Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.     

A suspended-particle rosette multi-sampler for discrete biogeochemical sampling in low-particle-density waters

To enable detailed investigations of early stage hydrothermal plume formation and abiotic and biotic plume processes we developed a new oceanographic tool. The Suspended Particulate Rosette sampling system has been designed to collect geochemical and microbial samples from the rising portion of deep-sea hydrothermal plumes. It can be deployed on a remotely operated vehicle for sampling rising plumes, on a wire-deployed water rosette for spatially discrete sampling of non-buoyant hydrothermal plumes, or on a fixed mooring in a hydrothermal vent field for time series sampling. It has performed successfully during both its first mooring deployment at the East Pacific Rise and its first remotely-operated vehicle deployments along the Mid-Atlantic Ridge. It is currently capable of rapidly filtering 24 discrete large-water-volume samples (30–100 L per sample) for suspended particles during a single deployment (e.g. >90 L per sample at 4–7 L per minute through 1 μm pore diameter polycarbonate filters). The Suspended Particulate Rosette sampler has been designed with a long-term goal of seafloor observatory deployments, where it can be used to collect samples in response to tectonic or other events. It is compatible with in situ optical sensors, such as laser Raman or visible reflectance spectroscopy systems, enabling in situ particle analysis immediately after sample collection and before the particles alter or degrade.     

Nebular mixing constrained by the Stardust samples

Abstract— Using X‐ray microprobe analysis of samples from comet Wild 2 returned by the Stardust mission, we determine that the crystalline Fe‐bearing silicate fraction in this Jupiter‐family comet is greater than 0.5. Assuming this mixture is a composite of crystalline inner solar system material and amorphous cold molecular cloud material, we deduce that more than half of Wild 2 has been processed in the inner solar system. Several models exist that explain the presence of crystalline materials in comets. We explore some of these models in light of our results.     

Calcium promotes cadmium elimination as vaterite grains by tobacco trichomes

In tobacco plants, elimination of Zn and Cd via the production of Ca-containing grains at the top of leaf hairs, called trichomes, is a potent detoxification mechanism. This study examines how Cd is incorporated in these biominerals, and how calcium growth supplement modifies their nature. Scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX), microfocused X-ray diffraction (μ-XRD), and microfocused X-ray absorption near edge structure (μ-XANES) spectroscopy were used to image the morphology of the grains, identify the crystallized mineral phases, and speciate Cd, respectively. The mineralogy of the grains and chemical form of Cd varied with the amount of Ca. When tobacco plants were grown in a nutrient solution containing 25 μM Cd and low Ca supplement (Ca/Cd = 11 mol ratio), most of the grains were oblong-shaped and low-Cd-substituted calcite. When exposed to the same amount of Cd and high Ca supplement (Ca/Cd = 131 mol ratio), grains were more abundant and diverse in compositions, and in total more Cd was eliminated. Most grains in the high Ca/Cd experiment were round-shaped and composed predominantly of Cd-substituted vaterite, a usually metastable calcium carbonate polymorph, and subordinate calcite. Calcium oxalate and a Ca amorphous phase were detected occasionally in the two treatments, but were devoid of Cd. The biomineralization of cadmium and implications of results for Cd exposure of smokers and phytoremediation are discussed.     

Iron oxyhydroxide mineralization on microbial extracellular polysaccharides

Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence (μXRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolated from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.