Combining sequential extractions with bulk and micro X-ray spectroscopy to elucidate iron and phosphorus speciation in sediments of an iron-treated peat lake.

In shallow lakes, mobilization of legacy phosphorus (P) from the sediments can be the main cause for persisting eutrophication after reduction of external P input. In-lake remediation measures can be applied to reduce internal P loading and to achieve ecosystem recovery. The eutrophic shallow peat lake Terra Nova (The Netherlands) was treated with iron (Fe) to enhance P retention in the sediment.

Sc, Zr, Hf, and Mn Metal Nanoparticles: Reactive Starting Materials for Synthesis Near Room Temperature.

Zerovalent scandium, zirconium, hafnium, and manganese nanoparticles are prepared by reduction of ScCl, ZrCl, HfCl, and MnCl with lithium or sodium naphthalenide in a one-pot, liquid-phase synthesis. Small-sized monocrystalline nanoparticles are obtained with diameters of 2.4 ± 0.

Np(V) Retention at the Illite du Puy Surface.

In this study, Np(V) retention on Illite du Puy (IdP) was investigated since it is essential for understanding the migration behavior of Np in argillaceous environments. The presence of structural Fe(III) and Fe(II) in IdP was confirmed by Fe K-edge X-ray absorption near-edge structure (XANES) and Fe Mössbauer spectroscopy. In batch sorption experiments, a higher Np sorption affinity to IdP was found than to Wyoming smectite or iron-free synthetic montmorillonite.

Characteristic of phosphorus rich compounds in the incinerated sewage sludge ashes: a case for sustainable waste management.

Growing concern over mineral resources supply forces us to search for alternative sources of Phosphorus. The possibility to recover phosphorus from incinerated sewage sludge ashes appears to be an important aspect in anthropogenic phosphorus cycle and sustainable economy. To make phosphorus recovery efficient it is important to learn the chemical and mineral composition of ash and phosphorus speciation.

Phonon confinement and interface lattice dynamics of ultrathin high- rare earth sesquioxide films: the case of EuO on YSZ(001).

The spatial confinement of atoms at surfaces and interfaces significantly alters the lattice dynamics of thin films, heterostructures and multilayers. Ultrathin films with high dielectric constants (high-) are of paramount interest for applications as gate layers in current and future integrated circuits. Here we report a lattice dynamics study of high- EuO films with thicknesses of 21.

Spatiotemporal Mineral Phase Evolution and Arsenic Retention in Microfluidic Models of Zerovalent Iron-Based Water Treatment.

Arsenic (As) is a toxic element, and elevated levels of geogenic As in drinking water pose a threat to the health of several hundred million people worldwide. In this study, we used microfluidics in combination with optical microscopy and X-ray spectroscopy to investigate zerovalent iron (ZVI) corrosion, secondary iron (Fe) phase formation, and As retention processes at the pore scale in ZVI-based water treatment filters. Two 250 μm thick microchannels filled with single ZVI and quartz grain layers were operated intermittently (12 h flow/12 h no-flow) with synthetic groundwater (pH 7.

Evaluation of thallium isotopic fractionation during the metallurgical processing of sulfides: An update.

In this study, we report combined Tl isotopic and Tl mineralogical and speciation data from a set of Tl-rich sulfide concentrates and technological wastes from hydrometallurgical Zn extraction. We also present the first evaluation of Tl isotopic ratios over a cycle of sulfide processing, from the ore flotation to pyro- and hydrometallurgical stages. The results demonstrate that the prevailing Tl form in all samples is Tl(I), without any preferential incorporation into sulfides or Tl-containing secondary phases, indicating an absence of Tl redox reactions.

Photoluminescence of Fully Inorganic Colloidal Gold Nanocluster and Their Manipulation Using Surface Charge Effects.

Fully inorganic, colloidal gold nanoclusters (NCs) constitute a new class of nanomaterials that are clearly distinguishable from their commonly studied metal-organic ligand-capped counterparts. As their synthesis by chemical methods is challenging, details about their optical properties remain widely unknown. In this work, laser fragmentation in liquids is performed to produce fully inorganic and size-controlled colloidal gold NCs with monomodal particle size distributions and an fcc-like structure.

Lattice Dynamics and Structural Phase Transitions in EuO.

Using the density functional theory, we study the structural and lattice dynamical properties of europium sesquioxide (EuO) in the cubic, trigonal, and monoclinic phases. The obtained lattice parameters and energies of the Raman modes show a good agreement with the available experimental data. The Eu-partial phonon density of states calculated for the cubic structure is compared with the nuclear inelastic scattering data obtained from a 20 nm thick EuO film deposited on a YSZ substrate.

Towards Heteroleptic Dicoordinate Cu Complexes.

In this work we detail our efforts to systematically generate stable dicoordinate Cu complexes. Initial experiments via metathesis reactions of a bulky potassium carbazolide (RK) with copper(II) salts indeed yielded a stable product, RCuOTf (1). However, subsequent attempts to grasp systematic synthetic access to complexes of the type RCuX (X=monoanionic ligand) proved difficult as many of the complexes rapidly decomposed in solution.

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration.

We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.

A multi-technique study of altered granitic rock from the Krunkelbach Valley uranium deposit, Southern Germany.

Herein, a multi-technique study was performed to reveal the elemental speciation and microphase composition in altered granitic rock collected from the Krunkelbach Valley uranium (U) deposit area near an abandoned U mine, Black Forest, Southern Germany. The former Krunkelbach U mine with 1-2 km surrounding area represents a unique natural analogue site with the rich accumulation of secondary U minerals suitable for radionuclide migration studies from a spent nuclear fuel (SNF) repository. Based on a micro-technique analysis using several synchrotron-based techniques such as X-ray fluorescence analysis, X-ray absorption spectroscopy, powder X-ray diffraction and laboratory-based scanning electron microscopy and Raman spectroscopy, the complex mineral assemblage was identified.

