Atomistic simulation of the structure and segregation to the (0001) and surfaces of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

The segregation of ten isovalent impurities (Al³⁺ Cr³⁺, Eu³⁺, Gd³⁺, Ho³⁺, La³⁺, Lu³⁺, Nd³⁺, Tb³⁺, Y³⁺) to the and the (0001) surfaces of haematite (-Fe₂O₃) have been studied using atomistic simulation where the forces between the atoms are modelled using the Born model of solids. Segregation is found to be energetically favoured in virtually every case. The results for the surface show that the most favourable impurity surface concentration is 33.33%. The (0001) surface has two possible terminations, one terminated by iron atoms and the other by oxygen. No minimum is calculated for the Fe termination of the (0001) surface at low temperatures, but when the effect of raising the temperature is considered, an energy minimum is found, also at 33.33% impurity coverage. In contrast, the O terminated (0001) surface has a minimum in the segregation energy for between 16.67 and 33.33% depending on the cation being considered.     

Local relaxation around [6]Cr 3+ in synthetic pyrope–knorringite garnets, [8]Mg 3 [6](Al 1-X Cr X 3+) 2 [4]Si 3O 12, from electronic absorption spectra

Pyrope-knorringite garnets, Mg₃(Al_1-X Cr³⁺_X)₂Si₃O₁₂ with X=0.25, 0.50, and 1.00, were synthesized between 9 and 16 GPa and 1300 and 1600 °C, using multianvil high-pressure techniques. The garnets with X=0.25 and 0.50 are fine-grained, pink and violet in color. The end-member knorringites with X=1.00 are black when compact and gray when coarse-grained. The fine powder is greenish gray in natural light and pale pink under a tungsten lamp. Powder remission spectra in the wavenumber range 30 000–10 000 cm^–1 on finely powdered crystals were measured by two different methods: (I.) by the use of a small integrating sphere for small samples or (II.) microscope-spectrometric measurement using diffusely reflected radiation from a 45° illuminated microsample. Both methods yielded similar diffuse reflectance spectra. The following crystal-field parameters of ^[6]Cr³⁺ were determined for garnets with X=0.25, 0.50, 1.00: 10 Dq=17 856, 17 596, 17 286 cm^–1; and B=654, 677, 706 cm^–1; nephelauxetic ratio =(B_field/B_free)= 0.71, 0.74, 0.77. The -values indicate decreasing covalency of the Cr–O bond with increasing Cr content. The 10 Dq value for together with the mean Cr–O distance in end-member knorringite, 1.96 Å (Novak and Gibbs 1971), were used to calculate from the spectral data, local mean Cr–O distances (Langer 2001a) as a function of composition. The results indicate relatively strong local site relaxation with a value of =0.77.     

Stable isotope geochemistry and phase equilibria of coesite-bearing whiteschists,Dora Maira Massif,western Alps

Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The ¹⁸O(smow) values of the quartz (after coesite) (¹⁸O=8.1 to 8.6, n=6), phengite (6.2 to 6.4, n=3), kyanite (6.1, n=2), garnet (5.5 to 5.8, n=9), ellenbergerite (6.3, n=1) and rutile (3.3 to 3.6, n=3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700–750 °C. Minimum pressures are 31–32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc+kyanite=pyrope+coesite+H₂O, the a(H₂O) must be reduced to 0.4–0.75 at 700–750 °C. The reduced a(H₂O) cannot be due to dilution by CO₂, as pyrope is not stable at X(CO₂)>0.02 (T=750 °C; P=30 kb). In the absence of a more exotic fluid diluent (e.g. CH₄ or N₂), a melt phase is required. Granite solidus temperatures are 680 °C/30 kb at a(H₂O)=1.0 and are calculated to be 70°C higher at a(H₂O)=0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H₂O) estimates for the whiteschist are 34±2 kb, 700–750 °C and 0.4–0.75. The oxygen isotope fractionation between quartz (¹⁸O=11.6) and garnet (¹⁸O=8.7) in the surrounding orthognesiss is identical to that in the coesitebearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (D(_SMOW)=-27 to-32), on secondary talc and chlorite rite after pyrope (D=-39 to -44) and on the surrounding biotite (D=-64) and phengite (D=-44) gneiss. All phases appear to be in nearequilibrium. The very high D values for the primary hydrous phases is consistent with an initial oceanicderived/connate fluid source. The fluid source for the retrograde talc+chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar D, but dissimilar ¹⁸O values of the coesite bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.     

