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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Linking water quality, fouling layer composition, and performance of reverse osmosis membranes

Fouling of polyamide membranes during reverse osmosis (RO) is a major challenge for adopting membrane technologies to treat highly contaminated waters, especially those containing organic foulants (e.g., natural organic matter (NOM), polysaccharides) and dominant cations (e.g., sodium, magnesium, calcium). Here, this work combines bench-scale membrane fouling experiments with detailed characterization of feedwater chemistry and fouling layer composition/morphology to reveal fundamental mechanisms of (in)organic fouling during RO. Divalent cations are shown to promote fouling by hydrophobic NOM containing aromatic and carboxyl groups, while NOM fouling in the presence of a monovalent cation, sodium, occurs by smaller fulvic acids containing larger fractions of carboxyl groups and other oxygen-rich moieties. Calcium-carboxyl bridging occurs in solution and near the membrane surface to induce NOM aggregation on nanometer length scales. In complex waters containing foulant mixtures, co-fouling by calcium-carboxyl bridging and CaCO 3 precipitation influence membrane performance at longer timeframes. However, the flux decline observed for the co-fouling mechanism was less significant than the sum of its parts, suggesting both synergistic and antagonistic fouling mechanisms should be considered in membrane design/operation. These results encourage the design of pretreatment processes to reduce concentrations of multivalent ions and hydrophobic NOM in RO feedwaters, and of membrane materials to limit attachment/deposition of aggregates to/on polyamide surfaces.

42 ENGINEERING↗
DOE OSTI2022

Process-Specific Effects of Sulfate on CaCO 3 Formation in Environmentally Relevant Systems

Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO 3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO 3 's formation and is seldom found to significantly affect multiple CaCO 3 formation processes. In this work, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO 3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO 3 precursors and nuclei, promoting CaCO 3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO 3 . Meanwhile, adsorbed sulfate on CaCO 3 nuclei may poison the surface of smaller CaCO 3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO 3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Dynamics of Electric Polarization and Relaxation of Ions at Humid Calcite Surfaces

Mobile ions at mineral surfaces can respond to an applied electric field, adopting a new distribution that effectively represents polarization of the electrical double layer. When the field is released, the ions relax to their equilibrium distribution. In both cases, the dynamics are characteristic of the interface. However, current models of electrokinetic phenomena are not sufficiently robust to accurately predict collective ion dynamics at structurally and chemically specific mineral–water interfaces. Here, in this study, we use electrostatic force microscopy (EFM) to investigate the dynamics of ion relaxation at hydrated calcite (104) surfaces at controlled relative humidity (RH). Electrically biased probes are used to polarize the distributions of calcium and carbonate ions that are intrinsic to this interface across a range of RH values. Polarization kinetics are tracked by monitoring the tip–sample force gradient during charging, and EFM imaging is used to characterize the spatial relaxation dynamics after the applied field is released. Electrostatic finite element modeling of the sample/probe system across length-scales from nanometers to millimeters reproduces the observed stretched exponential charging response. Together, these results allow us to estimate the ion diffusivities at the interface across a wide range of RH values. These diffusivities increase by roughly 5 orders of magnitude as the RH is increased from 5 to 90%, highlighting the critical role of adsorbed water for surface ion solvation that enables ion mobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Elucidation of Bottom-up Growth of CaCO3 Involving Prenucleation Clusters from Structure Predictions and Decomposition of Globally Optimized (CaCO3)n Nanoclusters

