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At least 199 records · Page 11

Mobility of heavy rare earth elements in magmatic-hydrothermal systems: Experimental determination of DyPO 4 solubility in supercritical fluids

Dysprosium (Dy) is part of the heavy rare earth elements (REE) and a critical component in the production of high-performance super magnets used in wind turbines, electric vehicles, and other green technologies. The HREE phosphate, xenotime, is commonly associated with hydrothermal systems, where the mobility, fractionation, and deposition of REE are controlled by the stability of aqueous complexes and solubility of REE minerals which depend on temperature, pressure, and fluid composition (salinity, pH, and ligand availability). Here, we conducted a series of synthetic DyPO 4 solubility experiments in NaCl-HCl-bearing aqueous solutions (pH of 2 at 25 °C) from 500 to 700 °C and 1.5 kbar using externally heated pressure vessels. DyPO 4 displays a strong prograde solubility with temperature across all studied fluid salinities (0–0.5 m NaCl). The DyPO₄ solubility isotherms at 500 °C, 600 °C, and 700 °C show a complex relationship with salinity where DyPO₄ solubility is highest (39.2–1552 ppm at 500–700 °C) in 0 m NaCl solutions, decreases strongly (21–331 ppm at 500–700 °C) in the 0.06 m NaCl solutions and remains relatively constant in the 0.25 m (42.8–248 ppm) and 0.5 m NaCl (40.2–124 ppm) solutions. Thermodynamic modeling suggests that pH increases as a function of temperature and salinity, and controls solubility due to the stability of chloride complexes (i.e., DyCl +2 and DyCl 2 + ) at 500–600 °C, transitioning to hydroxyl complexes (i.e., Dy(OH) 3 0 ) dominating at 700 °C and relatively alkaline pH. Comparison with NdPO 4 solubility data indicates that the light REE in monazite is significantly more soluble than the heavy REE in xenotime in saline fluids at high temperature (500–700 °C), implying efficient light/heavy REE fractionation in supercritical fluids. The lower solubility of DyPO 4 relative to NdPO 4 suggests that at high temperatures, acidic (pH 2–4), low-salinity (∼5 wt% NaCl) fluids will favor the precipitation of xenotime over monazite as it will cool from 700 °C to below 500 °C. These observations align with paragenetic mineral assemblages in NYF pegmatites (e.g., Baveno, Italy), where xenotime commonly immobilizes heavy REE during the high-temperature hydrothermal stages.

58 GEOSCIENCES↗

Evidence for Life on Earth before 3,800 Million Years Ago

It is unknown when life first appeared on Earth. The earliest known microfossils (approx. 3,500 Myr before present) are structurally complex, and if it is assumed that the associated organisms required a long time to develop this degree of complexity, then the existence of life much earlier than this can be argued. But the known examples of crustal rocks older than approx. 3,500 Myr have experienced intense metamorphism, which would have obliterated any fragile microfossils contained therein. It is therefore necessary to search for geochemical evidence of past biotic activity that has been preserved within minerals that are resistant to metamorphism. Here we report ion-microprobe measurements of the carbon-isotope composition of carbonaceous inclusions within grains of apatite (basic calcium phosphate) from the oldest known sediment sequences a approx. 3,800 Myr-old banded iron formation from the Isua supracrustal belt, West Greenland, and a similar formation from the nearby Akilia island that is possibly older than 3,850 Myr. The carbon in the carbonaceous inclusions is isotopically light, indicative of biological activity; no known abiotic process can explain the data. Unless some unknown abiotic process exists which is able both to create such isotopically light carbon and then selectively incorporate it into apatite grains, our results provide evidence for the emergence of life on Earth by at least 3,800 Myr before present.

