Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

Electrons in feldspar II: a consideration of the influence of conduction band-tail states on luminescence processes

 Most natural feldspars contain many charged impurities, and display a range of bond angles, distributed about the ideal. These effects can lead to complications in the structure of the conduction band, giving rise to a tail of energy states (below the high-mobility conduction band) through which electrons can travel, but with reduced mobility: transport through these states is expected to be thermally activated. The purpose of this article is twofold. Firstly, we consider what kind of lattice perturbations could give rise to both localized and extended conduction band-tail states. Secondly, we consider what influence the band tails have on the luminescence properties of feldspar, where electrons travel through the sample prior to recombination. The work highlights the dominant role that 0.04–0.05-eV phonons play in both the luminescence excitation and emission processes of these materials. It also has relevance in the dating of feldspar sediments at elevated temperatures. Received: 11 May 2001 / Accepted: 6 September 2001     

The Port Mouton Shear Zone: intersection of a regional fault with a crystallizing granitoid pluton

The peraluminous tonalite–monzogranite Port Mouton Pluton is a petrological, geochemical, structural, and geochronological anomaly among the many Late Devonian granitoid intrusions of the Meguma Lithotectonic Zone of southern Nova Scotia. The most remarkable structural feature of this pluton is a 4-km-wide zone of strongly foliated (040/subvertical) monzogranites culminating in a narrow (10–30 m), straight, zone of compositionally banded rocks that extends for at least 3 km along strike. The banded monzogranites consist of alternating melanocratic and leucocratic compositions that are complementary to the overall composition of that part of the pluton, suggesting an origin by mineral–melt and mineral–mineral sorting. Biotite and feldspar are strongly foliated in the plane of the compositional bands. These compositional variations and foliations originated by a process of segregation flow during shearing of the main magma with a crystallinity of 55–75%. Subsequent minor brittle fracturing of feldspars, twinning of microcline, development of blocky sub-grains in quartz, and kinking of micas demonstrate overprinting by a high-temperature deformation straddling the monzogranite solidus. Small folds and late sigmoidal dykes indicate dextral movement on the shear zone. This Port Mouton Shear Zone (PMSZ) is approximately co-linear with the only outcrops of Late Devonian mafic intrusions in the area, two of which are syn-plutonic with well-developed mingling textures in the marginal tonalite of the Port Mouton Pluton. Also closely co-linear with the mafic intrusions are a granitoid dyke that extends well beyond the outer contact of the Port Mouton Pluton, a swarm of large aligned angular xenolithic slabs, a zone of thin wispy schlieren banding, a large Be-bearing pegmatite, and a breccia pipe with abundant garnetiferous metapelitic xenoliths. In various ways, the shear zone may control all of these features. The Port Mouton Shear Zone is parallel to many other NE-trending faults and shear zones in the northern Appalachians, probably related to the docking of the Meguma Zone along the Cobequid–Chedabucto Fault system.     

A Model for the polar motion of the deformable Earth adequate for astrometric data

Refined analytical expressions for the frequencies corresponding to the Chandler motion of the pole and the diurnal rotation of the deformable Earth are derived. Numerical estimates of the period and amplitude of the polar oscillations are presented. The trajectory of the Chandler polar motion derived via numerical modeling is in qualitative and quantitative agreement with experimental data from the International Earth Rotation Service (IERS). An evolutionary model describing slow variations in the Earth’s rotation parameters under the action of the dissipative moments of the tidal gravitational forces on time scales considerably longer than the precession period of the Earth’s axis is constructed. The axis of the Earth’s figure tends to approach the angular momentum vector of the proper rotation.     

Origin of spongy textures in clinopyroxene and spinel from mantle xenoliths, Hessian Depression, Germany

