Time evolution of moduli of a polymer-induced liquid precursor (PILP) of calcium carbonate
The PILP of CaCO 3 droplets shows that their initial properties are either a liquid or a soft gel-like material.
Shao, Changyu↗
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Carbon-negative hydrogen: aqueous phase reforming (APR) of glycerol over NiPt bimetallic catalyst coupled with CO 2 sequestration
Herein we report the production of high-pressure (19.3 bar), carbon-negative hydrogen (H 2 ) from glycerol with a purity of 98.2 mol% H 2 , 1.8 mol% light hydrocarbons (mainly methane), and 400 ppm of CO. Aqueous phase reforming (APR) of 10 wt% glycerol solution was studied with a series of NiPt alumina bimetallic catalysts supported on alumina. The Ni 8 Pt 1 -450 catalyst had the highest hydrogen selectivity (95.6%) and the lowest alkanes selectivity (3.7%) of the tested catalysts. The hydrogen selectivity decreased in the order of Ni 8 Pt 1 -450 > Ni 8 Pt 1 -260 > Ni 1 Pt 1 -260 > Pt-260. The CO 2 was sequestered with CaO adsorbent which formed CaCO 3 . We measured the adsorption capacity of the CaO adsorbent at different temperatures. Life cycle analysis showed that the APR of glycerol coupled with CO 2 capture has net negative CO 2 equivalent greenhouse gas emissions. The CO 2 emissions are –9.9 kg CO 2 eq./kg H 2 and –50.1 kg CO 2 eq./kg H 2 when grid electricity and renewable electricity are used, respectively, and the CO 2 is allocated respectively to the mass of products produced. The cost of this H 2 (denoted as “green-emerald”) was estimated to be 2.4 USD per kg H 2 when grid electricity is used and 2.7 USD per kg H 2 when using renewable electricity. The cost of glycerol has the highest contribution of 1.71 USD per kg H 2 . As a result, participation in the carbon credit markets can further decrease the price of the produced H 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cold plasma activated CO 2 desorption from calcium carbonate for carbon capture
Cold plasmas powered by the renewable electricity can facilitate CO 2 desorption for carbon capture materials (CaCO 3 ) at low temperatures.
Zhong, Hongtao [Stanford Plasma Physics Laboratory↗
Influence of functional additives, fillers, and pigments on thermal and catalytic pyrolysis of polyethylene for waste plastic upcycling
Pyrolysis offers a relatively green and economical method to convert waste plastics into valuable chemicals and fuels without the need for harmful solvents, toxic chemicals, or costly high-pressure reactors. Despite its popularity among chemical upcycling technologies, industrial adoption suffers from feedstock heterogeneity, low-quality products, and catalyst deactivation. Most plastics in our daily lives are formulated with functional additives, fillers, and colorants. These additives remaining in end-of-life waste streams increase feedstock heterogeneity, creating a challenging issue in recycling plastics. Still, the potential impacts of additives on the chemical upcycling of plastics have been poorly understood. In this study, polyethylene compounded with a range of widely used additives (antioxidants, stabilizers, pigments, fillers, slip agents, and flame retardants) was subjected to both thermal pyrolysis and catalytic pyrolysis in different catalyst-to-feedstock contact modes. It showed that many inorganic additives, such as talc, kaolin, CaCO 3 , TiO 2 , carbon black, and zinc stearate, facilitated polymer decomposition during pyrolysis, increasing light hydrocarbons while also promoting aromatic and carbon residue formation. Conversely, antioxidants and stabilizers inhibited depolymerization, favoring heavier hydrocarbons. During catalytic pyrolysis with HZSM-5 zeolite, additives strongly enhanced aromatic and catalytic coke formation, especially when there was direct contact between plastics and catalysts. Although certain additives seem beneficial in the short term by promoting polymer cracking and improving the selectivity of aromatics, the transport of the additives and their degradation products and increased carbon coking can contaminate products, deactivate or modify catalysts, and foul reactors. These findings address a critical knowledge gap in effectively converting waste plastics via a greener route.
