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At least 55 records · Page 3

Paleobiology of distinctive benthic microfossils from the upper Proterozoic Limestone-Dolomite "Series," central East Greenland

Populations of Polybessurus bipartitus Fairchild ex Green et al., a large morphologically distinctive microfossil, occur in silicified carbonates of the Upper Proterozoic (700-800 Ma) Limestone-Dolomite "Series," central East Greenland. Large populations of well-preserved individuals permit reconstruction of P. bipartitus as a coccoidal unicell that "jetted" upward from the sediment by the highly unidirectional secretion of extracellular mucopolysaccharide envelopes. Reproduction by baeocyte formation is inferred on the basis of clustered envelope stalks produced by small cells. Sedimentological evidence indicates that P. bipartitus formed surficial crusts locally within a shallow peritidal carbonate platform. Among living microorganisms a close morphological, reproductive, and behavioral counterpart to Polybessurus is provided by populations of an as yet underscribed cyanobacterium found in coastal Bahamian environments similar to those in which the Proterozoic fossils occur. In general morphology and "jetting" behavior, this population resembles species of the genus Cyanostylon, Geitler (1925), but reproduces via baeocyte formation. Polybessurus is but one of the more than two dozen taxa in the richly fossiliferous biota of the Limestone-Dolomite "Series." This distinctive population, along with co-occurring filamentous cyanobacteria and other microfossils, contributes to an increasingly refined picture of ecological heterogeneity in late Proterozoic oceans.

NASA Discipline Exobiology↗

Fracture propagation in Indiana Limestone interpreted via linear softening cohesive fracture model

In this study, we examine the use of a linear softening cohesive fracture model (LCFM) to predict single-trace fracture growth in short-rod (SR) and notched 3-point-bend (N3PB) test configurations in Indiana Limestone. The broad goal of this work is to (a) understand the underlying assumptions of LCFM and (b) use experimental similarities and deviations from the LCFM to understand the role of loading paths of tensile fracture propagation. Cohesive fracture models are being applied in prediction of structural and subsurface fracture propagation in geomaterials. They lump the inelastic processes occurring during fracture propagation into a thin zone between elastic subdomains. LCFM assumes that the cohesive zone initially deforms elastically to a maximum tensile stress ( σ max ) and then softens linearly from the crack opening width at σ max to zero stress at a critical crack opening width w 1 . Using commercial finite element software, we developed LCFMs for the SR and N3PB configurations. After fixing σ max with results from cylinder splitting tests and finding an initial Young's modulus ( E ) with unconfined compressive strength tests, we manually calibrate E and w 1 in the SR model against an envelope of experimental data. We apply the calibrated LCFM parameters in the N3PB geometry and compare the model against an envelope of N3PB experiments. For accurate simulation of fracture propagation, simulated off-crack stresses are high enough to require inclusion of damage. Different elastic moduli are needed in tension and compression. We hypothesize that the timing and location of shear versus extensional micromechanical failures control the qualitative macroscopic force-versus-displacement response in different tests. For accurate prediction, the LCFM requires a constant style of failure, which the SR configuration maintains until very late in deformation. The N3PB configuration does not maintain this constancy. To be broadly applicable between geometries and failure styles, the LCFM would require additional physics, possibly including elastoplastic damage in the bulk material and more complicated cohesive softening models.

58 GEOSCIENCES↗

Mechanical properties and durability performance of concretes with Limestone Calcined Clay Cement (LC3)

