Characterization and adsorption of disperse dyes from wastewater onto cenospheres activated carbon composites

In the present research, coal fly ash, a waste by-product of thermal power plant, has been segregated to obtain hollow and spherical cenospheres which combined with activated carbon in different ratio for effectual remediation of wastewater. Fabricated cenospheres activated carbon (CNAC) composites were characterized by ATR-FTIR, SEM, XRD, BET and CILAS for functionality, surface modification, crystallinity, surface area, pore volume, pore size and particle size analysis, respectively. Batch adsorption has been applied to appraised maximum removal of Disperse Orange 25 (DO) and Disperse Blue 79:1 (DB) dyes at varying solution pH 2 to 12, adsorbent dose 0.1 g cenospheres + 0.1 g AC to 1.0 g cenospheres + 1.0 g AC, dye concentration 10 to 100 mg/L, agitation speed 80 to 240 rpm and contact time 5 to 300 min at three different temperatures (25, 35 and 45 °C). The maximum percentage removal was found to be 79 and 76% for DO and DB dyes, respectively, at optimized condition. Langmuir isotherm showed good interaction with adsorption data, and the obtained maximum equilibrium adsorption capacity was found to be 90.91 mg/g for DO and 83.33 mg/g for DB at 45 °C. Eventually, the negative ?G° (? 7.513 for DO and ? 7.767 for DB) has suggested the feasibility of dyes adsorption on CNAC composites.     

29Si and 27Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite

Thermal transformations of kaolinite of different degree of crystallinity have been monitored by ²⁷Al and ²⁹Si high-resolution NMR with magic-angle spinning (MAS NMR), X-ray diffraction, Fourier transform infrared, atomic absorption spectrophotometry and thermogravimetric analysis. NMR shows differences in the dehydroxylation process of kaolinites with different degree of crystallinity and reveals the presence of short-range order in metakaolinite. ²⁹Si NMR spectra acquired with a 30 s recycle delay of poorly and highly crystalline samples heated at 480 and 500° C, respectively, contain three distinct signals; we discuss their assignment in the light of experiments involving leaching of the samples with aqueous KOH. Ca. 40% of Si sites retain their original Q ³ symmetry just above the onset of dehydroxylation and the Q ⁴ environment is present showing that a small amount of amorphous silica has already segregated. The spectrum of samples treated at 1000° C contains a signal at -110ppm (from Q ⁴ silicons) and a faint resonance, from mullite, at ca. -87 ppm. ²⁹Si NMR also shows that cristobalite germs are already present at 950–1000° C. The ²⁷Al MAS NMR spectra of metakaolinite reveal the presence of 4-, 5-and 6-coordinated Al. Changes in the three Al populations as a function of temperature have been monitored quantitatively. Below 800° C, 4-and 5-coordinated Al appears at the expense of 6-coordinated Al, but above 800° C the amount of 6-coordinated Al increases again. We suggest a dehydroxylation scheme which accounts for the presence of 4-and 5 coordinated Al. Above 900–950° C the latter signal is no longer present in the ²⁷Al NMR spectra and new 4-and 6-coordinated Al species (mullite and γ-alumina) appear. We propose new ideas for the structure of metakaolinite.     

Stable hydrogen isotopes in iron oxides—II. DH variations among natural goethites

Goethite samples analyzed for this study have a δD range from ?202 to ?98 per mil with a corresponding δD range of associated waters from about ?110 to +7 per mil. Goethites with the most positive δD values are from marine environments. Goethite-water equilibrium $\text{D}\text{H}$ fractionation factors measured in this laboratory at 100°C and 145°C and estimated for sedimentary temperatures from data on natural samples have values of about 0.900 at all three temperatures. These data suggest that goethite δD values may be a direct, temperature-independent measure of the δD values of the waters with which the goethite last equilibrated. Most of the goethite δD values in this study reflect the δD values of the modern waters in the locales of origin.Substitution of Mn and/or Al for Fe in the goethite structure may affect the mineral-water fractionation factor. Manganese appears to decrease the value of α. The effect of Al substitution on α has not yet been measured, but preliminary arguments suggest that increasing Al content could increase α values.     

