A cathodoluminescence and petrographical study of marbles from the Pohorje area in Slovenia

Marbles from the Pohorje area in Slovenia are investigated by mineralogical-petrographical analyses of thin sections as well as by cathodoluminescence in order to detect their local variability in texture and mineral assemblages. The CL colours observed in a cold cathode device are related to the manganese contents. An attempt is made to relate the textures seen under CL to mineral reactions during the process of metamorphism. The predominantly calcite marbles from Pohorje exhibit orange luminescence with some dolomite lenses with red luminescence. The typical mineral assemblages are calcite+tremolite+phlogopite or calcite+dolomite+tremolite+phlogopite. Therefore, the estimated temperature from the stability of mineral assemblage is assumed at approximately 500 °C.     

Crystal chemistry and reaction relations of piemontites and thulites from highly oxidized low grade metamorphic rocks at Vitali,Andros Island,Greece

Piemontite- and thulite-bearing assemblages from highly oxidized metapelitic and metacalcareous schists associated with braunite quartzites at Vitali, Andros island, Greece, were chemically investigated. The Mn-rich metasediments are intercalated in a series of metapelitic quartzose schists, marbles, and basic metavolcanites which were affected by a regional metamorphism of the highP/T type (T=400–500° C,P>9 kb) and a later Barrovian-type greenschist metamorphism (T=400–500° C,P～-5–6 kb). Texturally and chemically two generations of piemontite (I and II) can be distinguished which may show complex compositional zoning. Piemontite I coexisted at highP/T conditions with braunite, manganian phengite (alurgite), Mn³⁺-Mn²⁺-bearing Na-pyroxene (violan), carbonate, quartz, hollandite, and hematite. Zoned grains generally exhibit a decreasing Mn³⁺ and an increasing Fe³⁺ and Al content towards the rim. Chemical compositions of piemontite I range from 2.0 to 32.1 mole % Mn³⁺, 0 to 25.6 mole % Fe³⁺, and 60.2 to 81.2 mole % Al. Up to 12.5 mole % Ca on the A(2) site can be substituted by Sr. Piemontites formed in contact or close to braunite (±hematite) attained maximum (Mn³⁺+Fe³⁺)Al_?1 substitution corrresponding to about 33 mole % Mn³⁺+Fe³⁺ in lowiron compositions and up to about 39 mole % Mn³⁺+ Fe³⁺ at intermediate Fe³⁺/(Fe³⁺+Mn³⁺) ratios. Piemontite II which discontinuously overgrows piemontite I or occurs as separate grains may have been formed by greenschist facies decomposition of manganian Na-pyroxenes according to the reaction: (1) $$\begin{gathered} {\text{Mn}}^{{\text{3 + }}} - Mn^{2 + } - bearing omphacite/chloromelanite \hfill \\ + CO_2 + H_2 O + HCl \pm hermatite \hfill \\ = piemontite + tremolite + albite + chlorite \hfill \\ + calcite + quartz + NaCl \pm O_2 . \hfill \\ \end{gathered} $$ Thulites crystallized in coexistence with Al-rich piemontite II. All thulites analysed are low-Fe³⁺ manganian orthozoisites with Mn^tot～-Mn³⁺ substituting for Al on the M(3) site. Their compositions range from 2.9 to 7.2 mole % Mn³⁺, 0 to 1.2 mole % Fe³⁺, and 91.8 to 96.7 mole % Al. Piemontites II in thulite-bearing assemblages range from 5.8 to 15.9 mole % Mn³⁺, 0 to 3.7 mole % Fe³⁺, and 83.7 to 93.6 mole % Al. By contrast, piemontites II in thulite-free assemblages are similarly enriched in Mn³⁺ + Fe³⁺ — and partially in Sr²⁺ — as core compositions of piemontite I (21.1 to 29.6 mole % Mn³⁺, 2.0 to 16.5 mole % Fe³⁺, 60.6 to 68.4 mole % Al, 0 to 29.4 mole % Sr in the A(2) site). The analytical data presented in this paper document for the first time a continuous low-Fe³⁺ piemontite solid solution series from 5.8 to 32.1 mole % Mn³⁺. Aluminous piemontite II is enriched by about 3 mole % Mn³⁺+Fe³⁺ relative to coexisting thulite in Fe³⁺-poor samples and by about 6 mole % Mn³⁺+Fe³⁺ in more Fe³⁺-rich samples. Mineral pairs from different samples form a continuous compositional loop. Compositional shift of mineral pairs is attributed to the effect of a variable fluid composition at constantP _fluid andT on the continuous reaction: (2) $$\begin{gathered} piemontite + CO_2 \hfill \\ = thulite + calcite + quartz \hfill \\ + Mn^{2 + } Ca_{ - 1} [calcite] + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ Further evidence for a variable \(x_{H_2 O} \) and/or \(f_{O_2 } \) possibly resulting from fluid infiltration and local buffering during the greenschist metamorphism is derived from the local decomposition of piemontite, braunite, and rutile to form spessartine, calcite, titanite, and hematite by the reactions: (3) $$\begin{gathered} piemontite + braunite + CO_2 \hfill \\ = sperssartine + calcite + quartz \pm hermatite \hfill \\ + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ and more rarely: (4) $$\begin{gathered} piemontite + quartz + rutile + braunite \hfill \\ = spessartine + titanite + hematite + H{_2} O + O{_2} . \hfill \\ \end{gathered} $$      

