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At least 199 records · Page 11

Unexpected mechanism for glucose-primed soil organic carbon mineralization under an anaerobic–aerobic transition

Redox reactions are important for cycling of carbon (C) in soils frequently subject to fluctuations in redox conditions, such as wetland soils, which contribute around one third of the global terrestrial C reservoir. Priming effects (PE), induction of changes in C mineralization due to additions of energy-rich organic carbon (OC) substrates, have been largely ignored during redox transitions in current modelling and experimental efforts for evaluating C cycles. In this study, we investigated the effects of glucose input on the mineralization of soil OC during an anaerobic-aerobic transition. Substantially more soil OC was mineralized under aerobic conditions in samples that received glucose under preceding anaerobic conditions compared to controls that did not receive glucose and to samples that received glucose under aerobic-only conditions. Our results reveal a novel PE by which glucose indirectly primes the mineralization of soil OC by increasing the reductive release of iron oxide-associated OC under anaerobic conditions, followed by a dramatic positive PE when aerobic conditions are reestablished. Inclusion of this novel indirect priming mechanism is crucial for accurately predicting the contribution of atmospheric greenhouse gases from soils experiencing redox fluctuations (e.g.,wetlands).

54 ENVIRONMENTAL SCIENCES↗

Loss of biological control of enamel mineralization in amelogenin-phosphorylation-deficient mice

Amelogenin, the most abundant enamel matrix protein, plays several critical roles in enamel formation. Importantly, we previously found that the singular phosphorylation site at Ser16 in amelogenin plays an essential role in amelogenesis. Studies of genetically knock-in (KI) modified mice in which Ser16 in amelogenin is substituted with Ala that prevents amelogenin phosphorylation, and in vitro mineralization experiments, have shown that phosphorylated amelogenin transiently stabilizes amorphous calcium phosphate (ACP), the initial mineral phase in forming enamel. Furthermore, KI mice exhibit dramatic differences in the enamel structure compared with wild type (WT) mice, including thinner enamel lacking enamel rods and ectopic surface calcifications. Here, we now demonstrate that amelogenin phosphorylation also affects the organization and composition of mature enamel mineral. In this work, we compared WT, KI, and heterozygous (HET) enamel and found that in the WT elongated crystals are co-oriented within each rod, however, their c-axes are not aligned with the rods' axes. In contrast, in rod-less KI enamel, crystalline c-axes are less co-oriented, with misorientation progressively increasing toward the enamel surface, which contains spherulites, with a morphology consistent with abiotic formation. Furthermore, we found significant differences in enamel hardness and carbonate content between the genotypes. ACP was also observed in the interrod of WT and HET enamel, and throughout aprismatic KI enamel. In conclusion, amelogenin phosphorylation plays crucial roles in controlling structural, crystallographic, mechanical, and compositional characteristics of dental enamel. Thus, loss of amelogenin phosphorylation leads to a reduction in the biological control over the enamel mineralization process.