The adoption of any binder system for structural concrete depends on the performance characteristics desired for addressing the long-term deformation and durability concerns. The major properties influencing the performance includes the shrinkage characteristics governing the long-term deformation, and durability characteristics related to various transport mechanisms, governing the performance in different service conditions. This paper describes the potential of Limestone Calcined Clay Cement (LC{sup 3}) for use in structural concrete in comparison with Ordinary Portland Cement (OPC) and fly ash based blended cement (FA30). Three types of concrete mixtures were designed for the study, two based on achieving an equivalent strength grade (M30 and M50 concrete grade) with each binder, and the third with equal binder content and w/b ratio. Mechanical properties such as compressive strength and elastic modulus, and autogenous and drying shrinkage, along with various durability parameters of the different concretes were assessed. Oxygen permeability, rapid chloride penetration, chloride migration, resistivity development and water sorptivity were the various parameters considered for evaluation of durability performance. The results indicate the superiority of LC{sup 3} binder over other binders in producing durable concrete, especially in a chloride laden environment. The major reason for the better performance was attributed to the more compact and dense microstructure of the system with the LC{sup 3} binder against OPC and FA30. The drying shrinkage performance was seen to be similar for concrete with all three binders.

36 MATERIALS SCIENCE↗

Mechanisms dominating thixotropy in limestone calcined clay cement (LC3)

Limestone calcined clay cement (LC3) is a green binder with great practical importance for the cement industry. Growing application has increased the need to understand the mechanisms governing its thixotropy for better control of workability. While formation of C-S-H bridges is understood to dominate the thixotropy of ordinary Portland cement, LC3 paste displayed unique thixotropy properties. In this study, focused beam reflectance measurement, zeta potential, 1H nuclear magnetic resonance relaxometry and micro X-ray computed tomography were used to track the colloidal interaction and hydration extent within LC3 paste. Results showed that flocculation due to the negative surface charge and water affinity of calcined clay appears to be the dominating factor. This leads to a reduction of water available to contribute to fluidity of the paste and, in turn, governing the development of thixotropy over time. In addition, the dilution effect due to high clinker substitution diminishes thixotropy growth with time.

36 MATERIALS SCIENCE↗

On the use of limestone calcined clay cement (LC3) in high-strength strain-hardening cement-based composites (HS-SHCC)

Highlights: • Use of LC{sup 3} slightly reduces flowability and shortens the setting time of fresh matrices. • Highly polymerized C-A-S-H gel and abundant ettringite benefit flexural strength of LC{sup 3}-matrices. • Use of LC{sup 3} enhances the bond strength between fiber and high-strength matrix. • LC{sup 3}-based HS-SHCC yields similar flexural performance as the composite with Portland cement. High-strength strain-hardening cement-based composites (HS-SHCC) demonstrate excellent mechanical and durability properties. However, high cement content typical to HS-SHCC results not only in high carbon footprint, but also in excessive hydration heat and severe autogenous shrinkage. In this investigation, Limestone Calcined Clay Cement (LC{sup 3}) was used to produce sustainable HS-SHCC. The LC{sup 3} substitution resulted in higher energy consumption during mixing and in shorter setting times of the fresh, plain matrices. Although the LC{sup 3} substitution slightly reduced the compressive strength, the formation of highly polymerized C-A-S-H gel and abundant ettringite benefited the flexural strength of the plain matrices. Additionally, single-fiber pullout experiments showed that the use of LC{sup 3} led to increased fiber-matrix bond strength and pullout energy. Finally, the replacement of Portland cement by LC{sup 3} resulted in HS-SHCC with similar mechanical performance to the reference composite, indicating a high potential for using LC{sup 3} in high-performance cement-based composites.

36 MATERIALS SCIENCE↗

3D printing of calcined clay-limestone-based cementitious materials

This paper aims to investigate the influences of high Portland cement substitutions (>60 wt%) by low-grade calcined clay (CC) and limestone (LF) on 3D concrete printability, stiffness evolution and early-age hydration. Results show that, with the same dosage of admixtures (superplasticizer and viscosity modifier), increasing LF and CC content reduced the slump, flowability and initial material flow rate, and significantly improved the buildability of fresh mixtures, which can be attributed to the reduced water film thickness (WFT). Furthermore, the stiffness evolution and SSA{sub total} development up to the first 3 h were accelerated by increasing CC content, which can also be linked to the change of WFT, and consumption of superplasticizer for the dispersion induced by hydration products. Additionally, the dilution effect on compressive strength and hydration caused by the high cement replacement was observed.