The structure and transformation of the nanomineral schwertmannite: a synthetic analog representative of field samples

The phase transformation of schwertmannite, an iron oxyhydroxide sulfate nanomineral synthesized at room temperature and at 75 °C using H₂O₂ to drive the precipitation of schwertmannite from ferrous sulfate (Regenspurg et al. in Geochim Cosmochim Acta 68:1185–1197, 2004), was studied using high-resolution transmission electron microscopy. The results of this study suggest that schwertmannite synthesized using this method should not be described as a single phase with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers in diameter, within a characteristic ‘pin-cushion’-like amorphous matrix. The difference in synthesis temperature affected the density of the needles on the schwertmannite surface. The needles on the higher-temperature schwertmannite displayed a dendritic morphology, whereas the needles on the room-temperature schwertmannite were more closely packed. Visible lattice fringes in the schwertmannite samples are consistent with the powder X-ray diffraction (XRD) pattern taken on the bulk schwertmannite and also matched d-spacings for goethite, indicating a close structural relationship between schwertmannite and goethite. The incomplete transformation from schwertmannite to goethite over 24 h at 75 °C was tracked using XRD and TEM. TEM images suggest that the sample collected after 24 h consists of aggregates of goethite nanocrystals. Comparing the synthetic schwertmannite in this study to a study on schwertmannite produced at 85 °C, which used ferric sulfate, reveals that synthesis conditions can result in significant differences in needle crystal structure. The bulk powder XRD patterns for the schwertmannite produced using these two samples were indistinguishable from one another. Future studies using synthetic schwertmannite should account for these differences when determining schwertmannite’s structure, reactivity, and capacity to take up elements like arsenic. The schwertmannite synthesized by the Regenspurg et al. method produces a mineral that is consistent with the structure and morphology of natural schwertmannite observed in our previous study using XRD and TEM, making this an ideal synthetic method for laboratory-based mineralogical and geochemical studies that intend to be environmentally relevant.     

Alteration of fluid properties during the initial operation of a geothermal plant: results from in situ measurements in Groß Schönebeck

Recently, the thermal fluid loop has been established and continuosly operated for 7 days at the geothermal in situ laboratory in Groß Schönebeck (North German Basin). During this initial phase of fluid production, the fluid temperature, measured at the surface, continuously increased until a stable value of about 98 °C was established. Fluid physicochemical properties (pH, redox, density, temperature, and pressure) were measured online and in situ with a newly developed fluid monitoring system (FluMo). Additionally, fluid samples have been collected at various temperatures (in 5–10 °C steps) directly at the production well at about 10 bar pressure. From the pressurized sampling tool, the fluid was directly transferred into a heated autoclave, which allowed filtration (0.2 μm) in the absence of oxygen. Physicochemical parameters [pH, redox, electric conductivity, total dissolved solids (TDS)] as well as acid capacity (K _S 4.3) of these samples have been measured onsite at atmospheric conditions. Concentrations of anions, total organic carbon, and metals were analyzed later in the laboratory. Both, measurements in collected samples or in situ (FluMo) analysis of most the parameters density, electric conductivity, or TDS indicated relatively constant values over the whole production time (1.17–1.18 g · cm^?3, 215–221 mS · cm^?1, 241–260 g · L^?1, respectively). Good correlation was also found for pH values (pH = 6.6–6.9), whereas the redox values varied between ?1 and 46 mV when determined at 25 °C and decreased strongly when measured in situ with increasing temperature (?110 mV at 90 °C). The elemental composition of collected samples remained also relatively constant for most compounds and was clearly higher as compared with samples collected in 2011. Results of this study demonstrate that realistic, comprehensive, and time-resolved physicochemical data can be obtained by FluMo. These detailed data sets can be crucial to understand the complex geochemical processes in a thermal water loop and eventually to take required measures on time.     

