Calcium Magnesium Carbonate Research Articles

Amorphous pectin/calcium magnesium carbonate @ konjac glucomannan for recovery phosphate from aqueous

To safeguard water quality and sustainable phosphorus cycling, it is imperative to recover phosphorus from high-content wastewater, particularly livestock wastewater, considering the low tolerance threshold for phosphate in surface water (below 0.5mg/L). Calcium carbonate and magnesium carbonate possess considerable potential for phosphate adsorption; however, their crystalline nature diminishes the reactivity of calcium and magnesium, resulting in the limited phosphate adsorption capacity. In this study, a novel phosphate adsorbent (PCCM@K) was synthesized through co-precipitation involving Ca, Mg, and pectin, followed by direct coating with konjac glucomannan, which eliminated the need for separation and cleaning steps. Pectin macromolecules interact with Ca and Mg to yield amorphous minerals, thereby enhancing the pore structure. The assessment of the phosphate adsorption performance of PCCM@K reveals robust alkali release, stable adsorption across a broad pH range (3-12), high adsorption capacity (61.9 mg-P/g), minimal interference from coexisting ions, and effective phosphate recovery in the actual biogas slurry. The primary mechanism underlying phosphate adsorption is chemisorption. During the adsorption process, ligand exchange takes place between carbonate and phosphate, leading to an increase in solution pH and the immobilization of phosphate via inner-sphere complexation with Ca and Mg. Overall, PCCM@K exhibits considerable potential for phosphorus recovery from wastewater, highlighting its significance in promoting environmentally sustainable practices.

A study on the mechanisms and influencing factors of interfacial physicochemical interactions between asphalt and mineral aggregates based on multiscale evaluation methods

The elucidation of interfacial physicochemical mechanisms between asphalt and mineral aggregates is vital for comprehending the interface formation in asphalt mixtures and enhancing their performance. To this end, multiscale evaluation methods were used to investigate the mechanisms and influencing factors of interfacial physicochemical interactions between asphalt and mineral aggregates (IPIAMA). Initially, the dynamic shear rheometer (DSR) was used to measure the complex shear modulus (G*) of various asphalt mastics. Subsequently, the interface film thickness was calculated using G* in conjunction with the Hashin and Mori-Tanaka (MT) micromechanical models. This indicator facilitated quantitative assessments and the analysis of influencing factors. The results indicated that the MT model underestimated the interface film thickness by approximately 0.08–0.29 % compared to the Hashin model, a discrepancy attributable to assumptions regarding aggregate particle interlocking. Moreover, the interface film thickness systematically varied with factors such as aggregate content, type of aggregate, and type of asphalt, ranging from 0.24 to 0.53 μm. To further elucidate the IPIAMA mechanisms behind these variations, the fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and the ultraviolet test (UV) testing were conducted. FTIR tests demonstrated that the primary components of mineral aggregates—dolomite, calcite, and quartz—contributed to the physical adsorption increments on asphalt functional groups by 0.0185, 0.0509, and 0.004, respectively. SEM images revealed that dolomite and calcite possessed more surface fissures and pores than quartz. XPS tests showed that calcium carbonate and magnesium carbonate chemically reacted with asphalt, resulting in electron shifts of 0.9 eV and 1.1 eV, respectively, while silicon oxide only exhibited electron shifts when combined with a silane coupling agent-modified asphalt. UV tests demonstrated that lighter asphalt fractions were preferentially absorbed into the pores and micro-cracks of mineral aggregates. Consequently, the complex IPIAMA involved physical adsorption, chemical reactions, and selective absorption, strongly correlating with factors such as mineral composition, surface morphology, and asphalt type.

Relative availability of five inorganic magnesium sources in non-pregnant non-lactating Holstein cows.

