Fe(II) reduction of pyrolusite (β-MnO<Subscript>2</Subscript>) and secondary mineral evolution

Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth’s crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (β-MnO₂) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and ⁵⁷Fe Mössbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3 mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with ⁵⁷Fe Mössbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3 mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.

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Isotope (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genetic features of manganese carbonates of the Mazul deposit (Krasnoyarsk region)

New isotope and mineral data on manganese carbonates of the Mazul deposit (Krasnoyarsk region) in combination with morphology of ore bodies suggest that the ores were formed in several stages with the involvement of meteoric solutions through infiltration and, possibly, exfiltration mechanisms. Based on the geological–geochemical data, manganese carbonates of the Mazul deposit may be ascribed to a new genetic subtype of the catagenesis (epigenesis) zone.     

Central Paratethys paleoenvironment during the Badenian (Middle Miocene): evidence from foraminifera and stable isotope (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) study in the Vienna Basin (Slovakia)

Stable isotope data of the foraminiferal carbonate shells and bulk sediment samples from the Central Paratethys were investigated to contribute to better knowledge of the paleoenvironmental changes in Badenian (Middle Miocene). Five benthic (Uvigerina semiornata, U. aculeata, Ammonia beccarii, Elphidium sp. and Heterolepa dutemplei) and three planktonic taxa (Globigerina bulloides, G. diplostoma and Globigerinoides trilobus), characterising the bottom, intermediate and superficial layers of the water column, were selected from the Vienna Basin (W Slovakia). The foraminiferal fauna and its isotope signal point out to temperature-stratified, nutrient-rich and consequently less-oxygenated marine water during the Middle/Late Badenian. Negative carbon isotope ratios indicate increased input of ¹²C-enriched organic matter to the bottom of the Vienna Basin. Positive benthic δ¹⁸O implies that the global cooling tendency recorded in the Middle Miocene has also affected the intramountain Vienna Basin. In this time, the Central Paratethys has been in the process of isolation. Our stable isotope trend suggests that the communication with Mediterranean Sea has been still more or less active on the south of Vienna Basin (Slovak part) in the Late Badenian, whereas the seawater exchange towards north was apparently reduced already during the Middle Badenian.     

A superlarge deposit—Kalahari manganese ore field (Northern Cape,South Africa): Geochemistry of isotopes (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis

Study of carbonate inclusions in the Mamatwan-type oxide ores (braunite lutites) made it possible to reveal residual microbial structures in them. Their presence in manganese ores, the type of manganese oxide mineralization, isotope signatures of manganese carbonates, and available literature data on the geology of the Kalahari manganese field suggest that manganese ore formation was widespread at the postsedimentary stage of transformation of the primary microbial sediment. The deposit can be referred to the hydrothermal-metasomatic type.     

Hydrated goethite (α-FeOOH) (1 0 0) interface structure: Ordered water and surface functional groups

Goethite(α-FeOOH), an abundant and highly reactive iron oxyhydroxide mineral, has been the subject of numerous studies of environmental interface reactivity. However, such studies have been hampered by the lack of experimental constraints on aqueous interface structure, and especially of the surface water molecular arrangements. Structural information of this type is crucial because reactivity is dictated by the nature of the surface functional groups and the structure or distribution of water and electrolyte at the solid-solution interface. In this study we have investigated the goethite (1 0 0) surface using surface diffraction techniques, and have determined the relaxed surface structure, the surface functional groups, and the three dimensional nature of two distinct sorbed water layers. The crystal truncation rod (CTR) results show that the interface structure consists of a double hydroxyl, double water terminated interface with significant atom relaxations. Further, the double hydroxyl terminated surface dominates with an 89% contribution having a chiral subdomain structure on the (1 0 0) cleavage faces. The proposed interface stoichiometry is ((H₂O)(H₂O)OH₂OHFeOOFeR) with two types of terminal hydroxyls; a bidentate (B-type) hydroxo group and a monodentate (A-type) aquo group. Using the bond-valence approach the protonation states of the terminal hydroxyls are predicted to be OH type (bidentate hydroxyl with oxygen coupled to two Fe³⁺ ions) and OH₂ type (monodentate hydroxyl with oxygen tied to only one Fe³⁺). A double layer three dimensional ordered water structure at the interface was determined from refinement of fits to the experimental data. Application of bond-valence constraints to the terminal hydroxyls with appropriate rotation of the water dipole moments allowed a plausible dipole orientation model as predicted. The structural results are discussed in terms of protonation and H-bonding at the interface, and the results provide an ideal basis for testing theoretical predictions of characteristic surface properties such as pK_a , sorption equilibria, and surface water permittivity.     