59 BASIC BIOLOGICAL SCIENCES↗

Interplay of microbial communities with mineral environments in coralline algae

Coralline algae are worldwide carbonate builders, considered to be foundational species and biodiversity hotspots. Coralline habitats face increasing pressure from human activities and effects related to Global Change, yet their ecological properties and adaptive responses remain poorly understood. The relationships of the algal microbiota with the mineral bioconstructions, as well as plasticity and resilience of coralline holobionts in a changing environment, are of particular interest. In the Gulf of California, Neogoniolithon trichotomum (Rhodophyta) is the main carbonate builder in tidal pools. We performed a multi-disciplinary assessment of the N. trichotomum microstructure using XRD, SEM microscopy and SR-FTIR spectromicroscopy. In the algal perithallus, magnesium-calcite and aragonite were spatially segregated and embedded in a polysaccharide matrix (rich in sulfated polysaccharides). Mg-calcites (18-19 mol% Mg) were the main mineral components of the thallus overall, followed by iron carbonates related to dolomite (ankerite) and siderite. Minerals of late evaporitic sequences (sylvite and bischofite) were also present, suggesting potential halophilic microenvironments within the algal thalli. The diverse set of abundant halophilic, halotolerant and oligotrophic taxa, whose abundance increase in the summer, further suggests this condition. We created an integrated model, based on environmental parameters and the microbiota distribution, that identified temperature and nutrient availability (particularly nitrate and silicate) as the main parameters related to specific taxa patterns. Among these, Hahella, Granulossicoccus, Ferrimonas, Spongiibacteraceae and cyanobacterial Xenococcaceae and Nostocaceae change significantly between seasons. These bacterial components might play relevant roles in algal plasticity and adaptive responses to a changing environment. This study contributes to the understanding of the interplay of the prokaryotic microbiota with the mineral microenvironments of coralline algae. Because of their carbonates with potential resistance to dissolution in a higher pCO 2 world and their seasonally dynamic bacteria, coralline algae are relevant targets to study coastal resilience and carbonated systems responses to changing environments.

54 ENVIRONMENTAL SCIENCES↗

Moisture-mineral interactions drive bacterial and organic matter turnover in glacier-sourced riparian sediments undergoing pedogenesis

Glacial recession is occurring at unprecedented rates resulting in increased sediment accumula-tions in some riverine ecosystems. Increased sediment deposition has implications for ecosystem stability (e.g., floods and river paths) and environmental services (e.g., carbon sequestration). Soils and sediments have an enormous potential to retain carbon (C), predominantly due to sorp-tion to mineral surfaces. However, C persistence may be sensitive to climate-change induced temperature and moisture variations. We coupled ultrahigh resolution organic matter composition classification with bacterial characterization and respiration measurements to test the combined effects of temperature (4 vs 20°C) and moisture (50 vs 100% water-filled pore space) on C turn-over in sediments maintained under different mineralogical conditions (illite-amended vs non-amended). Here we show that the inhibition of CO 2 emissions from the combined effect of in-creased moisture content and illite was reflected in the turnover of key molecular signatures, such as the nominal oxidation state of C, often irrespective of temperature. However, shifts in bacteri-al communities from a coupled moisture-mineral interaction, were temperature-dependent. Our results highlight the importance of moisture in driving mineral-organic interactions and suggest that C in clay-rich, water-saturated sediments is both thermodynamically unfavorable and miner-al-protected from microbial consumption.

58 GEOSCIENCES↗

Characterizing the localization of organic C on mineral surfaces: a correlative microscopy/spectroscopy approach

It is estimated that organic carbon (OC) in soils exceeds the amount of OC in atmosphere and in vegetation pools combined.1 Given the current changes in climate and increasing temperatures in the environment, the fraction of OC sequestered in soils and sediments is more sensitive to decomposition and release as CO 2 in the atmosphere. Evidence implies that sorption and association of dissolved OC with inorganic soil components, i.e., soil minerals, is a key mechanism that contributes to stabilization and retention of OC in soil environment. Studies have shown a direct correlation between sorption of dissolved OC and soil mineral surface properties and their surface area. In addition, properties of organic compounds such as chemical structure and functional groups play a significant role in interaction of dissolved organic species with mineral surfaces. Association of OC with minerals via ligand exchange reactions, polyvalent tertiary bonding, or complexation with metal ions, is found to be preferential and dependent on the organic compounds’ functional groups.