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.     

Isotopic fractionation of Mg(aq), Ca(aq), and Fe(aq) with carbonate minerals

Density-functional electronic structure calculations are used to compute the equilibrium constants for ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca isotope exchange between carbonate minerals and uncomplexed divalent aquo ions. The most reliable calculations at the B3LYP/6-311++G(2d,2p) level predict equilibrium constants K, reported as 10³ln (K) at 25 °C, of −5.3, −1.1, and +1.2 for ²⁶Mg/²⁴Mg exchange between calcite (CaCO₃), magnesite (MgCO₃), and dolomite (Ca_0.5Mg_0.5CO₃), respectively, and Mg²⁺(aq), with positive values indicating enrichment of the heavy isotope in the mineral phase. For ⁴⁴Ca/⁴⁰Ca exchange between calcite and Ca²⁺(aq) at 25 °C, the calculations predict values of +1.5 for Ca²⁺(aq) in 6-fold coordination and +4.1 for Ca²⁺(aq) in 7-fold coordination. We find that the reduced partition function ratios can be reliably computed from systems as small as and embedded in a set of fixed atoms representing the second-shell (and greater) coordination environment. We find that the aqueous cluster representing the aquo ion is much more sensitive to improvements in the basis set than the calculations on the mineral systems, and that fractionation factors should be computed using the best possible basis set for the aquo complex, even if the reduced partition function ratio calculated with the same basis set is not available for the mineral system. The new calculations show that the previous discrepancies between theory and experiment for Fe³⁺-hematite and Fe²⁺-siderite fractionations arise from an insufficiently accurate reduced partition function ratio for the Fe³⁺(aq) and Fe²⁺(aq) species.     

Mineralogical criteria in the origin of marine iron-manganese nodules

In iron-manganese nodules from the floor of Pacific ocean, Baltic, White Sea and Kara Sea, iron bydroxide '-FeOOH was analysed in the laboratory. In buried ooze, reduction processes generate Fe(HCO₃)₂ which migrates into the upper part of the bottom ooze and into near bottom sea water where Fe(OH)₂ is formed. The oxidation process of Fe²⁺ to Fe³⁺, without participation of iron bacteria, leads to the topotactic transformation of Fe(OH)₂ to '-FeOOH. Marine water does not contain Fe²⁺ and cannot be a direct source of iron deposited in the nodules. Discovery of '-FeOOH in marine nodules permits the consideration that both iron and manganese were derived from the buried bottom mud, which during diagenetic processes led to the transfer of these metals in solutions and their upward migration.     

Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995     

Zoning in eclogite garnets from Nordfjord,West Norway

Some of the garnets in eclogites within the quartzo-feldspathic gneisses of Nordfjord, West Norway, are zoned with higher calcium, iron and manganese in the cores and more magnesium at the rims. The zoning is discussed in terms of the apparent distribution coefficients of Fe²⁺/Mg between garnet and clinopyroxene (which will be aberrantly high for the garnet cores) and in terms of the metamorphic evolution of the eclogites.Publication nr. 32 in The Norwegian geotraverse project.     

Petrographical and geochemical investigation of the Triassic marbles associated with Menderes massif metamorphics,Kavaklıdere,Muğla,SW Turkey

Vast marble deposits occur in a cover sequence of the Menderes Massif, SW Turkey. Four major marble deposits are recognized in Mu?la province based on the stratigraphic levels. These are Permo-Carboniferous aged black marbles (1), Triassic aged marbles (2), Upper Cretaceous aged marbles (3), and Paleocene aged pelagic marbles (4). This study deals with Triassic aged marbles of the southern part of the Menderes Massif. The Triassic marbles from SW Turkey consist of two big marble horizons in the Çayboyu (ÇM) and Kestanecik (KM) regions. The characteristic samples are collected from different stratigraphic levels in marble deposits in the ÇM and KM horizons. Mineralogical and major, trace, and rare earth element (REE) analyses of marble, limestone, and schist were conducted on these samples to reveal their petrographical and geochemical characteristics. The ÇM horizon is represented by calcitic marble layers. Nickel, cobalt, manganese, and iron elements filled in fractures, fissures, and intergranular spaces of calcite crystals and these elements give the pinky colour to the marble from the ÇM horizon. KM marbles were deformed, metamorphosed, and recrystallized under greenschist facies P–T conditions. As a result of the metasomatic reaction of magnesium and manganese rich fluids with marbles, dolomite, and manganese, minerals such as rhodochrosite and pyrolusite have crystallized along vein walls and layers in the KM horizon. Dolomitization was determined in KM marbles, whereas ÇM marbles show the character of limestone. MgO, MnO, Fe₂O₃, Ni, and Zn contents of marbles from the KM horizon are higher than those of ÇM marbles due to metasomatic reactions. The Sr content in white coloured marbles ranges between 11.20 ppm and 112.20 ppm and this concentration reaches up to 272.70 ppm due to metasomatic reactions and fluid intake. The REE content of Triassic marbles is independent of the abundance of carbonate and the REE enrichment observed due to syn-metamorphic fluid flow. The significant negative Eu anomaly in REE patterns indicates that the protoliths of Triassic marbles are carbonate rocks of sedimentary origin.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along the (OH, F)-annite join

We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe²⁺ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QS_HH2.55 mm/s for Fe²⁺O₄(OH)₂ octahedra (cis and trans not resolved), QS_HF 2.35 mm/s for Fe²⁺O₄(OH)F octahedra (cis and trans not resolved), QS_cFF2.15 mm/s for cis-Fe²⁺O₄F₂ octahedra, and QS_tFF 1.5 mm/s for trans-Fe²⁺O₄F₂ octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe²⁺O₅(OH) and Fe²⁺O₅F octahedra probably also contribute to the overall Fe²⁺ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe³⁺ contributions are seen and interpreted as being due mainly to Fe³⁺O₅OH and Fe³⁺O₅F octahedra, respectively. Tetrahedral Fe³⁺ is seen only in the OH-annite end-member and the total Fe³⁺ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China     

