Comparison of field and laboratory weathering rates in carbonate rocks from an Eastern Mediterranean drainage basin

The rates of carbonate rock weathering affect the global carbon cycle over timescales of hundreds to thousands of years. While field measurements show that the rate of carbonate denudation increases with rainfall, significant variability exists. To determine whether the mineralogical composition of the rocks causes this variability, we compare published long-term field denudation rates determined from cosmogenic isotopes (^(36)Cl) with the weathering rates measured in laboratory experiments conducted on the same rock samples. The samples were collected from natural-rock outcrops across the Soreq drainage basin (Israel) that experience similar mean annual precipitation, but exhibit long-term denudation rates that vary from 6 mm ky^(−1) to 20 mm ky^(−1). In laboratory experiments, we found that the laboratory rates also varied, decreasing as the ratio of dolomite to calcite increased. However, no correlation was evident between the long-term denudation rates and mineral composition, suggesting that the variability in field rates was not controlled by the kinetics of dissolution. Other factors, such as rain intensity, biological activity, and mechanical erosion are likely to control the variability in the rates by inhibiting or accelerating the weathering of carbonate surfaces in natural settings

Oxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem

The ^(18)O/^(16)O of calcite fossils increased by ∼8‰ between the Cambrian and present. It has long been controversial whether this change reflects evolution in the δ^(18)O of seawater, or a decrease in ocean temperatures, or greater extents of diagenesis of older strata. Here, we present measurements of the oxygen and ‟clumped” isotope compositions of Phanerozoic dolomites and compare these data with published oxygen isotope studies of carbonate rocks. We show that the δ^(18)O values of dolomites and calcite fossils of similar age overlap one another, suggesting they are controlled by similar processes. Clumped isotope measurements of Cambrian to Pleistocene dolomites imply crystallization temperatures of 15–158 °C and parent waters having δ^(18)O_(VSMOW) values from −2 to +12‰. These data are consistent with dolomitization through sediment/rock reaction with seawater and diagenetically modified seawater, over timescales of 100 My, and suggest that, like dolomite, temporal variations of the calcite fossil δ^(18)O record are largely driven by diagenetic alteration. We find no evidence that Phanerozoic seawater was significantly lower in δ^(18)O than preglacial Cenozoic seawater. Thus, the fluxes of oxygen–isotope exchange associated with weathering and hydrothermal alteration reactions have remained stable throughout the Phanerozoic, despite major tectonic, climatic and biologic perturbations. This stability implies that a long-term feedback exists between the global rates of seafloor spreading and weathering. We note that massive dolomites have crystallized in pre-Cenozoic units at temperatures >40 °C. Since Cenozoic platforms generally have not reached such conditions, their thermal immaturity could explain their paucity of dolomites

AnaLog: Testing Analytical and Deductive Logic Learnability in Language Models

Acknowledgements We would like to thank the anonymous ARR and *SEM 2022 reviewers for their feedback and suggestions, as well as Ece Takmaz for her comments. Samuel Ryb and Arabella Sinclair worked on this project while affiliated with the University of Amsterdam. The project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 819455). 1The dataset is available at https://github.com/dmg-illc/analogPublisher PD

Experimental calibration of clumped isotope reodering in dolomite

Dolomite clumped isotope compositions are indispensable for determining the temperatures and fluid sources of dolomitizing environments, but can be misleading if they have modified since formation. Carbonate Δ_(47) values are susceptible to resetting by recrystallization during diagenesis, and, even in the absence of dissolution and reprecipitation reactions, alteration by solid-state reordering during prolonged residences at elevated temperatures. In order to understand the potential of dolomite Δ_(47) values to preserve the conditions of dolomitizationin ancient sections, the kinetic parameters of solid-state reordering in this phase must be determined. We heated mm-sized crystals of near-stoichiometric dolomite in a René-type cold seal apparatus at temperatures between 409 and 717 °C for 0.1–450 h. In order to prevent the decarbonation of dolomite to calcite, periclase, and CO_2 at these conditions, the system was pressurized with CO_2 to 0.45–0.8 kbar. Over the course of 31 temperature-time points and 128 individual Δ_(47) measurements of powdered dolomite crystals from these points, we observed the evolution of dolomite Δ_(47) values from the initial (unheated) composition of the crystals (0.452 ± 0.004‰, corresponding to a formation temperature of ∼145 °C) towards high-temperature equilibrium distributions. Complete re-equilibration occurred in the 563–717 °C experiments. As with previous heating experiments using calcite and apatite, dolomite Δ_(47) exhibited complex reordering behavior inadequately described by first-order Arrhenian-style models. Instead, we fit the data using two published models for clumped isotope reordering: the transient defect/equilibrium defect model of Henkes et al. (2014), and the exchange-diffusion model of Stolper and Eiler (2015). For both models, we found optimal reordering parameters by using global least-squares minimization algorithms and estimated uncertainties on these fits with a Monte Carlo scheme that resampled individual Δ_(47) measurements and re-fit the dataset of these new mean values. Because the exact Δ_(47)–T relationship between 250 and 800 °C is uncertain, we repeated these fitting exercises using three published high-temperature Δ_(47)–T calibrations. Regardless of calibration choice, dolomite Δ_(47) rate constants determined using both models are resolvably slower than those of calcite and apatite, and predict that high-grade dolomite crystals should preserve apparent equilibrium blocking temperatures of between ∼210 and 300 °C during cooling on geologic timescales. Best agreement between model predictions and natural dolomite marbles was found when using the exchange-diffusion model and the ab initio Δ_(63)–T calibration of Schauble et al. (2006), projected into the Δ_(47) reference frame by Bonifacie et al. (2017). Therefore, we recommend modeling dolomite Δ_(47) reordering using the exchange-diffusion model and this parameter set. In simple heating scenarios, the two models disagree. The transient defect/equilibrium defect model suggests that dolomite fabrics resist detectable reordering at ambient temperatures as high as 180 °C for tens of millions of years, while the exchange-diffusion model predicts incipient partial reordering perhaps as low as 150 °C. In either case, barring later recrystallization, dolomite Δ_(47) values should be faithful recorders of the conditions of dolomitization in sedimentary sections buried no hotter than ∼150 °C for tens of millions of years