Catalytic ozonation of dimethyl phthalate by Ce-substituted goethite

Dimethyl phthalate (DMP) is ubiquitous in aquatic environments due to extensively used as plasticizer, which has received increasing attention in recent years. In this study, the catalytic ozonation of dimethyl phthalate was performed using Ce-substituted goethite as a novel catalyst, which was prepared by isomorphous substitution method. The specific surface area, pHpzc and surface hydroxyl density of the catalyst were determined. The catalyst was characterized using X-ray diffraction, scanning electron microscope and Fourier transform infrared spectroscopy. The removal efficiency of DMP was almost 100% after 30 min, and about 40% DMP was mineralized after 60 min, which was nearly four times higher than single ozonation. During catalytic ozonation process, anions (PO₄ ^3?, SO₄ ^2?, Cl^?) affected DMP degradation, indicating that surface hydroxyl groups on the surface of catalyst were main active sites. The electron transfer process by redox reaction between Ce³⁺/Ce⁴⁺, Fe²⁺/Fe³⁺ was proposed, and their interaction could also promote the formation of hydroxyl radicals. Ce-substituted goethite was an efficient catalyst for degradation of DMP by catalytic ozonation.     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.     

Studies of Cd(II)-sulfate interactions at the goethite-water interface by ATR-FTIR spectroscopy

A combination of macroscopic experiments and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy was used to study Cd(II)-sulfate interactions on the goethite-water interface. The presence of SO₄ dramatically promoted Cd adsorption at lower pH (pH 5.5-6.5) and had a smaller effect at higher pH. ATR-FTIR studies indicated sulfate adsorption on goethite occurred via both outer- and inner-sphere complexation. The relative importance of both complexes was a function of pH and sulfate concentration. ATR-FTIR spectra provided direct evidence of the formation of Cd-SO₄ ternary surface complexes on goethite. In addition to ternary complexes, Cd specifically sorbed on goethite promoted SO₄ adsorption via changing the surface charge, and caused additional SO₄ adsorption as both inner- and outer-sphere complexes. The relative importance of ternary complexes versus electrostatic effects depended upon pH values and Cd concentration. Ternary complex formation was promoted by low pH and high Cd levels, whereas electrostatic effects were more pronounced at high pH and low Cd levels. A portion of SO₄ initially sorbed in inner-sphere complexes in the absence of Cd was transformed into Cd-SO₄ ternary complexes with increased Cd concentration.     

Limitations of the potentiometric titration technique in determining the proton active site density of goethite surfaces

Density of proton active surface sites at mineral surfaces is a property of fundamental importance in equilibrium modeling of surface complexation reactions. In this article, methods for an experimental determination of these sites at the surface of α-FeOOH (goethite) are explored. It is shown that previously obtained saturation data of goethite with respect to protons do not yield a site density that can be considered as an intrinsic sorbent property: the results are below crystallographically expected values and values for different ionic media in terms of composition and concentration yield different numbers—for example, chloride would yield higher values than nitrate at the same concentration, and higher electrolyte concentration would favor higher apparent maxima. Although site saturation might be explained by electrostatic repulsion, which is more efficient at high electrolyte concentration or for certain ions, further independent experimental results show that no saturation occurs on goethite down to ph ≡ −log[H⁺] = 2.2 and possibly to ph = 1.0 in 0.6 M NaCl. For those very low pH values, the experimental charging curve was obtained by coulometric back titration (using the Gran plot) or titrations with tris (hydroxymethyl)-aminomethane of the supernatant of acidified goethite suspension. These experimental data are to our knowledge the first high quality data at such low pHs. However, small errors in the determination of proton concentrations (1%) are shown to strongly affect the shape of the charging curve for ph < 2. Furthermore, goethite dissolution (proton consumption and iron reduction in coulometric titrations) and liquid junction effects interfere at low ph, hampering the straightforward application of coulometric Gran titrations over the whole pH range. From these experiments, it can nonetheless be ascertained that a minimum of 2.5 protons/nm² can be adsorbed at the goethite surface from the point of zero charge (ph 9.4) to pH 0.9. Although these studies are restricted to goethite, those studies in which titrations with excess acid and base have been used for the determination of proton active site concentrations of sorbents should be reconsidered.     