42 ENGINEERING↗
From particle attachment to space-filling coral skeletons
Reef-building corals and their aragonite (CaCO 3 ) skeletons support entire reef ecosystems, yet their formation mechanism is poorly understood. Here we used synchrotron spectromicroscopy to observe the nanoscale mineralogy of fresh, forming skeletons from six species spanning all reef-forming coral morphologies: Branching, encrusting, massive, and table. In all species, hydrated and anhydrous amorphous calcium carbonate nanoparticles were precursors for skeletal growth, as previously observed in a single species. The amorphous precursors here were observed in tissue, between tissue and skeleton, and at growth fronts of the skeleton, within a low-density nano- or microporous layer varying in thickness from 7 to 20 µm. Brunauer-Emmett-Teller measurements, however, indicated that the mature skeletons at the microscale were space-filling, comparable to single crystals of geologic aragonite. Nanoparticles alone can never fill space completely, thus ion-by-ion filling must be invoked to fill interstitial pores. Such ion-by-ion diffusion and attachment may occur from the supersaturated calcifying fluid known to exist in corals, or from a dense liquid precursor, observed in synthetic systems but never in biogenic ones. Concomitant particle attachment and ion-by-ion filling was previously observed in synthetic calcite rhombohedra, but never in aragonite pseudohexagonal prisms, synthetic or biogenic, as observed here. Models for biomineral growth, isotope incorporation, and coral skeletons’ resilience to ocean warming and acidification must take into account the dual formation mechanism, including particle attachment and ion-by-ion space filling.
59 BASIC BIOLOGICAL SCIENCES↗
X-ray linear dichroic ptychography
Biominerals such as seashells, coral skeletons, bone, and tooth enamel are optically anisotropic crystalline materials with unique nanoscale and microscale organization that translates into exceptional macroscopic mechanical properties, providing inspiration for engineering new and superior biomimetic structures. Using Seriatopora aculeata coral skeleton as a model, here, we experimentally demonstrate X-ray linear dichroic ptychography and map the c-axis orientations of the aragonite (CaCO 3 ) crystals. Linear dichroic phase imaging at the oxygen K-edge energy shows strong polarization-dependent contrast and reveals the presence of both narrow (<35°) and wide (>35°) c-axis angular spread in the coral samples. These X-ray ptychography results are corroborated by four-dimensional (4D) scanning transmission electron microscopy (STEM) on the same samples. Evidence of co-oriented, but disconnected, corallite subdomains indicates jagged crystal boundaries consistent with formation by amorphous nanoparticle attachment. We expect that the combination of X-ray linear dichroic ptychography and 4D STEM could be an important multimodal tool to study nano-crystallites, interfaces, nucleation, and mineral growth of optically anisotropic materials at multiple length scales.
4D scanning transmission electron microscopy↗
Quantitative texture analysis at the WAND 2 and HIDRA diffractometers
Data collection and analysis strategies have been developed for efficient and reliable crystallographic texture measurements at two recently upgraded neutron diffractometers: the Wide Angle Neutron Diffractometer Squared (WAND 2 ) and the High Intensity Diffractometer for Residual Stress Analysis (HIDRA) at the High Flux Isotope Reactor located at Oak Ridge National Laboratory. These methods are demonstrated using measurements on a variety of textured samples, including multi-phase steel composites and polycrystalline calcite (CaCO 3 ). Reference measurements were also made at VULCAN, the engineering diffractometer located at the Spallation Neutron Source. The texture data obtained on the different instruments are in agreement, and WAND 2 is more time efficient than HIDRA. Two analysis methods were investigated, single-peak fitting to obtain individual pole figures for inversion and Rietveld texture analysis using MAUD. Here, the impact of the differences between the various textures obtained was evaluated through the calculation of diffraction elastic constants, which is one application of the texture data collected. Both instruments were found to provide texture data that are suitable for complementing other analyses, such as residual stress mapping.