Evaluation of Basic Operational Parameters of Evacuated Tube Solar Collectors

The paper presents the results of a comparison of selected basic operating parameters of solar collectors with heat pipe vacuum tubes. During the evaluation were considered parameters, which are represented by the thermal efficiency and incidence angle modifier. The correct understanding of mentioned parameters allows the appropriate use of selected collectors within the various climatic conditions during their operation. The measurements were carried out on apparatus that allowing changes in the flow parameters and the angle of incidence of solar radiation. Each individual measurements were carried out in a dynamic operation. Results of measurements are presented in form of curves for the each selected parameters for all solar collector combined

Fluid Flow Analysis of Porous Metals in Solar Thermal Applications

Presented paper dealt with use of porous materials, in this case metal foam, in the solar thermal applications. First part of paper is engaged to the fluid flow analysis in the spatial structure of metal foam body, which represents simplified form of the solar absorber. From application point of view were desired properties of foam structure described with using of CFD tools based on finite element method. As a boundary conditions of simulation were set different heat transfer flow rates and properties of metal foam which is characterized by average pore diameter. According to obtained results of simulations were identified optimal conditions and flow regimes for metal foam that will be used as a full flow solar flat collector

Oxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem

The ^(18)O/^(16)O of calcite fossils increased by ∼8‰ between the Cambrian and present. It has long been controversial whether this change reflects evolution in the δ^(18)O of seawater, or a decrease in ocean temperatures, or greater extents of diagenesis of older strata. Here, we present measurements of the oxygen and ‟clumped” isotope compositions of Phanerozoic dolomites and compare these data with published oxygen isotope studies of carbonate rocks. We show that the δ^(18)O values of dolomites and calcite fossils of similar age overlap one another, suggesting they are controlled by similar processes. Clumped isotope measurements of Cambrian to Pleistocene dolomites imply crystallization temperatures of 15–158 °C and parent waters having δ^(18)O_(VSMOW) values from −2 to +12‰. These data are consistent with dolomitization through sediment/rock reaction with seawater and diagenetically modified seawater, over timescales of 100 My, and suggest that, like dolomite, temporal variations of the calcite fossil δ^(18)O record are largely driven by diagenetic alteration. We find no evidence that Phanerozoic seawater was significantly lower in δ^(18)O than preglacial Cenozoic seawater. Thus, the fluxes of oxygen–isotope exchange associated with weathering and hydrothermal alteration reactions have remained stable throughout the Phanerozoic, despite major tectonic, climatic and biologic perturbations. This stability implies that a long-term feedback exists between the global rates of seafloor spreading and weathering. We note that massive dolomites have crystallized in pre-Cenozoic units at temperatures >40 °C. Since Cenozoic platforms generally have not reached such conditions, their thermal immaturity could explain their paucity of dolomites

Mechanism of Solid-State Clumped Isotope Reordering in Carbonate Minerals from Aragonite Heating Experiments

The clumped isotope compositions of carbonate minerals are subject to alteration at elevated temperatures. Understanding the mechanism of solid-state reordering in carbonate minerals is important in our interpretations of past climates and the thermal history of rocks. The kinetics of solid-state isotope reordering has been previously studied through controlled heating experiments of calcite, dolomite and apatite. Here we further explore this issue through controlled heating experiments on aragonite. We find that Δ_(47) values generally decrease during heating of aragonite, but increase by 0.05–0.15‰ as aragonite starts to transform into calcite. We argue that this finding is consistent with the presence of an intermediate pool of immediately adjacent singly-substituted carbonate ion isotopologues (‘pairs’), which back-react to form clumped isotopologues during aragonite to calcite transformation, revealing the existence of kinetically preferred isotope exchange pathways. Our results reinforce the ‘reaction-diffusion’ model as the mechanism for solid-state clumped isotope reordering in carbonate minerals. Our experiments also reveal that the reordering kinetics in aragonite is faster than in calcite and dolomite, making its clumped isotope composition highly susceptible to alteration during early diagenesis, even before conversion to calcite