54 ENVIRONMENTAL SCIENCES↗

Understanding Trace Iron and Chromium Incorporation During Gibbsite Crystallization and Effects on Mineral Dissolution

Incorporation of pollutants, e.g., heavy metals, or critical elements, e.g., lithium, as impurities in mineral phases can significantly affect their mobility or sequestration in the environment. Even when present at low concentrations, impurities can alter the solubility and reactivity of the host mineral. Here, in this study, we investigate the incorporation of trace amounts of iron (Fe 3+ ) and chromium (Cr 3+ ) during the crystal growth of the aluminum (Al 3+ ) hydroxide, gibbsite, a major component of bauxite ores, an important soil mineral, and a dominant mineral phase in stored radioactive wastes. Using a comprehensive suite of analytical techniques, we show that both Cr 3+ and Fe 3+ can be incorporated into the gibbsite lattice during coprecipitation by replacing Al 3+ in octahedral sites. These small amounts are consistent with limited to no structural isomorphism shared between Al 3+ and Cr 3+ /Fe 3+ hydroxide precipitates, nor room temperature miscibility of their isostructural M 2 O 3 oxide forms, in contrast with oxyhydroxide forms where Al 3+ and Fe 3+ share similar structural topologies. Despite the limited uptake of Cr 3+ /Fe 3+ , we show that these impurities have significant implications for gibbsite dissolution behavior. The limited uptake of Cr 3+ /Fe 3+ (e.g. 0.43% Cr 3+ and 0.4% Fe 3+ ), we show that these impurities have significant implications for gibbsite dissolution behavior and subsequent reactivity in complex environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamics of Metal Carbonates and Bicarbonates and Their Hydrates for Mg, Ca, Fe, and Cd Relevant to Mineral Energetics

The heats of formation of carbonate, bicarbonate and bicarbonate/hydroxide metal complexes and hydrated versions these complexes of Mg 2+ , Ca 2+ , Fe 2+ , and Cd 2+ are predicted from atomization energies using correlated molecular orbital theory at the CCSD(T) level extrapolated to the complete basis set limit following the Feller-Peterson-Dixon (FPD) approach. Using the calculated gas phase values and the available experimental solid state values, the cohesive energies of selected minerals were calculated. The gas phase decomposition energies into MO, CO 2 and H 2 O follow the order Mg ~ Ca > Cd ~ Fe, and correlate with the hardness of the metal +2 ions. Gas phase hydration energies show that the order is Mg > Fe > Ca ~ Cd. There are a number of bulk hydrated Mg and Ca complexes that occur as minerals but there are few if any for Fe and Cd, suggesting that a number of factors are important in determining the stability of the bulk mineral hydrates. The FPD heats of formation were used to benchmark a range of density functional theory exchange-correlation functionals, including those commonly used in solid state mineral calculations. None of the functionals provided chemical accuracy agreement (± 1 kcal/mol) with the FPD results The best functionals are ωB97X and ωB97X-D with mean average unsigned errors of 10 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Recognition at Mineral Interfaces: Implications for the Beneficiation of Rare Earth Ores

Ce-bastnäsite is the single largest mineral source for light rare-earth elements. In view of the growing industrial importance of rare-earth minerals, it is critical to develop more efficient methods for separating the valuable rare-earth-containing minerals from the surrounding gangue. In this work, we employ a combination of periodic density functional theory (DFT) and molecular mechanics (MM) calculations together with the de novo molecular design program HostDesigner to identify bis-phosphinate ligands that preferentially bind to the (100) Ce-bastnäsite surface rather than the (104) calcite surface. DFT calculations for a simple phosphinate ligand were employed to qualitatively understand key behaviors involved in ligand–metal, ligand–solvent, and solvent–metal interactions. These insights were then used to guide the search for flexible, rigid, and semirigid hydrocarbon linkers to identify candidate bis-phosphinate ligands with the potential to bind preferentially to Ce-bastnäsite. Among the five most promising bis-phosphinate ligands suggested by theoretical studies, three ligands were synthesized and their adsorption characteristics to bastnäsite (100) interfaces were characterized using vibrational sum-frequency (vSFG) spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and isothermal titration calorimetry (ITC). The efficacy of the selective interfacial molecular binding was demonstrated by identifying a bis-phosphinate ligand capable of providing an overall higher surface coverage of alkyl groups relative to a monophosphinate ligand. The results highlight the interplay between adsorption binding strength and maximum surface coverage in determining ligand efficiency to render the mineral surface hydrophobic. DFT calculations further indicate that all tested ligands have higher affinity for Ce-bastnäsite than for calcite. Finally, this is consistent with the ITC data showing stronger adsorption enthalpy to bastnäsite than to calcite, making these ligands promising candidates for selective flotation of Ce-bastnäsite.

