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In the context of peaking carbon dioxide emissions and carbon neutrality, development of feasible methods for converting CO2 into high value-added chemicals stands out as a hot subject. In this study, P[D+COO-][Br-][DBUH+], a series of novel heterogeneous dual-ionic poly(ionic liquid)s (PILs) were synthesized readily from 2-(dimethylamino) ethyl methacrylate (DMAEMA), bromo-substituted aliphatic acids, organic bases and divinylbenzene (DVB). The structures, compositions and morphologies were characterized or determined by nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), infrared spectroscopy (IR), scanning electron microscopes (SEM), and Brunauer-Emmett-Teller analysis (BET), etc. Application of the P[D+COO-][Br-][DBUH+] series as catalysts in converting CO2 into cyclic carbonates showed that P[D+COO-][Br-][DBUH+]-2/1/0.6 was able to catalyze epiclorohydrin-CO2 cycloaddition the most efficiently. This afforded chloropropylene carbonate (CPC) in 98.4% yield with ≥ 99% selectivity in 24 hr under solvent- and additive-free conditions at atmospheric pressure. Reusability experiments showed that recycling of the catalyst 6 times only resulted in a slight decline in the catalytic performance. In addition, it could be used for the synthesis of a variety of differently substituted cyclic carbonates in good to excellent yields. Finally, key catalytic active sites were probed, and a reasonable mechanism was proposed accordingly. In summary, this work poses an efficient strategy for heterogenization of dual-ionic PILs and provides a mild and environmentally benign approach to the fixation and utilization of carbon dioxide.

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High-latitude ecosystems have been overlooked in carbon budgets, which traditionally focus on mangroves, salt marshes, and seagrasses. The benthic assemblages and their Nature Contributions to People in Namuncurá - Burdwood Bank I and II, two offshore sub-Antarctic Marine Protected Areas (MPAs), are the conservation values. Here we show that the carbon reservoirs of these MPAs can be greater than those of their Antarctic counterparts, which, together with their extension, emphasize the need to maintain their protected status. Considering their total area, these MPAs stored in biomass 52,085.78 Mg C, corresponding 34,964.16 Mg to organic carbon (OC) and 17,121.62 Mg to inorganic carbon (IC). Surficial sediments stored 933,258,336 Mg C with 188,089,629 Mg of OC and 745,168,707 Mg of IC. However, when accounting for CO2 production through CaCO3 precipitation, the IC fractions decrease to 3,150.37 Mg C and 137,111,042 Mg C for biomass and sediments, respectively. We assume low sediment deposition due to the oceanic location, as direct sedimentation rates for these areas are unavailable. Most blue carbon assessments have focused solely on OC, despite the formation of CaCO3 releases CO2, decreasing net carbon storage. We compared various approaches for incorporating carbonates into carbon estimations. These results underscore the importance of including IC into carbon assessments and highlights the importance of sub-Antarctic benthic ecosystems as nature-based solutions to climate change.

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This study shows how bacterial viruses (bacteriophages, phages) interact with calcium carbonate during precipitation from aqueous solution. Using electron microscopy, epifluorescence microscopy, X-ray diffraction, and image analysis, we demonstrate that bacteriophages can strongly influence the formation of the vaterite phase. Importantly, bacteriophages may selectively bind both amorphous calcium carbonate (ACC) and vaterite, and indirectly affect the formation of structural defects in calcite crystallites. Consequently, the surface properties of calcium carbonate phases precipitating in the presence of viruses may exhibit different characteristics. These findings may have significant implications in determining the role of bacterial viruses in modern microbially-rich carbonate sedimentary environments, as well as in biomedical technologies. Finally, the phage-vaterite system, as a biocompatible material, may serve as a basis for the development of promising drug delivery carriers.

