Dissolution kinetics of calcite at 50-70 °C: An atomic force microscopic study under near-equilibrium conditions

Direct measurements of calcite faces were performed using in situ atomic force microscopy (AFM) to reveal the dissolution processes as a function of solution saturation state and temperature. Time-sequential AFM images demonstrated that step velocities at constant temperature increased with increasing undersaturation. The anisotropy of obtuse and acute step velocities appeared to become more significant as solutions approached equilibrium and temperature increased. At saturation state Ω > 0.02, a curvilinear boundary was formed at the intersection of two acute steps and the initially rhombohedral etch pit exhibited a nearly triangular shape. This suggests that the and steps may not belong to the calcite-aqueous solution equilibrium system. Further increase in the saturation state (Ω ? 0.3) led to a lack of etch pit formation and dissolution primarily occurred at existing steps, in accordance with Teng (2004). Analysis of step kinetics at different temperatures yielded activation energies of 25 ± 6 kJ/mol and 14 ± 13 kJ/mol for obtuse and acute steps, respectively. The inconsistencies in etch pit morphology, step anisotropy, and step activation energies from the present study with those of studies far-from-equilibrium can be explained by increased influence of the backward reaction, or growth, near-equilibrium. We propose that the backward reaction occurs preferentially at the acute-acute kink sites. The kinetics and effective activation energies of near-equilibrium calcite dissolution presented in this work provide accurate experimental data under likely CO₂ sequestration conditions, and thus are crucial to the development of robust geochemical models that predict the long-term performance of mineral-trapped CO₂.     

Evidence for variations in cryogenic extraction deuterium biases of plant xylem water across foundational northeastern US trees

Measurements of oxygen and hydrogen isotopes in plant xylem water (²H, ¹⁸O) have helped to redefine conceptual and numerical models of the hydrological cycle and understand how plants compete for subsurface water. Recent experiments have shown that Cryogenic Vacuum Extraction (CVE) of plant xylem water can result in a δ²H bias. We tested if CVE δ²H-biases varied significantly across seven foundational northeastern US forest trees with a series of tree core rehydration experiments. Our analysis demonstrated that CVE δ²H-biases were well predicted by sample gravimetric water content and varied significantly with tree species identity. We show that species-level δ²H-bias corrections can result in substantially different understandings of plant water uptake and transpiration versus uncorrected data or generic bias corrections. This research demonstrates an urgent need for the critical evaluation of CVE for plant water extraction. In the absence of a stronger understanding of CVE δ²H-biases, we recommend that xylem water δ²H observations should not be used in plant water uptake studies.     

High-resolution garnet chronometry and the rates of metamorphic processes

Garnets in an amphibolite-facies metasediment from Sulitjelma, North Norway yield precise and concordant SmNd, UPb and RbSr ages that relate directly to the pressure (P) and temperature (T) conditions of mineral growth. Differential mineral reaction between graphitic and non-graphitic layers within this sample preserves a record of theP-T and time (t) history experienced during Barrovian regional metamorphism. Garnets in graphitic layers grew during prograde metamorphism at462 ± 16°C and5.2 ± 0.5 kbar under conditions of lowaH₂O, and yield indistinguishable¹⁴⁷Sm¹⁴³Nd and²³⁸U²⁰⁶Pb ages of434.1 ± 1.2 Ma and433.9 ± 1.0 Ma, respectively. In contrast, garnet growth in adjacent graphite-free layers did not occur untilP-T conditions of540 ± 18°C and8.0 ± 1.0 kbar were attained, with continued growth in response to minor heating and decompression with final matrix equilibration at544 ± 16°C and7.0 ± 1.0 kbar. The inclusion-free garnet rims in this assemblage record indistinguishable¹⁴⁷Sm¹⁴³Nd and²³⁸U²⁰⁶Pb ages of424.6 ± 1.2 Ma and423.4± 1.7 Ma, respectively. These results provide precise estimates for average heating and burial rates during prograde metamorphism of 8.6_−4.4^+7.5°C Ma⁻¹ and 0.8_−0.5^+0.9 km Ma⁻¹, respectively. Rb and Sr exchange between coexisting silicates in the graphite-free assemblage continued for some 37 Ma after the “peak” of metamorphism, and require an average cooling rate of about 4.0°C Ma⁻¹ during uplift. These results illustrate a clear relationship between reaction history and the timing of mineral growth and provide definitive constraints on the rates of thermal and tectonic processes accompanying regional metamorphism.     