Inorganic sources of Mg are commonly used in dairy cow diets, but their availability varies significantly. This study assessed the relative availability of 4 commonly used inorganic Mg sources and a novel alkalinizing proprietary mineral blend [PMB; Multesium (GLC Minerals, LLC, Green Bay, WI, USA)]. The study was a duplicated 6 × 6 Latin square, with 12 nonlactating, non-pregnant Holstein dairy cows assigned to a square based on BW and parity. Cows were fed 90% of their voluntary DMI (diet contained 0.21% Mg). Each experimental period lasted 7 d. On d 2 of each period, urinary catheters were fitted. Total urine collection started on d 3 for 48 h with samples collected and measured every 12 h. On d 4, 30 g of Mg were administered as boluses with gelatin capsules: negative control (one empty capsule), magnesium oxide (MgO), magnesium sulfate (MgSO4), calcium magnesium hydroxide [CaMg(OH)4], calcium magnesium carbonate [CaMg(CO3)2], and PMB [a blend of Ca and Mg sources that includes CaMg(CO3)2, CaMg(OH)4, and MgO]. Blood samples were collected at 0, 1, 2, 3, 12, and 24 h after treatment administration on d 4 of each treatment period. Urine and blood samples were analyzed for Mg and Ca concentration. Statistical analyses were conducted with PROC GLIMMIX including treatment, time, period, square, treatment × time, treatment × period, and time × period as fixed effects, and cow nested within square as a random effect in the model. Urinary Mg excretion for 4 of the Mg sources studied [PMB, MgO, CaMg(OH)4, and MgSO4] increased significantly, representing an increase of at least 40.8% relative to control. The supplementation of CaMg(CO3)2 did not significantly increase relative to control. There were no significant changes in blood Mg concentration with treatment; but, a significant treatment × time effect was observed. Calcium-rich sources [PMB, CaMg(OH)4, CaMg(CO3)2] had lower blood Mg concentrations at 12 or 24 h after treatment than control and CaMg(CO3)2. Based on urinary Mg excretion 24 h after treatment, 4 of the Mg sources evaluated (including PMB) showed a similar availability, however, the availability of the commercial CaMg(CO3)2 source included in our study was similar to the negative control (no-supplemented cows).

The Formation of Calcium–Magnesium Carbonate Minerals Induced by Curvibacter sp. HJ-1 under Different Mg/Ca Molar Ratios

The Formation of Calcium–Magnesium Carbonate Minerals Induced by Curvibacter sp. HJ-1 under Different Mg/Ca Molar Ratios

Amorphous Magnesium–Calcium Carbonate Phosphate: Crystallization Paced by the Reaction Solution Concentration

Amorphous Magnesium–Calcium Carbonate Phosphate: Crystallization Paced by the Reaction Solution Concentration

Supplementation of calcium magnesium carbonate, tylosin phosphate, or both on growth performance, carcass traits, liver outcomes, and rumination activity of yearling beef steers fed a finishing diet*

Supplementation of calcium magnesium carbonate, tylosin phosphate, or both on growth performance, carcass traits, liver outcomes, and rumination activity of yearling beef steers fed a finishing diet*

Mechanical, durability and microstructural characterization of cost-effective polyethylene fiber-reinforced geopolymer concrete

Portland cement is widely used in the construction industry. Its production contributes to carbon dioxide emissions, urging the need for sustainable alternatives. The present study aims to evaluate the strength, durability, microstructural properties, and cost-effectivity of geopolymer (GP) concrete containing polyethylene (PE) fibers, with fly ash (FA), ground-granulated blast furnace slag (GGBFS), and calcium magnesium carbonate (CaMg(CO3)2 known as dolomite) as binders. PE fiber used has an ultra-high molecular weight. Six different mixtures were produced with FA, GGBFS, dolomite, and/or PE fiber. The control mix used only FA as a binder without PE fiber. Fresh and mechanical properties, including slump value, compressive strength, and split tensile strength, were determined, and non-destructive tests, such as electrical resistivity and ultrasonic pulse velocity, were conducted. The durability of GP was evaluated through initial surface absorption and capillary suction absorption tests at different curing ages. Microstructural and mineralogical characteristics were analyzed using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR). The results revealed that the addition of PE fibers and CaMg(CO3)2 reduced the workability of GP by 30.22% in comparison with that of PE fiber along with GGBFS. Compared to the reference mix at 28 days, incorporating 20% GGBFS resulted in the highest improvement of 76.89% and 104.86% in compressive and split tensile strength, respectively. GP sample with 20% GGBFS replacement of FA presented the highest reduction of 44.4–41.63% for initial and secondary rate of absorption. SEM analysis showed that the addition of GGBFS and CaMg(CO3)2 to fiber-reinforced FA-based geopolymer mixes developed a denser and more homogenous matrix with improved mechanical behavior due to the co-existence of C−S−H and aluminosilicate gel. PE fibers improve the toughness properties by helping to absorb energy and bridging cracks. The development of a stronger matrix was characterized by C−S−H, calcium aluminate oxide (carbonate) hydroxide (C4AHx) and quartz. A one-way ANOVA analysis and cost analysis demonstrate the cost-effectiveness of partially replacing FA with CaMg(CO3)2 and GGBFS in PE fiber-reinforced GP concrete.