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The co-occurrence of halides and carbonates with uranium in the natural water poses a challenge to the uranium recovery for nuclear power due to the potential complexation. Hydrated titanium dioxide (HTD) contains a lot of surface hydroxyl (-OH) groups and waste polyacrylonitrile fiber (WPANF) has the advantages of both weather and chemical resistances. Herein, the nature differences of halide anions affecting the sorption of U(VI) by WPANF/HTD was investigated in the presence of carbonates. The sorption capacity (qe) decreased with the increases of initial pH, total carbonates, and halides but increased at high temperature and initial U(VI) concentration. The U(VI) sorption was a spontaneous chemisorption, which mainly involved surface sorption rather than intra-particle diffusion. The order of inhibitory ability on U(VI) sorption for the four halides was F > I âˆ¼ Br > Cl. The aqueous F- was shown to be the most strongly inhibited with the lowest qe value of 17.2 mg·g-1, due to the formation of U(VI)-F complex anions. The characteristic peaks with weakened relative intensity after U(VI) sorption for the surface -OH groups on HTD (HTD-OH), together with the results from DFT calculations, demonstrated a key role of HTD-OH in U(VI) sorption by WPANF/HTD via the coordination with U(VI) complex anions. This work unravels the nature differences of halide anions affecting U(VI) sorption in the presence of carbonates and provides a valuable reference for the U(VI) extraction toward halogen-rich natural uranium-containing water.

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Halide perovskite (HPs) nanostructures have recently gained extensive worldwide attentions because of their remarkable optoelectronic properties and fast developments. However, intrinsic instability against environmental factors-i.e., temperature, humidity, illumination, and oxygen-restricted their real-life applications. HPs are typically synthesized as colloids by employing organic solvents and ligands. Consequently, the precise control and tuning of complex 3D perovskite morphologies are challenging and have hardly been achieved by conventional fabrication methods. Here, we combine the benefits of self-assembly of biomolecules and an ion exchange reaction (IER) approach to customize HPs spatial shapes and composition. Initially, we apply a biomineralization approach, using biological templates (such as biopolymers, proteins, or protein assemblies), modulating the morphology of MCO3 (M = Ca2+, Ba2+) nano/microstructures. We then show that the morphology of the materials can be maintained throughout an IER process to form surface HPs with a wide variety of morphologies. The fabricated core-shell structures of metal carbonates and HPs introduce nano/microcomposites that can be sculpted into a wide diversity of 3D architectures suitable for various potential applications such as sensors, detectors, catalysis, etc. As a prototype, we fabricate disposable humidity sensors with an 11-95% detection range by casting the formed bio-templated nano/micro-composites on paper substrate.

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The presence of carbonates or humic substances (HS) will significantly affect the species and chemical behavior of U(VI) in solution, but lacking systematic exploration of the coupling effect of carbonates and HS under near real environmental conditions at present. Herein, the sorption behavior of U(VI) on illite was systematically studied in the co-existence of carbonates and HS including both humic acid (HA) and fulvic acid (FA) by batch technique. The distribution coefficients (Kd) increased as function of time and temperature but decreased with increasing concentrations of initial U(VI), Ca2+, and Mg2+, as well as ion strength. At pH 2.0-10.5, the Kd values first increased rapidly and then decreased visibly, with its maximum value appearing at pH 5.0, owning to the changes in the interaction between illite and the dominant species of U(VI) from electrostatic attraction to electrostatic repulsion. The sorption was a heterogeneous, spontaneous, and endothermic chemical process, which could be well described by pseudo-second-order kinetic and Flory-Huggins isotherm models. When carbonates and HA/FA coexisted, the Kd values always increased first and then decreased as a function of pH, with the only difference for HA and FA being the key pH (pHkey) at which the promoting and inhibiting effects on the sorption of U(VI) onto illite undergo a transition. The carbonates and HS have a synergistic inhibitory effect on the U(VI) sorption onto illite at pH 7.8. FTIR and XPS spectra demonstrated that the hydroxyl groups on the illite surface and in the HS were involved in U(VI) sorption on illite in the presence of carbonates. These results provide valuable data for a deeper understanding of U(VI) migration in geological media.

