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DOE OSTI2025

The effect of copper additives on hybrid Zr-based chemical conversion coating morphology and chemical compositions

In the realm of corrosion protection, Zr-based conversion coatings offer an environmentally friendly, chromate-free alternative to conventional coating. This study uses advanced X-ray, electron microscopy and electrochemical testing techniques to better understand the impact of varying Cu²⁺ ion concentrations on the characteristics of Zr-based coatings on Fe substrates. Our findings demonstrate that within the tested conditions, higher Cu²⁺ additive concentrations at 40 ppm enhance surface characteristics, increasing stability towards anti-corrosion capability, particularly under NaCl treatment. Conversely, at a lower Cu²⁺ concentration of 20 ppm, coatings exhibited more significant dissolution of Cu clusters and increased vulnerability to chloride-induced degradation. X-ray photoelectron spectroscopy and synchrotron X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) spectroscopy analyses revealed Cu²⁺ formation in Cu20, while Cu40 retained its metallic state (Cu⁰) with a slower reaction rate. Cu20 offers some protection but lacks durability, whereas in Cu40, lower I corr , and enhance corrosion resistance, making it ideal for protective coatings in salt-water environments. This study underscores the importance of balancing Cu²⁺ ions concentration in the coating solution to optimize performance, highlighting the role of Cu in enhancing both surface properties and long-term stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

An Ordered P2/P3 Composite Layered Oxide Cathode with Long Cycle Life in Sodium-Ion Batteries

Developing stable cathode materials represents a crucial step toward long-life sodium-ion batteries. P2-type layered oxides are important as cathodes for their reversibility, but their long-term performance in full cells remains a key challenge. Herein, we report Na 0.75 Co 0.125 Cu 0.125 Fe 0.125 Ni 0.125 Mn 0.5 O 2 with an intergrowth of ordered P2 and P3 phases, studied by neutron diffraction and Rietveld refinement. A stable electrochemical performance is achieved in Na half cells with 100% capacity retention at a rate of C/10 after 100 cycles (initial capacity of 90 mAh/g), 96% capacity retention at a rate of 1 C after 500 cycles (initial capacity of 70 mAh/g), and 85% capacity retention at a rate of 5 C after 1000 cycles (initial capacity of 55 mAh/g). Stable full cell performance is achieved with 84.2% capacity retention after 1000 cycles at a rate of 1 C. Synchrotron X-ray diffraction, spectroscopy, and imaging are applied to elucidate the relationship between chemical/structural evolution and battery performance. A reversible local and global structural evolution is observed during initial cycles. Meanwhile, the challenges with enabling prolonged cycling (beyond 1000 cycles) may be associated with Fe dissolution and formation of a copper oxide phase. This study implies that cathodes with complex chemical and structural formations may stabilize electrochemical performance and highlights the importance of decoupling the contribution of each transition metal to performance degradation.

25 ENERGY STORAGE↗

DOE OSTI2019

Polypyrrole-encapsulated amorphous Bi 2 S 3 hollow sphere for long life sodium ion batteries and lithium–sulfur batteries

Sodium ion batteries (SIBs) and lithium–sulfur (Li–S) batteries are considered as the most enticing next-generation energy storage devices to displace the widely used lithium ion batteries due to their inherent advantages. In this work, polypyrrole-encapsulated amorphous Bi 2 S 3 hollow spheres are prepared by the sulfuration of Bi–glycol spheres with a polypyrrole (PPy) coating. Benefiting from the unique hollow structure (Kirkendall effect) and the excellent conductivity and flexibility of the PPy coating, this material can be applied in both SIBs and Li–S batteries. For SIBs, the unconductive amorphous Bi 2 S 3 is electrochemically reduced to conductive metallic Bi, leading to a Bi–PPy core–shell structure. The resulting Bi acts as the main active material while the PPy coating accommodates the volume variation of Bi during sodiation/desodiation. For Li–S batteries, the outer double layer structure effectively prevents the dissolution and “shuttle effect” of polysulfides by physically containing and chemically adsorbing polysulfides, and tolerates the volume expansion of sulfur. Meanwhile, the residual polyvinyl pyrrolidone in the preparation process is chemically bonded with sulfur and exhibits the electrochemical properties, and results in additional discharging/charging capacity. Hence, this multifunctional electrode shows excellent rate capability and cycling life in SIBs and Li–S batteries. This research allows new insight into the design of multifunctional electrodes.