Low-energy minima structures for (CaCO3)n, n = 28, are predicted using bottom-up genetic algorithms in conjunction with density functional theory electronic structure calculations, in comparison with the frozen and relaxed top-down clusters generated by cuts from the calcite, vaterite, and aragonite crystal structures. Similarities in structural motifs for the bottom-up and relaxed top-down are revealed using a fragment recognition technique. Fragment energy decomposition analysis shows that the bottom-up and relaxed top-down clusters belong to two classes of amorphous clusters with distinct intracluster energy distributions, despite their structural similarity. The bottom-up clusters with >20 formula units are surface stabilized with negative surface energy densities. In contrast, the top-down clusters are interior stabilized with positive surface energy densities. We prove that the sign of the surface energy density determines whether the nucleation reaction energy as a function of nuclear size has a maximum or a minimum. The surface-stabilized bottom-up clusters are proposed to be a type of prenucleation cluster at the minimum of the nucleation reaction energy. A mechanism for mineralization of CaCO3 involving prenucleation clusters and nonclassical growth pathway is proposed on the basis of our theoretical findings, which is consistent with previous titration experiments.

calcium carbonate, prenucleation cluster, biominer↗
DOE OSTI2023

Spectral induced polarization monitoring of induced calcite precipitation in subsurface sediments

Co-precipitation of contaminants within the crystalline structure of calcite is a promising natural attenuation or remedial technology being considered at contaminated sites. We explore the sensitivity of the spectral induced polarization (SIP) method to induced calcite precipitation in natural sediments as a path forward to non-invasively monitor these sites. We performed time-lapse column experiments using phased (I-IV) injections over 40 days on natural sediments from the Hanford Site (Washington State, USA). In the phased injections, abiotic calcite precipitation was induced and confirmed to have occurred. Previous work in glass beads and homogeneous sand was limited to high frequency detection of calcite, however in this work we observed the development of two polarization mechanisms, one at high frequency (>100 Hz) and one at low frequency (< 100 Hz). Based on the characteristic frequencies from the SIP high and low frequency regimes, characteristic length scales (L) were computed where the adsorption mode of Na+ versus Ca2+ was compared by using diffusion coefficients corresponding to Na+ versus an arithmetically averaged value for Na+ and Ca2+. Using the diffusion coefficient of Na+, the high frequency L was found to correlate well with the size of the calcite crystals. The low frequency L correlated well with the individual natural sediment grain sizes within the columns. During late experimental times (day 36 and 40), the characteristic low frequency in two of the experimental columns shifted to lower frequencies (<0.001 Hz) which may signify SIP sensitivity of the formed calcite with the sediment grains. In field applications, the development of a low frequency polarization length scale to monitor calcite precipitation is promising for field monitoring applications, however further laboratory work needs to be performed to examine the SIP sensitivity of calcite formation in the presence of to natural sediments

calcium carbonate, calcite, precipitation, spectra↗
NASA NTRS1977

Mineralogic and petrologic study of the low-temperature minerals in carbonaceous chondrites

Samples and petrographic thin sections of the Orgueil, Ivuna, and Alais chondrites were examined by optical, X-ray, and SEM techniques. Mineral species identified as primary vein constituents were epsomite, gypsum, and a calcium-magnesium carbonate. Relative abundances and textural relationships have suggested that fracture mineralization was a multi stage process, with individual mineralizations closely associated with impact brecciation events. Mass balance considerations of carbonaceous chondrite matrix support the prevailing view that the source of the fracture filling minerals was local. By inference they also suggest that the phyllosilicate matrix has been chemically altered and that there are probably very few primitive mineral phases in the primitive Cl chondrites.

Wood, J. A.↗
NASA NTRS1990

Shell structure and distribution of Cloudina, a potential index fossil for the terminal Proterozoic