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The long-term study of the chemical composition of river sediments within urban areas and the establishment of baseline values of major and trace elements is an important task. Therefore, this study aims to provide a geochemical characterization of the sediments, establish a local geochemical baseline, unveil geochemical associations of elements, study the trend of changes in element pollution levels and the associated ecological risks. The results indicate that the change of the local physical characteristics across the river flow (canyon-flat relief surrounded by buildings-reservoir-flat relief under the influence of contamination sources) and locations of contamination sources conditioned the formation of positive extreme values detected for the majority of the studied elements. An analogous variation pattern of major and trace elements median values (2019-2023) was observed for Cr, V, Cu, Fe, Co, Zr Mn, Zn, K, Ba over 5 years representing the geochemical signature of the local geological composition (basalt, andesibasalts, andesite, tuff, K-feldspar). The pollution level and the ecological risk assessment showed that during the study period moderately and highly hazardous levels of multi-element pollution were detected in the southwestern part of the river located near the industrial enterprises. In the meantime, moderate (in 2020) and considerable (in 2021) ecological risk levels were observed at the site near the artificial reservoir. A hierarchical clustering combined with the geochemical ratio analysis reveals three groups of geochemical associations that have a natural (Fe, Mn, Co, V, Ti, Zr, K, Rb, Ba); anthropogenic (Cu, Zn, Pb, Mo) and mixed (Ca, Sr, Cr) origin. Moreover, the anthropogenic association shows affinity to Ca hence denominating the dominant role of carbonates in the fixation and coprecipitation of Cu2+, Pb2+, Mo2+, Zn2+ ions. The comparison of the baseline values of the studied elements with the upper continental crust values confirmed their applicability for differentiation of their origin.

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The study of Na-carbonates stability and their transformations in aqueous carbonate fluid under high P-T conditions is relevant from the point of view of the understanding geochemical processes of the Na-assisted carbon circulation in the Earth's crust and subduction zones. In situ Raman study of Na-bearing carbonate-water-Fe-metal system in diamond anvil cell (DAC) at high P-T conditions revealed that carbonates decompose with abiogenic formation of formates and other organic compounds that differs from behavior of carbonates in dry system. XRD and FTIR methods have been used additionally to determine the phase composition. Na-bearing carbonates (nahcolite NaHCO3, shortite Na2Ca2(CO3)3 and cancrinite Na7Ca[(CO3)1.5Al6Si6O24]⋅2H2O) in aqueous fluid decompose to form simple carbonates and formates (as dominant organic molecules) at moderate P-T parameters (above ∼0.2 GPa, 200 °C). Our experimental results directly confirm the hypothesis of Horita and Berndt (Science, 1999) about possible yield of organic formates in the carbonate-water-metal system. Nahcolite NaHCO3 in aqueous fluid in the presence of Fe metal decomposes into anhydrous phases: natrite γ-Na2CO3, siderite, magnetite (due to dissolution of Fe steel gasket), Na-formate and likely organic molecular crystalline solvate of Na-formate and methyl formate. Shortite decays into anhydrous phases: aragonite CaCO3, Na-Ca-formates and an amorphous phase. Cancrinite decomposes to unidentified carbonate-alumonosilicate phases, Na-Ca-formates and unknown organic molecular crystal. Magnetite is also formed in this system due to dissolution of Fe steel gasket used in DAC. The present study provides a new insight in processes of abiogenic formation of organic matter from carbonates in the crust and upper mantle.

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The Winter Wonderland ice cave, located at an elevation of 3140 m above sea level in the Uinta Mountains of northern Utah, USA, maintains a constant sub-zero temperature. Seasonal snowmelt and rain enter the cave, freeze on the surface of the existing ice, and contribute to a 3-m-thick layered ice mass. This ice mass contains organic matter and cryogenic cave carbonates (CCCs) that date back centuries. In this study, samples of ice, liquid water, and exposed CCCs were collected to examine the bacterial communities within the cave and to determine if these communities vary spatially and between sample types. Flow cytometry showed that cell counts are an order of magnitude higher in liquid water samples than in ice. Epifluorescence microscopy and scanning electron microscopy imaging revealed potential coccoid and bacillus microbial morphologies in water samples and putative cells or calcite spherules in the CCCs. The diversity of bacteria associated with soil, identified through sequence-based analysis, supports the hypothesis that water enters the cave by filtering through soil and bedrock. A differential abundance of bacterial taxa was observed between sample types, with the greatest diversity found in CCCs. This supports a geomicrobiological framework where microbes aggregate in the water, sink into a concentrated layer, and precipitate out of the ice with the CCCs, thereby reducing the cell counts in the ice. These CCCs may provide essential nutrients for the bacteria or could themselves be products of biomineralization.