Heat-capacity measurements and absolute entropy of ɛ-Mg2PO4OH

The low-temperature heat capacity of -Mg₂PO₄OH was measured between 10 and 400 K by adiabatic calorimetry. No phase transition was observed over this temperature range. A relative enthalpy increment of 22,119 J mol^–1 and an absolute entropy value of 127.13±0.25 J mol^–1 K^–1 at 298.15 K are derived from the results. The low-temperature heat-capacity data are compared with the DSC data obtained from 143 K to 775 K and show marginal differences in the common temperature range. The latter data are fitted by the polynomial

A 50-year record of NO<Subscript>x</Subscript> and SO<Subscript>2</Subscript> sources in precipitation in the Northern Rocky Mountains,USA

Ice-core samples from Upper Fremont Glacier (UFG), Wyoming, were used as proxy records for the chemical composition of atmospheric deposition. Results of analysis of the ice-core samples for stable isotopes of nitrogen (δ¹⁵N, ) and sulfur (δ³⁴S, ), as well as and deposition rates from the late-1940s thru the early-1990s, were used to enhance and extend existing National Atmospheric Deposition Program/National Trends Network (NADP/NTN) data in western Wyoming. The most enriched δ³⁴S value in the UFG ice-core samples coincided with snow deposited during the 1980 eruption of Mt. St. Helens, Washington. The remaining δ³⁴S values were similar to the isotopic composition of coal from southern Wyoming. The δ¹⁵N values in ice-core samples representing a similar period of snow deposition were negative, ranging from -5.9 to -3.2 ‰ and all fall within the δ¹⁵N values expected from vehicle emissions. Ice-core nitrate and sulfate deposition data reflect the sharply increasing U.S. emissions data from 1950 to the mid-1970s.     

Elastic properties of pyrope

Brillouin spectroscopy was used to measure the single crystal elastic properties of a pure synthetic pyrope and a natural garnet containing 89.9 mol% of the pyrope end member (Mg₃Al₂Si₃O₁₂). The elastic moduli, c _ij , of the two samples are entirely consistent and agree with previous estimates of the elastic properties of pyrope based upon the moduli of solid solutions. Our results indicate that the elastic moduli of pyrope end-member are c ₁₁=296.2±0.5, c ₁₂=111.1±0.6, c ₄₄=91.6±0.3, K_s=172.8±0.3, =92.0±0.2, all in units of GPa. These results differ by several percent from those reported previously for synthetic pyrope, but are based upon a much larger data set. Although the hydrous components of the two samples from the present study are substantially different, representing both dry and saturated samples, we find no discernable effect of structurally bound water on the elastic properties. This is due to the small absolute solubility of water in pyrope, as compared with other garnets such as grossular.     

The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

Background  

A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., ). To better understand the effect of ion activity ratios on CaCO₃ precipitation kinetics and Sr²⁺ co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω) for calcite was held constant at 9.4, but the ion activity ratio was varied between 0.0032 and 4.15.     