Mojzsis, S. J.↗

Prevention of hypercalciuria and stone-forming propensity during prolonged bedrest by alendronate

The bone loss and hypercalciuria induced by immobilization or the decreased gravitational forces of space are well described. Using a model of bedrest immobilization, the ability of a potent aminobisphosphonate, alendronate, to avert hypercalciuria and stone-forming propensity was tested. Sixteen male subjects participated in a randomized, placebo-controlled trial in which they received either 20 mg of alendronate or placebo 2 weeks prior to and during 3 weeks of strict bedrest. Parameters of bone and calcium metabolism and urinary crystallization of stone-forming salts were measured before and at the end of bedrest. In the placebo group, bedrest increased urinary calcium (209 +/- 47 to 267 +/- 60 mg/day, p < 0.01) and the saturation of calcium phosphate. Before bedrest, the alendronate group had a significantly lower serum calcium (8.8 +/- 0.4 vs. 9.6 +/- 0.5 mg/dl, p < 0.01) and higher serum PTH (62.4 +/- 33.1 vs. 23.1 +/- 7.5 pg/ml, p < 0.01) compared with the placebo group. Moreover, the alendronate group had a lower urinary calcium (75 +/- 41 mg/day) and saturation of calcium oxalate and calcium phosphate. These effects of alendronate were sustained during bedrest. Following bedrest in the alendronate group, urinary calcium rose to 121 +/- 50 mg/day, a value less than that in the placebo group before or during bedrest. Similarly, urinary saturation of calcium oxalate and calcium phosphate rose with bedrest in the alendronate-treated patients but remained lower than values obtained in placebo-treated patients before or during bedrest. Alendronate inhibits bone mineral loss and averts the hypercalciuria and increased propensity for the crystallization of stone-forming calcium salts which occurs during 3 weeks of strict bedrest.

Non-NASA Center↗

The solubility and speciation of REE phosphate endmembers (CePO 4 and YPO 4 ) in Cl-rich aqueous fluids from 350 to 450 °C and implications for natural systems

The rare earth elements (REE) are important metals used increasingly in advanced technologies. Within the crust, the elements Ce and Y are commonly more abundant compared to other lanthanides and comprise important end-member constituents of REE-bearing minerals. Specifically, Ce is part of the light (L) REE which have larger ionic radii than the heavy (H) REE, which are grouped together with Y. These differences in ionic radius can lead to important physico-chemical trends within the lanthanide group. Despite a recent increase in experimental and thermodynamic data for the REE at high temperature and pressure, there is still a significant lack of these data at supercritical conditions. In this study we conducted batch-type experiments to measure the solubility of REE phosphates (CePO 4 and YPO 4 ) at varying starting pH (1.5–10), and salinity (0.01–1.4 mol/kg NaCl) at 350 and P sat , and from 400 to 450 °C at 700 bar. Results show that the solubility of Ce (33–0.14 ppb) is generally higher than Y (13–0.13 ppb) and that Ce complexes more strongly with both chloride and hydroxyl ligands compared to Y. The solubilities of both REE phosphates are highly pH-dependent and, to a lesser extent, depend on salinity at the studied conditions. The solubility data from this study were implemented into the GEMSFITS program to optimize the thermodynamic properties of Ce and Y hydroxyl and chloride species. The updated standard partial molal Gibbs energies of formation (Δ f G 0 T,P ) are used within the experimental temperature and pressure range to accurately predict the CePO 4 and YPO 4 solubility and Ce and Y speciation behavior. Based on the updated thermodynamic properties we also provide formation constants (log β n Cl,OH ) for Ce and Y hydroxyl and chloride species. Updated thermodynamic properties are applied to model REE-apatite dissolution and REE mobility based on the Pea Ridge iron oxide apatite deposit in Missouri, USA. The apatite dissolution model replicates natural observations including the replacement of monazite and xenotime after apatite and is an example of the utility of the new thermodynamic constants applied to supercritical crustal fluids. Furthermore, the findings of this study advance the predictive capabilities of geochemical models, our understanding of the behavior of individual REE, and permit modeling the overarching fractionation trends between LREE and HREE in supercritical crustal fluids.