Elastic and thermoelastic properties of synthetic Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript> (åkermanite) and Ca<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> (hardystonite)

Elastic and thermoelastic constants of large single crystals of Ca₂MgSi₂O₇ and Ca₂ZnSi₂O₇ have been derived from ultrasonic resonance frequencies of plane-parallel plates and their shift upon variation of temperature, respectively. In addition, coefficients of thermal expansion and dielectric constants were determined. Both species possess quite similar properties. As observed in other isotypic magnesium and zinc compounds, the mean elastic stiffness and the deviation from the Cauchy relations are significantly larger in the zinc compound, due to a covalent contribution of the Zn–O bond. Positive thermoelastic constants T₄₄ and T₆₆ in Ca₂MgSi₂O₇ allow temperature-independent ultrasonic generators and oscillators to be manufactured.     

Fault rupture and stress changes associated with the November 27, 2005 Qeshm Island (Iran) earthquake (<Emphasis Type="Italic">M</Emphasis><Subscript>W</Subscript> = 6.0)

The November 27, 2005 Qeshm Island earthquake (M_w 6.0) occurred along the Zagros Thrust and Fold Belt which accommodates about half of the deformation caused by the Arabian and Eurasian Plates convergence. As typical for the belt, the earthquake was associated with buried reverse faulting and produced no surface rupture. Here, teleseismic broadband P velocity waveforms of the earthquake are inverted to obtain coseismic finite-fault slip distribution of the earthquake. It is obtained that rupture was controlled by failure of a single asperity with largest displacement of approximately 0.6 m, which occurred at a depth of 9 km. The slip model indicated radial rupture propagation from the hypocentre and confirmed blind reverse faulting within deeper part (below the depth of 6 km) of the sedimentary cover above the Hormuz Salt, lying between the cover and the basement, releasing a seismic moment of about 1.3?×?10¹⁸ Nm (M_W?=?6.0). The results also confirm that the Hormuz Salt behaves as a barrier for rupture propagation to the basement below and occurrence of the aftershock activity downdip from the rupture within the Hormuz Salt. Calculated Coulomb stress variations caused by the coseismic rupture indicates stress coupling between the 2005 Qeshm Island earthquake and both the largest aftershock several hours later and the 2008 Qeshm Island earthquake (M_W?=?5.9). The stress calculations further indicated stress load at the depth range (15–20 km) of the well-located aftershocks, corresponding to depths of the Hormuz Salt and top of the basement and providing plausible explanation for occurrence of the aftershocks within those layers.     

Space group and hydrogen sites of δ-AlOOH and implications for a hypothetical high-pressure form of Mg(OH)<Subscript>2</Subscript>

The space group and hydrogen positions of -(Al_0.84Mg_0.07Si_0.09)OOH are investigated using a single crystal synthesized using a multi-anvil apparatus under conditions of 1000 °C and 21 GPa. The space group determined by single-crystal X-ray diffraction is to Pnn2, with unit-cell parameters of a=4.6975(8) Å, b= 4.2060(6) Å, c=2.8327(4) Å, and V=55.97(1) ų. Partial occupancy of the Al site by Mg and Si suggests the possibility of a limited solid solution between -AlOOH, stishovite, and a hypothetical CaCl₂-type Mg(OH)₂ that is 16% denser than brucite. Difference-Fourier maps reveal two small but significant Fourier peaks attributable to hydrogen atoms. Atomic distances and angles around the first peak indicate a hydrogen bond with O···O distances of 2.511 Å, while those around the second peak are suggestive of a bifurcated hydrogen bond with O···O distances of 2.743 and 2.743 Å.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Heat capacity and thermodynamic functions of pretulite ScPO<Subscript>4</Subscript>(c) at 0–1600 K

The heat capacity of synthetic pretulite ScPO₄(c) was measured by adiabatic calorimetry within a temperature range of 12.13–345.31 K, and the temperature dependence of the pretulite heat capacity at 0–1600 K was derived from experimental and literature data on H ⁰(T)-H ⁰(298.15 K) for Sc orthophosphate. This dependence was used to calculate the values of the following thermodynamic functions: entropy, enthalpy change, and reduced Gibbs energy. They have the following values at 298.15 K: C _p ⁰ (298.15 K) = 97.45 ± 0.06 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 84.82 ± 0.18 J K⁻¹ mol⁻¹, H ⁰(298.15 K)-H ⁰(0) = 14.934 ± 0.016 kJ mol⁻¹, and Φ ⁰(298.15 K) = 34.73 ± 0.19 J K⁻¹mol⁻¹. The enthalpy of formation Δ _f H ⁰(ScPO₄, 298.15 K) = − 1893.6 ± 8.4 kJ mol⁻¹.     