Isotope fingerprinting of precipitation associated with western disturbances and Indian summer monsoons across the Himalayas

Precipitation samples were collected across the Himalayas from Kashmir (western Himalaya) to Assam (eastern Himalaya) to understand the variation of the stable isotopic content (\(\updelta ^{18}\)O and \(\updelta \)D) in precipitation associated with two dominant weather systems of the region: western disturbances (WDs) and Indian summer monsoon (ISM). Large spatial and temporal variations in isotopic values were noted with \(\updelta ^{18}\)O and \(\updelta \)D values ranging from \(-30.3\) to Open image in new window and \(-228\) to Open image in new window , respectively. The d-excess values also exhibit a large range of variation from \(-30\) to Open image in new window . In general, heavier isotopic values are observed in most of the samples in Jammu, whereas lighter values are observed in majority of the samples in Uttarakhand. Precipitation at Jammu seems to have undergone intense evaporation while that from Uttarakhand suggest normal Rayleigh fractionation/distillation of the air mass as it moves from the source region to the precipitation site and/or orographic lifting. The d-excess of rainfall in Kashmir has a distinctly higher median value of Open image in new window compared to other precipitation sites with a median of Open image in new window . Using distinct isotopic signatures, the regions receiving precipitation from two different weather systems have been identified.     

Titanium substitution and OH-bearing defects in hydrothermally grown pyrope crystals

A series of Ti-substituted pyrope crystals was synthesized in the system MgO-(Na₂O)-Al₂O₃-TiO₂-SiO₂-H₂O at P_H20 = P_tot between 25 and 30 kbars and 975 and 1000° C, using graphite heated piston-cylinder devices. The crystals, ranging up to 500 m in diameter, were studied by X-ray, electron-microprobe and FTIR-microscope spectrometric techniques. The pyrope crystals were colourless when hem/mt or mt/wu buffers were used during the synthesis, and pale blue with the wu/iron buffer and in unbuffered runs. Sodium was not found in the synthetic crystals, titanium was always near 0.06 Ti atoms pfu, independent on the Ti-excess used in the starting material. A substitution Al_2+[6]+Si_4+[4]+4O_2-= Ti_4+[6]+_[4]+[(OH)₃O^^5-, providing charge balance for octahedral Ti⁴⁺-substitution is found to be compatible with all properties (number, widths, position, integrated intensity) of the stretching vibrations of defect hydroxyls, which have energies 3684, 3568, 3525 cm^-1.This work was made possible through a research fellowship, generously provided by the Alexander von Humboldt-Stiftung, Bonn, Bad Godesberg, to V.M.K.     

Effect of grossular-content in garnet on the partitioning of Fe and Mg between garnet and biotite

In contrast to Ferry (1980) (X _Ca)-values in garnet even lower than 0.1 have a significant effect on the calculated equilibrium temperature using the experimental calibration of the Fe and Mg paritioning between garnet and biotite. Garnet compositions and Mg/Fe — distribution coefficients from samples of the Eoalpine staurolite — in zone in the southern Ötztal are related by the quadratic regression equation: InK _D= -1.7500 (±0.0226) + 2.978 (±0.5317)X _Ca ^Gt -5.906(±2.359)(X _Ca ^Gt )² Temperatures derived by the Ferry and Spear (1978) calibration using chemistry — correctedK _D values are petrologically realistic.Analysis of our data supports non ideal mixing of grossular with almandine — pyrope solid solution. The derived excess mixing energies are quite small for the almandine — pyrope solution (W _FeMg= –133 cal/mole) and about +2775 cal/mole for the difference between pyrope-grossular and almandine-grossular solutions (W _MgCa —W _FeCa) at metamorphic conditions of 570° C and 5,000 bar. The mixing parameters proposed by Ganguly and Saxena (1984) are not confirmed by our data as they would result in significantly lower temperatures.     

Optical absorption investigation of Cr3+ ion-bearing minerals in the temperature range 77–797 K

The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr³⁺ was studied for various point symmetries of the Cr³⁺-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr³⁺-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm^-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr³⁺-transitions derived from ⁴ A _2g ⁴ T _2g (F) and ⁴ T _1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr³⁺, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr³⁺-centered octahedra, _loc, were derived on the basis of the R _M-0 ^-5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging r_m-o for all the respective octahedral positions.     

