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At least 73 records · Page 4

Calcium is associated with specific soil organic carbon decomposition products at Blodgett Forest Research Center, Georgetown, California as analysed with scanning transmission X-ray microscopy carbon near-edge X-ray absorption fine structure spectroscopy

This data is from the paper calcium is associated with specific soil organic carbon decomposition products, published in SOIL. DOI: https://doi.org/10.5194/soil-11-381-2025, 2025.This file contains CSVs with spectral data and bulk soil data and there is no specific program required to open this data. The data includes Scanning transmission X-ray microscopy carbon near-edge X-ray absorption fine structure spectroscopy. data from the measurement of samples from the Whole-soil Warming project, run by the Belowground Biogeochemistry team at Blodgett Forest Research Center, Georgetown, California run by the University of California, Berkeley. It also includes bulk soil chemical properties. The University of California's Blodgett Forest Research Station (Forest) is situated in the Sierra Nevada foothills (1370 m a.s.l.) near Georgetown, California. The samples were collected from here: 38.912013, -120.661469, https://maps.app.goo.gl/291bCJ1zVqUhgktz6. The Forest soils were characterised as Alfisols, which are equivalent to Dystric Cambisols (IUSS Working Group WRB, 2015), and formed in granitic parent materials, in a temperate climate, under thinned, mixed-coniferous forest (Fig. S3; Gaudinski et al., 2009). With these analyses we aimed to answer the question, is calcium associated with a specific type of organic matter enriched in aromatic and phenolic carbon at the microscale in samples from Blodgett Forest Research Center? and how does this specific type of carbon respond to experiments targetted at removing and adding calcium to the soils, specifically cation exchange and incubation after calcium addition? Abstract from the paper can be found below: Calcium (Ca) may contribute to the preservation of soil organic carbon (SOC) in more ecosystems than previously thought. Here we provide evidence that Ca is co-located with SOC compounds that are enriched in aromatic and phenolic groups, across different acidic soil-types and locations with different ecosystem properties, differing in terms of climate, parent material, soil type, and vegetation. In turn, this co-localised fraction of Ca-SOC is removed through cation-exchange, and the association is then only re-established during decomposition in the presence of Ca (Ca addition incubation). Thus, highlighting a causative link between decomposition and the co-location of Ca with a characteristic fraction of SOC. Decomposition increases the relative proportion of negatively charged functional groups, which can increase the propensity for the association between SOC and Ca, and in turn, this association inhibits dissolved organic carbon export or further decomposition. We propose that this mechanism could be driven by Ca hotspots on the microscale shifting local decomposition processes and thereby explaining the colocation of Ca with SOC of a specific composition across different acidic soil environments. Incorporating this biogeochemical process into Earth System Models could improve our understanding, predictions, and management of carbon dynamics in soils, and account for their response to Ca-rich amendments.

54 ENVIRONMENTAL SCIENCES↗

Structural analyses of amorphous calcium carbonate before and after removing strontium ions from an aqueous solution

Amorphous calcium carbonate (ACC) is a precursor of crystalline calcium carbonate; hence, its structural information at the atomic level is very important for controlling the morphology of crystalline calcium carbonate. In this study, we attempted to elucidate the process of Sr extraction from aqueous solution by using ACC for the purpose of removal of radioactive Sr from the contaminated water leaked after the Fukushima Daiichi nuclear accident. Here, the pair distribution functions, g(r) obtained by X-ray and neutron diffraction (ND) measurements show that ACC has a structure partially similar to that of monohydrocalcite, suggesting that ACC is transferred to the crystalline calcium carbonate starting from its crystal nucleus. Rietveld analysis of the ND data showed that the ACC that removed Sr was crystallized to calcite. However, the Sr–O coordination analyzed using extended X-ray absorption fine structure (EXAFS) implies that the local environment of O around Sr is similar to that in crystalline calcium carbonate aragonite.

36 MATERIALS SCIENCE↗

Calcium Carbonate Cement: A Carbon Capture, Utilization, and Storage (CCUS) Technique

A novel calcium carbonate cement system that mimics the naturally occurring mineralization process of carbon dioxide to biogenic or geologic calcium carbonate deposits was developed utilizing carbon dioxide-containing flue gas and high-calcium industrial solid waste as raw materials. The calcium carbonate cement reaction is based on the polymorphic transformation from metastable vaterite to aragonite and can achieve >40 MPa compressive strength. Due to its unique properties, the calcium carbonate cement is well suited for building materials applications with controlled factory manufacturing processes that can take advantage of its rapid curing at elevated temperatures and lower density for competitive advantages. Examples of suitable applications are lightweight fiber cement board and aerated concrete. The new cement system described is an environmentally sustainable alternative cement that can be carbon negative, meaning more carbon dioxide is captured during its manufacture than is emitted.