Summary Spongy textures are observed in anhydrous Group 1 mantle xenoliths (harzburgite, lherzolite and wehrlite) hosted in Tertiary alkali basaltic lavas from the Hessian Depression, Germany. These textures are developed only on clinopyroxene and spinel, and occur as rims or cross-cutting veinlets and patches showing optical continuity with the host grain. They are often associated with pools of amorphous glassy material. There is no preferential development of spongy domains against the xenolith-lava contact suggesting that the host magma did not play any significant role in their formation. Spongy clinopyroxene and spinel occur in all rock types, but, are more pervasive in wehrlite. Chemically, spongy domains of clinopyroxene and spinel are more refractory than unaffected areas, which is consistent with their formation through a partial melting event. The associated glassy material shows chemical characteristics which suggest that the melt pools are genetically related to the development of the spongy textures. The partial melting event was probably triggered by the infiltration of a low-density fluid. The fluid may have evolved from a silicate melt responsible for the metasomatic Fe-enrichment recorded in wehrlite. In this context, the more pervasive development of spongy clinopyroxene in wehrlite may be explained by a higher concentration of the evolved fluid phase at proximity to its silicate melt source. Received March 15, 2000; revised version accepted September 6, 2001     

Dissolution channels in quartz and the role of pressure changes in gold and sulfide deposition in the Archean, greenstone-hosted, Hutti gold deposit, Karnataka, India

The pressure, temperature and composition of ore fluids that resulted in gold deposition in the Archean, greenstone-hosted Hutti deposit have been studied using fluid inclusions and the compositions of arsenopyrite and chlorite. Five types of fluids have been identified in fluid inclusions in quartz veins associated with mineralization. They are (1) monophase CO ₂-rich fluid; (2) low-salinity (0 to 14 wt% NaCl equivalent) and high-salinity (16 to 23 wt% NaCl equiv.) aqueous fluids; (3) high-salinity (28 to 40 wt% NaCl equiv.), polyphase aqueous fluids; (4) CO ₂–H ₂O–NaCl fluids of low salinity (0–8 wt% NaCl equiv.); and (5) a few carbonic inclusions with halite±nahcolite. The diversity of entrapped fluid composition is explained in terms of changes in fluid pressure and temperature which affect a more or less uniform supply of primary low-salinity CO ₂–H ₂O–NaCl fluid to the shear zone. Geothermobarometric studies indicate that during mineralization temperature ranged between 360 and 240 °C, and fluid pressure between 3,600 and 1,600 bar. The data are interpreted in terms of the cyclic fault-valve mechanism for active shear zones. Deposition of gold and sulfides has been studied on the basis of constraints from the composition of wall-rock chlorite, ore-mineral assemblages, and textural features. Tubular channels, 20 to 100 µm wide and up to 500 µm long that arise from fractures and C-planes in sheared quartz veins are reported for the first time. The channels have pyrrhotite, arsenopyrite, pyrite and gold at their distal ends, with calcite filling up the remaining part. These channels form in response to increases in T and P, by dissolution of quartz grains, guided by dislocations in them. At the P– T conditions of interest, gold and sulfide deposition takes place in the shears and fractures of quartz veins from CO ₂–H ₂O–NaCl ore fluid of low salinity and pH due to changes in phase compositions that occur during the process of shear failure of the enclosing rocks. In the wall rock where pH is buffered, gold deposition takes place from the predominant Au(HS) ₂ ^- species with progressive sulfide deposition and decrease in SS, from 0.01 to 0.001 mol/kg as T falls from 360 to 240 °C.     

Rare gas isotopes and parent trace elements in ultrabasic-alkaline-carbonatite complexes, Kola Peninsula: identification of lower mantle plume component