36 MATERIALS SCIENCE↗

Limestone calcined clay cement and concrete: A state-of-the-art review

This article reviews the rapidly developing state-of-the-art literature available on the subject of the recently developed limestone calcined clay cement (LC{sup 3}). An introduction to the background leading to the development of LC{sup 3} is first discussed. The chemistry of LC{sup 3} hydration and its production are detailed. The influence of the properties of the raw materials and production conditions are discussed. The mixture design of concrete using LC{sup 3} and the mechanical and durability properties of LC{sup 3} cement and concrete are then compared with other cements. At the end the economic and environmental aspects of the production and use of LC{sup 3} are discussed. The paper ends with suggestions on subjects on which further research is required.

36 MATERIALS SCIENCE↗

The effect of CO 2 -induced dissolution on flow properties in Indiana Limestone: An in situ synchrotron X-ray micro-tomography study

The injection of CO 2 -rich fluids in carbonate rocks results in an evolution of the pore space, with consequent changes in the hydraulic properties of the reservoir; how these properties evolve, particularly for parameters relevant to multiphase flow e.g. P c (s), remains a topic of active research despite several decades of study. We have carried out an in situ synchrotron X-ray microtomography experiment to monitor pore structure evolution during dissolution of an Indiana Limestone core; the experiment involved flowing CO 2 -saturated water through the core for 36 h and resulted in 10 volumes corresponding to different temporal stages of the dissolution process. The injection parameters corresponded to the flow velocities expected near the well-bore region of a shallow aqueous CO 2 injection; fast flow rates with high reactant availability. Analysis of the tomographic data shows flow-enhanced dissolution i.e. channeling, and provides a time-resolved map of pore space alteration. Using the resulting 4D pore space volume, we modeled the evolution of capillary-pressure curves; this exercise demonstrates how pore structure evolution could impact the invasion and remobilization of non-wetting fluids, dramatically decreasing the entry pressure and the P C in some parts of the sample. The modeling of permeability, using a Stokes solver approach, quantified the relationship of porosity vs. permeability; we found that a modest increase in porosity, especially when the channeling system is more developed, greatly affects permeability. Furthermore, these results demonstrate how movement of CO 2 saturated brine near injected plumes might alter drainage dynamics near the plume boundary, thus leading to mobilization across subtle capillary barriers.

58 GEOSCIENCES↗

Additive effects of acidification and mineralogy on calcium isotopes in Triassic/Jurassic boundary limestones

The end-Triassic mass extinction coincided with a negative δ 13 C excursion, consistent with release of 13 C-depleted CO 2 from the Central Atlantic Magmatic Province. However, the amount of carbon released and its effects on ocean chemistry are poorly constrained. The co upled nature of the carbon and calcium cycles allows calcium isotopes to be used for constraining carbon cycle dynamics and vice versa. We present a high-resolution calcium isotope (δ 44/40 Ca) record from 100 m of marine limestone spanning the Triassic/Jurassic boundary in two stratigraphic sections from northern Italy. Immediately above the extinction horizon and the associated negative excursion in δ 13 C, δ 44/40 Ca decreases by ca. 0.8‰ in 20 m of section and then recovers to preexcursion values. Coupled numerical models of the geological carbon and calcium cycles demonstrate that this δ 44/40 Ca excursion is too large to be explained by changes to seawater δ 44/40 Ca alone, regardless of CO 2 injection volume and duration. Less than 20% of the δ 44/40 Ca excursion can be attributed to acidification. The remaining 80% likely reflects a higher proportion of aragonite in the original sediment, based largely on high concentrations of Sr in the samples. Our study demonstrates that coupled models of the carbon and calcium cycles have the potential to help distinguish contributions of primary seawater isotopic changes from local or diagenetic effects on the δ 44/40 Ca of carbonate sediments. Finally, differentiating between these effects is critical for constraining the impact of ocean acidification during the end-Triassic mass extinction, as well as for interpreting other environmental events in the geologic past.