Study on the compositional dependence of the apparent partition coefficient of iron and magnesium between coexisting garnet and clinopyroxene solid solution

Compositional dependence of apparent partition coefficient of iron and magnesium between coexisting garnet and clinopyroxene from Mt. Higasiakaisi is studied by means of a multicomponent regular solution model. It is shown that garnet and clinopyroxene solid solutions are positively non-ideal, and the non-ideal parameters according to the symmetric regular solution model are 2.58 kcal and 2.39 kcal, respectively, assuming the equilibration temperature of the mass to be 550° C.Notations a _i ^h activity of component i in phase h - _ij interaction parameter of component i and j in a solid solution - _i activity coefficient of component i - X _i mole fraction of component i - K partition coefficient of Fe and Mg between coexisting garnet and clinopyroxene - K apparent partition coefficient of Fe and Mg between coexisting garnet and clinopyroxene - G ⁰ difference in free energy of the partition reaction - H ⁰ difference in enthalpy of the partition reaction - S ⁰ difference in entropy of the partition reaction - R gas constant - G garnet - Alm almandine component - Py pyrope component - Gr grossular component - Sp spessartine component - CPx clinopyroxene - Hd hedenbergite component - Di diopside component - Jd jadeite component - Ts Tschermac's molecule component Deceased on April 17, 1974.     

87Sr/86Sr and 18O/16O isotopic systematics and geochemistry of granitoid plutons across a steeply-dipping boundary between contrasting lithospheric blocks in western Idaho

A spatially abrupt geochemical boundary is preserved within four plutonic complexes along the western margin of the Cretaceous Idaho Batholith near McCall, Idaho. These intrusives ranging in composition from tonalite to granite were emplaced across a regional boundary between accreted oceanic-arc terranes and the continental margin, and their isotopic, major-element, and trace-element geochemistry provide detailed information about this change in crustal characteristics at depth, indicating that the boundary is nearly vertical and extends deep into the lithosphere. The Hazard Creek complex, emplaced west of the transition in wall-rock lithology, has initial ⁸⁷Sr/⁸⁶Sr (R_i) less than 0.7045 and ¹⁸O greater than 7.5, indicating little or no continental crust in its source region; however, elevated ¹⁸O requires some incorporation of rocks formed or altered at the earth's surface. A large shift in R_i and ¹⁸O is observed across the 5–8 km wide Little Goose Creek complex, which was emplaced across the wall-rock boundary. This is interpreted as mixing between: (1) a basaltic or andesitic magma with low K₂O and high Na₂O, Al₂O₃, and Sr, similar to that forming the Hazard Creek complex; and (2) materials similar to Precambrian sedimentary sedimentary rocks with low Sr, high ¹⁸O (+15) and high R_i (0.83 at 100 Ma). The Payette River complex, emplaced east of the wall-rock boundary, exhibits at least one additional component with low ¹⁸O (+6), moderate R_i (0.708) and mafic composition. This component is inferred to be old basaltic material in the lower crust or upper mantle similar to that inferred to be a minor part of the Peninsular Ranges Batholith in SE California (Silver et al. 1979; Hill et al. 1986). The easternmost complex in the Idaho transect is made up of granites that may contain a component of granitic cratonal basement. The entire west-to-east geochemical transition from oceanic-arc magmas to cratonal magmas takes place over a lateral distance of less than 20 km. Although the zone of transitional protolith dominated by metasedimentary rocks is unusually narrow and may have been in part tectonically removed, the striking geochemical similarities between this traverse and several other transects across much broader areas of Nevada and California suggest that the craton itself was not rifted apart, but that juxtaposition of the accreted oceanic-arc terranes occurred along the preexisting craton margin. The data confirm that the isotopic geochemistry of granitoid plutons can be used as a probe of deep lithospheric character, and that major lateral variations in the lithosphere on the order of one to two kilometers in width can be recognized in favorable circumstances.     

