Model biomimetic studies of templated growth and assembly of nanocrystalline FeOOH

We studied biomimetic mineralization of self-assembling polymer matrices in order to develop a model for biomineralization of iron oxides in nature. High-resolution transmission electron microscopy (HRTEM), rheology, and fluorescence probe analyses show self-assembly of acidic polysaccharide alginic acid (Alg) to form fibrils in dilute solutions. The resulting Alg fibrils are subsequently mineralized by FeOOH in a biomimetically controlled process. Experiments were conducted in pH 9.2 solutions containing millimolar concentrations of iron at 38°C. The unperturbed state of the hybrid mineral-organic structures was studied by characterization of samples of interfacial films collected from an inorganic-organic interface. Progress of mineralization over a 4-week period was followed by HRTEM, energy-dispersive X-ray analysis, and selected area electron diffraction. Morphologies of hybrid structures determined by HRTEM, X-ray powder diffraction, Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, and selected area electron diffraction suggest formation of iron (III) oxyhydroxide phases and their assembly through a variety of mechanisms, possibly occurring simultaneously. An initial step involves precipitation of nanometer-scale amorphous particles and two-line ferrihydrite in bulk solution. Some nanoparticles assemble into chains that recrystallize to form akaganeite (β-FeOOH), presumably via a solid-state transformation pathway. Small organic molecules may mediate this process by stabilizing the akaganeite structure and controlling particle assembly. Ferrihydrite particles also bind to acidic polysaccharide fibrils and are transformed to ordered arrays of akaganeite. The parallel orientation of adjacent akaganeite nanocrystals may be inherited from the orientation of precursor ferrihydrite, possibly conferred during attachment of ferrihydrite to the polyacid fibrils. Alternatively, particle-particle interactions may induce orientation, leading to recrystallization. Subsequently, akaganeite is transformed to goethite that is characterized by nanoscale porosity and fine-scale twinning on {021}. Dislocation, twin, and nanopore microstructures are consistent with coarsening by nanoparticle assembly, possibly templated by the substrate. Nanoparticle assembly to generate biomimetic hybrid materials may be relevant to formation of complex natural biominerals in natural systems where mineral nanoparticles, small organic molecules, and more complex polymers coexist.     

High-temperature single-crystal neutron diffraction study of natural chondrodite

The H-atom environment in a Tilly Foster chondrodite was analyzed using single-crystal neutron-diffraction data collected at 500, 700 and 900 K and previously published low temperature data collected at 10, 100 and 300 K on the same crystal (Mg_4.64Fe_0.28Mn_0.014Ti_0.023(Si_1.01O₄)₂F_1.16(OH)_0.84; Friedrich et al. in Am Mineral 86:981–989, 2001). The full mean square displacement matrix Σ of the O–H pair was determined from the temperature dependence of the anisotropic displacement parameters, enabling a proper correction of the O–H bond for thermal vibration without assumptions about the correlation of O and H movements. The results show that the perpendicular O–H motions in chondrodite are intermediate between the riding and the independent motion models. The corrected O–H bond lengths do not change with temperature whereas the corrected H···F distances show an increase of ~0.02 Å with temperature, as do the Mg–O distances. This result shows that spectroscopic observations on the strength of the covalent O–H bond cannot be interpreted unambiguously in terms of a corresponding behaviour of the associated H···O/F hydrogen bond.     

Arsenic incorporation into FeS2 pyrite and its influence on dissolution: A DFT study

FeS₂ pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.     

Assessment of future trends on groundwater quality in a nitrate vulnerable zone (Esposende–Vila do Conde sector,NW Portugal): towards a combined conceptual and mass transport modelling

Hydrogeology Journal - Nitrate contamination of groundwater is an important public health issue worldwide. For environmental and public health reasons, water should not contain more than...     

The tropical storm Noel and its effects on the territory of the Dominican Republic

In the period between the end of October and the beginning of November 2007, the Dominican Republic was hit by the tropical storm Noel, then turned into hurricane in its movement toward the Californian coasts. The passage of Noel was accompanied by huge precipitation especially in the south-western part of the country. In some areas, the rainfall registered in 6 days exceeded 700 mm, i.e., more than two-thirds of the mean annual precipitation. The return periods calculated for this rainfall event vary greatly from region to region: while they locally reach 200 years, such as in San José de Ocoa (50 km west of Santo Domingo), in other areas, as for instance in the territory of the capital Santo Domingo, return periods do not exceed 20 years. The tropical storm caused huge damage both in terms of human victims and economic losses, related to diffused inundations and landslide phenomena, which may be attributed only partially to the exceptionality of the event. As a matter of fact, in many regions, the inadequate answer of the territory—widely characterized by serious problems of land degradation and an almost complete lack of territorial planning—appears to be the major responsible for the occurred negative effects. The impact assessment, based on the calculation of an Impact Index, confirms this statement.     

