Differences in grain growth of calcite: a field-based modeling approach

Normal grain growth of calcite was investigated by combining grain size analysis of calcite across the contact aureole of the Adamello pluton, and grain growth modeling based on a thermal model of the surroundings of the pluton. In an unbiased model system, i.e., location dependent variations in temperature-time path, 2/3 and 1/3 of grain growth occurs during pro- and retrograde metamorphism at all locations, respectively. In contrast to this idealized situation, in the field example three groups can be distinguished, which are characterized by variations in their grain size versus temperature relationships: Group I occurs at low temperatures and the grain size remains constant because nano-scale second phase particles of organic origin inhibit grain growth in the calcite aggregates under these conditions. In the presence of an aqueous fluid, these second phases decay at a temperature of about 350 °C enabling the onset of grain growth in calcite. In the following growth period, fluid-enhanced group II and slower group III growth occurs. For group II a continuous and intense grain size increase with T is typical while the grain growth decreases with T for group III. None of the observed trends correlate with experimentally based grain growth kinetics, probably due to differences between nature and experiment which have not yet been investigated (e.g., porosity, second phases). Therefore, grain growth modeling was used to iteratively improve the correlation between measured and modeled grain sizes by optimizing activation energy (Q), pre-exponential factor (k₀) and grain size exponent (n). For n=2, Q of 350 kJ/mol, k₀ of 1.7×10²¹ mⁿs^–1 and Q of 35 kJ/mol, k₀ of 2.5×10^-5 mⁿs^–1 were obtained for group II and III, respectively. With respect to future work, field-data based grain growth modeling might be a promising tool for investigating the influences of secondary effects like porosity and second phases on grain growth in nature, and to unravel differences between nature and experiment.Editorial responsibility: J. Hoefs     

Cognate clinopyroxene from Paleogene mantle xenolith-bearing basanite lavas (East Serbia, SE Europe): the role of dissolution of mantle orthopyroxene

The study focuses on clinopyroxene from mantle xenolith-bearing East Serbian basanites and suggests that dissolution of mantle orthopyroxene played an important role in at least some stages of the crystallization of these alkaline magmas. Five compositional types of clinopyroxene are distinguished, some of them having different textural forms: megacrysts (Type-A), green/colourless-cored phenocrysts (Type-B), overgrowths and sieve-textured cores (Type-C), rims and matrix clinopyroxene (Type-D), and clinopyroxene from the reaction rims around orthopyroxene xenocrysts (Type-E). Type-A is high-Al diopside that probably crystallized at near-liquidus conditions either directly from the host basanite or from compositionally similar magmas in previous magmatic episodes. Type-B cores show high ^VIAl/^IVAl≥1 and low Mg# of mostly <75 and are interpreted as typical xenocrysts. Type-C, D and E are interpreted as typical cognate clinopyroxene. Type-D has Mg#<78, Al₂O₃?=?6–13?wt.%, TiO₂?=?1.5–4.5?wt.%, and Na₂O?=?0.4–0.8?wt.% and compositionally similar clinopyroxene is calculated by MELTS as a phase in equilibrium with the last 30?% of melt starting from the average host lava composition. Type-C has Mg#?=?72–89, Al₂O₃?=?4.5–9.5?wt.%, TiO₂?=?1–2.5?wt.%, Na₂O?=?0.35–1?wt.% and Cr₂O₃?=?0.1–1.5?wt.%. This clinopyroxene has some compositional similarities to Type-E occurring exclusively around mantle orthopyroxene. Cr/Al vs Al/Ti and Cr/Al vs Na/Ti plots revealed that Type-C clinopyroxene can crystallize from a mixture of the host basanite magma and 2–20?wt.% mantle orthopyroxene. Sieve-textured Type-C crystals show characteristics of experimentally produced skeletal clinopyroxene formed by orthopyroxene dissolution suggesting that crystallization of Type-C was both texturally and compositionally controlled by orthopyroxene breakdown. According to FeO/MgO^cpx/melt modelling the first clinopyroxene precipitating from the host basanite was Type-A (T?~?1250?°C, p?~?1.5?GPa). Dissolution of orthopyroxene produced decreasing FeO/MgO^melt and crystallization of Type-E and sieve-textured Type-C clinopyroxene (0.3–0.8?GPa and 1200–1050?°C). The melt composition gradually shifted towards higher FeO/MgO^melt ratios precipitating more evolved Type-C and Type-D approaching near-solidus conditions (<0.3?GPa; ~950?°C).     