36 MATERIALS SCIENCE↗

Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene

The catalytic conversion of ethanol to butanol and butadiene at 633 K and atmospheric pressure (7 vol% ethanol) was studied over calcium phosphate materials pretreated over a wide temperature range. For calcium phosphate pretreated at or below 923 K, the resulting solid had an apatite structure identified by X-ray diffraction and strong acid sites probed by triethylamine (TEA) adsorption microcalorimetry. The low temperature pretreated materials were not effective at ethanol coupling reactions but instead were highly selective to acid-catalyzed products ethene and diethyl ether. Pretreatment of calcium phosphate at 973 K transformed the apatite structure to β-tricalcium phosphate, which exposed both acid and base sites evaluated by TEA and CO 2 adsorption microcalorimetry. In conclusion, high temperature pretreated calcium phosphate catalysts formed the coupling products butanol and butadiene during ethanol reaction. The butadiene selectivity was improved by supporting calcium phosphate on zirconia.

09 BIOMASS FUELS↗

The Effect of Calcium on the Cohesive Strength and Flexural Properties of Low-Methoxyl Pectin Biopolymers

Pectin binds the mesothelial glycocalyx of visceral organs, suggesting its potential role as a mesothelial sealant. To assess the mechanical properties of pectin films, we compared pectin films with a less than 50% degree of methyl esterification (low-methoxyl pectin, LMP) to films with greater than 50% methyl esterification (high-methoxyl pectin, HMP). LMP and HMP polymers were prepared by step-wise dissolution and high-shear mixing. Both LMP and HMP films demonstrated a comparable clear appearance. Fracture mechanics demonstrated that the LMP films had a lower burst strength than HMP films at a variety of calcium concentrations and hydration states. The water content also influenced the extensibility of the LMP films with increased extensibility (probe distance) with an increasing water content. Similar to the burst strength, the extensibility of the LMP films was less than that of HMP films. Flexural properties, demonstrated with the 3-point bend test, showed that the force required to displace the LMP films increased with an increased calcium concentration ( p < 0.01). Toughness, here reflecting deformability (ductility), was variable, but increased with an increased calcium concentration. Similarly, titrations of calcium concentrations demonstrated LMP films with a decreased cohesive strength and increased stiffness. We conclude that LMP films, particularly with the addition of calcium up to 10 mM concentrations, demonstrate lower strength and toughness than comparable HMP films. These physical properties suggest that HMP has superior physical properties to LMP for selected biomedical applications.

Biochemistry & Molecular Biology↗

Calcium carbonate minerals as scavengers of metals and radionuclides: Their role in natural attenuation and remediation

Calcium carbonates (CaCO3) are ubiquitous naturally occurring minerals in subsurface sediments. Calcium carbonate coatings are common in many terrestrial environments and are known to coat a variety of reactive mineral surfaces in soils and sediments, altering their reactivity and chemical behavior. For these reasons, contaminant interactions with CaCO3 minerals are relevant to contaminant fate and transport. Significant advancements have been made recently toward identifying relevant contaminant (e.g., U, I, and Cr) attenuation mechanisms, which may also serve as a basis for in situ remediation strategies. Hence, the objective of this review paper is to 1) describe the state-of-knowledge of calcium carbonate minerals as universal scavengers of metals and radionuclides; 2) provide a state of the science of how calcium carbonate interactions affect contaminant fate and transport in the subsurface environmental systems; and 2) provide insights on the use of calcium carbonate natural attenuation mechanisms and their application to the remediation of complex sites. Knowledge gaps are also identified that, when closed, can advance the use of carbonate minerals for in situ remedy applications.