58 GEOSCIENCES↗

Deciphering the incipient phases of ice-mineral interactions as a precursor of physical weathering

Atmospheric ice formation influences Earth’s global hydrological cycle and is widely studied. In contrast, the intricacies of freeze-thaw processes in natural soils, such as whether ice nucleation on mineral surfaces is affected by biological activity, needs additional insight. In-situ ice formation on unreacted grains and grains exposed to field and laboratory weathering conditions was studied at the submicron scale using an ice nucleation chamber interfaced with an environmental scanning electron microscope. We found that ice nucleation activity differed by treatment. Unreacted grains and fungal-mineral interfaces displayed ice formation along edges and fractures. Conversely, grains with mineral coatings, seemingly from biological activity, exhibited water uptake and ice nucleation on the coatings themselves. Our results suggest that in natural soils, mineral coatings can influence where and how ice forms. This ultimately affects weathering and nutrient release to the biosphere, with direct consequences for interactions between the atmosphere and geosphere.

Lybrand, Rebecca A.↗

Organo–organic and organo–mineral interfaces in soil at the nanometer scale

The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo–mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo–organic interfaces in contrast to exclusively organo–mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo–organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo–mineral interface, 88% (72–92%) and 33% (16–53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo–organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.

58 GEOSCIENCES↗

Iron mineral dissolution releases iron and associated organic carbon during permafrost thaw

It has been shown that reactive soil minerals, specifically iron(III) (oxyhydr)oxides, can trap organic carbon in soils overlying intact permafrost, and may limit carbon mobilization and degradation as it is observed in other environments. However, the use of iron(III)-bearing minerals as terminal electron acceptors in permafrost environments, and thus their stability and capacity to prevent carbon mobilization during permafrost thaw, is poorly understood. We have followed the dynamic interactions between iron and carbon using a space-for-time approach across a thaw gradient in Abisko (Sweden), where wetlands are expanding rapidly due to permafrost thaw. We show through bulk (selective extractions, EXAFS) and nanoscale analysis (correlative SEM and nanoSIMS) that organic carbon is bound to reactive Fe primarily in the transition between organic and mineral horizons in palsa underlain by intact permafrost (41.8 ±10.8 mg carbon per g soil, 9.9 to 14.8% of total soil organic carbon). During permafrost thaw, water-logging and O 2 limitation lead to reducing conditions and an increase in abundance of Fe(III)-reducing bacteria which favor mineral dissolution and drive mobilization of both iron and carbon along the thaw gradient. By providing a terminal electron acceptor, this rusty carbon sink is effectively destroyed along the thaw gradient and cannot prevent carbon release with thaw.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super-hydration and reduction of manganese oxide minerals at shallow terrestrial depths

Manganese oxides are ubiquitous marine minerals which are redox sensitive. As major components of manganese nodules found on the ocean floor, birnessite and buserite have been known to be two distinct water-containing minerals with manganese octahedral interlayer separations of ~7 Å and ~10 Å, respectively. We show here that buserite is a super-hydrated birnessite formed near 5 km depth conditions. As one of the most hydrous minerals containing ca. 34.5 wt. % water, super-hydrated birnessite, i.e., buserite, remains stable up to ca. 70 km depth conditions, where it transforms into manganite by releasing ca. 24.3 wt. % water. Subsequent transformations to hausmannite and pyrochroite occur near 100 km and 120 km depths, respectively, concomitant with a progressive reduction of Mn 4+ to Mn 2+ . Our work forwards an abiotic geochemical cycle of manganese minerals in subduction and/or other aqueous terrestrial environments, with implications for water storage and cycling, and the redox capacity of the region.