58 GEOSCIENCES↗

Lead in Martian Meteorites-- Observations and Inconsistencies: I. Chassigny

The history of Pb isotope analyses of the martian meteorites (SNC) and their interpretations is laden with difficulties. Two different analytical groups have interpreted their ancient (≥ 4 Ga) shergottite Pb ages as primary [1-5]. A Nakhla age of approximately 4.3 Ga has been interpreted to be primary as well [2]. This is in stark contrast to the young (≤ 1.4 Ga) crystallization ages defined by the Rb-Sr, Sm-Nd, Lu-Hf, and KAr systems [6]. Possibly, a better interpretation for the ancient Pb ages is that they reflect the formation times of the various SNC source regions [7]. A difficulty in dealing with Pb is that terrestrial contamination is ubiquitous, unlike the other chronometer systems noted above. This issue is complicated by the fact that radioactive decay causes localized mineral damage. So washing and leaching to remove Pb contamination tends to remove in situ radiogenic Pb. This issue is further compounded because U and Th are often concentrated in phosphates and other minor phases, so the leaching process tends to remove these, especially phosphates. Another difficulty is that it is not clear whether the observed Pb isotopic variation in leachates, residues, and ion-microprobe analyses is due to terrestrial or to indigenous martian Pb contamination [e.g., 8]. A third difficulty is that the shergottites on the one hand, and the nakhlites and chassignites on the other, appear to have come from separate source regions with different chemical compositions [e.g., 7]. Thus, it is expected that their Pb isotopic characteristics would be different. And even if all these meteorite types came from the same source region, their igneous ages differ considerably. The nakhlites and chassignites are ~1.4 Ga and the shergottites are ≤ 600 Ma [e.g., 6]. This age difference alone should assure that the two distinct SNC groups have differing Pb isotopic signatures.

Jones, J. H.↗

FTIR Analysis of Water in Pyroxene and Plagioclase in ALH 84001 and Nakhlites

Determining the volatile budget of the interior of Mars is crucial for our understanding of that planet's formation, geodynamics, cooling history and the origin of its volcanism and atmosphere as well as its potential for life. Surficial water is evident from spacecraft and rover data in polar caps and the atmosphere, in the presence of river channels, and in the detection of water-bearing minerals. Meteorites, however, are our best candidates for estimating the amount of water present at depth, even if all are crustal samples. The last 10 years have seen a blooming of studies measuring water and halogens in Martian meteorites. The bulk of these studies target phosphate, a typically late-stage phase in the igneous Martian meteorites that potentially would concentrate incompatible element hydrogen (H quantified traditionally as "water", i.e., H2O concentrations in weight) near the end of the crystallization sequence. However, determining the amount of water, F, and Cl in the magma from which a phosphate crystallized from is not straightforward and in most instances not possible. On the other hand, phosphates have turned out to be very useful in identifying hydrothermal processes that could have added water while or after the magma flowed and crystallized. Another caveat of analyzing Martian meteorite phases for water is that shocked phases such as maskelynite and impact melts appear to have incorporated water from the Martian atmosphere, as evidenced by high H isotope ((delta)D) signatures, and therefore their water concentrations cannot be interpreted in terms of deep planetary processes. The best candidates for estimating the water content of the Martian interior have been melt inclusions (glass or amphibole-bearing) which the enclosing mineral (usually olivine) would have prevented from exchanging volatiles with the surroundings after crystallization. Even some of these, however, have high (delta)D, meaning they were affected by H exchange via impact events or with crustal reservoirs or hydrothermal fluids. Here, nominally anhydrous minerals (pyroxene, olivine, plagioclase, or maskelynite) in orthopyroxenite ALH 84001 and selected nakhlites are analyzed for water and major elements, in order to determine 1) whether they contain any water; 2) if they do, what controls its distribution (crystallization, degassing, hydrothermal or impact processes); and 3) if any of these measurements can be used to infer the water contents of the parent magma and their mantle sources. A shock-reverberation experiment was also performed on terrestrial orthopyroxenes (opx) to simulate the heavily shocked conditions of ALH 84001 (> 31 GPa [17]).

Peslier, A. H.↗

Dataset for "Enrichment of phosphates, lead, and mixed soil-organic particles in INPs at the Southern Great Plains site"

Ice nucleating particles (INPs) are rare particles that initiate primary ice formation, a critical step required for subsequent important cloud microphysical processes that ultimately govern cloud phase and cloud radiative properties. Laboratory studies have found that organic-rich dusts, such as those found in soils, are more efficient INPs compared to mineral dust. However, the atmospheric relevance of these organic-rich dusts are not well understood, particularly in regions with significant agricultural activity. The Agricultural Ice nuclei at the Southern Great Plains field campaign (AGINSGP) was conducted in rural Oklahoma to investigate how soil dusts contribute to INP populations in the Great Plains. We present chemical characterization of ambient and ice crystal residual particles from a single day of sampling using single particle mass spectrometry (SPMS) and scanning microscopy. Ambient particle concentrations were primarily carbonaceous or secondary aerosol, while dust particles were enhanced in the residual particles. Dust particles measured during residual sampling contained elevated signals for phosphate ($^{63}$PO$_2^-$ and $^{79}$PO$_3^-$) and lead ($^{208}$Pb$_2^+$). Nitrate was slightly depleted relative to ambient dust, and strong sulfate signals were not seen in the residual particles measured by the miniSPLAT. The residual and ambient particles measured by the miniSPLAT were approximately the same size, though this may be a reflection of the SPMS size-dependent transmission efficiency and not that of physical truth. This study shows that organic-rich soils may be important contributors to the ambient INP population in agricultural regions.