A non-classical crystallization mechanism of microbially-induced disordered dolomite

Non-classical crystallization pathways, involving the formation of complex precursors prior to nucleation, have been observed during the calcification process of invertebrate skeletons and shells. However, these pathways were rarely documented in microbially-induced carbonate precipitation. In this study, we presented experimental evidence demonstrating that a halophilic bacterium (Halomonas sp. strain JBHLT-1) catalyzed the biomineralization of disordered dolomite through an amorphous calcium-magnesium carbonate (ACMC) with a stoichiometry near that of dolomite. During the ACMC formation, strain JBHLT-1 significantly enhanced the incorporation of Mg2+ ions compared to abiotic ACMC that was synthesized without any microbial biomass. In the stage of ACMC crystallization, the presence of microbial biomass reduced the dissolution-reprecipitation rate and induced bias towards a solid-state reaction pathway. This observation was supported by the negligible loss of structural Mg2+ ions in the presence of cells of strain JBHLT-1. The microbially-induced growth of disordered dolomite appeared to follow a spherulitic growth mechanism, as evidenced by its hierarchical structure composed of coalesced nano-spheres, eventually growing into micron-sized spheroids and dumbbells with extended incubation times. Since disordered dolomite is considered as a crucial crystalline precursor of ordered sedimentary dolomite, the findings of this study have important implications for understanding the formation mechanism of natural dolomite.

Efficient synthesis of rare sugars from galactose in hot compressed water using eggshells as an environmentally friendly catalyst

Aqueous galactose solutions containing eggshell was heated at 120 °C to produce calcium supplements containing rare sugars. Galactose was isomerized to rare sugars with improving rare sugar yields compared to those without eggshell. Organic acids were also formed as byproducts during the reaction. These acids were neutralized by dissolving eggshells with increasing the calcium ion concentration in the solution.When eggshell components (calcium carbonate, magnesium carbonate, or calcium phosphate) were used for the treatment, rare sugars were also formed. Especially, addition of magnesium carbonate improved rare sugar yield, but byproduct formation became more pronounced.Eggshells used in the treatment were used for repeated treatments. When eggshells were used three times, rare sugar yield changed only slightly but the selectivity of rare sugars improved significantly. By these processes, we obtained an aqueous solution of rare sugars containing calcium ion at 295 mg/L, which has potential as ingredients for dietary supplements.

Geophysical, hydrogeological and laboratory assessment of groundwater quality and its health implication in some urban communities in cross river state

The electrical resistivity technique which involved the Schlumberger depth sounding method, electrical resistivity tomography and geochemical analyses of water samples collected from boreholes were used to investigate the quality of groundwater in some urban communities in Cross River State, also the health implication of the said groundwater was also investigated. Forty nine electrical resistivity data were collected, modeled, and interpreted after calibration with lithologic logs. Ten electrical resistivity tomography data was were also collected, modeled and interpreted. Forty nine borehole water samples were collected and analyzed to determine anion, cation concentrations and some physical and chemical parameters, such as water colour, temperature, total dissolved solids, and electrical conductivity. The results show that the lithostratigraphy of the study area is composed of sands, sandstones (fractured, consolidated and loosed), siltstones, shales (compacted and fractured) of the Asu River Group, Eze-Aku Formation which comprises the aquifer units, and the Nkporo Shale Formation. The aquifer conduits are known to be rich in silicate minerals, and the groundwater samples in some locations show a significant amount of Ca2+, Mg2+, and Na+. These cations balanced the consumption of H+ during the hydrolytic alteration of silicate minerals. The geochemical analysis of groundwater samples revealed dominant calcium–magnesium–carbonate– bicarbonate water faces. The groundwater quality was observed to be influenced by the interaction of some geologic processes but was classified to be good to excellent, indicating its suitability for domestic and irrigation purposes.