25 ENERGY STORAGE↗

DOE OSTI2018

Study of Material Compatibility for a Thermal Energy Storage System with Phase Change Material

The suitability of stainless steel 316L and Inconel 625 for use in a latent heat thermal energy storage (TES) system was investigated. A NaCl–NaF eutectic mixture with a melting temperature of 680 °C was used as the phase change material (PCM). Containers were filled with the PCM prior to heating to 750 °C, then examined after 100 and 2500 h of high-temperature exposure by analyzing the material surface and cross-section areas. A small amount of corrosion was present in both samples after 100 h. Neither sample suffered significant damage after 2500 h. The undesirable inter-granular grain boundary attack found in SS316L samples was in the order of 1–2 µm in depth. On Inconel 625 sample surface, an oxide complex formed, resisting material dissolution into the PCM. The surface morphology of tested samples remained largely unchanged after 2500 h, but the corrosion pattern changed from an initially localized corrosion penetration to a more uniform type. After 2500 h, the corrosion depth of Inconel 625 remained at roughly 1–2 µm, indicating that the corrosion rate decelerated. Both materials demonstrated good compatibility with the chosen NaF–NaCl eutectic salt, but the low corrosion activity in Inconel 625 samples shows a performance advantage for long term operation.

25 ENERGY STORAGE↗

DOE OSTI2023

Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium–Sulfur Batteries

Lithium-sulfur (Li-S) batteries are promising owing to their high energy density, environmental benignity, and low cost. Most of the commonly used binders in Li-S battery cathodes are inert and have no significant effect on the challenges of sulfur as a cathode material, such as the polysulfide shuttle effect, low ionic/electronic conductivity, and a sluggish redox reaction. In this work, we demonstrate the use of poly(vinylferrocene) (PvFc) as a binder additive that can effectively increase the ionic conductivity of the cathode and act as a sulfide confining agent. Electrochemical tests performed with PvFc as part of the binder mixture used to cast the cathodes demonstrate an increase in rate capability and cycle life when compared to the baseline samples. Ionic conductivity measurements and X-ray photoelectron spectroscopy suggest that the π-cation molecular interaction between the cyclopentadienyl rings from ferrocene and Li + act like an ion couple with ferrocene acting as a static, covalently bound acceptor of Li + ions that enhances their mobility through the cathode. This coupled with the affinity between the ferrocenyl cations and the Li salt anions, which provides more distribution of counterions for Li + movement and improves accessibility to the cathode S reservoir, make PvFc a promising ionomer for Li-S batteries. In addition, the π-cation bonds between cyclopentadienyl and lithium polysulfides produce a sulfide confining effect that mitigates capacity fade through polysulfide dissolution. Furthermore, this work demonstrates an expansion in the utility of PvFc as a component in Li-ion batteries, which so far is mostly limited to use as an active material in organometallic batteries.

25 ENERGY STORAGE↗

DOE OSTI2022

Comparing the extraction performance of cyclodextrin-containing supramolecular deep eutectic solvents versus conventional deep eutectic solvents by headspace single drop microextraction