Heat capacity and thermodynamic functions of xenotime YPO<Subscript>4</Subscript>(c) at 0–1600 K

The heat capacity of xenotime YPO₄(c) was measured by adiabatic calorimetry at 4.78–348.07 K. Our experimental and literature data on H ⁰(T)-H ⁰(298.15 K) of Y orthophosphate were utilized to derive the C _p ⁰(T) function of xenotime at 0–1600 K, which was then used to calculate the values of thermodynamic functions: entropy, enthalpy change, and reduced Gibbs energy. These functions assume the following values at 298.15 K: C _p ⁰ (298.15 K) = 99.27 ± 0.02 J K⁻¹ mol⁻¹, S ⁰(298.15 K) = 93.86 ± 0.08 J K⁻¹ mol⁻¹, H ⁰(298.15 K) − H ⁰(0) = 15.944 ± 0.005 kJ mol⁻¹, Φ⁰(298.15 K) = 40.38 ± 0.08 J K⁻¹ mol⁻¹. The value of the free energy of formation Δ _f G ⁰(YPO₄, 298.15 K) is −1867.9 ± 1.7 kJ mol⁻¹.     

Geochemistry of isotopes (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and depositional environment of the upper Kazanian carbonate sediments in the Volga-Vyatka interfluve

This work reports the results of lithological and isotopic study of carbonate rocks from the Pechishchi stratotype section (Kazan) and three adjacent sections of Kazanian rocks of the Volga-Vyatka region at the eastern Russian Platform. These sections were recovered by the Kremeshki, Popovtsevo, and Chimbulat quarries (near the town of Sovetsk, southeastern Kirov district). Lithological features and wide variations of δ¹³C (from −6.0 to 6.8‰) and δ¹⁸ O (from 22.9 to 33.4 ‰) indicate that the rocks were formed in a shallow-marine basin with rapidly varying conditions of sedimentation which characterize different facies (and/or paleoecological) zones: lagoonal, supralittoral, littoral, shoal. They also suggest processes of postsedimentary alteration (mainly, under supergene conditions). Numerous short-term hiatuses are also recorded.     

Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Synthetic ringwoodite γ-(Mg_1?x Fe _x )₂SiO₄ of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by ^VIFe²⁺ and ^VIFe³⁺, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe³⁺/Fe_total ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed ⁵ T _2g → ⁵ E _g transitions of ^VIFe²⁺ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm^?1 weakly depend on temperature, whilst the Fe²⁺/Fe³⁺ IVCT band at ~16,400 cm^?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe³⁺ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of ^VIFe²⁺ (the bands at ~8,600 and ~12,700 cm^?1) and Fe²⁺/Fe³⁺ IVCT transition (~18,100 cm^?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm^?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)₂SiO₄-spinels and that the single band is caused by the split spin-allowed ⁵ E → ⁵ T ₂ transition of ^IVFe²⁺. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).     

Geology and geochronology of the Betara region in south-southeastern Brazil: Evidence for possible Statherian (1.80–1.75 Ga) and Calymmian (1.50–1.45 Ga) extension events

The results of geological mapping, chemical analysis and radiometric dating of metabasic rocks of Betara Formation, and mapping and dating of those present in the Betara basement nucleus together with mylonitic granodiorite and syenogranite are reported here. U–Pb analysis of bulk zircon fractions from the metabasic rocks of the basement nucleus yielded a Statherian age of 1790 ± 22 Ma, while the metabasic rocks from the upper part of the Betara Formation yielded a Calymmian age between 1500 and 1450 Ma. This age is a minimum for the deposition of the Betara Formation. The older metabasic rocks are associated with post-tectonic, possibly anorogenic syenogranite, while the younger ones are gabbro or very porphyritic ankaramite whose REE patterns are consistent with crystallization from an N-MORB parent magma. The observations and data point to the probable events associated with extensional processes of the end of Paleoproterozoic and early Mesoproterozoic. Similar registers of Statherian (1.80–1.75 Ga) and Calymmian (1.50–1.45 Ga) extensional events are recorded in other parts of the South American and African continents. The Neoproterozoic witnessed the formation and junction of the tectonic slices which formed the Apiaí domain during the assemblage of western Gondwana.     