Cloudina-bearing biosparites and biomicrites in the lower part of the Nama Group, Namibia, contain a wide morphological diversity of shell fragments that can all be attributed to the two named species C. hartmannae and C. riemkeae. The curved to sinuous tubular shells of Cloudina were multi-layered. Each shell layer was 8 to 50 micrometers thick and in the form of a slightly flaring tube with one end open and the other closed. Growth appears to have been periodic with successive shell layers forming within older layers. Each added layer was slightly elevated from the previous layer at the proximal end and was asymmetrically placed within the older layer so that only a portion of the new shell layer was fused to the previous layer. This type of growth left a relatively large unminerialized area between the shell layers which was often partially or fully occluded by early marine cements. The thin shell layers exhibit both plastic and brittle deformation and were likely formed of a rigid CaCO3-impregnated organic-rich material. Often the shell layers are preferentially dolomitized suggesting an original mineralogy of high-magnesian calcite. Both species in the Nama Group formed thickets, or perhaps bioherms, and this sedentary and gregarious habit suggests that Cloudina was probably a filter-feeding metazoan of at least a cnidarian grade of organization. The unusual shell structure of Cloudina gives rise to a characteristic suite of taphonomic and diagenetic features that can be used to identify Cloudina-bearing deposits within the Nama Group and in other terminal Proterozoic deposits around the world. Species of Cloudina occur in limestones from Brazil, Spain, China, and Oman in sequences consistent with a latest Proterozoic age assignment. In addition, supposed lower Cambrian, pre-trilobitic, shelly fossils from northwest Mexico and the White-Inyo Mountains in California and Nevada, including Sinotubulites, Nevadatubulus, and Wyattia, are all either closely related to or con-generic with Cloudina. Hence, it is probable that these outcrops are latest Proterozoic in age, and that Cloudina or Cloudina-like organisms were widely distributed at that time. It is possible, moreover, to suggest that metazoan biomineralization occurred on a global scale by the latest Proterozoic, at the same time that evidence for complex multicellularity and locomotion in animals appears in siliciclastic "Ediacaran" rocks in the form of body and trace fossils.

NASA Program Exobiology↗
NASA NTRS1992

Stromatolites of the Mescal Limestone (Apache Group, middle Proterozoic, central Arizona): taxonomy, biostratigraphy, and paleoenvironments

The 25- to 30-m-thick Algal Member of the Mescal Limestone (middle Proterozoic Apache Group) contains two distinct stromatolitic units: at the base, a 2- to 3-m-thick unit composed of columnar stromatolites and above, a thicker unit of stratiform and pseudocolumnar stromatolites. Columnar forms from the first unit belong to the Group Tungussia, and two new Forms are described: T. mescalita and T. chrysotila. Among the pseudocolumnar stromatolites of the thicker unit, one distinctive new taxon, Apachina henryi, is described. Because of the low stromatolite diversity, the biostratigraphic value of this assemblage is limited. The presence of Tungussia is consistent with the generally accepted isotopic age for the Apache Group of 1200 to 1100 Ma. The Mescal stromatolites do not closely resemble any other known Proterozoic stromatolites in the southwestern United States or northwestern Mexico. Analyses of sedimentary features and stromatolite growth forms suggest deposition on a stable, flat, shallow, subtidal protected platform during phases of Tungussia growth. Current action probably influenced the development of columns, pseudocolumns, and elongate stromatolitic ridges; these conditions alternated with phases of relatively quiet water characterized by nonoriented stromatolitic domes and stratiform stromatolites. Stable conditions favorable for development of the Mescal stromatolites were short-lived and did not permit the development of thick, stromatolite-bearing units such as those characteristic of many Proterozoic sequences elsewhere.

Non-NASA Center↗
DOE OSTI2024

Breakthrough innovations in carbon dioxide mineralization for a sustainable future