A headspace single drop microextraction (HS-SDME) method coupled with high performance liquid chromatography was developed to compare the extraction of eighteen aromatic organic pollutants from aqueous solutions using cyclodextrin-based supramolecular deep eutectic solvents (SUPRADESs) and alkylammonium halide-based conventional deep eutectic solvents (DESs). Different derivatives of beta-cyclodextrin (β-CD) were employed as hydrogen bond acceptors (HBA) in SUPRADESs and the extraction performance investigated. SUPRADES comprised of the 20 wt% native β-CD HBA provided the highest enrichment factors of analytes compared to SUPRADESs comprised of other derivatives of β-CD (random methylated β-cyclodextrin, heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin, and 2-hydroxypropyl β-cyclodextrin). In addition, native β-CD and its derivatives were dissolved in the neat DESs and their effect on the extraction of analytes examined. Dissolution of 20 wt% native β-CD in the choline chloride ([Ch + ][Cl - ]):2Urea DES resulted in a significant increase in the extraction efficiencies of target analytes compared to the neat [Ch + ][Cl - ]:2Urea DES. Under optimum conditions, the extraction method required a solvent microdroplet of 6.5 μL, 1000 rpm stir rate, 30% (w/v) salt concentration, and a temperature of 40 °C. The tetrabutylammonium chloride: 2 lactic acid DES resulted in the highest enrichment factors while the [Ch + ][Cl - ]:2Urea DES had the lowest for most of the analytes among the evaluated solvents. The method provided limits of detection (LODs) down to 35 μg L -1 . Finally, the developed method was applied for the analysis of spiked tap and lake water, where relative recoveries ranging from 83.7% -119.7% and relative standard deviations lower than 19.2% were achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Developmental assembly of multi-component polymer systems through interconnected synthetic gene networks in vitro

Abstract Living cells regulate the dynamics of developmental events through interconnected signaling systems that activate and deactivate inert precursors. This suggests that similarly, synthetic biomaterials could be designed to develop over time by using chemical reaction networks to regulate the availability of assembling components. Here we demonstrate how the sequential activation or deactivation of distinct DNA building blocks can be modularly coordinated to form distinct populations of self-assembling polymers using a transcriptional signaling cascade of synthetic genes. Our building blocks are DNA tiles that polymerize into nanotubes, and whose assembly can be controlled by RNA molecules produced by synthetic genes that target the tile interaction domains. To achieve different RNA production rates, we use a strategy based on promoter “nicking” and strand displacement. By changing the way the genes are cascaded and the RNA levels, we demonstrate that we can obtain spatially and temporally different outcomes in nanotube assembly, including random DNA polymers, block polymers, and as well as distinct autonomous formation and dissolution of distinct polymer populations. Our work demonstrates a way to construct autonomous supramolecular materials whose properties depend on the timing of molecular instructions for self-assembly, and can be immediately extended to a variety of other nucleic acid circuits and assemblies.

Science & Technology - Other Topics↗

DOE OSTI2016

Surface protected lithium-metal-oxide electrodes

A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

25 ENERGY STORAGE↗

DOE OSTI2014

Surface protected lithium-metal-oxide electrodes

Thackeray, Michael M.↗

DOE OSTI2015

An atomistically informed mesoscale model for growth and coarsening during discharge in lithium-oxygen batteries

An atomistically informed mesoscale model is developed for the deposition of a discharge product in a Li-O{sub 2} battery. This mescocale model includes particle growth and coarsening as well as a simplified nucleation model. The model involves LiO{sub 2} formation through reaction of O{sub 2}{sup −} and Li{sup +} in the electrolyte, which deposits on the cathode surface when the LiO{sub 2} concentration reaches supersaturation in the electrolyte. A reaction-diffusion (rate-equation) model is used to describe the processes occurring in the electrolyte and a phase-field model is used to capture microstructural evolution. This model predicts that coarsening, in which large particles grow and small ones disappear, has a substantial effect on the size distribution of the LiO{sub 2} particles during the discharge process. The size evolution during discharge is the result of the interplay between this coarsening process and particle growth. The growth through continued deposition of LiO{sub 2} has the effect of causing large particles to grow ever faster while delaying the dissolution of small particles. The predicted size evolution is consistent with experimental results for a previously reported cathode material based on activated carbon during discharge and when it is at rest, although kinetic factors need to be included. The approach described in this paper synergistically combines models on different length scales with experimental observations and should have applications in studying other related discharge processes, such as Li{sub 2}O{sub 2} deposition, in Li-O{sub 2} batteries and nucleation and growth in Li-S batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Management of HL deposits for the D and D of UP1 reprocessing plant - retrieval and treatment scenarios - 15295

