice cover. As a result of vigorous convective mixing, the ocean temperature, salinity and density were either uniform in the vertical direction or weakly stratified in a few locations. Our results are based on a model that couples ice flow and ocean circulation, and is driven by a weak geothermal heat flux under a global ice cover about a kilometre thick. Compared with the modern ocean, the Snowball Earth ocean had far larger vertical mixing rates, and comparable horizontal mixing by ocean eddies. The strong circulation and coastal upwelling resulted in melting rates near continents as much as ten times larger than previously estimated. Although we cannot resolve the debate over the existence of global ice cover, we discuss the implications for the nutrient supply of photosynthetic activity and for banded iron formations. Our insights and constraints on ocean dynamics may help resolve the Snowball Earth controversy when combined with future geochemical and geological observations.

Authigenic carbonate and the history of the global carbon cycle.

We present a framework for interpreting the carbon isotopic composition of sedimentary rocks, which in turn requires a fundamental reinterpretation of the carbon cycle and redox budgets over Earth's history. We propose that authigenic carbonate, produced in sediment pore fluids during early diagenesis, has played a major role in the carbon cycle in the past. This sink constitutes a minor component of the carbon isotope mass balance under the modern, high levels of atmospheric oxygen but was much larger in times of low atmospheric O(2) or widespread marine anoxia. Waxing and waning of a global authigenic carbonate sink helps to explain extreme carbon isotope variations in the Proterozoic, Paleozoic, and Triassic.

Biologically induced initiation of Neoproterozoic snowball-Earth events.

The glaciations of the Neoproterozoic Era (1,000 to 542 MyBP) were preceded by dramatically light C isotopic excursions preserved in preglacial deposits. Standard explanations of these excursions involve remineralization of isotopically light organic matter and imply strong enhancement of atmospheric CO(2) greenhouse gas concentration, apparently inconsistent with the glaciations that followed. We examine a scenario in which the isotopic signal, as well as the global glaciation, result from enhanced export of organic matter from the upper ocean into anoxic subsurface waters and sediments. The organic matter undergoes anoxic remineralization at depth via either sulfate- or iron-reducing bacteria. In both cases, this can lead to changes in carbonate alkalinity and dissolved inorganic pool that efficiently lower the atmospheric CO(2) concentration, possibly plunging Earth into an ice age. This scenario predicts enhanced deposition of calcium carbonate, the formation of siderite, and an increase in ocean pH, all of which are consistent with recent observations. Late Neoproterozoic diversification of marine eukaryotes may have facilitated the episodic enhancement of export of organic matter from the upper ocean, by causing a greater proportion of organic matter to be partitioned as particulate aggregates that can sink more efficiently, via increased cell size, biomineralization or increased CN of eukaryotic phytoplankton. The scenario explains isotopic excursions that are correlated or uncorrelated with snowball initiation, and suggests that increasing atmospheric oxygen concentrations and a progressive oxygenation of the subsurface ocean helped to prevent snowball glaciation on the Phanerozoic Earth.

The immobility of CO(2) in marine sediments beneath 1500 meters of water.

Injecting liquid CO(2) into deep-sea sediments below ca. 3 km of seawater has been suggested for the permanent storage of anthropogenic CO(2). At the pressures and temperature found below 3 km of seawater, CO(2) becomes denser than seawater and so is likely to remain permanently sequestered in the sediment. Deepwater engineering, however, is expensive and seawater depths of greater than 3 km are often only reached far from shore. Here, we consider the less expensive alternative of injecting CO(2) into marine sediments at depths shallower than required for denser-than-seawater CO(2) storage. We compare the mobility of liquid CO(2) that has been injected into deep-sea reservoirs with the mobility of supercritical CO(2) that has been injected into geologically equivalent (i.e., identical porosity, permeability, and effective stress) reservoirs with terrestrial pressure and temperature conditions. We demonstrate that buoyant liquid CO(2) with a density of about 90 % that of seawater is sufficiently immobile that it can be considered trapped by gravity and capillarity. In contrast, supercritical CO(2) under typical terrestrial conditions is highly mobile and only trapped by the appropriate confining layer in either a structural or stratigraphic trap. As a result of its very high mobility under terrestrial conditions, CO(2) injected in an unconfined formation would spread beneath the confining layer to produce a large flat cylindrical-shaped plume of pure-phase CO(2). In contrast, the less mobile CO(2) in a typical deep-sea reservoir produces a spherical-shaped plume, resulting in a pure-phase-CO(2) footprint that is much smaller than the pure-phase-CO(2) footprint formed in the confined-terrestrial reservoir.

Explaining the structure of the Archean mass-independent sulfur isotope record.