Electron tunneling properties of outer-membrane decaheme cytochromes from Shewanella oneidensis

We have characterized the outer-membrane decaheme cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 at the single-molecule level using scanning tunneling microscopy (STM) and tunneling spectroscopy (TS). These cytochrome proteins are of great interest because they are thought to mediate bacterial electron transfer reactions in anoxic waters that control the reductive dissolution of oxide minerals. In our study, to characterize the electron transfer properties of these proteins on a model surface, the purified cytochromes were chemically immobilized as molecular monolayers on Au(111) substrates via a recombinant tetra-cysteine sequence as verified by X-ray photoelectron spectroscopy. Atomic force microscopy images confirm the monolayer films were ∼5-8 nm thick which is consistent with the apparent lateral dimensions of individual cytochrome molecules obtained with STM. Current-voltage TS of single cytochrome molecules revealed that OmcA and MtrC have different abilities to mediate tunneling current despite having otherwise very similar molecular and biochemical properties. These observations suggest that, based on their electron tunneling properties, the two cytochromes could have specific roles during bacterial metal reduction. Additionally, this study establishes single-molecule STM/TS as an effective means for revealing insights into biogeochemical redox processes in the environment.     

Effectiveness of structural control based on control energy perspectives

A computational algorithm for maximizing the control efficiency in actively controlling the elastic structural responses during earthquake is proposed. Study of optimal linear control using a single degree of freedom shows that applying active control is very effective in reducing the structural displacement and velocity responses for long‐period structures, but at the same time it has an adverse effect in increasing the absolute acceleration response. The extent of this adverse effect reduces the effectiveness of the control system, and therefore it poses a limit on the maximum control force in order to provide maximum control efficiency. In view of this shortcoming, maximum control energy dissipation is used to define the most effective optimal linear control law. Less displacement and velocity response are expected as larger control force is applied, but there is always a limit that maximum control energy can be dissipated. This study shows that this limit depends on the structural characteristics as well as the input ground motion, and a general trend is that the maximum control energy decreases as damping increases. Finally, application of the proposed algorithm on a six‐storey hospital building is presented to show the effectiveness of using optimal linear control on a multi‐degree‐of‐freedom system from the control energy perspectives. Copyright © 2001 John Wiley & Sons, Ltd.     

Effects of terrain smoothing on topographic shielding correction factors for cosmogenic nuclide‐derived estimates of basin‐averaged denudation rates

Estimation of spatially averaged denudation rates from cosmogenic nuclide concentrations in sediments depends on the surface production rates, the scaling methods of cosmic ray intensities, and the correction algorithms for skyline, snow and vegetation shielding used to calculate terrestrial cosmogenic nuclide production. While the calculation of surface nuclide production and application of latitude, altitude and palaeointensity scaling algorithms are subjects of active research, the importance of additional correction for shielding by topographic obstructions, snow and vegetation is the subject of ongoing debate. The derivation of an additional correction factor for skyline shielding for large areas is still problematic. One important issue that has yet to be addressed is the effect of the accuracy and resolution of terrain representation by a digital elevation model (DEM) on topographic shielding correction factors. Topographic metrics scale with the resolution of the elevation data, and terrain smoothing has a potentially large effect on the correction of terrestrial cosmogenic nuclide production rates for skyline shielding. For rough, high‐relief landscapes, the effect of terrain smoothing can easily exceed analytical errors, and should be taken into account. Here we demonstrate the effect of terrain smoothing on topographic shielding correction factors for various topographic settings, and introduce an empirical model for the estimation of topographic shielding factors based on landscape metrics. Copyright © 2008 John Wiley and Sons, Ltd.     