Cornwell, Gavin C↗

Soluble minerals in chemical evolution. I - Adsorption of 5-prime-AMP on CaSO4 - A model system

The adsorption of 5-prime-AMP onto solid CaSO4-2H2O was studied in a saturated suspension as a function of pH and electrolyte concentration. The adsorption is pH-dependent and is directly correlated with the charge on the 5-prime-AMP molecule which is determined by the state of protonation of the N-1 nitrogen of the purine ring and the phosphate oxygens. It is proposed that the binding that occurs between the nucleotide and the salt is electrostatic in nature. The adsorption decreases with increasing ionic strength of the solution which means that in a fluctuating environment of wetting and drying cycles, a biomolecule similar to 5-prime-AMP could be expected to desorb during the drying phase. The results indicate that CaSO4-2H2O can serve as a concentrating surface for biomolecules. The significance of this is discussed with regard to the possible role of soluble minerals and their surfaces in a geochemical model consistent with the evolution of the earth and the origin of life.

Orenberg, J. B.↗

Enrichment of Phosphates, Lead, and Mixed Soil–Organic Particles in INPs at the Southern Great Plains Site

Ice nucleating particles (INPs) are rare particles that initiate primary ice formation, a critical step required for subsequent important cloud microphysical processes that ultimately govern cloud phase and cloud radiative properties. Laboratory studies have found that organic-rich dusts, such as those found in soils, are more efficient INPs compared to mineral dust. However, the atmospheric relevance of these organic-rich dusts are not well understood, particularly in regions with significant agricultural activity. The Agricultural Ice nuclei at the Southern Great Plains field campaign (AGINSGP) was conducted in rural Oklahoma to investigate how soil dusts contribute to INP populations in the Great Plains. We present chemical characterization of ambient and ice crystal residual particles from a single day of sampling, using single particle mass spectrometry (SPMS) and scanning microscopy. Ambient particles were primarily carbonaceous or secondary aerosol, while the fraction of dust particles was higher in the residual particles. We also observed an unusual particle type consisting of a carbonaceous core mixed with dust fragments on the surface, which was found in higher proportion in residuals. Dust particles measured during residual sampling contained greater proportions of phosphate $(^{63}\text{PO}^-_2$ and $^{79}\text{PO}^-_3)$ and lead ( 206 Pb + ). Strong sulfate signals were not seen in the residual dust particles measured by the SPMS, while nitrate was slightly depleted relative to ambient dust. This study shows that organic-rich soils may be important contributors to the ambient INP population in agricultural regions.

54 ENVIRONMENTAL SCIENCES↗

Chitosan as a Canvas for Studies of Macromolecular Controls on CaCO 3 Biological Crystallization

A mechanistic understanding of how macromolecules, typically as an organic matrix, nucleate and grow crystals to produce functional biomineral structures remains elusive. Advances in structural biology indicate that polysaccharides (e.g., chitin) and negatively charged proteoglycans (due to carboxyl, sulfate, and phosphate groups) are ubiquitous in biocrystallization settings and play greater roles than currently recognized. This review highlights studies of CaCO 3 crystallization onto chitinous materials and demonstrates that a broader understanding of macromolecular controls on mineralization has not emerged. With recent advances in biopolymer chemistry, it is now possible to prepare chitosan-based hydrogels with tailored functional group compositions. By deploying these characterized compounds in hypothesis-based studies of nucleation rate, quantitative relationships between energy barrier to crystallization, macromolecule composition, and solvent structuring can be determined. Finally, this foundational knowledge will help researchers understand composition-structure-function controls on mineralization in living systems and tune the designs of new materials for advanced applications.