The influence of additive MgO and its content on the carbonation resistance of alkali-activated slag concrete with different activators

The influence of additive MgO and its content on both the compressive strength and carbonation depth of alkali-activated slag concrete (AASC) was investigated under an accelerated carbonation environment. Furthermore, the modification mechanism of MgO on the carbonation resistance of AASC was explored by multiple analytical techniques. Results showed that the incorporation of MgO effectively enhanced the post-carbonation compressive strength and diminished the carbonation depth of concrete. As the MgO content increased, there was a gradual reduction in carbonation depth. The incorporation of MgO promotes the hydration of slag, altering the Al environment, and promoting the formation of C-S-H and Mg-Al hydrotalcite phases. Moreover, the addition of MgO resulted in the emergence of magnesium carbonate and calcium magnesium carbonate in the carbonation products, which filled the pores and prevented the further diffusion of CO2 into the interior. In addition, the improvement effects are more pronounced in the water glass system compared to the NaOH system.

371 Effect of Calcium Magnesium Carbonate And/Or Tylosin Phosphate Supplementation on Behavior, Rumination Activity, Feedlot Growth Performance and Carcass Characteristics in Yearling Beef Steers

Abstract The objective of this study was to evaluate the effects of calcium magnesium carbonate (CMC) and/or tylosin phosphate (TYL) supplementation on behavior, rumination activity, growth performance and carcass characteristics of yearling beef steers. Treatments were arranged in a 2 × 2 factorial including CMC and TYL. Beef steers (n = 156; 469 ± 18 kg) were randomly assigned to treatment pens (7 to 8 steers/pen) with pen (n = 20 pens total, 10 pens/main effect mean, and 5 pens/simple effect mean) as experimental unit. Cattle were transitioned from a 30% roughage diet to a 7% roughage finishing diet based on dry-rolled corn, dried distillers grains plus solubles, liquid supplement, and oat silage over the initial 20 d period. The CMC was included at 1.5% of the diet (DM basis) in replacement of dry-rolled corn and TYL was provided at 90 mg·animal·d-1. Behavior and rumination activity were monitored during a 24 h period on d 42. Data was collected on a pen-basis, every 10 min from 0800 h to 0750 h the next day and included minutes spent drinking (DR), eating (EA), active (AC), ruminating (RU), and resting (RE). Cattle were shipped for harvest on d 105 to a commercial beef abattoir. Growth performance was calculated on a carcass-adjusted basis (HCW/0.625). Data were analyzed as a randomized complete block design with fixed effects of CMC, TYL, or their interaction; block was a random effect. An interaction was observed between CMC and TYL for time spent DR (P = 0.03) and RU (P = 0.01). Control steers ruminated 28% longer compared with CMC/-TYL steers (P = 0.05) and 20% longer than -CMC/TYL steers (P = 0.05). The main effect of CMC tended to increase time spent EA by 19.3% (P = 0.06). Dry matter intake was decreased (P ≤ 0.02) by 4.57% when CMC was fed and increased by 1.96% when TYL was fed. However, no difference (P ≥ 0.26) was observed for G:F or gain efficiency in either treatment. No differences (P ≥ 0.28) were observed in any dietary net energy utilization outcomes in either main effect treatment. Carcass weight tended (P = 0.07) to be lighter with CMC supplementation compared with CON (432 vs 439 kg). Supplementation of TYL resulted in a 11.7% reduction (P = 0.04) in percentage of abscessed livers. No differences (P ≥ 0.12) were observed in DP, marbling, YG, or EBF in either main effect treatments. These results indicate that supplementation of CMC did not result in any appreciable improvements in growth, carcass or dietary net energy utilization performance, but TYL supplementation resulted in a positive effect on liver abscess prevalence.