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The interaction between multi-component rare earth element (REE) aqueous solutions and carbonate grains (dolomite, aragonite, and calcite) are studied at hydrothermal conditions (21-210 °C). The effect of ionic radii of five REEs (La, Ce, Pr, Nd, Dy) on solid formation are analyzed using two solution types: equal REE concentrations and concentrations normalized to Post Archean Australian Shale Standard (PAAS). The interaction replaces the host Ca-Mg carbonate grains with a series of REE minerals (lanthanite → kozoite → bastnäsite → cerianite). At 165 °C, equal concentration solutions promote kozoite crystallization, maintaining similar REE ratios in solids and solution. PAAS solutions result in zoned REE-bearing crystals with heterogeneous elemental distributions and discreet REE phases (e.g., cerianite). Chemical signatures indicate metastable REE-bearing phases transforming into more stable polymorphs, along with symplectite textures formed by adjacent phase reactions. Overall, experiments highlight the dependence of polymorph selection, crystallization pathway, mineral formation kinetics, and chemical texture on REE concentrations, ionic radii, temperature, time, and host grain solubility.

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The cycloaddition of CO2 to epoxides to afford versatile and useful cyclic carbonate compounds is a highly investigated method for the nonreductive upcycling of CO2. One of the main focuses of the current research in this area is the discovery of readily available, sustainable, and inexpensive catalysts, and of catalytic methodologies that allow their seamless solvent-free recycling. Water, often regarded as an undesirable pollutant in the cycloaddition process, is progressively emerging as a helpful reaction component. On the one hand, it serves as an inexpensive hydrogen bond donor (HBD) to enhance the performance of ionic compounds; on the other hand, aqueous media allow the development of diverse catalytic protocols that can boost catalytic performance or ease the recycling of molecular catalysts. An overview of the advances in the use of aqueous and biphasic aqueous systems for the cycloaddition of CO2 to epoxides is provided in this work along with recommendations for possible future developments.

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Understanding an animal's metabolic rate and thermal history is pivotal for ecological research. Recent studies have proposed the use of stable carbon and oxygen isotopes (δ13C and δ18O) in biogenic carbonates as proxies of metabolic rate and experienced temperature, respectively, to overcome the challenges of directly measuring these data in the field. Our study represents the first experimental investigation to develop δ13C and δ18O proxies in octopus. Octopus berrima hatchlings were raised in captivity, at varying water temperatures, for up to 110 days. O. berrima statoliths were then subsequently analysed for δ13C and δ18O values. The proportion of metabolically derived carbon, or respired carbon (Cresp), increased as the octopus grew (slope = 0.076, R2 = 0.72), suggesting an influence of somatic growth rate and body mass on δ13C values. Additionally, we identified an inverse correlation between δ18O values and environmental temperature (slope = -0.163, R2 = 0.91), which was subsequently used to develop a thermal reconstruction model. Our experiment aids in interpreting stable isotopic values in statoliths and their application as temperature and metabolic proxies in wild-caught octopus. Such proxies will increase our monitoring capabilities of these ecologically and commercially significant cephalopods and contribute to their conservation and effective management.

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Carbon dioxide (CO2) plays a crucial role in carbon chain elongation with ethanol serving as an electron donor. In this study, the impacts of various carbonates on CO2 concentration, hexanoic acid production, and microbial communities during ethanol-butyric acid fermentation were explored. The results showed that the addition of MgCO3 provided sustained inorganic carbon and facilitated interspecific electron transfer, thereby increasing hexanoic acid yield by 58%. MgCO3 and NH4HCO3 inhibited the excessive ethanol oxidation and decreased the yield of acetic acid by 51% and 42%, respectively. The yields of hexanoic acid and acetic acid in the CaCO3 group increased by 19% and 15%, respectively. The NaHCO3 group exhibited high headspace CO2 concentration, promoting acetogenic bacteria enrichment while reducing the abundance of Clostridium_sensu_stricto_12. The batch addition of NaHCO3 accelerated the synthesis of hexanoic acid and increased its production by 26%. The relative abundance of Clostridium_sensus_stricto_12 was positively correlated with hexanoic acid production.