47 OTHER INSTRUMENTATION↗
Introduction to Carbon Sensing in Soil. A surface-level review of traditional and alternative methods of soil carbon measurement
Soil carbon can be divided into two categories: organic and inorganic. Soil inorganic carbon (SIC) is present in carbonate minerals in the soil and is often found in dry, arid regions. Examples of SIC include calcium carbonate (CaCO 3 ) and magnesium carbonate (MgCO 3 ), both of which play important roles in soil health. Soil organic carbon (SOC) is found in fresh plant matter (available SOC) and as humus or charcoal (inert SOC). Both types of carbon act as storage in the global carbon cycle. As a carbon sink, soil carbon has the potential to store carbon that would otherwise remain in the atmosphere as CO 2 , one of the primary greenhouse emissions. As such, soil is under increasing attention and research to be used as a sequestration (i.e., isolation) method to reduce the amount of carbon in the atmosphere. This type of carbon sequestration is called biological sequestration. SOC typically stores carbon for several decades (depending on decomposition rates) while SIC can store carbon for more than 70,000 years. Common sequestration techniques for SOC usually fall under the category of land management: planting perennials, keeping plant residue and composting, reducing tilling, and other agricultural practices that vary by region. SIC sequestration through carbonates naturally takes thousands of years but there have been studies to increase SIC sequestration through the addition of silicates.
47 OTHER INSTRUMENTATION↗
Microbial Curing of Cement for Energy Applications
Rutgers University, Lawrence Livermore National Laboratory, and the University of Arizona executed this program over 36 months with a 4-Task Program: (M1)-Microbial Engineering (M2)-Microstructure Modelling, (M3) Cement and Concrete Formulation, (M4)-Techno-economic analysis (TEA) and lifecycle assessment (LCA). This program developed a new carbonate cement concrete manufacturing process called microbial curing (MBC). MBC utilizes in-situ microbial production of CO 2 that dissolves into pore-bound water to carbonate a cementitious material creating a bonding matrix of CaCO 3 and SiO 2 that hardens and densifies the material. This is the first work of this type where calcium silicate was used in microbial studies. All other work reported in the literature always used a soluble form of calcium. This final report describes the work done in the final quarter, the best procedures and results, and the final techno-economic and lifecycle analyses. This quarter, we cast and cured twenty-five (4”x8”) cylinder samples. The compressive strength, split tensile, Young’s modulus, chloride permeability, and creep measurements were performed. These measurements demonstrated that MBC of calcium silicate concrete exhibits scaling problems due to the escape of ammonia gas, a product of the microbial reaction to generate CO 2 . As curing proceeds, the ability for the gas to escape from within the cylinder is restricted by the outer cylindrical portions densifying, making the outer portion highly impermeable to gas flow. In contrast, the small samples cured are uniformly cured, forming materials whose mechanical properties are 7x better than the large samples. This problem needs to be solved before this technology can be commercialized. The techno-economic and lifecycle analyses indicate that the technology developed in this program exhibits a significant opportunity to reduce the cost of cement and CO 2 emissions associated with concrete, provided the curing issue associated with larger samples can be addressed.
36 MATERIALS SCIENCE↗
Surface Modified Fly Ash for Value Added Products (SuMo Fly Ash)
The objective of this project is to develop a technology to encapsulate coal fly ash particles in sulfurized vegetable oil, enhancing physical and mechanical properties of the fly ash as a filler material when applied in commercial products. This project significantly advances the knowledge base and technology for synthesizing coated fly ash particles for application in different polymer matrices to increase cross-linking, compatibility, air-entrainment and to decrease the leaching potential of metals of concern. Specifically, the project focuses on (a) collection, and characterization of fly ash material from coal power plants; (b) development of Sulfurized Vegetable Oil (SVO) modified (SuMo) fly ash and their detailed characterization; (c) evaluation of the mechanical properties of the SuMo fly ash incorporated plastic and rubber composites for potential replacement of CaCO 3 or carbon black as filler materials with SuMo fly ash in plastic and rubber composites; (d) leaching potential of SuMo fly ash and SuMo fly ash-incorporated plastic and rubber composites to determine the rate of release of trace metals. The major findings of this project are: i) Sulfurized Vegetable Oil coated fly ash (SuMo fly ash) was successfully prepared with a particle size of ≤ 45 micron which exhibited hydrophobicity of contact angle > 90°; ii) the coating reduces leaching of metals (e.g., B, Cr) from fly ash when exposed to water; iii) incorporation of SuMo fly ash increases thermal stability and yield strength of plastics; iv) SuMo coating helps disperse fly ash particles into cured rubbers, natural rubber; (v) SuMo fly ash-incorporated plastic/cured rubbers compounds protects against leaching of toxic elements.