Dauphiné twinning and texture memory in polycrystalline quartz. Part 3: texture memory during phase transformation

Samples of quartz-bearing rocks were heated above the α (trigonal)–β (hexagonal) phase transformation of quartz (625–950°C) to explore changes in preferred orientation patterns. Textures were measured both in situ and ex situ with neutron, synchrotron X-ray and electron backscatter diffraction. The trigonal–hexagonal phase transformation does not change the orientation of c- and a-axes, but positive and negative rhombs become equal in the hexagonal β-phase. In naturally deformed quartzites measured by neutron diffraction a perfect texture memory was observed, i.e. crystals returned to the same trigonal orientation they started from, with no evidence of twin boundaries. Samples measured by electron back-scattered diffraction on surfaces show considerable twinning and memory loss after the phase transformation. In experimentally deformed quartz rocks, where twinning was induced mechanically before heating, the orientation memory is lost. A mechanical model can explain the memory loss but so far it does not account for the persistence of the memory in quartzites. Stresses imposed by neighboring grains remain a likely cause of texture memory in this mineral with a very high elastic anisotropy. If stresses are imposed experimentally the internal stresses are released during the phase transformation and the material returns to its original state prior to deformation. Similarly, on surfaces there are no tractions and thus texture memory is partially lost.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.     

Considerations on the European Standard EN 14157 Test Methods: Abrasion Resistance of Natural Stones Used for Flooring in Buildings

In Europe, the Wide Wheel abrasion (WWA) test and the B?hme abrasion (BA) test are among the most widely used standard test methods for determining abrasion resistance of natural stones, the former being the reference test method in EN 14157 Standard. However, it is stated in the Annex-A (Informative) of EN 14157 Standard that very limited data are available to provide correlations between these two test methods. To be able to fill this gap, in this study, 25 different natural stones belonging to sedimentary, metamorphic and igneous groups were tested for their abrasion resistance as well as physico-mechanical properties. Also, for a better interpretation of abrasion resistance characteristics of the tested stone materials, relationships between abrasion resistance and physico-mechanical properties were statistically examined. A statistically significant linear correlation (R ² = 0.85; P value = 0.000) was established between the WWA test and the BA test, which could be used in practice for converting the measured abrasion resistance values from one testing method to another. It was also found that the correlation between these two test methods improved significantly (R ² = 0.93; P value = 0.001) when relatively high-porosity stone materials (porosity ≥1%) were separately evaluated. Both methods of abrasion resistance employed in the present study showed statistically significant linear correlations with uniaxial compressive strength and Brazilian tensile strength, the former proving to be a more influencing parameter on resistance to abrasion. Also, from the point view of representing actual abrasion mechanism of stone materials in practice, the necessity of simulating multi-directional foot traffic in abrasion testing methods was discussed. In this respect, the reference test method in the EN 14157 Standard was criticized for not fully meeting this requirement. It was also pointed out that the reference method could have some drawbacks when applied to coarse-grained granitic rocks having cleavable minerals such as plagioclase and orthoclase feldspars.     

离子色谱法测定水样中S~(2-)、SO_3~(2-)、SO_4~(2-)、S_2O_3~(2-)

该种方法利用离子色谱仪的电导检测器与电化学检测器串联 ,十几分钟即可连续完成水中S2 - 、SO2 - 3 、SO2 - 4、S2 O2 - 3 的测定 ,方法具有快速、高效、方便、灵敏、选择性好等特点。方法的检出限分别为 :S2 - 12 5 μg/L ;SO2 - 3 2 2 4 μg/L ;SO2 - 45 0 μg/L ;S2 O2 - 35 0 μg/L。相对标准偏差在 1 5 %～ 6 9%之间 ,能够满足水中S2 - 、SO2 - 3 、SO2 - 4、S2 O2 - 3四种阴离子分析测试的需要。     

Environmental controls on clay mineralogy of an Early Jurassic mudrock (Blue Lias Formation,southern England)