15 GEOTHERMAL ENERGY↗

Mineralogy of Meteorite Groups

Approximately 275 mineral species have been identified in meteorites, reflecting diverse redox environments, and, in some cases, unusual nebular formation conditions. Anhydrous ordinary, carbonaceous and R chondrites contain major olivine, pyroxene and plagioclase; major opaque phases include metallic Fe-Ni, troilite and chromite. Primitive achondrites are mineralogically similar. The highly reduced enstatite chondrites and achondrites contain major enstatite, plagioclase, free silica and kamacite as well as nitrides, a silicide and Ca-, Mg-, Mn-, Na-, Cr-, K- and Ti-rich sulfides. Aqueously altered carbonaceous chondrites contain major amounts of hydrous phyllosilicates, complex organic compounds, magnetite, various sulfates and sulfides, and carbonates. In addition to kamacite and taenite, iron meteorites contain carbides, elemental C, nitrides, phosphates, phosphides, chromite and sulfides. Silicate inclusions in IAB/IIICD and lIE iron meteorites consist of mafic silicates, plagioclase and various sulfides, oxides and phosphates. Eucrites, howardites and diogenites have basaltic to orthopyroxenitic compositions and consist of major pyroxene and calcic plagioclase and several accessory oxides. Ureilttes .are made up mainly of calcic, chromian olivine and low-Ca clinopyroxene embedded in a carbonaceous matrix; accessory phases include the C polymorphs graphite, diamond, lonsdaleite and chaoite as well as metallic Fe-Ni, troilite and halides. Angrites are achondrites rich in fassaitic pyroxene (i.e. , AI-Ti diopside); minor olivine with included magnesian kirschsteinite is also present. Martian meteorites comprise basalts, Iherzolites, a dunite and an orthopyroxenite. Major phases include various pyroxenes and olivine; minor to accessory phases include various sulfides, magnetite, chromite and Ca-phosphates. Lunar meteorites comprise mare basalts with major augite and calcic plagioclase and anorthositic breccias with major calcic plagioclase. Several meteoritic phases were formed by shock metamorphism. Martensite (a2-fe,Ni) has a distorted body-centered-cubic structure and formed by a shear transformation from taenite during shock reheating and rapid cooling. The C polymorphs diamond, lonsdaleite and chaoite formed by shock from graphite. Suessite formed in the North Haig ureilite by reduction of Fe and Si (possibly from olivine) via reaction with carbonaceous matrix material. Ringwoodite, the spinel form of (Mg,Fe)2Si04, and majorite, a polymorph of (Mg,Fe)Si03 with the garnet structure, formed inside shock veins in highly shocked ordinary chondrites. Secondary minerals in meteorite finds that formed during terrestrial weathering include oxides and hy-. droxides formed directly from metallic Fe-Ni by oxidation, phosphates formed by the alteration of schreibersite, and sulfates formed by alteration of troilite.

Rubin, Alan E.↗

The Role of Process-Directing Agents on Enamel Lesion Remineralization: Fluoride Boosters

The aim of this study was to investigate the effects of two process-directing agents (polyaspartic acid and osteopontin) used in a polymer-induced liquid-precursor (PILP) process on the remineralization of bacteria-induced enamel demineralization. Enamel demineralization lesions (depths of about 180–200 µm) were created and exposed to Streptococcus mutans, cultured with a 10% sucrose solution for 21 days, and remineralized using a PILP process (pH = 7.4, 14 days) with a calcium phosphate solution containing either polyaspartic acid or osteopontin in the presence or absence of fluoride (0.5 ppm). The specimens were examined under scanning electron microscopy. The fluoride was successfully incorporated into the PILP remineralization process for both polyaspartic acid and osteopontin. When the fluoride was added to the PILP remineralization solution, there was more uniform remineralization throughout the lesion than with either polyaspartic acid or osteopontin alone. However, in the absence of these process-directing agents, fluoride alone showed less remineralization with the formation of a predominantly surface-only layer. The PILP remineralization process relies on the ability of process-directing agents to stabilize calcium phosphate ions and holds promise for enamel lesion remineralization, and these agents, in the presence of fluoride, seem to play an important role as a booster or supplement in the continuation of remineralization by reducing the mineral gains at the surface layer.