20 FOSSIL-FUELED POWER PLANTS↗
Investigating Material Properties of Subsurface Rock Formations Modified by Engineering Mineral Precipitation (Final Scientific and Technical Report)
Montana State University’s (MSU) Energy Research Institute (ERI), in collaboration with the Center for Biofilm Engineering (CBE) and the Department of Civil Engineering (CE), has conducted a long‐term research program aimed at developing a novel cementing agent to address wellbore integrity and reduce the unwanted upward migration of fluids and greenhouse gases from the subsurface. The primary technology developed through this research program is known as ureolysis‐induced calcite precipitation (UICP), which harnesses bio‐chemical processes to precipitate calcium carbonate (CaCO 3 ). The same general process can also be called microbially-induced calcium carbonate precipitation (MICP) when microbes provide the process-catalyzing urease enzyme. Both terms are used in this report. Results have conclusively demonstrated that, if properly controlled, UICP can successfully seal fractures, high permeability zones, and compromised cement in the vicinity of wellbores and in nearby caprock. This technology has been successfully deployed to mitigate annular leakage in two test wells and over sixty commercial wells with a 100% success rate. This success in downhole deployment generates consideration of other subsurface applications where UICP could provide benefit to the energy sector, such as shale property modification for unconventional oil and gas recovery. The focus of this research project was to investigate fundamental material and mechanical properties of select shale cores and analyze how these properties change due to engineered mineral precipitation with the intent to control these properties to achieve a range of engineering objectives. Ultimately, the project aim was to identify valuable new areas where application of UICP might contribute to national energy security and environmental protection. The research workplan coupled UICP treatment of core samples, nuclear magnetic resonance (NMR) characterization, and mechanical strength testing at MSU with advanced X‐Ray micro-computed tomography (μCT) imaging and numerical modeling performed by collaborators at two national laboratories, the National Energy Technology Laboratory (NETL) and Lawrence Berkeley National Laboratory (LBNL). Experimental results are useful to inform geo-mechanical models which could be applied to predict mineralized rock formation behavior at field scale. Our findings suggest that NMR and μCT methods to detect and quantify biomineral formation in shale fractures are complementary and consistent with each other. Either could be used to estimate the volume of new mineral formed by UICP in shale fractures. The use of surfactants and guar gum to enhance biomineral precipitation in shale fractures merits further research. UICP can, under some conditions, increase the tensile strength of sealed shale fractures beyond that of the intact shale. These findings demonstrate that continued research in this area may be valuable to understanding and improving shale resource recovery techniques.
58 GEOSCIENCES↗
FEED Study of CarbonCapture Inc DAC and CarbonCure Utilization Technologies Using United States Steel’s Gary Works Plant Waste Heat (Final Report)
The University of Illinois at Urbana-Champaign (UIUC) led this project to produce a front-end engineering design (FEED) study of an advanced Direct Air Capture and Utilization System (DACUS) system that can remove a minimum of 5,000 tonnes/yr net of carbon dioxide from air (based on cradle-to-gate LCA) and utilizing the CO 2 to produce low carbon intensity ready mix concrete. The designed system, if built, would be larger than any currently existing Direct Air Capture (DAC) collector in the U.S. Such carbon capture technologies are critical to meeting the goals of the DOE’s program to accelerate climate-critical technology. In addition to the power sector, industrial facilities for the manufacture of steel and cement/concrete are among the major sources of anthropogenic CO 2 . DAC is a promising new technology for reducing CO 2 , a potent greenhouse gas, in the atmosphere but is expensive, in part due to the energy required to adsorb and desorb captured CO 2 during cycles. By integrating CarbonCapture Inc. (CCI) DAC modules at United States Steel's Gary Works (USS) and utilizing the site's waste heat, energy, and location this project evaluates the feasibility of utilizing the captured