Built in 1958 on the Marcoule CEA site, the UP1 facility, was the 1. French industrial (500 t U / year) reprocessing plant based on the PUREX process. The plant, which has stopped operation in 1997, constitutes with its auxiliary workshop (vitrification workshop, glass canister storage), one of the largest and most challenging decommissioning project in France. In about 40 years of operation, various type of fuels elements such as metallic uranium, U-Al fuel rods, Phenix breeder elements or PWR fuel have been reprocessed, thereby requiring several plant and process adaptations. Resulting from these complex process chemistry and operation history, significant fouling of the chemical plant circuits and components has occurred. The fission product (FP) concentration process is particularly concerned. Preliminary investigation performed in 2010 in the evaporator's feeding tanks revealed the presence of significant amounts of sludge and dose rates as high as 250 Gy/h. Therefore a thorough investigation campaign, including visual inspection, volume quantification, deposits sampling, and radiological characterization of the components of this workshop has been initiated in 2013. Chemical analysis performed so far show that the solids are mainly composed of zirconium phosphates, 'MoZr' compounds and nitrate salt precipitates. But the presence of insoluble fines arising from the dissolution workshop and organic residues resulting from the TBP decomposition has also been evidenced in some of the tanks. The numerous constraints associated with the management of such highly active sludge, with Cs-137 specific activity ranging from 1 to 10 GBq/g, and a complex physico-chemical composition, lead CEA to investigate the implementation of an in situ conditioning treatment able to produce a waste package complying with existing evacuation routes and/or on-site storage facilities. The full paper presents an overview of the UP1 D and D project and then focuses on the possible dismantling scenarios for the FP concentration workshop, including the evaluation of different strategies for the highly active deposits management. The investigations and deposits characterization program will be developed so as the sampling methodologies that has been specifically tuned. In the light of the best actual knowledge of the deposits properties, the recovery and conditioning treatment scenarios will be exposed, considering, as a case study, the development of a specific vitrification tool to be implemented In Situ and specifically designed to match the requirements and constraints of the D and D project: adequately dimensioned, compact, flexible with respect to the feed composition, for a limited duration of use and designed to be dismantled. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Thermal effects on geologic carbon storage

One of the most promising ways to significantly reduce greenhouse gases emissions, while carbon-free energy sources are developed, is Carbon Capture and Storage (CCS). Non-isothermal effects play a major role in all stages of CCS. In this paper, we review the literature on thermal effects related to CCS, which is receiving an increasing interest as a result of the awareness that the comprehension of non-isothermal processes is crucial for a successful deployment of CCS projects. We start by reviewing CO 2 transport, which connects the regions where CO 2 is captured with suitable geostorage sites. The optimal conditions for CO 2 transport, both onshore (through pipelines) and offshore (through pipelines or ships), are such that CO 2 stays in liquid state. To minimize costs, CO 2 should ideally be injected at the wellhead in similar pressure and temperature conditions as it is delivered by transport. To optimize the injection conditions, coupled wellbore and reservoir simulators that solve the strongly non-linear problem of CO 2 pressure, temperature and density within the wellbore and non-isothermal two-phase flow within the storage formation have been developed. CO 2 in its way down the injection well heats up due to compression and friction at a lower rate than the geothermal gradient, and thus, reaches the storage formation at a lower temperature than that of the rock. Inside the storage formation, CO 2 injection induces temperature changes due to the advection of the cool injected CO 2 , the Joule-Thomson cooling effect, endothermic water vaporization and exothermic CO 2 dissolution. These thermal effects lead to thermo-hydro-mechanical-chemical coupled processes with non-trivial interpretations. These coupled processes also play a relevant role in “Utilization” options that may provide an added value to the injected CO 2 , such as Enhanced Oil Recovery (EOR), Enhanced Coal Bed Methane (ECBM) and geothermal energy extraction combined with CO 2 storage. If the injected CO 2 leaks through faults, the caprock or wellbores, strong cooling will occur due to the expansion of CO 2 as pressure decreases with depth. Finally, we conclude by identifying research gaps and challenges of thermal effects related to CCS.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

3D dual-confined sulfur encapsulated in porous carbon nanosheets and wrapped with graphene aerogels as a cathode for advanced lithium sulfur batteries