Origin of rapidly solidified metal-troilite grains in chondrites and iron meteorites

Inclusions of troilite and metallic Fe,Ni 0.2–4 mm in size with a dendritic or cellular texture were observed in 12 ordinary chondrites. Cooling rates in the interval 1400?950°C calculated from the spacing of secondary dendrite arms or cell widths and published experimental data range from 10^?7 to 10⁴°C/sec. In 8 of these chondrites, which are breccias containing some normal slow-cooled metal grains, the inclusions solidified before they were incorporated into the breccias. Their cooling rates of 1–300 °C/sec indicate cooling by radiation, or by conduction in contact with cold silicate or hot silicate volumes only 6–40 mm in size. This is quantitative evidence that these inclusions and their associated clasts were melted on the surface of a parent body (by impact), and were not formed at depth from an internally derived melt. In Ramsdorf, Rose City and Shaw, which show extensive reheating to ? 1000°C, Fe-FeS textures in melted areas are coarser and indicate cooling rates of 10^?1 to 10^?4°C/sec during solidification. This metal may have solidified inside hot silicate volumes that were 10–300 cm in size. As Shaw and Rose City are breccias of unmelted and melted material, their melted metal did not necessarily cool through 1000°C within a few m of the surface. Shock-melted, fine-grained, irregular intergrowths of metal and troilite formed in situ in many irons and some chondrites by rapid solidification at cooling rates of ? 10⁵°C/sec. Their kamacite and taenite compositions may result from annealing at ~250°C of metallic glass or exceedingly fine-grained quench products.     

Fluid inclusion and sulfur isotope thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) mineralization, NW TURKEY

The Inkaya Cu-Pb-Zn-(Ag) mineralization, located about 20 km west of the Simav (Kütahya-Turkey), is situated in the northern part of the Menderes Massif Metamorphics. The mineralization is located along an E-W trending fault in the Cambrian Simav metamorphics consisting of quartz-muscovite schist, quartz-biotite schist, muscovite schist, biotite schist and the Ar?kayas? formation composed of marbles. Mineralized veins are 30–35 cm in width. The primary mineralization is represented by abundant galena, sphalerite, chalcopyrite, pyrite, fahlore and minor amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, limonite, hematite and goethite with gangue quartz. Fluid inclusion studies on the quartz samples collected from the mineralized veins indicate that the temperature range of the fluids is 235°C to 340°C and the salinities are 0.7 to 4.49 wt. % NaCl equivalent. The wide range of homogenization temperatures indicates that two different fluid generations were trapped in quartz. Sulfur isotope studies of the sulfide minerals showed that all of the δ ³⁴S values are between ?2.1 and 2.6 per mil. These values are a typical range for hydrothermal sulfide minerals that have sulfur derived from a magmatic source. Pyrite-galena and pyrite-chalcopyrite sulfur isotope fractionation is consistent with an approach to isotopic equilibrium, and calculated temperatures are 254.6 and 277.4°C for pyrite-galena and 274.7°C for pyrite-chalcopyrite. The microthermometric data and sulfur isotope thermometry indicate the existence of a hydrothermal fluid that circulated along the fault crossing the Simav metamorphics and Ar?kayas? formation. Fluid inclusion and sulfur isotope thermometry can be used in combination with ore petrographical and geological information to provide site-specific targets for meso-hypothermal metal concentrations.     

NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars

The oxidation of surface functional groups on biochar increases its reactivity and may contribute to the cation exchange capacity of soil. In this study, two Eucalyptus wood biochars, produced at 450 °C (B450) and 550 °C (B550), were incubated separately in each of the four contrasting soils for up to 2 years at 20 °C, 40 °C and 60 °C. Carbon functional groups of the light fraction (< 1.8 g/cm³) of the control and biochar amended soils (fresh and aged for 1 and 2 years at 20 °C, 40 °C and 60 °C) were investigated using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). The spectra of biochar and light fractions of the control and biochar amended soils showed two distinct peaks at ∼285.1 eV and 288.5 eV, which were attributed to the C1s-π¹_CC transitions of aromatic C and C1s-π¹_CO transitions of carboxylic C, carboxyamide C and carbonyl C. The proportion of aromatic C was substantially greater in the light fraction of the biochar amended soils than the corresponding light fraction of the control soils. Also, the proportion of aromatic C was much higher in the light fraction of the B550 amended soils than in the corresponding B450 amended soils. Neither NEXAFS nor XPS results show any consistent change in the proportion of aromatic C of biochar amended soils after 1 year ageing. However, XPS analysis of hand-picked biochar samples showed an increase in the proportion of carboxyl groups after ageing for 2 years, with an average value of 8.9% in the 2 year aged samples compared with 3.0% in the original biochar and 6.4% in the control soil. Our data suggest that much longer ageing time will be needed for the development of a significant amount of carboxyl groups on biochar surfaces.     

Surface complexation model for strontium sorption to amorphous silica and goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr²⁺ and SrOH⁺ complexes on the β-plane and a monodentate Sr²⁺complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH⁺ complexes and a tetradentate binuclear Sr²⁺ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr²⁺ and SrOH⁺ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces.     

Hydrogeochemical investigations of thermal waters in the northeastern part of Morocco

Northeastern Morocco is characterised by a large number of surface geothermal manifestations. Thermal waters are hosted within sedimentary rocks, and in particular the Liassic dolomitic limestones act as a reservoir. The presence of geothermal waters is closely related to important fault systems. Meteoric water infiltrates along those fractures and faults, gets heated, and then returns to the surface through hydrothermal conduits. Most of the thermal waters are of Na–Cl and Ca–Mg–HCO₃ types. In this paper different geochemical approaches were applied to infer the reservoir temperature. Na–K–Mg^1/2 ternary diagram points to temperatures ranging from 100 to 180 °C. Cation geothermometers suggest an average reservoir temperature of about 100 °C. Mineral solution equilibria analysis yields temperatures ranging from 50 to 185 °C. The silica enthalpy mixture model gives an average value (about 110 °C) higher than that inferred from cation geothermometers.     

The Impact of Surface Charge on the Mechanical Behavior of High-Porosity Chalk

We present rock mechanical test results and analytical calculations which demonstrate that a negative surface charge, resulting from sulfate adsorption from the pore water, impacts the rock mechanical behavior of high-porosity chalk. Na₂SO₄ brine flooded into chalk cores at 130 °C results in significantly reduced bulk modulus and yield point compared with that of NaCl brine at the same conditions. The experimental results have been interpreted using a surface complexation model combined with the Gouy-Chapman theory to describe the double layer. The calculated sulfate adsorption agrees well with the measured data. A sulfate adsorption of about 0.3 μmol/m² and 0.7–1 μmol/m² was measured at 50 and 130 °C, respectively. Relative to a total sites of 5 sites/nm² these values correspond to an occupation of 4 % and 8–13 % which sufficiently explains the negative charging of the calcite surfaces. The interaction between charged surfaces specifically in the weak overlaps of electrical double layer gives rise to the total disjoining pressure in granular contacts. The net repulsive forces act as normal forces in the grains vicinity, counteracting the cohesive forces and enhance pore collapse failure during isotropic loading, which we argue to account for the reduced yield and bulk modulus of chalk cores. The effect of disjoining pressure is also assessed at different sulfate concentrations in aqueous solution, temperatures, as well as ionic strength of solution; all together remarkably reproduce similar trends as observed in the mechanical properties.     