59 BASIC BIOLOGICAL SCIENCES↗

Chemical Composition by the APXS along the Downhill Traverse of the Mars Exploration Rover Spirit at Gusev Crater

The Alpha Particle X-ray Spectrometer (APXS) onboard the Mars Exploration Rover Spirit continues to determine the elemental composition of samples at Gusev Crater. Starting around sol 600 the rover descended Husband Hill, which is part of the Columbia Hills, visited the inner basin with a large dune field, called 'El Dorado', and parked at Low Ridge to conserve energy during the martian winter. Many unique samples were discovered by the instruments onboard Spirit during her downhill traverse. Here, we report only on the chemical data obtained by the APXS. The compositions of some of the soil samples are comparable to the mean soil determined along the earlier traverse. However, a light-toned subsurface sample (disturbed by the rover wheels), called Dead Sea Samra , showed the highest sulfur content of all soil samples, the lowest Na, Mg, Al, Cl, K, Ca, Ti, Mn, and Zn, among the lowest Si and P, and among the highest Cr, Fe and Ni. Assuming ferric sulfate as a major mineral, large amounts of a pure silica phase must be present. Color and quantity of Dead Sea Samra resemble somewhat an earlier soil called Paso Robles , though the latter is a mixture of sulfates with phosphate-rich soil. Manganese in Dead Sea Samra is so low that the Fe/Mn ratio exceeds 300, a value that has never been found previously on Mars (Fe/Mn ratio of 46 for Gusev basalts), indicating that only Fe(3+) occurs. The dune field El Dorado contained granulated material that exhibited the highest Mg and Ni concentrations and the lowest S and Cl compared to all other soils implying an enrichment of olivine-rich sands. Two outcrops, called Algonquin and Comanche , revealed compositions that differ significantly from those of earlier outcrops as they have the highest concentrations of Mg, Fe, and Ni (except for Ni in Independence) and the lowest of Al, K (detection limit), Ca, and Ti of all brushed and almost all abraded rocks. Normative estimates assign them the highest olivine contents ever found for martian rocks and a very mafic nature based on their high Mg/(Mg+Fe) and low Al, Ca and Na. Their significantly high Ni contents point to a different source than the Gusev plains basalts. The elemental compositions of samples encountered during the downhill traverse revealed a larger chemical diversity of the Columbia Hills than the uphill trek already published.

Bruckner, J.↗

Binding mechanism and binding free energy of amino acids and citrate to hydroxyapatite surfaces as a function of crystallographic facet, pH, and electrolytes

Hydroxyapatite (HAP) is the major mineral phase in bone and teeth. The interaction of individual amino acids and citrate ions with different crystallographic HAP surfaces has remained uncertain for decades, creating a knowledge gap to rationally design interactions with peptides, proteins, and drugs. In this contribution, we quantify the binding mechanisms and binding free energies of the 20 end-capped natural amino acids and citrate ions on the basal (001) and prismatic (010)/(020) planes of hydroxyapatite at pH values of 7 and 5 for the first time at the molecular scale. We utilized over 1500 steered molecular dynamics simulations with highly accurate potentials that reproduce surface and hydration energies of (hkl) hydroxyapatite surfaces at different pH values. Charged residues demonstrate a much higher affinity to HAP than charge-neutral species due to the formation of superficial ion pairs and ease of penetration into layers of water molecules on the mineral surface. Binding free energies range from 0 to -60 kJ/mol and were determined with ~10% uncertainty. The highest affinity was found for citrate, followed by Asp(-) and Glu(-), and followed after a gap by Arg(+), Lys(+), as well as by His(+) at pH 5. The (hkl)-specific area density of calcium ions, the protonation state of phosphate ions, and subsurface directional order of the ions in HAP lead to surface-specific binding patterns. Amino acids without ionic side groups exhibit weak binding, between -3 and 0 kJ/mol, due to difficulties to penetrate the first layer of water molecules on the apatite surfaces. We explain recognition processes that remained elusive in experiments, in prior simulations, discuss agreement with available data, and reconcile conflicting interpretations. In conclusion, the findings can serve as useful input for the design of peptides, proteins, and drug molecules for the modification of bone and teeth-related materials, as well as control of apatite mineralization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fragments of ancient lunar crust: Ferroan noritic anorthosites from the descartes region of the Moon