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Significant quantities of Posidonia oceanica deposit on some beaches and coastlines every year, which generates high costs associated with the disposal of this waste. Pyrolysis may be an adequate way for its valorization. However, it would imply to know how the process takes place and if the removal of its natural detrital inorganic matter (epiphytes, marine salt and sand) is necessary, which are the objectives of this research. Pyrolysis by thermogravimetry-mass spectrometry was carried out on both the washed and unwashed samples. During this waste pyrolysis, the following occurs: (i) the high alkali metal chloride content promotes fragmentation reactions of carbohydrates and O formation, which increases HCOOH intensities at temperatures between 250 and 360 °C; (ii) from 500 °C to 650 °C, Fe2O3 and decomposition of carbonates seem to be involved in reactions that produce O release and steam and CO2 reforming of hydrocarbons and oxygenated organic compounds with H2 generation; (iii) from 650 °C to 750 °C, Fe2O3, high alkali metal content and carbonate decomposition generate char gasification, an increase in O release, SO2 capture and HCOOH formation. In general, the abundance of inorganic matter (chlorides, carbonates, etc.) minimizes the release of various compounds during pyrolysis, including SO2 and HCl, while increasing HCOOH production. Thus, this high content of inorganic matter may represent an advantage for its pyrolysis, producing value-added chemical products with a reduced environmental impact. Therefore, this study may be the starting point for defining the optimal pyrolysis conditions for this waste valorisation.

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The formation of intracellular amorphous calcium carbonate (ACC) by various cyanobacteria is a widespread biomineralization process, yet its mechanism and importance in past and modern environments remain to be fully comprehended. This study explores whether calcium (Ca) isotope fractionation, linked to ACC-forming cyanobacteria, can serve as a reliable tracer for detecting these microorganisms in modern and ancient settings. Accordingly, we measured stable Ca isotope fractionation during Ca uptake by the intracellular ACC-forming cyanobacterium Cyanothece sp. PCC 7425. Our results show that Cyanothece sp. PCC 7425 cells are enriched in lighter Ca isotopes relative to the solution. This finding is consistent with the kinetic isotope effects observed in the Ca isotope fractionation during biogenic carbonate formation by marine calcifying organisms. The Ca isotope composition of Cyanothece sp. PCC 7425 was accurately modeled using a Rayleigh fractionation model, resulting in a Ca isotope fractionation factor (Δ44Ca) equal to -0.72 ± 0.05‰. Numerical modeling suggests that Ca uptake by these cyanobacteria is primarily unidirectional, with minimal back reaction observed over the duration of the experiment. Finally, we compared our Δ44Ca values with those of other biotic and abiotic carbonates, revealing similarities with organisms that form biogenic calcite. These similarities raise questions about the effectiveness of using the Ca isotope fractionation factor as a univocal tracer of ACC-forming cyanobacteria in the environment. We propose that the use of Δ44Ca in combination with other proposed tracers of ACC-forming cyanobacteria such as Ba and Sr isotope fractionation factors and/or elevated Ba/Ca and Sr/Ca ratios may provide a more reliable approach.

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This study introduces an efficient strategy for synthesizing polyhydroxyurethane-based multicomponent hydrogels with enhanced rheological properties. In a single-step process, 3D materials composed of Polymer 1 (PHU) and Polymer 2 (PVA or gelatin) were produced. Polymer 1, a crosslinked polyhydroxyurethane (PHU), grew within a colloidal solution of Polymer 2, forming an interconnected network. The synthesis of Polymer 1 utilized a Non-Isocyanate Polyurethane (NIPU) methodology based on the aminolysis of bis(cyclic carbonate) (bisCC) monomers derived from 1-thioglycerol and 1,2-dithioglycerol (monomers A and E, respectively). This method, applied for the first time in Semi-Interpenetrating Network (SIPN) formation, demonstrated exceptional orthogonality since the functional groups in Polymer 2 do not interfere with Polymer 1 formation. Optimizing PHU formation involved a 20-trial methodology, identifying influential variables such as polymer concentration, temperature, solvent (an aprotic and a protic solvent), and the organo-catalyst used [a thiourea derivative (TU) and 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU)]. The highest molecular weights were achieved under near-bulk polymerization conditions using TU-protic and DBU-aprotic as catalyst-solvent combinations. Monomer E-based PHU exhibited higher Mw¯ than monomer A-based PHU (34.1 kDa and 16.4 kDa, respectively). Applying the enhanced methodology to prepare 10 multicomponent hydrogels using PVA or gelatin as the polymer scaffold revealed superior rheological properties in PVA-based hydrogels, exhibiting solid-like gel behavior. Incorporating monomer E enhanced mechanical properties and elasticity (with loss tangent values of 0.09 and 0.14). SEM images unveiled distinct microstructures, including a sponge-like pattern in certain PVA-based hydrogels when monomer A was chosen, indicating the formation of highly superporous interpenetrated materials. In summary, this innovative approach presents a versatile methodology for obtaining advanced hydrogel-based systems with potential applications in various biomedical fields.