Removal of hazardous hexavalent chromium from aqueous solution using divinylbenzene copolymer resin

This paper presents the removal of hazardous hexavalent chromium from liquid waste streams using divinylbenzene copolymer resin Amberlite IRA 96. Important sorption parameters such as contact time, pH, resin dosage and initial metal concentration were studied at 30?°C. The kinetic study was conducted using pseudo-first and pseudo-second-order kinetics at 30?°C. The sorption process was found to be pH dependent. Maximum removal was obtained at pH 2 under optimized conditions. The sorption process was rapid and 99?% of the removal was achieved in first 30?min. The equilibrium data were fitted to both Langmuir and Freundlich models. The better regression coefficient (R ²) in Freundlich model suggests the multilayer sorption process. The value of Gibbs free energy for sorption process was found to be ?12.394?kJmol^?1. The negative value indicated the spontaneity of the sorption process. Scanning electron microscope and energy dispersive X-ray spectroscopy studies were conducted to find the role of surface morphology during sorption process. The Fourier transform infrared study was conducted to identify the functional groups responsible for interaction between the resin and chromium. Desorption and regeneration studies were also carried out.     

Thermal behavior of ferric selenite hydrates (Fe2(SeO3)3·3H2O,Fe2(SeO3)3·5H2O) and the water content in the natural ferric selenite mandarinoite

Any progress in our understanding of low-temperature mineral assemblages and of quantitative physico-chemical modeling of stability conditions of mineral phases, especially those containing toxic elements like selenium, strongly depends on the knowledge of structural and thermodynamic properties of coexisting mineral phases. Interrelation of crystal chemistry/structure and thermodynamic properties of selenium-containing minerals is not systematically studied so far and thus any essential generalization might be difficult, inaccurate or even impossible and erroneous. Disagreement even exists regarding the crystal chemistry of some natural and synthetic selenium-containing phases. Hence, a systematic study was performed by synthesizing ferric selenite hydrates and subsequent thermal analysis to examine the thermal stability of synthetic analogues of the natural hydrous ferric selenite mandarinoite and its dehydration and dissociation to unravel controversial issues regarding the crystal chemistry. Dehydration of synthesized analogues of mandarinoite starts at 56–87?°C and ends at 226–237?°C. The dehydration happens in two stages and two possible schemes of dehydration exist: (a) mandarinoite loses three molecules of water in the first stage of the dehydration (up to 180?°C) and the remaining two molecules of water will be lost in the second stage (>180?°C) or (b) four molecules of water will be lost in the first stage up to 180?°C and the last molecule of water will be lost at a temperature above 180?°C. Based on XRD measurements and thermal analyses we were able to deduce Fe₂(SeO₃)₃·(6-x)H₂O (x?=?0.0–1.0) as formula of the hydrous ferric selenite mandarinoite. The total amount of water apparently affects the crystallinity, and possibly the stability of crystals: the less the x value, the higher crystallinity could be expected.     

Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens

The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p_3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.     

Age of Cu(-Fe)-Au mineralization and thermal evolution of the Punta del Cobre district, Chile