New aspects on the formation of hydrocarbon source rocks

Episodic volcanism favors, as shown by examples from Europe, the USA, and Brazil, the formation of organic-rich sediments (hydrocarbon source rocks). The examples examined from Europe comprise the Lower Carboniferous Oil-Shale Group, Scotland; Upper Carboniferous Coal Measures, western Germany; Upper Jurassic Kimmeridge Shale, North Sea area; Lower Cretaceous Blättertonstein, northwest Germany; and Eocene Messel Oil Shale, Rheingraben. Examples from the USA are Devonian/Mississippian Gas Shales, Permian Phosphoria Shale, Middle Cretaceous Mowry Shale, Eocene Green River Shale, and Miocene Monterey Shale. Examples from Brazil are Permian Iratí Oil Shale and Oligocene Paraiba-Valley Oil Shale. Volcanism is reflected during sedimentation (1) by exhalation of SO₂ and/or CO₂, (2) volcanic ashfalls, (3) by generation of anoxia and preservation of organic matter, and (4) by halmyrolytic alteration of volcanic ashes into highly surface-active clay minerals (montmorillonite).

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Zusammenfassung Episodisch auftretender Vulkanismus begünstigt, wie an Beispielen aus Europa, aus den USA und aus Brasilien gezeigt wird, die Bildung von Sedimenten, die reich an organischer Substanz sind (Erdöl- und Erdgasmuttergesteine). Beispiele aus Europa sind: unterkarbonische Oil-Shale Group, Schottland; oberkarbonische Steinkohle, W-Deutschland; oberjurassischer Kimmeridge Shale, Nordsee-Raum; unterkretazischer Blättertonstein, NW-Deutschland; und eozäner Messel-Ölschiefer, Rheingraben. Beispiele aus den USA sind oberdevonische/unterkarbonische Gas-Shales, östliche USA; permische Phosphoria-Formation, mittlere Rocky Mountains; mittelkretazischer Mowry-Shale, nördliche Rocky Mountains; eozäner Green River Shale, südliche Rocky Mountains; und miozäner Monterey Shale, Kalifornien. Aus Brasilien sind permischer Irati Oil Shale und oligozäner Paraiba-Valley Oil Shale beschrieben. Der Vulkanismus äußert sich während der Sedimentation vor allen durch: (1) Exhalation von SO₂ und/oder CO₂, (2) Einwehung vulkanischer Asche, (3) Schaffung anoxischer Verhältnisse und Konservierung der organischen Substanz und (4) halmyrolytische Umwandlung der vulkanischen Aschen in oberflächenaktive Tone (Montmorillonit).

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Résumé Divers exemples pris en Europe, aux U.S.A. et au Brésil, montrent que des manisfestations volcaniques épisodiques favorisent la formation de sédiments riches en matières organiques (roches-mères de pétrole ou de gaz naturel). Les exemples d'Europe sont: l'Oil-Shale Group carbonifère inférieur en Ecosse, les formations houillères du Carbonifère supérieur en Allemagne, les shales kimmeridgiens en Mer du Nord, le Blättertonstein crétacé inférieur du NW de l'Allemagne, les schistes bitumineux éocènes de Messel dans le graben du Rhin. Les exemples aux U.S.A. sont: les »Gas Shales« dévoniens sup./carbonifères inf. de l'Est des U.S.A., la formation permienne Phosphoria dans les Rocheuses moyennes, le Mowry Shale méso-crétacé dans les Rocheuses septentrionales, le Green River Shale eocene au S des Rocheuses, le Monterey Shale miocène en Californie.Les exemples au Brésil sont: l'Irati Oil shale permien et le Paraiba-Valley Oil shale oligocène. Le volcanisme se manifeste au cours de la sédimentation par: (1) des exhalaisons de SO₂ et/ou de CO₂; (2) des chutes de cendres; (3) la production d'un milieu anaérobie avec conservation des matières organiques; (4) la transformation halmyrolitique des cendres en produits argileux gonflants (montmorillonite).