Although lithium–sulfur (Li–S) batteries have attracted much attention due to their high theoretical specific energy and low cost, their practical applications have been severely hindered by poor cycle life, inadequate sulfur utilization, and the insulating nature of sulfur. Here, we report a rationally designed Li–S cathode with a dual-confined configuration formed by confining sulfur in 2D carbon nanosheets with an abundant porous structure followed by 3D graphene aerogel wrapping. The porous carbon nanosheets act as the sulfur host and suppress the diffusion of polysulfide, while the graphene conductive networks anchor the sulfur-adsorbed carbon nanosheets, providing pathways for rapid electron/ion transport and preventing polysulfide dissolution. As a result, the hybrid electrode exhibits superior electrochemical performance, including a large reversible capacity of 1328 mA h g -1 in the first cycle, excellent cycling stability (maintaining a reversible capacity of 647 mA h g -1 at 0.2 C after 300 cycles) with nearly 100% Coulombic efficiency, and a high rate capability of 512 mA h g -1 at 8 C for 30 cycles, which is among the best reported rate capabilities.

25 ENERGY STORAGE↗

DOE OSTI2012

Actual-Waste Testing of Ultraviolet Light to Augment the Enhanced Chemical Cleaning of SRS Sludge

In support of Savannah River Site (SRS) tank closure efforts, the Savannah River National Laboratory (SRNL) conducted Real Waste Testing (RWT) to evaluate Enhanced Chemical Cleaning (ECC), an alternative to the baseline 8 wt% oxalic acid (OA) chemical cleaning technology for tank sludge heel removal. ECC utilizes a more dilute OA solution (2 wt%) and an oxalate destruction technology using ozonolysis with or without the application of ultraviolet (UV) light. SRNL conducted tests of the ECC process using actual SRS waste material from Tanks 5F and 12H. The previous phase of testing involved testing of all phases of the ECC process (sludge dissolution, OA decomposition, product evaporation, and deposition tank storage) but did not involve the use of UV light in OA decomposition. The new phase of testing documented in this report focused on the use of UV light to assist OA decomposition, but involved only the OA decomposition and deposition tank portions of the process. Compared with the previous testing at analogous conditions without UV light, OA decomposition with the use of UV light generally reduced time required to reach the target of <100 mg/L oxalate. This effect was the most pronounced during the initial part of the decomposition batches, when pH was <4. For the later stages of each OA decomposition batch, the increase in OA decomposition rate with use of the UV light appeared to be minimal. Testing of the deposition tank storage of the ECC product resulted in analogous soluble concentrations regardless of the use or non-use of UV light in the ECC reactor.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2015

On the mobilization of metals by CO 2 leakage into shallow aquifers: exploring release mechanisms by modeling field and laboratory experiments

The dissolution of CO 2 in water leads to a pH decrease and a carbonate content increase in affected groundwater, which in turn can drive the mobilization of metals from sediments. The mechanisms of metal release postulated in various field and laboratory studies often differ. Drawing primarily on previously published results, we examine contrasting metal mobilization behaviors at two field tests and in one laboratory study, to investigate whether the same mechanisms could explain metal releases in these different experiments. Numerical modeling of the two field tests reveals that fast Ca-driven cation exchange (from calcite dissolution) can explain the release of most major and trace metal cations at both sites, and their parallel concentration trends. The dissolution of other minerals reacting more slowly (superimposed on cation exchange) also contributes to metal release over longer time frames, but can be masked by fast ambient groundwater velocities. Therefore, the magnitude and extent of mobilization depends not only on metal-mineral associations and sediment pH buffering characteristics, but also on groundwater flow rates, thus on the residence time of CO 2 -impacted groundwater relative to the rates of metal-release reactions. Sequential leaching laboratory tests modeled using the same metal-release concept as postulated from field experiments show that both field and laboratory data can be explained by the same processes. Finally, the reversibility of metal release upon CO 2 degassing by de-pressurization is also explored using simple geochemical models, and shows that the sequestration of metals by resorption and re-precipitation upon CO 2 exsolution is quite plausible and may warrant further attention.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Enhancing catalytic activity of rhodium towards methanol electro-oxidation in both acidic and alkaline media by alloying with iron