CO 2 and the logistics of transportation. CarbonCapture Inc. has developed an innovative DAC system using novel adsorbents to cost-effectively capture CO 2 . The captured, liquified gas will be trucked to ready-mix concrete plants within the region, the closest of which is approximately 3.5 miles away, where CarbonCure will inject it into concrete during the mixing process at the facilities. The carbon dioxide reacts with concrete, mineralizing into calcium carbonate (CaCO 3 ), permanently locking the greenhouse gas into the matrix of the building material. This FEED study demonstrated a full CO 2 value chain for DACUS from industrial facilities. It also provided a means for Visage Energy Corp. (Visage) to assess the impact of this holistic approach on job creation, regional economic impact, and environmental justice. The project team also included Sargent & Lundy (S&L) to provide the constructability review and costing of the integration of the DAC with the steel plant. Ecotek Engineering USA, LLC designed the outside battery limit (OSBL) infrastructure to connect the DAC and the plant. Activities performed during the project included: (1) Project Management Plan; (2) Technology Maturation Plan (TMP); (3) Initial Workforce Readiness Plan; (4) Workforce Readiness Plan; (5) Front-End Engineering Design (FEED) Study; (6) Project Design Basis; (7) Hazards and Operability (HAZOP) Study; (8) Constructability Review; (9) Project Cost Assessment; (10) Logistics Analysis of CO 2 Transportation to the Utilization Site; (11) Business Case Analysis; (12) Life Cycle Analysis (LCA); (13) Environmental Health and Safety (EH&S) Analysis; (14) Environmental Justice Analysis; and (15) Economic Revitalization and Job Creation Outcomes Analysis. This report provides a summary of the outcomes and results of the project, which was performed between Oct. 1, 2022, through Sept. 30, 2024.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
CarbStor: Development, Analysis and Modification of Carbon Storing Model Soil Communities
Soil microbial communities carry out a number of key processes including plant growth promotion, bioremediation and cycling of nutrients. Carbon cycling is among the most important of these nutrients that are metabolized and processed by the soil microbial community. Many of the carbon inputs are converted to alternative organic forms of carbon that can be used by plants or act as biomass for microbial growth. However, inorganic forms of carbon can also be produced by soil microbial communities including calcium carbonate (CaCO 3 ). Production of calcium carbonate is beneficial for the ecosystem in several ways: it can stabilize soils and improve soil health, especially denser soils with high clay content, it can act as a method of bioremediation, it can serve as an alternative carbon source for plants and it can be a way to store carbon in soil in a stable, inorganic manner for the long term. While the chemistry surrounding individual species carrying out this process is well known what is lacking is an understanding of how species interact in a community to drive carbonate production. As all microbial species in soil exist in a community setting gaining this knowledge is critical to our predicting and controlling this microbial phenotype to greatly improve soil health. The CarbStor project is focused on developing, analyzing and modifying defined microbial soil consortia that express phenotypes at both the species and community level to convert carbon into recalcitrant stable sources such as precipitated carbonate or microbial necromass. To take full advantage of the soil community for this process we will need to fill several key knowledge gaps (KG), three of which are the focus of CarbStor. KG1: Whether and to what degree microbial communities can be developed that produce precipitated carbon via microbial metabolism. KG2: What interspecies interactions drive the individual member phenotypes in defined communities that lead to carbon precipitation. KG3: How can these interactions be modified to enhance carbon sequestration beyond what native communities are capable of. We hypothesize that in a carbon sequestering community only a subset of species will express phenotypes related to carbon storage processes. We also hypothesize that these phenotypes are expressed as a result of interactions with other species in the community that are not involved in carbon storage processes and that these interactions can be harnessed to enhance community carbon sequestration.