The ICL Network on “Landslides and Cultural & Natural Heritage (LACUNHEN)”

In recent decades, the concept of cultural heritage has evolved into one that encompasses an understanding of the history of humanity, together with scientific knowledge and intellectual attitudes. This changing concept has prompted a subsequent re-evaluation of what constitutes the outstanding universal values of World Heritage sites and the operational methods for implementing the UNESCO World Heritage Convention. The scope has broadened from studying a single monument in isolation to one that values a multidimensional, multiregional, and inter-disciplinary approach and encapsulates vast spans of human history. Within this broader view, landslides and more generally slope instabilities are an important factor endangering cultural heritage sites, especially prehistoric sites, earth/rock monuments, and archaeological sites affected by environmental processes and degradation. Natural and cultural heritage sites, as well as cultural landscapes, are then tied into a common framework that the Geological Society of America has defined “Men’s legacy to Earth and Earth’s legacy to Man”. On the other hand, not too much effort has been expended in the past to develop conservation policies systematically integrating geological, geomorphological, and engineering geological aspects into daily practices. The purpose of the “LAndslides and CUltural & Natural HEritage” thematic Network (LACUNHEN) is to create a platform for scientists and practitioners who are ready to jointly contribute to safeguarding relevant endangered Natural and Cultural Heritage sites (e.g., Machu Picchu). They will share and disseminate their respective experience, demonstrating how these special “objects” require approaches, techniques, and solutions that go far beyond traditional civil engineering perspectives.     

Fractionation of Carbonate Carbon (C<Subscript>carb</Subscript>) Accumulation between Continents and Oceans in the Late Mesozoic–Cenozoic

The C_carb masses per time unit was determined for separate oceanic basins and for the entire World Ocean using lithological–facies mapping of the Neo– and Eopleistocene age sections of the Pleistocene pelagic zones in the World Ocean. These parameters are compared with those of continents, continental shelves and slopes, and oceans, which were recalculated using data by Ronov (1993) for the Upper Jurassic–Pliocene. At the Mesozoic–Cenozoic boundary, carbonate accumulation was shifted from continents to oceans. The accumulation of carbonate sediments on continents is determined by areas of epicontinental seas. Significant role in the history of oceanic carbonate sedimentation is played by the nutrient fluxes from continents into the World Ocean. Subduction and evolution of the carbonate compensation depth (CCD) play significant role in calculating the quantitative parameters of carbonate accumulation in ocean.     

Electrical conductivity,thermopower and <Superscript>57</Superscript>Fe Mössbauer spectroscopy of aegirine (NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)

DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi₂O₆) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity _DC was determined by extrapolating AC data to zero frequency. In both directions, the log _DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of E_A 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of _DC [001] with _DC(300 K) 2.0 × 10^{–6 –1}cm^–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to _DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () ^s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to _DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe²⁺ Fe³⁺ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. ⁵⁷Fe Mössbauer spectroscopy was applied to detect Fe²⁺ in addition to the dominating concentration of Fe³⁺.     

用γ-射线吸收法及散射γ-射线法(γ-γ法)测定岩(矿)石密度

在找矿、勘探、开采过程中,常常需要知道岩(矿)石的密度值。习惯上常用物理方法测量岩(矿)石的密度(例如石腊方法等)。这些测密度方法与γ法相比,后者具有工作方法简单快速、精确、代表性好、费用低等优点。     

The Laalam (Algeria) damaging landslide triggered by a moderate earthquake (M<Subscript>w</Subscript> = 5.2)

On March 20th, 2006, a moderate earthquake (M_w = 5.2) struck the Laalam (NE-Algeria). The damage was centred in the Laalam village where four deaths, 68 injured and more than 40 housing units destroyed making dozens of peoples homeless. Damage and casualties are directly related to an earthquake-induced landslide occurred at 10 km far from the epicenter (ISC relocation). The landslide rupture, mapped by using a ground based survey, is striking NE-SW along a 1-km length rupture with a 45 cm of lateral displacement. The rupture plan is dipping 40° at the surface and showing horizontal striations. A 75 cm of pre-2006 lateral displacement is also observed indicating a repetitive behaviour of the landslide. The last time where the landslide was activated extends back to 1974 following another moderate earthquake. This landslide reminds us the high level hazard of induced ground failures due slope instabilities in mountainous zones of seismically active areas.