The methanol electrooxidation catalysts in the form of Rh and FeRh thin films were prepared by magnetron sputtering deposition. To activate the FeRh catalyst, the as-prepared FeRh films were cycled in 0.1 M HClO 4 electrolyte in potential window from -0.25 V to 0.8 V (vs. Ag/AgCl). The dissolution of Fe atoms during the cycling leads to the formation of Rh-skeleton surface. Obtained FeRh catalysts exhibit significantly enhanced activity to methanol electrooxidation in both acidic and alkaline environments comparing to pure Rh catalyst. The optimal concentration of Fe is found to be 50%. Electrochemical impedance spectroscopy investigations show the higher rate of methanol dehydrogenation as well as better tolerance to CO intermediates poisoning of the FeRh catalysts. Furthermore, this study demonstrates that Rh-based catalysts can be considered as alternative to Pt-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Polymer–Peptide Conjugates Disassemble Amyloid β Fibrils in a Molecular-Weight Dependent Manner

Amyloid aggregation and deposition are associated with many intractable human diseases. Although the inhibition of amyloid protein aggregation has been well-studied, the disaggregation and dissolution of existing amyloid fibrils is less known. Taking a fibrillar assembly of amyloid β (Aβ) peptide as the model system, in this paper we report multivalent polymer–peptide conjugates (mPPCs) that disassemble preformed Aβ fibrils into dispersible sub-100 nm structures. Atomic force microscopy and dynamic light scattering studies show that the disassembly rate of preformed Aβ fibrils is controlled by the molecular weight of mPPCs. Rate equations on fibril disappearance are deduced from a simple model, which indicate that the disassembly reaction is first-order in the concentration of Aβ fibrils and a pseudo-first-order reaction in the concentration of peptide moieties on mPPCs, respectively. We eliminate the possibility that the disassembly occurs by the association between mPPCs and Aβ monomer/oligomers based on circular dichroism and Thioflavin T fluorescence assays. It is mostly likely that the mPPCs disassemble Aβ fibrils through a direct interaction. Finally, the mPPCs may thus offer a general macromolecular design concept that breaks down existing amyloid fibrils in a predictable fashion.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2011

CLIMATE INSTABILITY ON TIDALLY LOCKED EXOPLANETS

Feedbacks that can destabilize the climates of synchronously rotating rocky planets may arise on planets with strong day-night surface temperature contrasts. Earth-like habitable planets maintain stable surface liquid water over geologic time. This requires equilibrium between the temperature-dependent rate of greenhouse-gas consumption by weathering, and greenhouse-gas resupply by other processes. Detected small-radius exoplanets, and anticipated M-dwarf habitable-zone rocky planets, are expected to be in synchronous rotation (tidally locked). In this paper, we investigate two hypothetical feedbacks that can destabilize climate on planets in synchronous rotation. (1) If small changes in pressure alter the temperature distribution across a planet's surface such that the weathering rate goes up when the pressure goes down, a runaway positive feedback occurs involving increasing weathering rate near the substellar point, decreasing pressure, and increasing substellar surface temperature. We call this feedback enhanced substellar weathering instability (ESWI). (2) When decreases in pressure increase the fraction of surface area above the melting point (through reduced advective cooling of the substellar point), and the corresponding increase in volume of liquid causes net dissolution of the atmosphere, a further decrease in pressure will occur. This substellar dissolution feedback can also cause a runaway climate shift. We use an idealized energy balance model to map out the conditions under which these instabilities may occur. In this simplified model, the weathering runaway can shrink the habitable zone and cause geologically rapid 10{sup 3}-fold atmospheric pressure shifts within the habitable zone. Mars may have undergone a weathering runaway in the past. Substellar dissolution is usually a negative feedback or weak positive feedback on changes in atmospheric pressure. It can only cause runaway changes for small, deep oceans and highly soluble atmospheric gases. Both instabilities are suppressed if the atmosphere has a high radiative efficiency. Our results are most relevant for atmospheres that are thin, have low greenhouse-gas radiative efficiency, and have a principal greenhouse gas that is also the main constituent of the atmosphere. ESWI also requires land near the substellar point, and tectonic resurfacing (volcanism, mountain-building) is needed for large jumps in pressure. These results identify a new pathway by which habitable-zone planets can undergo rapid climate shifts and become uninhabitable.

79 ASTRONOMY AND ASTROPHYSICS↗