58 GEOSCIENCES↗

Thermodynamic modeling of hydrated white Portland cement–metakaolin–limestone blends utilizing hydration kinetics from {sup 29}Si MAS NMR spectroscopy

Hydration kinetics for the principal phases of Portland cement blends have been incorporated in thermodynamic modeling (GEMS package), utilizing degrees of hydration from {sup 29}Si MAS NMR. An empirical relationship for the reaction of these phases is established which includes three variable parameters that all can be estimated from the degrees of hydration. This approach is compared with thermodynamic equilibrium modeling (full hydration) for white Portland cement–metakaolin (0–30 wt.%) blends and for ternary blends of white Portland cement (65 wt.%)–metakaolin–limestone. The predicted phase assemblages have been compared with the phases identified by XRD, {sup 27}Al and {sup 29}Si MAS NMR which reveals that the incorporation of hydration kinetics improves the agreement between modeling and experiments. The results show also that the formation of strätlingite depends critically on the quantity of charge-balancing anions in the AFm phases, especially carbonate and sulfate anions, and on the degree of hydration for metakaolin.

36 MATERIALS SCIENCE↗

Role of calcium on chloride binding in hydrated Portland cement–metakaolin–limestone blends

Chloride binding is investigated for Portland cement–metakaolin–limestone pastes exposed to CaCl{sub 2} and NaCl solutions. The phase assemblages and the amount of Friedel's salt are evaluated using TGA, XRD and thermodynamic modeling. A larger amount of Friedel's salt is observed in the metakaolin blends compared to the pure Portland cement. A higher total chloride binding is observed for the pastes exposed to the CaCl{sub 2} solution relative to those in the NaCl solution. This is reflected by the fact that calcium increases the quantity of Friedel's salt in the metakaolin blends by promoting the transformation of strätlingite and/or monocarbonate to Friedel's salt. Calcium increases also the amount of chloride in the diffuse layer of the C-S-H for the pure cement. A linear correlation between the total bound chloride and the uptake of calcium from the CaCl{sub 2} solution is obtained and found to be independent on the type of cement blend.

36 MATERIALS SCIENCE↗

Ecohydrologic processes and soil thickness feedbacks control limestone-weathering rates in a karst landscape

Here, chemical weathering of bedrock plays an essential role in the formation and evolution of Earth's critical zone. Over geologic time, the negative feedback between temperature and chemical weathering rates contributes to the regulation of Earth climate. The challenge of understanding weathering rates and the resulting evolution of critical zone structures lies in complicated interactions and feedbacks among environmental variables, local ecohydrologic processes, and soil thickness, the relative importance of which remains unresolved. We investigate these interactions using a reactive-transport kinetics model, focusing on a low-relief, wetland-dominated karst landscape (Big Cypress National Preserve, South Florida, USA) as a case study. Across a broad range of environmental variables, model simulations highlight primary controls of climate and soil biological respiration, where soil thickness both supplies and limits transport of biologically derived acidity. Consequently, the weathering rate maximum occurs at intermediate soil thickness. The value of the maximum weathering rate and the precise soil thickness at which it occurs depend on several environmental variables, including precipitation regime, soil inundation, vegetation characteristics, and rate of groundwater drainage. Simulations for environmental conditions specific to Big Cypress suggest that wetland depressions in this landscape began to form around beginning of the Holocene with gradual dissolution of limestone bedrock and attendant soil development, highlighting large influence of age-varying soil thickness on weathering rates and consequent landscape development. While climatic variables are often considered most important for chemical weathering, our results indicate that soil thickness and biotic activity are equally important. Weathering rates reflect complex interactions among soil thickness, climate, and local hydrologic and biotic processes, which jointly shape the supply and delivery of chemical reactants, and the resulting trajectories of critical zone and karst landscape development.