Greenhouse gas emissions and climate change concerns have prompted worldwide initiatives to lower carbon dioxide (CO 2 ) levels and prevent them from rising in the atmosphere, thereby controlling global warming. Effective CO 2 management through carbon capture and storage is essential for safe and permanent storage, as well as synchronically meeting carbon reduction targets. Lowering CO 2 emissions through carbon utilization can develop a wide range of new businesses for energy security, material production, and sustainability. CO 2 mineralization is one of the most promising strategies for producing thermodynamically stable solid calcium or magnesium carbonates for long-term sequestration using simple chemical reactions. Current advancements in CO 2 mineralization technologies, focusing on pathways and mechanisms using different industrial solid wastes, including natural minerals as feedstocks, are briefly discussed. However, the operating costs, energy consumption, reaction rates, and material management are major barriers to the application of these technologies in CO 2 mineralization. Further, the optimization of operating parameters, tailor-made equipment, and smooth supply of waste feedstocks require more attention to make the carbon mineralization process economically and commercially viable. Here, carbonation mechanisms, technological options to expedite mineral carbonation, environmental impacts, and prospects of CO 2 mineralization technologies are critically evaluated to suggest a pathway for mitigating climate change in the future. The integration of industrial wastes and brine with the CO 2 mineralization process can unlock its potential for the development of novel chemical pathways for the synthesis of calcium or magnesium carbonates, valuable metal recovery, and contribution to sustainability goals while reducing the impact of global warming.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1993

Crustal structure and igneous processes in a chondritic Io

Liquid sulfur can form when metal-free C1 or C2 chondrites are heated. It may be obtained either by direct melting of native sulfur in disequilibrated C1 or C2 chondrites or by incongruent melting of pyrite and other sulfides in thermodynamically equilibrated rocks of the same composition. Hence, Lewis considered C2 chondrites to be the best meteoritic analog for Io's bulk composition. Metal-bearing C3 and ordinary chondrites are too chemically reduced to yield liquid sulfur and are not thought to represent plausible analogs of Io's bulk composition. An important aspect of Lewis' work is that CaSO4 and MgSO4 are predicted to be important in Io. Real C1 and C2 chondrites contain averages of, respectively, 11 percent and 3 percent by mass of salts (plus water of hydration). The most abundant chondritic salts are magnesium and calcium sulfates, but other important components include sulfates of sodium, potassium, and nickel and carbonates of magnesium, calcium, and iron. It is widely accepted that chondritic salts are formed by low-temperature aqueous alteration. Even if Io originally did not contain salts, it is likely that aqueous alteration would have yielded several percent sulfates and carbonates. In any event, Io probably contains sulfates and carbonates. This report presents the results of a model of differentiation of a simplified C2 chondrite-like composition that includes 1.92 percent MgSO4, 0.56 percent CaSO4, 0.53 percent CaCO3, and 0.094 percent elemental sulfur. The temperature of the model is gradually increased; ensuing fractional melting results in these components extruding or intruding at gravitationally stable levels in Io's crust. Relevant phase equilibria were reviewed. A deficiency of high-pressure phase equilibria renders the present model qualitative.

Kargel, J. S.↗
NASA NTRS2005

A potential cause for kidney stone formation during space flights: enhanced growth of nanobacteria in microgravity

BACKGROUND: Although some information is available regarding the cellular/molecular changes in immune system exposed to microgravity, little is known about the reasons of the increase in the kidney stone formation in astronauts during and/or after long duration missions at zero gravity (0 g). In our earlier studies, we have assessed a unique agent, nanobacteria (NB), in kidney stones and hypothesized that NB have an active role in calcium phosphate-carbonate deposition in kidney. In this research we studied effect of microgravity on multiplication and calcification of NB in vitro. METHODS: We examined NB cultures in High Aspect Rotating Vessels (HARVs) designed at the NASA's Johnson Space Center, which are designed to stimulate some aspects of microgravity. Multiplication rate and calcium phosphate composition of those NB were compared with NB cultured on stationary and shaker flasks. Collected aliquots of the cultures from different incubation periods were analyzed using spectrophotometer, SEM, TEM, EDX, and x-ray diffraction techniques. RESULTS: The results showed that NB multiplied 4.6x faster in HARVs compared to stationary cultures, and 3.2x faster than shaker flask conditions. X-ray diffraction and EDX analysis showed that the degree of apatite crystal formation and the properties of the apatite depend on the specific culture conditions used. CONCLUSION: We now report an increased multiplication rate of NB in microgravity-simulated conditions. Thus, NB infection may have a potential role in kidney stone formation in crew members during space flights. For further proof to this hypothesis, screening of the NB antigen and antibody level in flight crew before and after flight would be necessary.