The Punta del Cobre belt is located 15?km south of Copiapó, northern Chile. It comprises several Cu(-Fe)-Au deposits in the Punta del Cobre and Ladrillos districts, east of the Copiapó river, and the Ojancos Nuevo district, with the new Candelaria mine, and Las Pintadas district, west of the river. The mineralization in the Punta del Cobre belt is characterized by a simple hypogene mineral assemblage of chalcopyrite, pyrite, magnetite, and hematite. Average ore grades are 1.1 to 2% Cu, 0.2 to 0.6?g/t Au, and 2 to 8?g/t Ag. Massive magnetite occurs as veins and irregularly shaped bodies. The ore is spatially associated with alkali metasomatism and in particular with potassic alteration. The Cu(-Fe)-Au deposits are hosted mainly in volcanic rocks of the Punta del Cobre Formation (pre-upper Valanginian) that underlie Neocomian limestones of the Chañarcillo Group. This region experienced backarc basin formation in the Neocomian, uplift and granitoid intrusions in the middle Cretaceous, and eastward migration of the magmatic front of about 30?km between middle Cretaceous and Paleocene. To determine the timing of ore deposition and to reconstruct parts of the thermal history of the Punta del Cobre district, in the eastern part of the belt, we have obtained ⁴⁰Ar/³⁹Ar incremental-heating and Rb-Sr analyses of mineral and whole-rock samples. An ⁴⁰Ar/³⁹Ar incremental-heating experiment on hydrothermal biotite, formed synchronous with the Cu(-Fe)-Au mineralization, yielded an inverse isochron age of 114.9?±?1.0 Ma (all errors reported at ±2σ), consistent with a Rb-Sr isochron of 116.8?±?2.7 Ma calculated from 7 whole-rock samples. These data are interpreted to represent the age of potassic alteration that accompanies mineralization. Ore formation temperatures of 400?°C to 500?°C were previously estimated based on paragenetic relationships. Shearing at the Candelaria deposit occurred after ore deposition and before the main stage of batholith emplacement. Published K-Ar ages for the middle Cretaceous batholith near the Punta del Cobre belt range from 119 to 97?Ma. Our data suggest that the mineralization is related to the earlier stages of batholith emplacement. The biotite age spectrum indicates that the Punta del Cobre district was not affected by temperatures above ～300?°C–350?°C, the closure temperature for argon in biotite, during the contact metamorphic overprint produced by later emplaced batholithic intrusions. Whole-rock ⁴⁰Ar/³⁹Ar ages are considerably younger; incremental-heating experiments yielded an inverse isochron age of 90.7?±?1.2?Ma and weighted mean plateau ages of 89.8?±?0.6?Ma and 89.5?±?0.6?Ma. These samples are dominantly K-feldspar, for which we assume an argon closure temperature of ～150?°C, thus they give the age of cooling below ～150?°C–200?°C.     

Outer-sphere adsorption of Pb(II)EDTA on goethite

Fourier transform infrared (FTIR) and extended X-ray absorption fine structure (EXAPS) spectroscopic measurements were performed on Pb(II)ethylenediaminetetraacetic (EDTA) adsorbed on goethite as a function of pH (4–6), Pb(II)EDTA concentration (0.11–72 μM), and ionic strength (16 μM–0.5 M). FTIR measurements show no evidence for carboxylate-Fe(III) bonding or protonation of EDTA at Pb:EDTA = 1:1. Both FTIR and EXAFS spectroscopic measurements suggest that EDTA acts as a hexadentate ligand, with all four of its carboxylate and both of its amine groups bonded to Pb(II). No evidence was observed for inner-sphere Pb(II)-goethite bonding at Pb:EDTA = 1:1. Hence, the adsorbed complexes should have composition Pb(II)EDTA²⁻. Because substantial uptake of PbEDTA(II)²⁻ occurred in the samples, we interpret that Pb(II)EDTA²⁻ adsorbed as outer-sphere complexes and/or as complexes that lose part of their solvation shells and hydrogen bond directly to goethite surface sites. We propose the term “hydration-sphere” for the latter type of complexes because they should occupy space in the primary hydration spheres of goethite surface functional groups and to distinguish this mode of sorption from common structural definitions of inner- and outer-sphere complexes. The lack of evidence for inner-sphere EDTA-Fe(III) bonding suggests that previously proposed metal/ligand-promoted dissolution mechanisms should be modified, specifically to account for the presence of outer-sphere precursor species.