36 MATERIALS SCIENCE↗

Global stocks and capacity of mineral-associated soil organic carbon

Abstract Soil is the largest terrestrial reservoir of organic carbon and is central for climate change mitigation and carbon-climate feedbacks. Chemical and physical associations of soil carbon with minerals play a critical role in carbon storage, but the amount and global capacity for storage in this form remain unquantified. Here, we produce spatially-resolved global estimates of mineral-associated organic carbon stocks and carbon-storage capacity by analyzing 1144 globally-distributed soil profiles. We show that current stocks total 899 Pg C to a depth of 1 m in non-permafrost mineral soils. Although this constitutes 66% and 70% of soil carbon in surface and deeper layers, respectively, it is only 42% and 21% of the mineralogical capacity. Regions under agricultural management and deeper soil layers show the largest undersaturation of mineral-associated carbon. Critically, the degree of undersaturation indicates sequestration efficiency over years to decades. We show that, across 103 carbon-accrual measurements spanning management interventions globally, soils furthest from their mineralogical capacity are more effective at accruing carbon; sequestration rates average 3-times higher in soils at one tenth of their capacity compared to soils at one half of their capacity. Our findings provide insights into the world’s soils, their capacity to store carbon, and priority regions and actions for soil carbon management.

54 ENVIRONMENTAL SCIENCES↗

Emergent temperature sensitivity of soil organic carbon driven by mineral associations

Abstract Soil organic matter decomposition and its interactions with climate depend on whether the organic matter is associated with soil minerals. However, data limitations have hindered global-scale analyses of mineral-associated and particulate soil organic carbon pools and their benchmarking in Earth system models used to estimate carbon cycle–climate feedbacks. Here we analyse observationally derived global estimates of soil carbon pools to quantify their relative proportions and compute their climatological temperature sensitivities as the decline in carbon with increasing temperature. We find that the climatological temperature sensitivity of particulate carbon is on average 28% higher than that of mineral-associated carbon, and up to 53% higher in cool climates. Moreover, the distribution of carbon between these underlying soil carbon pools drives the emergent climatological temperature sensitivity of bulk soil carbon stocks. However, global models vary widely in their predictions of soil carbon pool distributions. We show that the global proportion of model pools that are conceptually similar to mineral-protected carbon ranges from 16 to 85% across Earth system models from the Coupled Model Intercomparison Project Phase 6 and offline land models, with implications for bulk soil carbon ages and ecosystem responsiveness. To improve projections of carbon cycle–climate feedbacks, it is imperative to assess underlying soil carbon pools to accurately predict the distribution and vulnerability of soil carbon.

54 ENVIRONMENTAL SCIENCES↗

Mechanisms and heterogeneity of in situ mineral processing by the marine nitrogen fixer Trichodesmium revealed by single-colony metaproteomics

The keystone marine nitrogen fixer Trichodesmium thrives in high-dust environments. While laboratory investigations have observed that Trichodesmium colonies can access the essential nutrient iron from dust particles, less clear are the biochemical strategies underlying particle–colony interactions in nature. Here we demonstrate that Trichodesmium colonies engage with mineral particles in the wild with distinct molecular responses. We encountered particle-laden Trichodesmium colonies at a sampling location in the Southern Caribbean Sea; microscopy and synchrotron-based imaging then demonstrated heterogeneous associations with iron oxide and iron-silicate minerals. Metaproteomic analysis of individual colonies by a new low-biomass approach revealed responses in biogeochemically relevant proteins including photosynthesis proteins and metalloproteins containing iron, nickel, copper, and zinc. The iron-storage protein ferritin was particularly enriched implying accumulation of mineral-derived iron, and multiple iron acquisition pathways including Fe(II), Fe(III), and Fe-siderophore transporters were engaged. While the particles provided key trace metals such as iron and nickel, there was also evidence that Trichodesmium was altering its strategy to confront increased superoxide production and metal exposure. Chemotaxis regulators also responded to mineral presence suggesting involvement in particle entrainment. These molecular responses are fundamental to Trichodesmium’s ecological success and global biogeochemical impact, and may contribute to the leaching of particulate trace metals with implications for global iron and carbon cycling.

