Mineralogy of the clay fraction of alfisols in two slope curvatures: IV - spatial correlation with physical properties

Although the influence of clay mineralogy on soil physical properties has been widely studied, spatial relationships between these features in Alfisols have rarely been examined. The purpose of this work was to relate the clay minerals and physical properties of an Alfisol of sandstone origin in two slope curvatures. The crystallographic properties such as mean crystallite size (MCS) and width at half height (WHH) of hematite, goethite, kaolinite and gibbsite; contents of hematite and goethite; aluminium substitution (AS) and specific surface area (SSA) of hematite and goethite; the goethite/(goethite+hematite) and kaolinite/(kaolinite+gibbsite) ratios; and the citrate/bicarbonate/dithionite extractable Fe (Fe d) were correlated with the soil physical properties through Pearson correlation coefficients and cross-semivariograms. The correlations found between aluminium substitution in goethite and the soil physical properties suggest that the degree of crystallinity of this mineral influences soil properties used as soil quality indicators. Thus, goethite with a high aluminium substitution resulted in large aggregate sizes and a high porosity, and also in a low bulk density and soil penetration resistance. The presence of highly crystalline gibbsite resulted in a high density and micropore content, as well as in smaller aggregates. Interpretation of the cross-semivariogram and classification of landscape compartments in terms of the spatial dependence pattern for the relief-dependent physical and mineralogical properties of the soil proved an effective supplementary method for assessing Pearson correlations between the soil physical and mineralogical properties.

Mineralogy of the clay fraction of alfisols in two slope curvatures: IV - spatial correlation with physical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The Dutung-Thaktote extensional fault zone and nappe structures documented by illite crystallinity and clay-mineral paragenesis in the Tethys Himalaya between Spiti river and Tso Morari, NW India

Numerous measurements by XRD of the Scherrer width at half-peak height (001 reflection of illite), coupled with analyses of clay-size assemblages, provide evidence for strong variations in the conditions of low temperature metamorphism in the Tethyan Himalaya metasediments between the Spiti river and the Tso Morari. Three sectors can be distinguished along the Spiti river-Tso Morari transect. In the SW, the Takling and Parang La area is characterised by a metamorphism around anchizone-epizone boundary conditions. Further north, in the Dutung area, the metamorphic grade abruptly decreases to weak diagenesis, with the presence of mixed-layered clay phases. At the end of the profile towards the NE, a progressive metamorphic increase up to greenschist facies is recorded, marked by the appearance of biotite and chloritoid. The combination of these data with the structural. observations permits to propose that a nappe stack has been crosscut by the younger Dutung-Thaktote extensional fault zone (DTFZ). The change in metamorphism across this zone helps to assess the displacements which occurred during synorogenic extension. In the SW and NE parts of the studied transect, a burial of 12 km has been estimated, assuming a geothermal gradient of 25 degrees C/km. In the SW part, this burial is due to the juxtaposition of the Shikar Beh and Mata nappes and in the NE part, solely to burial beneath the Mata nappe. In the central part of the profile, the effect of the DTFZ is to bring down diagenetic sediments in-between the two aforesaid metamorphic zones. The offset along the Dutung-Thaktote normal faults is estimated at 16 km.

Characterization of mineral surfaces using FIB and TEM: a case study of naturally weathered alkali feldspars

Using a focused ion beam (FIB) instrument, electron-transparent samples (termed foils) have been cut from the naturally weathered surfaces of perthitic alkali feldspars recovered from soils overlying the Shap granite, northwest England. Characterization of these foils by transmission electron microscopy (TEM) has enabled determination of the crystallinity and chemical composition of near-surface regions of the feldspar and an assessment of the influence of intragranular microtextures on the microtopography of grain surfaces and development of etch pits. Damage accompanying implantation of the 30 kV Ga+ ions used for imaging and deposition of protective platinum prior to ion milling creates amorphous layers beneath outer grain surfaces, but can be overcome by coating grains with > 85 nm of gold before FIB work. The sidewalls of the foil and feldspar surrounding original voids are also partially amorphized during later stages of ion milling. No evidence was found for the presence of amorphous or crystalline weathering products or amorphous "leached layers" immediately beneath outer grain surfaces. The absence of a leached layer indicates that chemical weathering of feldspar in the Shap soils is stoichiometric, or if non-stoichiometric, either the layer is too thin to resolve by the TEM techniques used (i.e., <=similar to 2.5 nm) or an insufficient proportion of ions have been leached from near-surface regions so that feldspar crystallinity is maintained. No evidence was found for any difference in the mechanisms of weathering where a microbial filament rests on the feldspar surface. Sub-micrometer-sized steps on the grain surface have formed where subgrains and exsolution lamellae have influenced the propagation of fractures during physical weathering, whereas finer scale corrugations form due to compositional or strain-related differences in dissolution rates of albite platelets and enclosing tweed orthoclase. With progressive weathering, etch pits that initiated at the grain surface extend into grain interiors as etch tubes by exploiting preexisting networks of nanopores that formed during the igneous history of the grain. The combination of FIB and TEM techniques is an especially powerful way of exploring mechanisms of weathering within the "internal zone" beneath outer grain surfaces, but results must be interpreted with caution owing to the ease with which artifacts can be created by the high-energy ion and electron beams used in the preparation and characterization of the foils.