307 Effect of Calcium Magnesium Carbonate and/or Tylosin Phosphate Supplementation on Receiving Period Growth Performance in Yearling Beef Steers

Abstract The objective of this study was to evaluate the effects of CaMg(CO3)2 (MIN-AD, Papillon Agricultural Company, Easton, MD; MA) and/or tylosin phosphate (Tylan, Elanco, Indianapolis, IN; TY) supplementation on growth performance of yearling beef steers during transition to a finishing diet during the first 28 days on feed. Treatments were arranged in a 2 × 2 factorial arrangement including MA and TY. Beef steers (n = 156; initial BW = 469 ± 18.0 kg) were randomly assigned to dietary treatments pens (7 to 8 steers/pen) with pen (n = 20 pens total, 10 pens/main effect mean, and 5 pens/simple effect mean) serving as the experimental unit. Cattle were transitioned from a 30 % roughage receiving diet to a 7 % roughage finishing diet based on dry-rolled corn, dried distillers grains plus solubles, a liquid supplement, and oat silage over the initial 20 d period. Monensin sodium was included in the diet at 30 mg/kg (DM basis). The MA was included at 1.5 % of the diet (DM basis) in replacement of dry-rolled corn and TY was provided at 90 mg/animal·d-1. Data were analyzed according to a randomized complete block design with the fixed effects of MA, TY, or their interaction; block was considered a random effect. No interaction was noted between MA or TY (P ≥ 0.68) for any variables measured. The main effect of TY did not influence d 28 BW, ADG, DMI, or G:F (P ≥ 0.43). The main effect of MA reduced DMI by 1.9 % (P = 0.01), but did not appreciably influence d 28 BW, ADG, or G:F (P ≥ 0.42). MA may decrease DMI while maintaining similar BW gain and efficiency compared with non-supplemented calves.

PSI-6 Effect of Calcium Magnesium Carbonate And/or Tylosin Phosphate Supplementation on Behavior and Rumination Activity in Yearling Beef Steers Fed a Finishing Diet

Abstract The objective of this study was to evaluate the effects of CaMg(CO3)2 (MIN-AD, Papillon Agricultural Company, Easton, MD; MA) and or tylosin phosphate (Tylan, Elanco, Indianapolis, IN; TY) supplementation on 24-hour behavior and rumination activity of yearling beef steers fed a finishing diet. A 2 × 2 factorial arrangement of treatments was used resulting in 4 dietary treatments: no MA and no TY (-MA/-TY), MA and no TY (MA/-TY), no MA and TY (-MA/TY), or MA and TY (MA/TY). Beef steers (n = 158; 469 ± 18.0 kg) were randomly assigned to dietary treatments with pen (n = 20 pens total, 10 pens/main effect mean, and 5 pens/simple effect mean) serving as the experimental unit. The MA was included at 1.5% of the diet (DM basis) in replacement of dry-rolled corn and TY was provided at 90 mg·animal-1·d-1. Observation began at 0800 h and ended at 0750 h the following day, resulting in a 24-hour observation period. Observations were recorded on a pen basis, with number of animals/type of activity recorded every 10 minutes on d 42 on feed (22 d on finisher). Activity categories included number of animals drinking (DR), eating (EA), active (standing; AC), ruminating (RU), and resting (RE) per pen. Chewing (CHE) was determined as the sum of eating and ruminating activity. Data were analyzed as a randomized complete block design with the fixed effects of MA, TY, and their interaction; block (pen location) was considered a random effect. An interaction was noted between MA and TY for time spent drinking (P = 0.03) and ruminating (P = 0.01). Steers from -MA/TY spent more time drinking compared with the -MA/-TY and MA/TY steers; steers from MA/-TY were intermediate (P < 0.10). Steers from -MA/-TY ruminated 28% longer compared with MA/-TY steers (P = 0.05) and 20% longer than -MA/TY (P = 0.05), steers from MA/TY ruminated 16% longer than steers from MA/-TY (P = 0.05), while steers from -MA/TY were intermediate (P > 0.10). The main effect of MA tended to increase time spent eating by 19.3% (P = 0.06); however, no differences (P ≥ 0.28) were noted for the main effects of MA or TY for minutes/day spent chewing, resting, or active. These results indicate that supplementation of MA may alter feeding behavior, resulting in increased minutes/day spent eating. In addition, supplementation of TY and MA may result in increased water intake, and alter time spent ruminating per day.