During the Devonian magmatism (370 Ma ago) ∼20 ultrabasic-alkaline-carbonatite complexes (UACC) were formed in the Kola Peninsula (north-east of the Baltic Shield). In order to understand mantle and crust sources and processes having set these complexes, rare gases were studied in ∼300 rocks and mineral separates from 9 UACC, and concentrations of parent Li, K, U, and Th were measured in ∼70 samples. ⁴He/³He ratios in He released by fusion vary from pure radiogenic values ∼10⁸ down to 6 × 10⁴. The cosmogenic and extraterrestrial sources as well as the radiogenic production are unable to account for the extremely high abundances of ³He, up to 4 × 10⁻⁹ cc/g, indicating a mantle-derived fluid in the Kola rocks. In some samples helium extracted by crushing shows quite low ⁴He/³He = 3 × 10⁴, well below the mean ratio in mid ocean ridge basalts (MORB), (8.9 ± 1.0) × 10⁴, indicating the contribution of ³He-rich plume component. Magnetites are principal carriers of this component. Trapped ³He is extracted from these minerals at high temperatures 1100°C to 1600°C which may correspond to decrepitation or annealing primary fluid inclusions, whereas radiogenic ⁴He is manly released at a temperature range of 500°C to 1200°C, probably corresponding to activation of ⁴He sites degraded by U, Th decay.Similar ⁴He/³He ratios were observed in Oligocene flood basalts from the Ethiopian plume. According to a paleo-plate-tectonic reconstruction, 450 Ma ago the Baltica (including the Kola Peninsula) continent drifted not far from the present-day site of that plume. It appears that both magmatic provinces could relate to one and the same deep-seated mantle source.The neon isotopic compositions confirm the occurrence of a plume component since, within a conventional ²⁰Ne/²²Ne versus ²¹Ne/²²Ne diagram, the regression line for Kola samples is indistinguishable from those typical of plumes, such as Loihi (Hawaii). ²⁰Ne/²²Ne ratios (up to 12.1) correlate well with ⁴⁰Ar/³⁶Ar ones, allowing to infer a source ⁴⁰Ar/³⁶Ar ratio of about 4000 for the mantle end-member, which is 10 times lower than that of the MORB source end-member. In (³He/²²Ne)_PRIM versus (⁴He/²¹Ne)_RAD plot the Kola samples are within array established for plume and MORB samples; almost constant production ratio of (⁴He/²¹Ne)_RAD ≅ 2 × 10⁷ is translated via this array into (³He/²²Ne)_PRIM ∼ 10. The latter value approaches the solar ratio implying the non-fractionated solar-like rare gas pattern in a plume source.The Kola UACC show systematic variations in the respective contributions of in situ-produced radiogenic isotopes and mantle-derived isotopes. Since these complexes were essentially plutonic, we propose that the depth of emplacement exerted a primary control on the retention of both trapped and radiogenic species, which is consistent with geological observations. The available data allow to infer the following sequence of processes for the emplacement and evolution of Kola Devonian UACC: 1) Ascent of the plume from the lower mantle to the subcontinental lithosphere; the plume triggered mantle metasomatism not later than ∼700 to 400 Ma ago. 2) Metasomatism of the lithosphere (beneath the central part of the Kola Peninsula), including enrichment in volatile (e.g., He, Ne) and in incompatible (e.g., U, Th) elements. 3) Multistage intrusions of parental melts, their degassing, and crystallisation differentiation ∼370 Ma ago. 4) Postcrystallisation migration of fluids, including loss of radiogenic and of trapped helium. Based on model compositions of the principle terrestrial reservoirs we estimate the contributions (by mass) of the plume material, the upper mantle material, and the atmosphere (air-saturated groundwater), into the source of parent melt at ∼2%, 97.95%, and ∼0.05%, respectively.     

Kinetics of Mn(II) oxidation by Leptothrix discophora SS1

The kinetics of Mn(II) oxidation by the bacterium Leptothrix discophora SS1 was investigated in this research. Cells were grown in a minimal mineral salts medium in which chemical speciation was well defined. Mn(II) oxidation was observed in a bioreactor under controlled conditions with pH, O₂, and temperature regulation. Mn(II) oxidation experiments were performed at cell concentrations between 24 mg/L and 35 mg/L, over a pH range from 6 to 8.5, between temperatures of 10°C and 40°C, over a dissolved oxygen range of 0 to 8.05 mg/L, and with L. discophora SS1 cells that were grown in the presence of Cu concentrations ranging from zero to 0.1 μM. Mn(II) oxidation rates were determined when the cultures grew to stationary phase and were found to be directly proportional to O₂ and cell concentrations over the ranges investigated. The optimum pH for Mn(II) oxidation was approximately 7.5, and the optimum temperature was 30°C. A Cu level as low as 0.02 μM was found to inhibit the growth rate and yield of L. discophora SS1 observed in shake flasks, while Cu levels between 0.02 and 0.1 μM stimulated the Mn(II) oxidation rate observed in bioreactors. An overall rate law for Mn(II) oxidation by L. discophora as a function of pH, temperature, dissolved oxygen concentration (D.O.), and Cu concentration is proposed. At circumneutral pH, the rate of biologically mediated Mn(II) oxidation is likely to exceed homogeneous abiotic Mn(II) oxidation at relatively low (≈μg/L) concentrations of Mn oxidizing bacteria.