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH I experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost similar to 9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >similar to 2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction. (C) 2008 Elsevier Ltd. All rights reserved.

The influence of heat treatment on the phase relations in mineral growth systems

ABSTRACT Corundum is one of the most famous gems materials. Different heat treatment methods for enhancement purposes are commonly applied and accepted in the gem market. With this reason, the identification of the natural, unheated corundum is intensively investigated. In this study, aluminium hydroxide minerals and zircon are focused to observe the crystallization and phase change of these minerals during heat treatment procedures. Aluminium hydroxide minerals can be transformed to alumina with the corundum structure by heating. The reaction history of aluminium hydroxide minerals containing corundum was investigated comparing it with diaspore, boehmite, gibbsite and bayerite by TG and DTA methods. These hydroxide minerals were entirely transformed to corundum after heating at 600°C. Zircon inclusions in corundums from Ilakaka, Madagascar, were investigated for the influence of different heat-treatment temperatures on the recovery of their crystalline structure and on possible reactions within and with the host crystals. The host corundum was heated at 500, 800, 1000, 1200, 1400, 1600 and 1800°C. The crystallinity, the trapped pressure, and the decomposition of the zircon inclusions within the host corundum have been investigated by Raman spectroscopy. Radiation-damaged zircon inclusions may be used as an indicator for unheated Ilakaka corundum crystals. They are fully recrystallized after heating at 1000°C influencing the lowering of the 3 Raman band shift, the decreasing of FWHM of the 3 Raman band and the decreasing of the trapped pressure between the inclusion and the host corundum. Under microscopic observation, surface alterations of the inclusions can be firstly seen from transparent into frosted-like appearance at 1400°C. Then, between 1600°C and 1800 °C, the inclusion becomes partly or even completely molten. The decomposition of the zircon inclusion to m-ZrO2 and SiO2-glass phases begins at the rim of the inclusion after heating from 1200°C to 1600°C which can be detected by the surface change, the increase of the 3 Raman band position and the trapped pressure. At 1800°C, the zircon inclusions entirely melt transforming to solid phases during cooling like m-ZrO2 and SiO2-glass accompanied by an increase of pressure between the transformed inclusion and its host.

Clay mineral and heavy metal composition of sea-bed surface sediments and pre-Holocene sediment samples taken during POLARSTERN cruise ANT-XXIII/9

Surface mineralogical compositions and their association to modern processes are well known from the east Atlantic and south-west Indian sectors of the Southern Ocean, but data from the interface of these areas - the Prydz Bay-Kerguelen region - is still missing. The objective of our study was to provide mineralogical data of reference samples from this region and to relate these mineralogical assemblages to hinterland geology, weathering, transport and depositional processes. Clay mineral assemblages were analysed by means of X-ray diffraction technique. Heavy mineral assemblages were determined by counting of gravity-separated grains under a polarizing microscope. Results show that by use of clay mineral assemblages four mineralogical provinces can be subdivided: i) continental shelf, ii) continental slope, iii) deep sea, iv) Kerguelen Plateau. Heavy mineral assemblages in the fine sand fraction are relatively uniform except for samples taken from the East Antarctic shelf. Our findings show that mineralogical studies on sediment cores from the study area have the potential to provide insights into past shifts in ice-supported transport and activity and provenance of different water masses (e.g. Antarctic slope current and deep western boundary current) in the Prydz Bay-Kerguelen region.

Clay mineral and stratigraphic record of two sediment cores from the Aegean Sea

Different source areas, oceanography and climate regimes influenced the clay mineral assemblages and grain size distribution of two sediment cores from the North and South Aegean Sea during the last glacial and the Holocene. In the North Aegean Sea, clay mineral composition is mainly controlled by sea level evolution, melting of southeastern European glaciers, and establishment of the connection between the Black Sea and Aegean Sea. The long-term development of clay mineral assemblages in the South Aegean Sea reflects changes in the Nile discharge and African dust input. At this site, the establishment of pluvial conditions in the Nile catchment during the early to middle Holocene resulted in a substantial rise in smectite/illite ratios. In the late Holocene, stepwise aridification of the southern borderlands caused an increase in windblown sediment material and a decrease in Nile suspended material. The clay mineral records exhibit periodic millennial-scale fluctuations. In the North Aegean Sea, the changes are centred at a period of 1.3-1.8 ka and can be attributed to short-term climate and weathering changes in the northern borderlands. The changes in the South Aegean Sea are centred at periods of 3.2-4.3, 1.9-2.4 and 1.3-1.7 ka reflecting short-term changes in wind strength and Northeast African hydrology.