In situ speciation and spatial mapping of Zn products during pulsed laser ablation in liquids (PLAL) by combined synchrotron methods.

Pulsed laser ablation in liquids is a hierarchical multi-step process to produce pure inorganic nanoparticle colloids. Controlling this process is hampered by the partial understanding of individual steps and structure formation. In situ X-ray methods are employed to resolve macroscopic dynamics of nanosecond PLAL as well to analyse the distribution and speciation of ablated species with a microsecond time resolution.

Thallium and co-genetic trace elements in hydrothermal Fe-Mn deposits of Central Spain.

Thallium (Tl) is a hazardous trace metal that can harm human and environmental health. Tl pollution can result from the mining and smelting of Tl-bearing minerals, but also the natural weathering of Tl-bearing sulfide minerals may induce Tl release to the environment. In this study, hydrothermal deposits hosted in dolostone rocks sited along fossil thermal springs in the Lodares region (Soria province, central Spain) were studied.

The potential wildfire effects on mercury remobilization from topsoils and biomass in a smelter-polluted semi-arid area.

Wildfires can be responsible for significant mercury (Hg) emissions especially in contaminated areas. Here, we investigated the Hg distribution in topsoils and vegetation samples and temperature-dependent Hg mobilization from biomass-rich topsoils collected near a copper (Cu) smelter in Tsumeb (semi-arid Namibia), where Hg-rich Cu concentrates are processed. The thermo-desorption (TD) experiments conducted on representative biomass-rich topsoils (3.

Effects of metal cation substitution on hexavalent chromium reduction by green rust.

Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust's layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase.

The behaviour of irrigation induced Se in the groundwater-soil-plant system in Punjab, India.

Selenium is of special interest in different research fields due to its narrow range between beneficial and toxic effects. On a global scale, Se deficiency is more widespread. Biofortification measures have successfully been applied to specifically increase Se concentrations in food crops.

The role of soil components in synthetic mixtures during the adsorption and speciation changes of Cr(VI): Conjunction of the modeling approach with spectroscopic and isotopic investigations.

This study investigates redox transitions associated with the adsorption of Cr(VI) on commonly occurring soil components (silicates, oxides and humic acids) and their synthetic mixtures by coupling the mechanistic surface complexation modeling with spectroscopic and isotopic analyses. The mixtures of soil components were prepared to reflect the composition of the real anthroposol sample, determined by X-ray Powder Diffraction (XRD), total organic carbon (TOC) measurement and extraction methods. The effect of different initial Cr(VI) concentrations (2×10, 5×10, 10, 10, and 10M), background electrolyte (10, 10, and 10M KNO), pH values (3-9), and sorbate/sorbent ratios (2g/L - 20g/L) were investigated.

Synthesis and Structural Characterization of a Pure ZnAl(OH)(SO)·2.6HO Layered Double Hydroxide.

The phase purity of a series of ZnAl(OH)SO· nHO layered double hydroxides (ZnAl-LDH) obtained from a reaction of bayerite (Al(OH)) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e.

Historical roasting of thallium- and arsenic-bearing pyrite: Current Tl pollution in the Riotinto mine area.

Samples of an open-air pyrite roasting heap from the 19th century in the Riotinto mine area (SW Spain) and surrounding sediments and soil along a seasonal surface runoff channel were analyzed to study thallium (Tl) phase transformations during historical roasting of Tl-bearing arsenian pyrite, secondary weathering processes, Tl dispersion and current environmental pollution. Results from Electron Probe Microanalyses (EPMA) indicate an even distribution of Tl in pyrite grains of an ore sample (22 mg kg total Tl), suggesting that Tl is incorporated in the pyrite structure rather than in discrete Tl-sulfide microparticles. The roasting residue (122 mg kg total Tl) consists mainly of hematite.

Parasitoid biology preserved in mineralized fossils.

About 50% of all animal species are considered parasites. The linkage of species diversity to a parasitic lifestyle is especially evident in the insect order Hymenoptera. However, fossil evidence for host-parasitoid interactions is extremely rare, rendering hypotheses on the evolution of parasitism assumptive.

Thallium contamination of desert soil in Namibia: Chemical, mineralogical and isotopic insights.

We studied arid desert soils from Namibia (Rosh Pinah) that were contaminated with up to 7 mg kg of thallium (Tl) via dust emitted from a local flotation tailing dam. Chemical extractions of waste and soil materials indicated that most of the Tl is strongly bound, in accordance with X-ray diffraction and X-ray absorption spectroscopy data that point to the predominant association of Tl with metal sulfides and phyllosilicates. The isotope fractionation factor εTl of the soil samples (from -0.

Hematite (α-FeO) - A potential Ce carrier in red mud.

Cerium is the most abundant rare earth element (REE) within the waste product of alumina production (red mud), but its speciation in this complex material is still barely understood. Previous studies showed evidence for a correlation between Ce and the main constituent of red mud, iron oxides, which led us to investigate the most abundant iron oxide in red mud, hematite, as possible carrier phase for Ce. Synthetic hematite can incorporate up to 1.

Response to lead pollution: mycorrhizal Pinus sylvestris forms the biomineral pyromorphite in roots and needles.

The development of mycorrhized pine seedlings grown in the presence of lead was assessed in order to investigate how higher plants can tolerate lead pollution in the environment. Examination with scanning electron microscopy (SEM) revealed that Pb uptake was prominent in the roots, while a smaller amount was found in pine needles, which requires symplastic uptake and root-to-shoot transfer. Lead was concentrated in nanocrystalline aggregates attached to the cell wall and, according to elemental microanalyses, is associated with phosphorus and chlorine.