Middle and Late Devonian microbial carbonates,reefs and mounds in Guilin,South China and their sequence stratigraphic,paleoenvironmental and paleoclimatic significance

The importance of calcimicrobes and microbialite in carbonate platform and reefal environments has been stressed in recent literature. Burne and Moore[1] introduced the term microbialite to describe the clotted, laminated and undifferentiated fabrics formed by mi-crobial communities. Microbialites are organosedi-mentary deposits that have accreted as a result of ben-thic (prokaryotic or eukaryotic) communities, trapping and binding detrital sediment[1]. Microbial organisms and microbialite are…     

Dust production and the release of iron oxides resulting from the aeolian abrasion of natural dune sands

Global dust trajectories indicate that signi?cant quantities of aeolian‐transported iron oxides originate in contemporary dryland areas. One potential source is the iron‐rich clay coatings that characterize many sand‐sized particles in desert dune?elds. This paper uses laboratory experiments to determine the rate at which these coatings can be removed from dune sands by aeolian abrasion. The coatings impart a red colour to the grains to which previous researchers have assigned variable geomorphological signi?cance. The quantities of iron removed during a 120 hour abrasion experiment are small (99 mg kg^?1) and dif?cult to detect by eye; however, high resolution spectroscopy clearly indicates that ferric oxides are released during abrasion and the re?ectance of the particles alters. One of the products of aeolian abrasion is ?ne particles (<10 µm diameter) with the potential for long distance transport. Copyright © 2004 John Wiley & Sons, Ltd.     

Mapping the Land Cover of Mexico Using AVHRR Time‐Series Data Sets

Abstract

An important methodological and analytical requirement for analyzing spatial relationships between regional habitats and species distributions in Mexico is the development of standard methods for mapping the country's land cover/land use formations. This necessarily involves the use of global data such as that produced by the Advanced Very High Resolution Radiometer (AVHRR). We created a nine‐band time‐series composite image from AVHRR Normalized Difference Vegetation Index (NDVI) bi‐weekly data. Each band represented the maximum NDVI for a particular month of either 1992 or 1993. We carried out a supervised classification approach, using the latest comprehensive land cover/vegetation map created by the Mexican National Institute of Geography (INEGI) as reference data. Training areas for 26 land cover/vegetation types were selected and digitized on the computer's screen by overlaying the INEGI vector coverage on the NDVI image. To obtain specific spectral responses for each vegetation type, as determined by its characteristic phenology and geographic location, the statistics of the spectral signatures were subjected to a cluster analysis. A total of 104 classes distributed among the 26 land cover types were used to perform the classification. Elevation data were used to direct classification output for pine‐oak and coastal vegetation types. The overall correspondence value of the classification proposed in this paper was 54%; however, for main vegetation formations correspondence values were higher (60‐80%). In order to obtain refinements in the proposed classification we recommend further analysis of the signature statistics and adding topographic data into the classification algorithm.     

Reducing wind power curtailment in China: comparing the roles of coal power flexibility and improved dispatch

Renewable energy curtailment is a critical issue in China, impeding the country’s transition to clean energy and its ability to meet its climate goals. This paper analyzes the impacts of more flexible coal-fired power generation and improved power dispatch towards reducing wind power curtailment. A unit commitment model for power dispatch is used to conduct the analysis, with different scenarios demonstrating the relative impacts of more flexible coal-fired generation and improved power dispatch. Overall, while we find both options are effective in reducing wind power curtailment, we find that improved power dispatch is more effective: (1) the effect of ramping down coal-fired generators to reduce wind power curtailment lessens as the minimum output of coal-fired generation is decreased; and (2) as a result, at higher wind capacity levels, wind curtailment is much more significantly reduced with improved power dispatch than with decreased minimum output of coal-fired generation.

Key policy insights

• China should emphasize both coal power flexibility and dispatch in its policies to minimize renewable power curtailment and promote clean energy transition.

• China should accelerate the process of implementing spot market and marginal cost-based economic dispatch, while making incremental improvements to the existing equal share dispatch in places not ready for spot market.

• A key step in improving of dispatch is incorporating renewable power forecasts into the unit commitment process and updating the daily unit commitment based on the latest forecast result.

• China should expand the coal power flexibility retrofit programme and promote the further development of the ancillary service market to encourage more flexibility from coal-fired generation.