54 ENVIRONMENTAL SCIENCES↗
Cyclotron production of 43Sc and 44gSc from enriched 42CaO, 43CaO, and 44CaO targets
Introduction: 43 Sc and 44g Sc are both positron-emitting radioisotopes of scandium with suitable half-lives and favorable positron energies for clinical positron emission tomography (PET) imaging. Irradiation of isotopically enriched calcium targets has higher cross sections compared to titanium targets and higher radionuclidic purity and cross sections than natural calcium targets for reaction routes possible on small cyclotrons capable of accelerating protons and deuterons. Methods: In this work, we investigate the following production routes via proton and deuteron bombardment on CaCO 3 and CaO target materials: 42 Ca(d,n) 43 Sc, 43 Ca(p,n) 43 Sc, 43 Ca(d,n) 44g Sc, 44 Ca(p,n) 44g Sc, and 44 Ca(p,2n) 43 Sc. Radiochemical isolation of the produced radioscandium was performed with extraction chromatography using branched DGA resin and apparent molar activity was measured with the chelator DOTA. The imaging performance of 43 Sc and 44g Sc was compared with 18 F, 68 Ga, and 64 Cu on two clinical PET/CT scanners. Discussion: The results of this work demonstrate that proton and deuteron bombardment of isotopically enriched CaO targets produce high yield and high radionuclidic purity 43 Sc and 44g Sc. Laboratory capabilities, circumstances, and budgets are likely to dictate which reaction route and radioisotope of scandium is chosen.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synthesis of DOTA-Based 43 Sc Radiopharmaceuticals Using Cyclotron-Produced 43 Sc as Exemplified by [ 43 Sc]Sc-PSMA-617 for PSMA PET Imaging
The implementation of theranostics in oncologic nuclear medicine has exhibited immense potential in improving patient outcomes in prostate cancer with the implementation of [ 68 Ga]Ga-PSMA-11 PET and [ 177 Lu]Lu-PSMA-617 into clinical practice. However, the correlation between radiopharmaceutical biodistributions seen with [ 68 Ga]Ga-PSMA-11 PET imaging and downstream [ 177 Lu]Lu-PSMA-617 therapy remains imperfect. This suggests that prostate cancer theranostics could potentially be further refined through the implementation of true theranostics, tandem pairs of diagnostic and therapeutic radiopharmaceuticals that utilize the same ligand and element, thus yielding identical pharmacokinetics. The radioscandiums are one such group of true theranostic radiopharmaceuticals. The radioscandiums consist of two β+ emitting scandium isotopes ( 43 Sc/ 44 Sc), as well as a β − emitting therapeutic isotope ( 47 Sc), which can all conjugate with PSMA-targeting PSMA-617. This potential has led to extensive investigations into the production of the radioscandiums as well as pre-clinical assessments with several ligands; however, there is a lack of literature extensively describing the complete synthesis of scandium radiopharmaceuticals. which therefore limits the accessibility of radioscandium research in theranostics. As such, this work aims to present an easily translatable protocol for the synthesis of [ 43 Sc]Sc-PSMA-617 from a [ 42 Ca]CaCO 3 starting material, including target formation, nuclear production via 42 Ca(d,n) 43 Sc reaction, chemical separation, radiolabeling, solvent reformulation, and target recycling.
62 RADIOLOGY AND NUCLEAR MEDICINE↗
Experiments and Simulations to Describe Alkalinity Release from Particle-Containing Oil-in-Water Emulsions and Particle Suspensions
Among the most common amendments added to groundwater during site remediation are compounds used to adjust or maintain the pH. This research describes an approach to encapsulate mineral particles (MgO and CaCO 3 ) within oil droplets suspended within an aqueous phase for the purpose of delivery to the subsurface environment. A series of batch experiments was combined with mathematical modeling to illustrate the encapsulation and understand the influence of particle encapsulation on rates and extents of alkalinity release. The encapsulation of the alkalinity-releasing particles results in slower rates of amendment release as compared to rates obtained using suspensions of bare mineral particles, allowing for the possibility of control as a function of the pH. The results indicate that the alkalinity release from particle suspensions followed a mineral dissolution mechanism that could not explain the rate of the alkalinity release of the encapsulated particles. The reduction in mineral dissolution rates observed with the encapsulated particles was found to result from a mass transfer limitation. This limitation was well described using a linear driving force expression to account for the resistance to mass transfer at the oil–water interface.
EVO↗
Galacturonomannan and Golgi-derived membrane linked to growth and shaping of biogenic calcite
The coccolithophores are valuable models for the design and synthesis of composite materials, because the cellular machinery controlling the nucleation, growth, and patterning of their calcitic scales (coccoliths) can be examined genetically. The coccoliths are formed within the Golgi complex and are the major CaCO(3) component in limestone sediments-particularly those of the Cretaceous period. In this study, we describe mutants lacking a sulfated galacturonomannan and show that this polysaccharide in conjunction with the Golgi-derived membrane is directly linked to the growth and shaping of coccolith calcite but not to the initial orientated nucleation of the mineral phase.
NASA Discipline Cell Biology↗
Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality
The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.
Calcium Carbonate/metabolism↗