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Abstract Introduction: The sea urchin Diadema mexicanum, due to its bioerosion activity, is considered of ecological importance. This phenomenon could negatively or positively affect coral reef ecosystems. The bioerosion process varies according to the abundance and size of the sea urchin. Objective: Juvenile organisms possess different metabolic needs compared to adults, so knowing their stomach content according to size allows us to quantify the selection of substrate bioeroded. Methods: To determine this, D. mexicanum individuals were collected in 12 sites from January 2009 to September 2010 along the Eastern Tropical Pacific coast. The stomach content was categorized in Carbonated Fraction (CF), Non-Carbonated Fraction (NCF), and Organic Matter (OM). Stomach content was analyzed according to a) juvenile (< 2.5 cm) or adult (> 2.5 cm) stage and b) locality. Results: Juveniles presented the following stomach content average percentages: 20.7 % OM, 12 % NCF and 67.9 % CF; and adults: 11.4 % OM, 14.8 % NCF and 73.8 % CF. Based on a Wilcoxon test and a Kendall linear regression, the following results were obtained. The carbonated fraction in the stomach increased by 0.47 units on average for every cm of growth (p < 0.05). OM consumed by D. mexicanum increases only 0.05 units for every cm of growth (p < 0.05). We found a difference of stomach content depending on the site (p < 0.05) and life stage (p < 0.05). Localities like Huatulco and Coco presented significant differences that could be related to local oceanographic conditions. Conclusions: We relate these changes of the stomach fractions to the necessity of the juvenile sea urchins for nutrients to maintain their growth. The amount of OM is crucial for the development of early stages, meaning that there is a difference in substrate selection associated with growth.

Resumen Introducción: El erizo de mar Diadema mexicanum, por su actividad de bioerosión, es considerado de importancia ecológica. Este fenómeno podría afectar negativa o positivamente a los ecosistemas de arrecifes de coral. El proceso de bioerosión varía según la abundancia y el tamaño del erizo de mar. Objetivo: Los organismos juveniles poseen diferentes necesidades metabólicas en comparación con los adultos, por lo que conocer el contenido estomacal según el tamaño, nos permite cuantificar la selección de sustrato bioerosionado. Métodos: Para determinar esto, se recolectaron individuos de D. mexicanum en 12 sitios desde enero de 2009 hasta septiembre de 2010 a lo largo de la costa del Pacífico Tropical Oriental. El contenido estomacal se clasificó en Fracción Carbonatada (FC), Fracción No Carbonatada (NCF) y Materia Orgánica (MO). El contenido estomacal se analizó según a) estadio juvenil (< 3 cm) o adulto (> 3 cm) y b) localidad. Resultados: Los juveniles presentaron los siguientes porcentajes promedio del contenido estomacal: 20.7 % OM, 12 % NCF y 67.9 % CF; y adultos: 11.4 % OM, 14.8 % NCF y 73.8 % CF. Con base en una prueba de Wilcoxon y una regresión lineal de Kendall, se obtuvieron los siguientes resultados. La fracción carbonatada en el estómago aumentó en promedio 0.47 unidades por cada cm de crecimiento (p < 0.05). La MO consumida por D. mexicanum aumenta solo 0.05 unidades por cada cm de crecimiento (p < 0.05). Encontramos una diferencia en el contenido estomacal según el sitio (p < 0.05) y el estadio de vida (P < 0.05). Localidades como Huatulco y Coco presentaron diferencias significativas que podrían estar relacionadas con las condiciones oceanográficas locales. Conclusiones: Relacionamos estos cambios de la composición porcentual del contenido estomacal con la necesidad de los erizos de mar juveniles de nutrientes para mantener su crecimiento. La cantidad de MO es crucial para el desarrollo de las primeras etapas, lo que significa que existe una diferencia en la selección de sustrato asociada con el crecimiento.