We present a dataset including clay mineralogy, gamma-ray spectrometry, organic matter content and magnetic susceptibility of the Hettangian to lowest Sinemurian successions of Dorset and Somerset, southern UK (Blue Lias Formation, Bristol Channel and Wessex basins). In both areas, the clay assemblages comprise predominantly detrital illite, kaolinite and illite/smectite mixed layers. Clays probably originated from the erosion of the Hercynian massifs, the relative proportions of kaolinite and illite being modulated by arid-humid climatic fluctuations. The organic matter (OM) content (types II to IV) ranges up to 12% in both areas. A clear stratigraphical trend in clay mineral assemblages is apparent in Somerset, whereas in Dorset sharp contrasts between adjacent horizons and a greater dilution by carbonate mask the long-term evolution. Correlations between both areas based on similar vertical trends in clay mineral abundance support the suggestion of a hiatus within the angulata Zone of the Dorset succession. As expected, the kaolinite/illite ratio correlates with the Th/K ratio deduced from gamma-ray spectrometry. However, significant departures from the correlation occur in OM-rich intervals, suggesting that Th may be partly adsorbed on to OM particles. Surprisingly, high magnetic susceptibility correlates with abundant kaolinite, not with Fe-rich clays, indicating either that kaolinite is accompanied by a soil-inherited magnetisable phase (possibly iron oxide) or that illite-rich rocks are more strongly diluted by carbonate than are kaolinite-rich strata.     

Arsenic in contaminated soils and anthropogenic deposits at the Mokrsko,Roudný, and Kašperské Hory gold deposits,Bohemian Massif (CZ)

Soil, mine tailing, and waste dump profiles above three mesothermal gold deposits in the Bohemian Massif with different anthropogenic histories have been studied. Their mineralogical, major element, and arsenic (As) contents and the contents of secondary arsenic minerals were analyzed. The As-bearing minerals were concentrated and determined using X-ray diffraction (XRD) analysis, the Debye-Scherrer powder method, scanning electron microscopy (SEM), and energy-dispersive microanalysis (EDAX). The amorphous hydrous ferric oxides (HFO), As-bearing goethite, K-Ba- or Ca-Fe- and Fe- arsenates pharmacosiderite, arseniosiderite, and scorodite, and sulfate-arsenate pitticite were determined as products of arsenopyrite or arsenian pyrite oxidation. The As behaviour in the profiles studied differs in dependence on the surface morphology, chemical and mineralogical composition of the soil, mine wastes or tailings, oxidation conditions, pH, presence of (or distance from) primary As mineralization in the bedrock, and duration of the weathering effect. Although the primary As mineralization and the bedrock chemical composition are roughly similar, there are distinct differences in the As behaviour amongst the Mokrsko, Roudný and Kaperské Hory deposits.     

Investigations and assessment of the landslide hazards of Fengdu county in the reservoir region of the Three Gorges project on the Yangtze River

The spatial database of landslides in Fengdu County of the reservoir region of the Three Gorges project (TGP) on the Yangtze River was compiled from a variety of different sources including field investigations on landslides, existing catalogues and archives on landslides, reports of meteorological events and human engineering activities that triggered slope failures. The major factors that are found to have affected the slope stabilities are outlined, and an assessment and zonation of landslide hazards of the region is made using an integrated information model, which is divided into destructive, disastrous, likely disastrous and essentially non-disastrous areas from the assessment of landslide hazards. The destructive and disastrous areas are respectively 1.9 and 13.8% of the total region, mostly being nearby townships, highways along the south bank of the Yangtze River and residential quarters along two flanks of the Yangtze River and its distributaries, that will impose direct impact to highway transportation and residential lives, and may effect to some degree the navigation of the Yangtze River, reservoir banks, and building of cities and towns.     

The effect of chemical composition and oxygen fugacity on the electrical conductivity of dry and hydrous garnet at high temperatures and pressures

The in situ electrical conductivity of hydrous garnet samples (Py₂₀Alm₇₆Grs₄–Py₇₃Alm₁₄Grs₁₃) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe₂O₃ + Fe₃O₄, Ni + NiO, Fe + Fe₃O₄, Fe + FeO, and Mo + MoO₂). Experimental results indicate that within a frequency range from 10⁻² to 10⁶ Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py₂₀Alm₇₆Grs₄, Py₃₀Alm₆₇Grs₃, Py₅₆Alm₄₃Grs₁, and Py₇₃Alm₁₄Grs₁₃) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py₇₃Alm₁₄Grs₁₃ garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm³/mol, respectively. The results show that small hopping polarons ( \textFe_\textMg ^· ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH ^· {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.