Sulfur isotopes in ancient sediments provide a record of past environmental conditions. The long-time-scale variability and apparent asymmetry in the magnitude of minor sulfur isotope fractionation in Archean sediments remain unexplained. Using an integrated biogeochemical model of the Archean sulfur cycle, we find that the preservation of mass-independent sulfur is influenced by a variety of extra-atmospheric mechanisms, including biological activity and continental crust formation. Preservation of atmospherically produced mass-independent sulfur implies limited metabolic sulfur cycling before approximately 2500 million years ago; the asymmetry in the record indicates that bacterial sulfate reduction was geochemically unimportant at this time. Our results suggest that the large-scale structure of the record reflects variability in the oxidation state of volcanic sulfur volatiles.

Calibrating the Cryogenian.

The Neoproterozoic was an era of great environmental and biological change, but a paucity of direct and precise age constraints on strata from this time has prevented the complete integration of these records. We present four high-precision U-Pb ages for Neoproterozoic rocks in northwestern Canada that constrain large perturbations in the carbon cycle, a major diversification and depletion in the microfossil record, and the onset of the Sturtian glaciation. A volcanic tuff interbedded with Sturtian glacial deposits, dated at 716.5 million years ago, is synchronous with the age of the Franklin large igneous province and paleomagnetic poles that pin Laurentia to an equatorial position. Ice was therefore grounded below sea level at very low paleolatitudes, which implies that the Sturtian glaciation was global in extent.

Storage of carbon dioxide in offshore sediments.

The battle to reduce greenhouse gas emissions and prevent the most dangerous consequences of climate change will be waged across multiple fronts, including efforts to increase energy efficiency; efforts to deploy nonfossil fuel sources, including renewable and nuclear energy; and investment in adaptation to reduce the impacts of the climate change that will occur regardless of the actions we take. But with more than 80% of the world's energy coming from fossil fuel, winning the battle also requires capturing CO2 from large stationary sources and storing that CO2 in geologic repositories. Offshore geological repositories have received relatively little attention as potential CO2 storage sites, despite their having a number of important advantages over onshore sites, and should be considered more closely.

A contemporary microbially maintained subglacial ferrous "ocean".

An active microbial assemblage cycles sulfur in a sulfate-rich, ancient marine brine beneath Taylor Glacier, an outlet glacier of the East Antarctic Ice Sheet, with Fe(III) serving as the terminal electron acceptor. Isotopic measurements of sulfate, water, carbonate, and ferrous iron and functional gene analyses of adenosine 5'-phosphosulfate reductase imply that a microbial consortium facilitates a catalytic sulfur cycle. These metabolic pathways result from a limited organic carbon supply because of the absence of contemporary photosynthesis, yielding a subglacial ferrous brine that is anoxic but not sulfidic. Coupled biogeochemical processes below the glacier enable subglacial microbes to grow in extended isolation, demonstrating how analogous organic-starved systems, such as Neoproterozoic oceans, accumulated Fe(II) despite the presence of an active sulfur cycle.

Snowball prevention questioned.

The 'snowball Earth' hypothesis interprets geological evidence as indicating multi-million-year episodes of global glaciation near the beginning and end of the Proterozoic eon. On the basis of a coupled carbon cycle-climate model, Peltier et al. propose that temperature-dependent remineralization of organic carbon in a Neoproterozoic ocean with 100-1,000x more dissolved organic carbon than today could create a negative climate feedback, thereby preventing a snowball Earth. Their results are sensitive to initial conditions and model parameters; moreover, important geological observations and components of the carbon cycle are not considered-notably the absence of sources or sinks of carbon. Their model results fall short of explaining the geological evidence in the absence of global glaciation.

Consequences of a rapid cellulose extraction technique for oxygen isotope and radiocarbon analyses.

We use infrared, radiocarbon, and stable isotope analyses to investigate the purity of cellulose extracted from wood using a rapid processing technique. Replicate laboratory standards processed using the standard Brendel method are not significantly different with respect to delta(18)O from those prepared using traditional techniques, although the process does result in a slight acetylation of the wood samples. Radiocarbon comparisons, however, show significant differences. We conclude that the standard Brendel method is appropriate for developing stable isotope time series for high-resolution isotope dendroclimatology but must be used with caution for precision radiocarbon measurements.

A sulfur dioxide climate feedback on early Mars.

Ancient Mars had liquid water on its surface and a CO2-rich atmosphere. Despite the implication that massive carbonate deposits should have formed, these have not been detected. On the basis of fundamental chemical and physical principles, we propose that climatic conditions enabling the existence of liquid water were maintained by appreciable atmospheric concentrations of volcanically degassed SO2 and H2S. The geochemistry resulting from equilibration of this atmosphere with the hydrological cycle is shown to inhibit the formation of carbonates. We propose an early martian climate feedback involving SO2, much like that maintained by CO2 on Earth.

Preparing to capture carbon.

Carbon sequestration from large sources of fossil fuel combustion, particularly coal, is an essential component of any serious plan to avoid catastrophic impacts of human-induced climate change. Scientific and economic challenges still exist, but none are serious enough to suggest that carbon capture and storage will not work at the scale required to offset trillions of tons of carbon dioxide emissions over the next century. The challenge is whether the technology will be ready when society decides that it is time to get going.