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Diammonium phosphate (DAP) has been proven effective in improving the stiffness of weak or acid-damaged carbonates, thereby preserving hydraulic fracture conductivity. The reaction between DAP and calcite in chalk formations primarily produces hydroxyapatite (HAP), which is stiffer than calcite. However, the optimal reaction outcomes vary greatly with factors such as DAP concentration and reaction conditions. This study investigated the DAP-calcite reaction duration, pressure, and temperature effects on the stiffness magnitude of soft Austin chalk. Also, the catalyst effect and depth of HAP formation were examined. The study involved the assessment of stiffness non-destructively (impulse hammering), mineralogy (XRD, SEM), and elemental composition (XRF). The study tested 15 different DAP-chalk reaction variations, where the pressure, temperature, aging time and catalyst addition were modified in each case. The samples' elastic stiffness distributions were then collected and compared to the pre-reaction ones. The results showed that the elastic stiffness increased in all treated samples, with an 181% maximum increase achieved after 72 h at 6.9 MPa and 75 °C. However, the pressure effect was minor compared to the temperature. The SEM images revealed different HAP morphology corresponding to different treatment conditions. Although the treated samples showed an increased intensity of phosphorus throughout the entire sample, the near-surface zone (4-6 mm) was the most affected, as inferred from the XRF elemental analysis. The study's findings can help optimize hydraulic fracturing operations in weak carbonate reservoirs, improving production rates and overall well performance.

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Rising carbon dioxide (CO2) levels in the atmosphere are recognized as a threat to atmospheric stability and life. Although this greenhouse gas is being produced on a large scale, there are solutions to reduction and indeed utilization of the gas. Many of these solutions involve costly or unstable technologies, such as air-sensitive metal-organic frameworks (MOFs) for CO2 capture or "non-green" systems such as amine scrubbing. Conjugated microporous polymers (CMPs) represent a simpler, cheaper, and greener solution to CO2 capture and utilization. They are often easy to synthesize at scale (a one pot reaction in many cases), chemically and thermally stable (especially in comparison with their MOF and covalent organic framework (COF) counterparts, owing to their amorphous nature), and, as a result, cheap to manufacture. Furthermore, their large surface areas, tunable porous frameworks and chemical structures mean they are reported as highly efficient CO2 capture motifs. In addition, they provide a dual pathway to utilize captured CO2 via chemical conversion or electrochemical reduction into industrially valuable products. Recent studies show that all these attractive properties can be realized in metal-free CMPs, presenting a truly green option. The promising results in these two fields of CMP applications are reviewed and explored here.

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Paired petrography and acid maceration has shown that preferential silicification of shelly faunas can bias recovery based on taxon and body size. Here, silicified fossils from the Upper Ordovician Edinburg Formation, Strasburg Junction, Virginia, USA, were analyzed using X-ray tomographic microscopy (µCT) in conjunction with recovered residues from acid maceration of the same materials to further examine sources of potential bias. Results reveal that very small (<~1 mm) fossils are poorly resolved in µCT when scanning at lower resolutions (~30 µm), underestimating abundance of taxa including ostracods and bryozoans. Acid maceration, meanwhile, fails to recover poorly silicified fossils prone to disarticulation and/or fragmentation during digestion. Tests for patterns of breakage, however, indicate no significant size or taxonomic bias during extraction. Comparisons of individual fossils from 3-D fossil renders and maceration residues reveal patterns of fragmentation that are taxon-specific and allow the differentiation of biostratinomic and preparational breakage. Multivariate ordinations and cluster analyses of µCT and residue data in general produce concordant results but indicate that the variation in taxonomic composition of our samples is compromised by the resolvability of small size classes in µCT imaging, limiting the utility of this method for addressing paleoecological questions in these specific samples. We suggest that comparability of results will depend strongly on the sample size, taphonomic history, textural, and compositional characteristics of the samples in question, as well as µCT scan parameters. Additionally, applying these methods to different deposits will test the general applicability of the conclusions drawn on the relative strengths and weaknesses of the methods.

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