Simultaneous desalination and consolidation treatment through the application of electrokinetic techniques

The vast majority of building materials that are heavily affected by salts require desalination and subsequent consolidation treatments. This double intervention entails a risk associated with the loss of material due to continuous contact with the affected surface. This study evaluates the effectiveness of an electrokinetic process of simultaneous desalination-consolidation of two types of stones (dolostone and limestone). The results show that it is possible to reduce the salts up to percentages of 100% and at the same time to fill the pores and fractures with insoluble compounds compatible with the materials to be treated, such as calcium-magnesium carbonates.

Glass transition temperatures and crystallization kinetics of a synthetic, anhydrous, amorphous calcium-magnesium carbonate.

We report the first calorimetric observations of glass transition temperatures and crystallization rates of anhydrous, amorphous calcium-magnesium carbonate using fast scanning differential scanning calorimetry. Hydrous amorphous Ca0.95Mg0.05CO3 · 0.5H2O (ACMC) solid was precipitated from a MgCl2-NaHCO3 buffered solution, separated from the supernatant, and freeze-dried. An aliquot of the freeze-dried samples was additionally dried at 250°C for up to 6 h in a furnace and in a high-purity N2 atmosphere to produce anhydrous ACMC. The glass transition temperature of the anhydrous Ca0.95Mg0.05CO3 was determined by applying different heating rates (1000-6000 K s-1) and correcting for thermal lag to be 376°C and the relaxational heat capacity was determined to be Cp = 0.16 J/(g K). Additionally, the heating rate dependence of the temperature that is associated with the corrected crystallization peaks is used to determine the activation energy of crystallization to be 275 kJ mol-1. A high-resolution transmission electron microscopy study on the hydrous and anhydrous samples provided further constraints on their compositional and structural states. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Biochar as a soil conditioner for common bean plants

Biochar is a carbon-rich material produced during organic waste pyrolysis. In this context, two experiments were performed to evaluate the effect of biochar produced from rice husks and cattle manure on soil fertility and common bean production, as well as to identify the optimal dose of cattle manure biochar to be applied. The first experiment (Experiment I) was conducted according to a completely randomized design (factorial scheme 2 × 2 × 2 + 1) with six replicates: two types of biochar (cattle manure biochar and rice husk biochar), with and without acidity correction [addition of calcium carbonate and magnesium carbonate (PA) in a proportion of 4:1 (Ca:Mg) to raise the soil base saturation to 60%], with or without the addition of 120 mg dm-3 of phosphorus (P) as ammonium phosphate, and a control treatment (without biochar, acidity correction, and P). Based on the results of Experiment I, a second experiment was conducted according to a completely randomized design, with five treatments (doses of biochar from cattle manure) and four replications. Rice husk biochar, as a conditioner of soil chemical properties, had less prominent effects than cattle manure biochar. Cattle manure biochar functioned as a corrective for soil acidity and a source of nutrients (mainly phosphorus). The dose corresponding to 5.46% of the soil volume led to the maximum grain production by common bean plants.