Noritic anorthosite clasts from breccia 67016 have bulk compositions similar to that of the upper crust of the Moon and petrogenetic affinities with pristine ferroan anorthosites. Rb-Sr and Sm-Nd isotopic compositions of mineral separates from one of these clasts suggest very old (greater than or = 4.4 Ga) ages, but interpretation of these data is complicated by the multi-stage history of the clasts which involved magmatic crystallization, brecciation, subsolidus recrystallization, and sulfide metasomatism. These clasts record some of the earliest events on the Moon, including early crust formation, accretionary bombardment, and degassing of the lunar interior. Modal analyses of these clasts show they are now composed of about 70 percent plagioclase, 28 percent pyroxene, 2 percent troilite, and minor amounts of ilmenite and chromite. No metallic iron, phosphates, or other trace phases were observed. Olivine is very rare, occurring only as relicts within secondary troilite+pyroxene intergrowths which may reflect reaction of olivine with sulfurous vapors. PIXE proton microprobe analyses of the sulfides show that the metasomatism was accompanied by enrichments of Cu, Zn, Ni, Se, and Sb. The clasts have been only mildly shocked since the observed texture was established. Major and minor element mineral compositions are very homogeneous and strikingly similar to those of pristine ferroan anorthosites. Pyroxene compositions indicate equilibration temperatures of 850-900 C. Except for the sulfide and chalcophile element metasomatism, these clasts appear to be essentially monomict and probably represent a noritic member of the ferroan anorthosite suite. Their low Ni contents and Ni/Co ratios are consistent with the interpretation of these clasts as igneous rocks which have escaped mixing with meteoritic material.

Norman, M. D.↗

Media Robustness and Scalability of Phosphate Regulated Promoters Useful for Two-Stage Autoinduction in E. coli

A key challenge in synthetic biology is the successful utilization of characterized parts, such as promoters, in different biological contexts. We report the evaluation of the media robustness of a small library of E. coli PhoB regulated promoters that enable heterologous protein production in two-stage cultures. Expression levels were measured both in a rich Autoinduction Broth as well as a minimal mineral salts media. Expression was both media and promoter dependent. Of the 16 promoters tested, 4 were identified to have tightly controlled expression, which was also robust to media formulation. Improved promoter robustness led to more predictable scale up and consistent expression in instrumented bioreactors. Furthermore, this subset of PhoB activated promoters, useful for two-stage autoinduction, highlights the impact of the environment on the performance of biological parts and the importance of robustness testing in synthetic biology.

59 BASIC BIOLOGICAL SCIENCES↗

Electrochemically recovered struvite matches conventional fertilizers in soil nutrient supply

Phosphorus (P) is an essential macronutrient for agriculture, yet global reliance on finite phosphorite reserves raises concerns about long-term food and nutrient security. Struvite (MgNH 4 PO 4 ·6H 2 O), a mineral recovered from municipal wastewater, represents a sustainable and circular source of P, but uncertainty remains regarding its nutrient availability relative to conventional fertilizers. This study evaluated the fertilizer value and environmental safety of electrochemically recovered struvite (RecoP) in comparison with diammonium phosphate (DAP), triple superphosphate (TSP), and rock phosphate (RockP). Nutrient availability, potential contaminant concentrations, and soil P and nitrogen (N) dynamics were assessed using standardized chemical analyses and an 8-week incubation experiment across three soils with contrasting soil types. RecoP contained 14.7% citrate-soluble P, significantly greater than RockP and comparable to DAP and TSP. Across all soils, RecoP increased both readily available and moderately labile P pools (p < 0.01), matching the performance of conventional fast-release fertilizers. Despite containing approximately half the total of DAP, RecoP stimulated nitrification rates that were 2.2 times greater than the control and exceeded those of TSP, suggesting that fertilizer-derived N bioavailability, rather than total N loading, governed microbial N transformation responses. Concentrations of potentially toxic elements in RecoP were consistently well below US Environmental Protection Agency regulatory limits thresholds. Collectively, these results indicate that RecoP functions as a readily available source of both P and N, comparable to widely used conventional fertilizers, while meeting environmental safety standards. RecoP therefore represents a viable component of sustainable nutrient management strategies that support P recycling and agricultural productivity.

Kharal, Sudarshan [Ohio Univ., Athens, OH (United ↗