Held, Noelle A.↗

Cyclic strain enhances the early stage mineral nucleation and the modulus of demineralized bone matrix

The adaptive response of bones to mechanical loading is essential for musculoskeletal development. Despite the importance of collagen in bone mineralization, little is known about how cyclic strain influences physicochemical responses of collagen, especially at the early stage of mineralization when the levels of strain are higher than those in mature bones. The findings in this study show that, without any cell-mediated activity, cyclic strain increases nucleation rates of calcium phosphate (CaP) nanocrystals in highly-organized collagen matrices. The cyclic strain enhances the transport of mineralization fluids with nucleation precursors into the matrix, thus forming more CaP nanocrystals and increasing the elastic modulus of the collagen matrix. The results also suggest that the multiscale spatial distribution of nanocrystals in the fibrous collagen network determines tissue-level mechanical properties more critically than the total mineral content. Furthermore, by linking nano- and micro-scale observations with tissue-level mechanical properties, we provide new insights into designing better biomaterials.

36 MATERIALS SCIENCE↗

Oxygen isotopes of anhydrous primary minerals show kinship between asteroid Ryugu and comet 81P/Wild2

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here, we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16 O-rich (associated with refractory inclusions) and 16 O-poor (associated with chondrules). Both the 16 O-rich and 16 O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outward. The abundance ratios of the 16 O-rich to 16 O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

79 ASTRONOMY AND ASTROPHYSICS↗

Jeankempite, Ca 5 (AsO 4 ) 2 (AsO 3 OH) 2 (H 2 O) 7 , a new arsenate mineral from the Mohawk Mine, Keweenaw County, Michigan, USA

Abstract Jeankempite, Ca 5 (AsO 4 ) 2 (AsO 3 OH) 2 (H 2 O) 7 , is a new mineral species (IMA2018-090) discovered amongst coatings of arsenate minerals on oxidised copper arsenides from the Mohawk No. 2 mine, Mohawk, Keweenaw County, Michigan, USA. The new mineral occurs as lamellar bundles of colourless to white plates up to 1 mm wide and is visually indistinguishable from guérinite, with which it forms intergrowths. Jeankempite is transparent to translucent with a waxy lustre and white streak, is non-fluorescent under longwave and shortwave ultraviolet illumination, has a Mohs hardness of ~1.5 and brittle tenacity with uneven fracture. Crystals are flattened on {01 $\bar{1}$ } and exhibit perfect cleavage on {01 $\bar{1}$ }. Optically, jeankempite is biaxial (+), α = 1.601(2), β = 1.607(2), γ = 1.619(2) (white light); 2V meas. = 72(2)° and 2V calc. = 71.0°. The empirical formula is (Ca 4.97 Na 0.013 Mg 0.017 )(As 3.99 S 0.01 ) 4 O 23 H 16 , based on 23 O and 16 H atoms per formula unit. Thermogravimetric analysis indicates that jeankempite undergoes four weight losses totalling 16.82%, close to the expected loss of 16.30%, corresponding to eight H 2 O. Jeankempite is triclinic, P $\bar{1}$ , a = 6.710(6), b = 14.901(14), c = 15.940(15) Å, α = 73.583(12)°, β = 81.984(12)°, γ = 82.754(12)°, V = 1507(2) Å 3 and Z = 3. The final structure was refined to R 1 = 0.0591 for 2781 reflections with I obs > 3σ I . The crystal structure of jeankempite is built from a network of edge- and vertex-sharing CaO 6 , CaO 7 and AsO 4 polyhedra, and we hypothesise that the new mineral has formed due to a topotactic reaction brought on by dehydration of preexisting guérinite.

Mineralogy↗