Weightlessness↗
DOE OSTI2022

Watershed-scale liming reveals the short- and long- term effects of pH on the forest soil microbiome and carbon cycling

Soil microbial community composition routinely correlates with pH, reflecting both direct pH effects on microbial physiology and long-term biogeochemical feedbacks. For this work, we used two watershed-scale liming experiments to identify short- (2 years) and long-term (25 years) changes in the structure and function of bacterial and fungal communities in organic horizons (O e and O a ) of acid forest soils. Liming increased soil pH, extractable calcium, and soil carbon stocks, reduced biomass-specific respiration, and caused major changes in the soil microbiome in the short and long term. More taxa responded to liming in the short term (70%) than in the long term (30%), with most showing consistent directional responses at both sites. The ratio of change in relative abundance between limed and reference sites was twofold higher at the long than the short-term site, indicating that the effects of liming grew over time. Liming impacts were most pronounced in fungi, as steep declines of dominant ectomycorrhizal fungi ( Cenococcum and Russula ) occurred at both sites. Liming favoured neutrophilic bacteria over acidophilic populations according to estimated environmental pH optima. Collectively, these results demonstrate that a liming-induced change of one pH unit has an immediate and persistent effect on the structure and function of microbial communities in acid forest soils. The corresponding suppression of respiration indicates that anthropogenic alterations of soil pH, as driven by acid deposition or liming, can affect forest floor C stocks due to pH-driven shifts in community structure.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2014

Nanophase Carbonates on Mars: Implications for Carbonate Formation and Habitability

Despite having an atmosphere composed primarily of CO2 and evidence for abundant water in the past, carbonate minerals have only been discovered in small amounts in martian dust [1], in outcrops of very limited extent [2, 3], in soils in the Northern Plains (the landing site of the 2007 Phoenix Mars Scout Mission) [4] and may have recently been detected in aeolian material and drilled and powdered sedimentary rock in Gale Crater (the Mars Science Laboratory [MSL] landing site) [5]. Thermal analysis of martian soils by instruments on Phoenix and MSL has demonstrated a release of CO2 at temperatures as low as 250-300 degC, much lower than the traditional decomposition temperatures of calcium or magnesium carbonates. Thermal decomposition temperature can depend on a number of factors such as instrument pressure and ramp rate, and sample particle size [6]. However, if the CO2 released at low temperatures is from carbonates, small particle size is the only effect that could have such a large impact on decomposition temperature, implying the presence of extremely fine-grained (i.e., "nanophase" or clay-sized) carbonates. We hypothesize that this lower temperature release is the signature of small particle-sized (clay-sized) carbonates formed by the weathering of primary minerals in dust or soils through interactions with atmospheric water and carbon dioxide and that this process may persist under current martian conditions. Preliminary work has shown that clay-sized carbonate grains can decompose at much lower temperatures than previously thought. The first work took carbonate, decomposed it to CaO, then flowed CO2 over these samples held at temperatures >100 degC to reform carbonates. Thermal analysis confirmed that carbonates were indeed formed and transmission electron microsopy was used to determine crystal sized were on the order of 10 nm. The next step used minerals such as diopside and wollastonite that were sealed in a glass tube with a CO2 and H2O source. After reacting these materials for a number of hours, thermal analysis demonstrated the formations of carbonates that decomposed at temperatures as low as 500 degC [7]. Further work is underway to carry out the weathering process under more Mars-like conditions (low pressure and low temperature) to determine if the carbonate decomposition temperature can be shifted to even lower temperatures, consistent with what has been detected by thermal analysis instruments on Mars.

Archer, P. Douglas, Jr.↗
DOE OSTI2021

X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal

Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Additionally, crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic K syn and ηsyn identifying the most likely elastic constants C 33 and C 13 for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E 11 =107 GPa and E 33 =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues.

36 MATERIALS SCIENCE↗