Study of diversity of mineral-forming bacteria in sabkha mats and sediments of mangrove forest in Qatar

The involvement of microorganisms in carbonate minerals and modern dolomite formation in evaporitic environments occupied with microbial mats (i.e., sabkha) and in mangrove forests is evidenced, while its potential diversity requires further elucidation. Microorganisms can create supersaturated microenvironments facilitating the formation of various carbonate minerals through specific metabolic pathways. This is particularly important in arid environments, where deposition and sedimentary structures can occur. This study investigated the biodiversity of halophilic, heterotrophic, and aerobic mineral-forming bacteria in mangrove forests and living and decaying mats of Qatari sabkha. The diversity study was performed at the protein level using MALDI-TOF mass spectrometry protein profiles combined with principal component analysis (PCA), which revealed a high diversity of isolated strains at the taxonomy and protein profile levels. The diversity of the minerals formed in pure cultures was evidenced by SEM/EDS and XRD analysis. Different types of carbonate minerals (calcium carbonate, magnesium carbonates, and high-magnesium calcites) were formed in pure cultures of the studied strains, which might explain their occurrence in the bulk composition of the sediments from where the strains were isolated. These results illuminate the diversity of biological mineral-formation processes in the extreme environments of Qatari sabkhas and mangroves, explaining the high diversity of minerals in these environments.

Dual clumped (Δ47-Δ48) isotope data for amorphous carbonates and transformation products reveal a novel mechanism for disequilibrium clumped isotope effects

Amorphous precursors to minerals have been observed in laboratory materials and in nature, including across diverse phyla. These metastable phases allow for the incorporation of cations at higher concentrations than classical crystallization pathways, thus, their chemistry and behavior have implications in an array of disciplines. Currently, little is known about the isotopic composition of the anion in amorphous carbonates and how isotopic values evolve during transformation into a mineral. Here, we examined the evolution of isotopic values in amorphous carbonates and mineral transformation products to identify the potential origins of disequilibrium isotopic compositions in carbonate minerals that form from an amorphous precursor. We measured dual carbonate clumped isotopes (13C18O16O - Δ47; 12C18O18O - Δ48), bulk stable isotope ratios (δ13C, δ18O), and chemical and structural data throughout the transformation of amorphous calcium magnesium carbonate (ACMC) into high Mg-calcite (HMC) over 1 year, with crystallization occurring in solutions from 10 to 60 °C. The Δ47, Δ48, and δ18O values evolved significantly during transformation, indicating dissolution of ACMC and reprecipitation of HMC. After crystallization, the Δ47 and Δ48 values achieved a disequilibrium steady state, while δ18O values continued to evolve. For the fully crystallized HMC samples, the low temperature samples formed at 10 °C had the greatest extent of oxygen isotope disequilibrium (measured value – equilibrium value = −39‰); conversely; the greatest clumped isotope disequilibrium was observed in high temperature samples formed at 40 and 60 °C (0.068‰ for Δ47, 0.072‰ for Δ48). These results are consistent with a new potential mechanism of disequilibrium clumped isotope values in carbonate minerals. Specifically, the dissolution of ACMC during transformation causes disequilibrium oxygen and clumped isotope values in the dissolved inorganic carbon (DIC) pool. The extent of isotopic disequilibrium in DIC during transformation is temperature dependent, and is recorded by the forming mineral. Isotopic results may also reflect mixing effects, as scanning electron microscopy (SEM) showed ACMC and HMC existing simultaneously during transformation, indicating that ACMC likely progressively dissolves and reprecipitates as the DIC pool isotopically evolves. This may result in heterogeneous isotopic values in HMC. In total, these data suggest a highly dynamic localized environment could exist in biomineralizing organisms and abiotic systems that utilize amorphous precursors to form carbonate minerals, potentially resulting in isotopic values that are not representative of formation temperature.

STUDY OF THE INFLUENCE OF NITRIC ACID ENRICHMENT OF PHOSPHORITES OF THE CENTRAL KYZYLKUM ON THE PROCESS OF OBTAINING PHOSPHORUS-CONTAINING FERTILIZERS BASED ON THEM

An analysis of the literature shows that natural phosphates are suitable for de-composition with nitric acid, which does not contain significant amounts of cal-cium carbonate, magnesium carbonate and silicates, iron and aluminium com-pounds, which are easily decomposable acids, and as a result, complicate the processing of phosphates and degrade the quality of fertilizers. The best way to obtain phosphorus-containing fertilizers is the phosphoric acid decomposition of phosphate raw materials.