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.     

High-Resolution Records of the Holocene Paleoenvironmental Variation Reflected by Carbonate and Its Isotopic Compositions in Bosten Lake and Response to Glacial Activities

Abstract: The Early Holocene paleoclimate in Bosten Lake on the northern margin of the Tarim Basin, southern Xinjiang, is reconstructed through an analysis of a 953 cm long core (BSTC2000) taken from Bosten Lake. Multiple proxies of this core, including the mineral components of carbonate, carbonate content, stable isotopic compositions of carbonate, Ca/Sr, TOC and C/N and C/S of organic matter, are used to reconstruct the climatic change since 8500 a B.P. The chronology model is made by nine AMS 14C ages of leaves, seeds and organic matter contained in two parallel cores. The climate was cold and wet during 8500 to 8100 a B.P. Temperature increased from 8100 to 6400 a B.P., the climate was warm and humid, and the lake expanded. The lake level was highest during this stage. Then from 6400 to 5100 a B.P., the climate became cold and the lake level decreased slightly. During the late mid-Holocene, the climate was hot and dry from 5100 to 3100 a B.P., but there was a short cold period during 4400 to 3800 a B.P. At this temporal interval, a mass of ice and snow melting water supplied the lake at the early time and made the lake level rise. The second highest lake level stage occurred during 5200 to 3800 a B.P. The climate was cool and wet during 3100 to 2200 a B.P., when the lake expanded with decreasing evaporation. The lake had the last short-term high level during 3100 to 2800 a B.P. After this short high lake level period, the lake shrank because of the long-term lower temperature and reduced water supply. From 2200 to 1200 a B.P., the climate was hot and dry, and the lake shrank greatly. Although the temperature decreased somewhat from 1200 a B.P. to the present, the climate was warm and dry. The lake level began to rise a little again, but it did not reach the river bed altitude of the Konqi River, an outflow river of the Bosten Lake.     

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.     

Quartz latite rheoignimbrite flows of the Etendeka Formation,north-western Namibia

The Etendeka Formation of north-western Namibia consists of a sequence of interbedded quartz latites and tholeiitic basalts and forms part of the Karoo Igneous Province in southern Africa. The age of the Etendeka Formation is approximately 130–135 Ma. The quartz latites make up a significant proportion of the stratigraphic succession (<25% of the total stratigraphic thickness) and form as much as 60% of the outcrop area in the southern Etendeka. Apart from some systematic differences between pitchstones and devitrified quartz latite, largely explained by alteration processes, individual quartz latite units exhibit remarkably uniform compositions with no significant vertical or lateral variation. Geochemistry can be used as a primary criterion for the correlation of major quartz latite units over much of the southern Etendeka area enabling the reconstruction of the Etendeka Formation stratigraphy in this region. Individual quartz latite units occur as voluminous (400–2600 km³), widespread (up to 8800 km²), sheet-like deposits typically between 40 and 300 m thick. Each unit consists of basal, main and upper zones. The main zone generally constitutes over 70% of the thickness of the unit and typically consists of texturally featureless devitrified quartz latite. In contrast the basal and upper zones of the flow are characterised by flow banding, pitchstone lenses and breccia, with rare occurrences of pyroclastic textures. The quartz latites are sparsely porphyritic (<10% phenocrysts) with glassy or devitrified groundmass textures. The phenocrysts consist of plagioclase, pyroxene, titanomagnetite and rare ilmenite. Pyroxene geothermometry indicates high (1000–1100°C) temperatures of crystallisation which, coupled with the absence or primary hydrous phases, indicates that the quartz latites were relatively hot, H₂O-undersaturated magmas. The quartz latites display features common to both rhyolite lavas and ignimbrites and are clearly the products of an unusual eruption style. The local preservation of pyroclastic textures and the broad areal extent of these units lead to the conclusion that the quartz latites are high-temperature rheomorphic ignimbrites (i.e. rheoignimbrites). A combination of high eruption temperature and relatively low viscosity helps to explain the often completely welded and homogeneous textures observed in most quartz latite outcrops in the Etendeka area.     

An Analysis of Spatial and Temporal Dimension of Drought Vulnerability in Turkey Using the Standardized Precipitation Index

Drought has become a recurrent phenomenon in Turkey in the last few decades. Significant drought conditions were observed during years of late 1980s and the trend continued in the late 1990s. The countrys agricultural sector and water resources have been under severe constraints from the recurrent droughts. In this study, spatial and temporal dimensions of meteorological droughts in Turkey have been investigated from vulnerability concept. The Standardized Precipitation Index (SPI) method was used to detail geographical variations in the drought vulnerability based on frequency and severity of drought events at multiple time steps. Critical (threshold) rainfall values were derived for each station at multiple-time steps in varying drought categories to determine least amount of rainfall required to avoid from drought initiation. The study found that drought vulnerability portrays a very diverse but consistent picture with varying time steps. At regional scale, south-eastern and eastern Anatolia are characterized with moderate droughts at shorter time steps, while the occurrence of severe droughts at shorter time steps is observed at non-coastal parts of the country. A similar picture was observed with very severe droughts. The critical (threshold) values exhibited rising numbers during the growing season at 3-month step in the South-eastern Anatolia, which might have significant consequences considering presence of large irrigation projects under-development in the region. In general, rainfall amounts required for non-drought conditions decrease from the coastal parts toward the interiors with increasing time steps.