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Experimental determination of the hydrothermal solubility of ReS2 and the Re–ReO2 buffer assemblage and transport of rhenium under supercritical conditions

To understand the aqueous species important for transport of rhenium under supercritical conditions, we conducted a series of solubility experiments on the Re–ReO₂ buffer assemblage and ReS₂. In these experiments, pH was buffered by the K–feldspar–muscovite–quartz assemblage; in sulfur-free systems was buffered by the Re–ReO₂ assemblage; and and in sulfur-containing systems were buffered by the magnetite–pyrite–pyrrhotite assemblage. Our experimental studies indicate that the species ReCl₄ ⁰ is dominant at 400°C in slightly acidic to near-neutral, and chloride-rich (total chloride concentrations ranging from 0.5 to 1.0 M) environments, and ReCl₃ ⁺ may predominate at 500°C in a solution with total chloride concentrations ranging from 0.5 to 1.5 M. The results also demonstrate that the solubility of ReS₂ is about two orders of magnitude less than that of ReO₂. This finding not only suggests that ReS₂ (or a ReS₂ component in molybdenite) is the solubility-controlling phase in sulfur-containing, reducing environments but also implies that a mixing process involving an oxidized, rhenium-containing solution and a solution with reduced sulfur is one of the most effective mechanisms for deposition of rhenium. In analogy with Re, TcS₂ may be the stable Tc-bearing phase in deep geological repositories of radioactive wastes.     

Hydration-induced climb dissociation of dislocations in naturally deformed mantle olivine

Widely dissociated dislocations have been observed in mantle olivine from the Erro-Tobbio peridotite in N.W. Italy. Analysis of diffraction contrast in transmission electron microscopy (TEM) indicates that the dissociation reaction involves the climb dissociation on (001) and {021} planes of b=[001] unit dislocations into partial dislocations with Burgers vectors approximately equal to 1/x 011. In the most extreme case a unit dislocation dissociates into four partials which bound three planar defects. The unusually wide dissociation and the greater extent of dissociation in olivine from amphibole-bearing rocks suggests that the dissociation is related to hydration. The occurrence of fluid inclusions along the dislocations confirms that the partials and planar defects are saturated with volatiles. Analysis of possible planar defect structures in Fo₉₀ shows that; (i) the most likely partial Burgers vectors are b=0 3/11 1/4; (ii) two of the planar defects are cation-deficient and can be stabilised by segregation of H⁺ to produce (Mg, Fe) (OH)₂ layers which are iso-structural with the OH-rich interlayer of the humite group minerals; (iii) the central planar defect is formed by removing a stoichiometric olivine (002) layer so does not produce any local chemical changes. The climb dissociation provides a possible mechanism for the transformation of olivine to a humite group mineral. OH-rich interlayers may nucleate on dislocations and extend into the crystal by climb resulting in a gradual increase of (Mg, Fe) (OH)₂ content. The only addition of material required is hydrogen which can rapidly diffuse into olivine. If the dissociation is stable and occurs at high temperatures and pressures it may significantly influence the nature and kinetics of deformation mechanisms and the olivine — spinel shear transformation mechanism in hydrated olivine.     

Petrogenesis of cordierite-orthoamphibole assemblages from the Springton region,South Australia