54 ENVIRONMENTAL SCIENCES↗

Functional activity and functional gene diversity of a Cu-contaminated soil remediated by aided phytostabilization using compost, dolomitic limestone and a mixed tree stand

Trace elements (TEs) availability, biochemical activity and functional gene diversity was studied in a Cu-contaminated soil, revegetated for six years with a mixed stand of willow, black poplar, and false indigo-bush, and amended or not with compost plus dolomitic limestone (OMDL). The OMDL amendment significantly reduced Cu and As availability and soil toxicity, and increased the biochemical activity and microbial functional diversity assessed with the GEOCHIP technique, as compared to the unamended soil (Unt). The OMDL soil showed significantly higher abundance of 25 functional genes involved in decomposition organic compounds, and 11, 3 and 11 functional genes involved in the N, P and S biogeochemical cycles. Functional gene abundance was positively correlated with nutrient contents but negatively correlated with Cu availability and soil toxicity. The abundance of microbial functional genes encoding for resistance to various TEs also increased, possibly due to the microbial proliferation and lower Cu exposure in the presence of high total soil Cu concentration. Genes encoding for antibiotic resistance due to the co-occurrence of TEs and antibiotic resistant genes on genetic mobile elements. Finally, overall, phytomanagement confirmed its potential to restore the biological fertility and diversity of a severely Cu-contaminated soil, but the increase of TEs and antibiotic resistant gene abundances deserve attention in future studies.

54 ENVIRONMENTAL SCIENCES↗

Scaled experiments on cavity confined explosions in limestone and poly(methyl methacrylate)

A scaled experiment comprising a laser-driven explosion in a cavity is used to characterize the coupling of mechanical energy into the surrounding solid material. Experiments are performed using poly(methyl methacrylate) and dry Salem limestone as the explosion containment blocks materials, in which are milled scaled spherical cavities of various dimensions. Measurements of the coupled shock, taken with fiber optic probes at the cavity wall, show the critical radius where wall deformation transitions from plastic to elastic deformation. These measurements also provide a diagnostic of the air blast, which is validated against GEODYN simulation code. The measurement of the coupled shock amplitude taken farther from the wall in the linear region indicates increased coupling efficiency in small cavities over the range of scaled cavity radii from 6 to 20 m/kt 1/3 , a phenomenon not previously observed in experiments. A comparison of results taken in this experiment with a parallel experiment using high explosive (HE) as the source shows that coupled shocks generated with HE are characteristically different with much larger amplitude than those produced by a high energy density laser-driven source with the same yield. This experimental technique potentially provides a rapid and cost-effective method to analyze the consequences of a full-scale, low yield, buried explosion.

58 GEOSCIENCES↗

Portland Limestone Cement for Reduced Shrinkage and Enhanced Durability of Concrete

Here in this research, different cementitious systems have been used to investigate shrinkage of concrete under plastic, and drying conditions. Emphasis has been laid on portland limestone cement (Type IL (10)) with replacement amounts of 10% of portland cement. Comparisons have been made with a cement type with low Blaine fineness, i.e. coarse ground cement. Results indicate that Type IL cement has good shrinkage results, without adversely affecting other engineering properties of concrete, such as strength, resistivity, degree of hydration, and setting time. This is likely due to an improved particle packing, access to more nucleation sites for the hydration products, and the formation of calcium carbo-aluminate hydrates. Scanning electron micrographs of coarse ground cement paste also indicate a retarded degree of hydration compared to Type I/II portland cement paste.

36 MATERIALS SCIENCE↗

Direct Air Capture Case Studies: Limestone Looping Screening-Level Analysis

A screening-level techno-economic analysis of a passive limestone looping direct air capture system is presented. The base case examined in this report does not represent an optimized system and makes many simplifying assumptions due to the nascence of the technology and lack of publicly available information. The base case serves as a reference for detailed and informative sensitivity analyses. This initial study (1) reveals that improving reaction rate and tray configuration can potentially significantly reduce cost, and (2) indicates that LL has the potential to be cost competitive with other DAC technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