Mineral, chemical and isotope compositions of clay subfractions from formations of the Srednii Peninsula, Murmansk coast of the Barents Sea

Fine-grained clay subfractions (SFs) with particle size of <0.1, 0.1-0.2, 0.2-0.3, 0.3-0.6, 0.6-2.0, and 2-5 µm separated from claystone of Upper Precambrian Pumanskaya and Poropelonskaya formations on the Srednii Peninsula were studied by transmission electron microscopy, X-ray diffraction, and Rb-Sr methods. All subfractions consist of low-temperature illite and chlorite, and contribution of chlorite decreases with diminishing particle size. The crystallinity index and I002/I001 ratio increase from coarse- to fine-grained SFs. Leaching by ammonium acetate solution and Rb-Sr systematics in combination with mineralogical and morphological data indicate that illite in Upper Proterozoic claystone from the Srednii Peninsula formed during three time intervals: 810-830, 610-620, and about 570 Ma ago. The first generation of this mineral with low Rb/Sr ratio dominates in coarse-grained SFs while the second and third generations with a high Rb/Sr ratio prevail in fine-grained SFs. All of three generations are known in Poropelon claystone, whereas Puman claystone contains only illite of the first and second generations. Geological processes responsible for multistage illite evolution in claystones are discussed.

Zinc deposits and related mineralization of the Burketown mineral field, including the world-class Century Deposit, Northern Australia: Fluid inclusion and stable isotope evidence for basin fluid sources

The stratiform Century Zn-Pb deposit and the discordant Zn-Pb lode deposits of the Burketown mineral field, northern Australia, host ore and gangue minerals with primary fluid inclusions that have not been affected by the Isan orogeny, thus providing a unique opportunity to investigate the nature of the ore-forming brines. All of the deposits are hosted in shales and siltstones belonging to the Isa superbasin and comprise sphalerite, pyrite, carbonate, quartz, galena, minor chalcopyrite, and minor illite. According to Pb model ages, the main ore stage of mineralization at Century formed at I575 Ma, some 20 m.y. after deposition of the host shale sequence. Microthermometry on undeformed, primary fluid inclusions hosted in porous sphalerite shows that the Zn at Century was transported to the deposit by a homogeneous, Ca2+- and Na+-bearing brine with a salinity of 21.6 wt percent NaCl equiv. delta D-fluid of the fluid inclusion water ranges from -89 to -83 per mil, consistent with a basinal brine that evolved from meteoric water. Fluid inclusion homogenization temperatures range between 74 degrees and 125 degrees C, which are lower than the 120 degrees to 160 degrees C range calculated from vitrinite reflectance and illite crystallinity data from the deposit. This discrepancy indicates that mineralization likely formed at 50 to 85 Mpa, corresponding to a depth of 1,900 to 3,100 m. Transgressive galena-sphalerite veins that cut stratiform mineralization at Century and breccia-filled quartz-dolomite-sphalerite-galena veins in the discordant Zn-Pb lodes have Pb model ages between 1575 and 1485 Ma. Raman spectroscopy and microthermometry reveal that the primary fluid inclusions in these veins contain Ca2+, Na+. but they have lower salinities between 23 and 10 wt percent NaCl equiv and higher delta D-fluid values ranging from -89 to -61 per mil than fluid inclusions in porous sphalerite from Century. Fluid inclusion water from sphalerite in one of the lode deposits has delta O-18(fluid) values of 1.6 and 2.4 per mil, indistinguishable from delta O-18(fluid) values between -0.3 to +7.4 per mil calculated from the isotopic composition of coexisting quartz, dolomite, and illite. The trend toward lower salinities and higher delta D-fluid values relative to the earlier mineralizing fluids is attributed to mixing between the fluid that formed Century and a seawater-derived fluid from a different source. Based on seismic data from the Lawn Hill platform and paragenetic and geochemical results from the Leichhardt River fault trough to the south, diagenetic aquifers in the Underlying Calvert superbasin appear to have been the most likely sources for the fluids that formed Century and the discordant lode deposits. Paragenetically late sphalerite and calcite cut sphalerite, quartz, and dolomite in the lode deposits and contain Na+-dominated fluid inclusions with much lower salinities than their older counterparts. The isotopic composition of calcite also indicates delta O-18(fluid) from 3.3 to 10.7 per mil, which is larger than the range obtained from synmineralization minerals, supporting the idea that a unique fluid source was involved. The absolute timing of this event is unclear, but a plethora of Pb model, K-Ar, and Ar-40/Ar-39 ages between 1440 and 1300 Ma indicate that a significant volume of fluid was mobilized at this time. The deposition of the Roper superbasin from ca. 1492 +/- 4 Ma suggests that these late veins formed from fluids that may have been derived from aquifers in overlying sediments of the Roper superbasin. Clear, buck, and drusy quartz in veins unrelated to any form of Pb-Zn mineralization record the last major fluid event in the Burketown mineral field and form distinct outcrops and ridges in the district. Fluid inclusions in these veins indicate formation from a low-salinity, 300 degrees +/- 80 degrees C fluid. Temperatures approaching 300 degrees C recorded in organic matter adjacent to faults and at sequence boundaries correspond to K-Ar ages spanning 1300 to 1100 Ma, which coincides with regional hydrothermal activity in the northern Lawn Hill platform and the emplacement of the Lakeview Dolerite at the time of assemblage of the Rodinia supercontinent.