Textural evidence for the partial breakdown of staurolite-biotite and andalusite-biotite assemblages to cordierite-orthoamphibole implies high temperature metasomatic depletion of K₂O in semi-pelitic rocks from Springton, South Australia. The origin of the reaction textures is discussed with reference to K₂O-T diagrams derived from the topologically equivalent K₂O–(-H₂O) diagram showing both discontinuous and Fe–Mg continuous reactions. The involvement of fluids in the metasomatic process is implied by the scale of K₂O removal and suggests that the outcrop pattern of cordierite-gedrite rocks reflects, at least in part, a heterogeneous distribution of advecting fluids in the metamorphic pile at high temperatures.Mineral abbreviations used in text and figures ab albite - alm almandine - als aluminosilicate - and andalusite - anth anthophyllite - bt biotite - cd cordierite - fe-bt Fe-rich biotite - fe-cd Fe-rich cordierite - fe-oa Fe-rich orthoamphibole - fe-st Fe-staurolite - gt garnet - ksp potassium feldspar - ky kyanite - mg-cd Mg-rich cordierite - mg-oa Mg-rich orthoamphibole - mg-st Mg-rich staurolite - mu muscovite - oa orthoamphibole - phl phlogopite - plag plagioclase - py pyrope - sill sillimanite - st staurolite - v vapour     

Trace hydrogen zoning in diopside

Summary ¶The trace hydrogen content of a colourless to light-green zoned diopside single-crystal from Zillertal was investigated by IR microspectroscopy. The light-green part of the crystal reveals pleochroic OH absorption bands centred at 3645, 3463, and 3358cm^–1 which are attributed to structural OH defects. The OH absorptions of the colourless crystal part are characterised by weak bands at 3645 and 3662cm^–1 and by a strong band at 3676cm^–1. The bands at 3662 and 3676cm^–1 are attributed to the presence of amphibole lamellae. The analytical water content due to the structural OH defect concentration of the light-green crystal part amounts to 0.0016wt.%, that of the colourless part is lowered by a factor of about 50. According to optical absorption spectra, the light-green colour of the crystal is essentially caused by an Fe²⁺–Fe³⁺ charge transfer. The relatively high concentration of OH defects in the light-green crystal part associated with higher Al contents relative to the colourless part suggests that OH is incorporated as hydrodiopside component, CaMg(SiAlO₅OH). It is concluded that increasing water activity during the crystallisation process causes the formation of amphibole lamellae under consumption of nearly all of the water available in the fluid phase. It is further concluded that the observed hydrogen content of diopside represents a primary incorporation and not the result of late hydrothermal alteration processes.Received July 11, 2002; accepted October 30, 2002 Published online February 24, 2003     

Local structural heterogeneity,mixing behaviour and saturation effects in the grossular–spessartine solid solution

Local structural heterogeneities in crystals of the binary grossular–spessartine solid solution have been analyzed using powder IR absorption spectroscopy. Wavenumber shifts of the highest energy Si–O stretching mode in spectra collected at room temperature are consistent with variations in Si–O bond length from structural data. They show a smaller positive deviation from linearity across the join than is seen for the grossular–pyrope and grossular–almandine binaries. The effective line widths, corr, of three selected wavenumber regions all deviate positively from linear behaviour. An empirical calibration of this excess spectroscopic property, obtained by comparison with calorimetric enthalpy of mixing data, gives an estimate for the symmetric Margules parameter of W^H_spec = 14.4(7) kJ mol^–1 in H^mix = W^H_specX_GrX_Sp. W^H_spec values derived on the same basis for four aluminosilicate garnet solid solutions analyzed by IR spectroscopy vary with V², where V represents the difference in molar volume between the end members of each binary system. Measurements of lattice parameters and IR spectra were made over a range of temperatures for seven samples with different compositions. Positive excess molar volumes of mixing at low temperature (30 K) may be larger than the excess molar volumes at room temperature. The saturation temperatures of the molar volumes show no correlation with composition, however, in contrast with what had been expected on the basis of data for the grossular–pyrope binary. Saturation temperatures for spectroscopic parameters and lattice parameters of samples with compositions Gr15Sp85 and Gr60Sp40 seem to be outliers in all experiments. It is concluded that the data hint at systematic changes in saturation temperatures across the solid solution, with implications for both the excess entropy of mixing and the excess volume of mixing, but more precise data or further sample characterization are needed to prove that this composition dependence is real in garnet solid solutions.