Qafoku, Nikolla↗

Calcium fluoride as a dominating matrix for quantitative analysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS): A feasibility study

Here, calcium fluoride formed by the reaction between ammonium bifluoride and calcium chloride was investigated as a dominating matrix for quantitative analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Transformation from a solid sample to the calcium fluoride-based matrix permitted quantitative analysis based on calibration standards made from elemental standards. A low abundance stable calcium isotope, i.e. 44 Ca + , was monitored as the internal standard for quantitative analysis by LA-ICP-MS. Correlation coefficient factors for multiple elements were obtained with values over 0.999. The results for multiple elements in a certified reference material of soil (NIST SRM 2710a) agreed with the certified values in the range of expanded uncertainty, indicating the present method was valid for quantitation of elements in solid samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental demonstration of a 5 kW th granular-flow reactor for solar thermochemical energy storage with aluminum-doped calcium manganite particles

A two-step cycle was discussed for solar thermochemical energy storage based on aluminum-doped calcium manganite reduction/oxidation reactions for direct integration into Air Brayton cycles. The two steps encompassed 1) the storage of concentrated solar direct irradiation via the thermal reduction of aluminum-doped calcium manganite and 2) the delivery of heat to an Air-Brayton cycle via re-oxidation of oxygen-deficient aluminum-doped calcium manganite. The re-oxidized aluminum-doped calcium manganite was fed back to the first step to complete the cycle. A 5 kWth solar thermochemical reactor operating under vacuum was fabricated and tested to examine the first cycle reduction step. Reactor operating conditions and high-flux solar simulator control were tuned for continuous reactor operation with particle temperatures > 1073 K. Continuous operation was achieved using intermittent, dense granular flows. A maximum absorption efficiency of 64.7% was shown, accounting for both sensible and chemical heat storage.

25 ENERGY STORAGE↗

Influence of calcium nitrate timing on the structural and textural characteristics of mesoporous SiO 2 -CaO nanoparticles

Mesoporous bioactive glass nanoparticles (MBGNPs) are promising materials for drug delivery due to their high pore volume and specific surface area. This study investigates how the timing of calcium nitrate addition affects the structural and textural characteristics of MBGNPs synthesized via a microemulsion-assisted sol-gel method. Delayed calcium nitrate addition reduced calcium incorporation from 14.2 to 9.5 mol% and increased particle size from 178 ± 51 nm to 256 ± 30 nm. The specific surface area values increased with the delayed addition of calcium nitrate, as observed through BET and USAXS/SAXS measurements. The proportion of Q Si n units slightly changed, but no cytotoxicity was observed in osteoblast-like cells. These findings provide valuable insights into optimizing MBGNP synthesis for biomedical applications.

Calcium nitrate tetrahydrate↗

Aluminum-doped calcium manganite particles for solar thermochemical energy storage: Reactor design, particle characterization, and heat and mass transfer modeling

A two-step cycle is discussed for solar thermochemical energy storage based on particulate aluminum-doped calcium manganite reduction/oxidation reactions for direct integration into Air Brayton cycles. The two steps encompass 1) the storage of concentrated solar irradiation within endothermic reduction of aluminum-doped calcium manganite and 2) the delivery of heat to an Air-Brayton cycle via exothermic re-oxidation of oxygen-deficient aluminum-doped calcium magnanite. A 5 kW th scale solar thermochemical reactor operating under vacuum was designed, modeled, and optimized to thermally reduce a continuous, gravity-driven flow of aluminum-doped calcium manganite particles. The granular flows were characterized in a tilt-flow rig, and particle image velocimetry was used to determine flow properties via frictional and velocity scaling relationships. Flow properties were integrated into a detailed heat and mass transfer model of the solar thermochemical reactor. A reactor design with 31° inclination angle, 230 g/min of particles, and 5.2 kW th radiative input from the high-flux solar simulator was discovered to produce an outlet flow temperature of 1158 K, with stoichiometric deviations of 0.076 and a storage efficiency of 0.628 while avoiding particle overheating and promoting longer particle residence times.

14 SOLAR ENERGY↗

Non-stoichiometry Governs the Pathway from Amorphous to Crystalline Calcium Carbonate

The controlled crystallization of calcium carbonate underlies the elaborate architectures of marine corals, the design of biomimetic materials, and the global carbon cycle. Despite its ubiquity, the chemical mechanisms that govern the crystallization of calcium carbonate from its amorphous precursor, amorphous calcium carbonate (ACC), remain elusive, largely due to the difficulty in resolving the structure and chemistry of this transient amorphous state. Here, we use time-lapse photography, image analysis, spatially resolved pH determination, in situ synchrotron pair distribution function (PDF) analysis, and dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) spectroscopy to reveal pervasive compositional variability in ACC that underpins its metastability and crystallization. By evaluating the kinetics of the amorphous-to-crystalline transition across different solution chemistries, we demonstrate that ACC is non-stoichiometric and CO 3 -deficient. Counterions from the precursor (e.g., NO 3 - from Ca(NO 3 ) 2 ) substitute into the ACC network, displacing CO 3 ions and mediating both ACC stability and transformation. Crystallization proceeds through refinement of the stoichiometry toward CaCO 3 and uptake of free CO 3 2- anions. Furthermore, these findings are consistent across a wide range of concentrations and different carbonate sources, explaining the diverse behaviors observed for ACC and providing a chemical framework for controlling calcium carbonate crystallization.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Geometrically frustrated interactions drive structural complexity in amorphous calcium carbonate