Characterization of a natural magnetite

Single crystals of a rock magnetite were separated from steatite cobbles collected in a geological site near the city of Serro (18° 36′ 47′′ S 43° 22′ 46′′ W), Minas Gerais, Brazil. A typically well-shaped magnetite single crystal was characterized by chemical analysis, ⁵⁷Fe Mössbauer spectrometry at 300, 77 and 4 K and under an applied magnetic field of 6 T at 10 K, magnetization measurements and electronic microprobe. From Mössbauer data, the sample is stoichiometric with a tetrahedral and octahedral site occupancy ratio of 1:2. Elemental chemical analysis and point-to-point electron microscope probing show some inclusions of lamellar ilmenite (≤ 1 mass%) randomly distributed throughout the magnetite matrix, and also that the magnetite matrix is constituted only by Fe²⁺ and Fe³⁺, with no isomorphic substitution. Results are discussed on the basis of the magnetization curve and of the temperature dependence of the AC magnetic susceptibility. The Verwey transition occurs in the temperature range of 100–115 K, observed by a sudden change in the temperature dependence of the magnetization.     

The origin of groundwater arsenic and fluorine in a volcanic sedimentary basin in central Mexico: a hydrochemistry hypothesis

A groundwater sampling campaign was carried out in the summer of 2013 in a low-temperature geothermal system located in Juventino Rosas (JR) municipality, Guanajuato State, Mexico. This groundwater presents high concentrations of As and F^? and high Rn counts, mainly in wells with relatively higher temperature. The chemistry of major elements was interpreted with different methods, like Piper and D’Amore diagrams. These diagrams allowed for classification of four groundwater types located in three hydrogeological environments. The aquifers are hosted mainly in alluvial-lacustrine sediments and volcanic rocks in interaction with fault and fracture systems. The subsidence, faults and fractures observed in the study area can act as preferential channels for recharge and also for the transport of deep fluids to the surface, especially in the basin plain. The formation of a piezometric dome and the observed hydrochemical behavior of groundwater suggest a possible origin of the As and F^?. Geochemical processes occurring during water–rock interaction are related to high concentrations of As and F^?. High temperatures and alteration processes (like rock weathering) induce dissolution of As and F^?-bearing minerals, increasing the content of these elements in groundwater.     

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH,with and without microbial catalysis

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H₂SO₄ solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl⁻ concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.     

Bedrock bedding,landsliding and erosional budgets in the Central European Alps

We explore the controls of the litho‐tectonic architecture on the erosional flux in the 370‐km² Glogn basin (European Alps). In this basin, the bedding and schistosity of the bedrock dip parallel to the topographic slope on the NW valley flank, leading to a non‐dip slope situation on the opposite SE valley side. While the dip slope condition has promoted the occurrence of landslides (e.g. the c. 30‐km² deep‐seated Lumnezia landslide), the opposite non‐dip slope side of the valley hosts >100‐m‐deeply incised tributary streams. ¹⁰Be concentrations of stream sediments yield catchment‐averaged denudation rates that vary between 0.27 ± 0.03 and 2.19 ± 0.37 mm a^?1, while the spatially averaged denudation rate of the entire basin is 1.99 ± 0.34 mm a^?1. Our ¹⁰Be‐based approach reveals that the Lumnezia landslide front contributes c. 30–65% of the entire sediment budget, although it covers <5% of the Glogn basin. This suggests a primary control of the bedrock bedding on erosion rates and processes.     

Structural investigations of the two polymorphs of synthetic Fe-cordierite and Raman spectroscopy of hexagonal Fe-cordierite

The crystal structures of synthetic hexagonal and orthorhombic Fe-cordierite polymorphs with the space groups P6/mcc and Cccm were refined from single-crystal X-ray diffraction data to R _{1, hex}?=?3.14 % and R _{1, ortho}?=?4.48 %. The substitution of the larger Fe²⁺ for Mg leads to multiple structural changes and an increase of the unit cell volumes, with a, c (hex)?=?9.8801(16) Å, 9.2852(5) Å and a, b, c (ortho)?=?17.2306(2) Å, 9.8239(1) Å, 9.2892(1) Å in the end-members. Furthermore Fe incorporation results in an increase of the volumes of the octahedra, although the diameters of the octahedra in direction of the c-axis decrease in both polymorphs. X-ray powder diffraction analysis indicates a high degree of Al/Si ordering in the orthorhombic polymorph, the Miyashiro distortion index is ~0.24. Estimations of site occupancies based on the determined tetrahedral volumes result in the following values for hexagonal Fe-cordierite: ~73 % Al for T₁ and ~28 % Al for T₂. For the first time Raman spectroscopy was performed on the hexagonal Fe-cordierite polymorph. In the hexagonal Fe-cordierite polymorph most Raman peaks are shifted towards lower wavenumbers when compared with the Mg-end-member.