Amorphous calcium carbonate is an important precursor for biomineralization in marine organisms. Key outstanding problems include understanding the structure of amorphous calcium carbonate and rationalizing its metastability as an amorphous phase. Here we report high-quality atomistic models of amorphous calcium carbonate generated using state-of-the-art interatomic potentials to help guide fits to X-ray total scattering data. Exploiting a recently developed inversion approach, we extract from these models the effective Ca∙∙∙Ca interaction potential governing the structure. This potential contains minima at two competing distances, corresponding to the two different ways that carbonate ions bridge Ca 2+ -ion pairs. We reveal an unexpected mapping to the Lennard-Jones–Gauss model normally studied in the context of computational soft matter. The empirical model parameters for amorphous calcium carbonate take values known to promote structural complexity. We thus show that both the complex structure and its resilience to crystallization are actually encoded in the geometrically frustrated effective interactions between Ca 2+ ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mineralogy of microbially induced calcium carbonate precipitates formed using single cell drop-based microfluidics

Microbe-mineral interactions are ubiquitous and can facilitate major biogeochemical reactions that drive dynamic Earth processes such as rock formation. One example is microbially induced calcium carbonate precipitation (MICP) in which microbial activity leads to the formation of calcium carbonate precipitates. A majority of MICP studies have been conducted at the mesoscale but fundamental questions persist regarding the mechanisms of cell encapsulation and mineral polymorphism. Here, we are the first to investigate and characterize precipitates on the microscale formed by MICP starting from single ureolytic E. coli MJK2 cells in 25 µm diameter drops. Mineral precipitation was observed over time and cells surrounded by calcium carbonate precipitates were observed under hydrated conditions. Using Raman microspectroscopy, amorphous calcium carbonate (ACC) was observed first in the drops, followed by vaterite formation. ACC and vaterite remained stable for up to 4 days, possibly due to the presence of organics. The vaterite precipitates exhibited a dense interior structure with a grainy exterior when examined using electron microscopy. Autofluorescence of these precipitates was observed possibly indicating the development of a calcite phase. The developed approach provides an avenue for future investigations surrounding fundamental processes such as precipitate nucleation on bacteria, microbe-mineral interactions, and polymorph transitions.

58 GEOSCIENCES↗

Structural evolution of amorphous calcium sulfate nanoparticles into crystalline gypsum phase

The involvement of amorphous calcium sulfate (ACS) as a precursor to calcium sulfate crystallization remains an important but poorly understood phenomenon, especially the mechanism by which ACS evolves into crystalline phase. In this study, we captured the ACS nanoparticles as a precursor to calcium sulfate crystallization in a concentrated CaCl 2 solution at 90 °C and observed several stages of its evolution. The ACS nanoparticles grew by simultaneous fusion and internal structural evolution. Aggregation of the ACS nanoparticles gave birth to bulk ACS particles within which nanocrystalline domains sprouted and developed into crystalline gypsum. This work deepens the understanding of the evolution of ACS nanoparticles and its role in multistage crystallization of calcium sulfate.

36 MATERIALS SCIENCE↗

Nanocapsules of unprecedented internal volume seamed by calcium ions

The inception of an unprecedented class of voluminous Platonic solids displaying hierarchical geometry based on pyrogallol[4]arene moieties seamed by divalent calcium ion is described. Single-crystal X-ray structural determination has established the highly conserved geometry of two original Ca 2+ -seamed nanocapsules to be essentially cubic in shape with C-ethylpyrogallol[4]arene units located along the twelve edges of the cube which are then bridged by metallic polyatomic cations ([Ca 4 Cl] 7+ or [Ca(HCO 2 )Na 4 ] 5+ ) at the six cube faces. The accessible volume of the nanocapsules is ca. 3500 Å 3 and 2500 Å 3 and is completely isolated from the exterior of the capsules. These remarkable nanocapsule discoveries cast a spotlight on a marginalized area of synthetic materials chemistry and encourage future exploration of diversiform supramolecular assemblies, networks, and capsules built on calcium, with clear benefits deriving from the intrinsic biocompatibility of calcium. Finally, a proof-of-concept is demonstrated for fluorescent reporter encapsulation and sustained release from the calcium-seamed nanocapsules, suggesting their potential as delivery vehicles for drugs, nutrients, preservatives, or antioxidants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-scale Simulation, Calibration, and Optimization of Calcium Carbonate Precipitation in Microbial Communities

Ensuring the efficient engineering of microbially induced calcium carbonate precipitation (MICP) is crucial for a variety of environmental and civil engineering applications, such as soil stabilization and carbon sequestration. Addressing this need, we present a comprehensive multi-scale workflow that begins with the isolation of calcium carbonate-producing microbes from soil samples, followed by metagenomic sequencing and metabolic reconstruction. We then characterize microbial growth phenotypes under diverse nutrient conditions, compare observed growth with metabolic model predictions, and apply the Consistent Reproduction of Phenotype (CROP) algorithm to refine these models. Furthermore, we analyze metabolite consumption and production, and develop a consumer-resource model that is calibrated using time-series measurements of growth rates, pH levels, and calcium carbonate precipitation. The primary benefit of our approach lies in its ability to predict and control MICP outcomes, facilitated by a Bayesian methodology that incorporates priors on initial conditions and parameters. This allows us to compute posteriors by integrating experimental data, and to solve a risk optimization problem under uncertainty to identify nutrient conditions that maximize calcium carbonate production. In contrast to non-Bayesian methods, which fail to quantify uncertainty accurately, our approach provides a more reliable pathway to optimizing nutrient conditions, enhancing the likelihood of achieving desired MICP outcomes. This positions our method as a superior alternative in the quest to improve MICP through engineered microbial consortia.

54 ENVIRONMENTAL SCIENCES↗

The Kinetics of Aragonite Formation from Solution via Amorphous Calcium Carbonate

Magnesium doped Amorphous Calcium Carbonate was synthesised from precursor solutions containing varying amounts of calcium, magnesium, H2O and D2O. The Mg/Ca ratio in the resultant Amorphous Calcium Carbonate was found to vary linearly with the Mg/Ca ratio in the precursor solution. All samples crystallised as aragonite. No Mg was found in the final aragonite crystals. Changes in the Mg to Ca ratio were found to only marginally effect nucleation rates but strongly effect crystal growth rates. These results are consistent with a dissolution-reprecipitation model for aragonite formation via an Amorphous Calcium Carbonate intermediate.

36 MATERIALS SCIENCE↗

Splitting tensile strength of shale cores: intact versus fractured and sealed with ureolysis-induced calcium carbonate precipitation (UICP)

Ureolysis-induced calcium carbonate precipitation (UICP) is a biomineral solution where the urease enzyme converts urea and calcium into calcium carbonate. The resulting biomineral can bridge gaps in fractured shale, reduce undesired fluid flow, limit fracture propagation, better store carbon dioxide, and potentially enhance well efficiency. The mechanical properties of shale cores were investigated using a modified Brazilian indirect tensile strength test. An investigation of intact shale using Eagle Ford and Wolfcamp cores was conducted at varying temperatures. Results show no significant difference between shale types (average tensile strength = 6.19 MPa). Eagle Ford displayed higher strength at elevated temperature, but temperature did not influence Wolfcamp. Comparatively, cores with a single, lengthwise heterogeneous fracture were sealed with UICP and further tested for tensile strength. UICP was delivered via a flow-through method which injected 20–30 sequential patterns of ureolytic microorganisms and UICP-promoting fluids into the fracture until permeability reduced by three orders of magnitude or with an immersion method which placed cores treated with guar gum and UICP-promoting fluids into a batch reactor, demonstrating that guar gum is a suitable inclusion and may reduce the number of flow-through injections required. Tensile results for both delivery methods were variable (0.15–8 MPa), and in some cores the biomineralized fracture split apart, possibly due to insufficient sealing and/or heterogeneity in the composite UICP-shale cores. Notably in other cores the biomineralized fracture remained intact, demonstrating more cohesion than the surrounding shale, indicating that UICP may produce a strong seal for subsurface application.

58 GEOSCIENCES↗