Corundum-bearing metasomatic rocks in the Central Pamirs

The Muzkol metamorphic complex in the Central Pamirs contains widespread occurrences of corundum mineralization, sometimes with gem-quality corundum. These occurrences are spatially related to zones of metasomatic alterations in calcite and dolomite marbles and crystalline schists. The calcite marbles contain corundum together with muscovite, scapolite, and biotite; the dolomite marbles contain corundum in association with biotite; and the schists bear this mineral coexisting with biotite and chlorite. All these rocks additionally contain tourmaline, apatite, rutile, and pyrite. The biotite is typically highly aluminous (up to 1.9 f.u. Al), and the scapolite is rich in the marialite end member (60–75 mol %). The crystallization parameters of corundum were estimated using mineral assemblages at T = 600–650°C, P = 4–6 kbar, X _{CO 2} = 0.2–0.5 at elevated alkalinity of the fluid. The Sr concentration in the calcite and dolomite marbles is low (345–460 and 62–110 ppm, respectively), as is typical of recrystallized sedimentary carbonates. The variations in the ⁸⁷Sr/⁸⁶Sr ratio in the calcite and dolomite marbles (0.70852–0.70999 and 0.70902–0.71021, respectively) were controlled by the introduction of radiogenic ⁸⁷Sr during the metasomatic transformations of the rocks. The isotopic-geochemical characteristics obtained for the rocks and the results of numerical simulations of the fluid-rock interactions indicate that the corundum-bearing metasomatic rocks developed after originally sedimentary Phanerozoic carbonate rocks, with the desilication of the terrigenous material contained in them. This process was a manifestation of regional alkaline metasomatism during the closing stages of Alpine metamorphism. In the course of transformations in the carbonate reservoir, the juvenile fluid flow became undersaturated with respect to silica, which was a necessary prerequisite for the formation of corundum.     

Uplift-related retrogression history of aragonite marbles in Western Crete (Greece)

In the low-grade, high-pressure (400°C, 10 kbar) metamorphic Phyllite-Quartzite Unit of Western Crete, widespread occurrences of aragonite marbles have been discovered recently. A sedimentary precursor is proved by relic structures (bedding, fossils). Partial or complete transformation of aragonite into calcite is ubiquitous. Compositional and microstructural features reflect the metamorphic history: (1) The high-pressure stage is documented by aragonite that is chemically characterized by incorporation of variable amounts of Sr and the lack of Mg. The most Sr-rich aragonite has about 9 wt% SrO (X _Sr ^arag =0.09). A compositional zoning observed in some aragonite crystals may be due to the prograde divariant calcitearagonite transformation in the system CaCO₃-SrCO₃. Because the parent rocks probably were Sr-poor calcite limestones, one can speculate that strontium has been supplied from an external source under high-pressure conditions. (2) During uplift, calcite replacing aragonite did not equilibrate with unreplaced aragonite. Disequilibrium is indicated by highly variable compositions of calcite crystals that show topotactic relations to the host aragonite. The calcite compositions range from that of the host aragonite (Sr-rich and Mg-free) to Mg-bearing and Sr-poor. (3) Calcite that recrystallized during retrogression is generally Sr-poor (mean value ofX _Sr<0.005), Mg-bearing (X _Mg0.010), and chemically homogeneous. Because practically no Sr remains in the calcite, an interaction with a fluid phase is indicated. In fine-grained calcite marbles rich in solid organic matter, microstructural features indicative of former aragonite may be present. (4) The last stage of retrogression is documented by the appearance of radiating aragonite in veins and nodules. This aragonite, which shows neither deformation nor retrogression, was probably formed metastably in a near-surface environment.     

Quantitative cathodoluminescence (CL) spectroscopy of minerals: possibilities and limitations

Summary ?The luminescence spectrum of a mineral contains complex information related to the intrinsic crystal and the defect structure. For quantitative analysis of cathodoluminescence (CL) the spectra have to be deconvoluted by fitting and filtering procedures to identify and measure individual peaks. Peak-width, peak-position and transition probability of the luminescence centres are influenced by effects such as interactions within the defects themselves, and interaction between defects and the surrounding crystal lattice. For calcite and feldspar a linear correlation between the defect concentration of manganese and the Mn²⁺-activated CL-intensity is documented. Combined Micro-Particle Induced X-ray Emission (μ-PIXE) and CL-spectroscopy analyses of REE-doped synthetic calcite suggest a linear correlation between REE-activated CL intensity and REE-concentration at REE-concentration levels below approximately 500 ppm. Sensitising and quenching by other REE are dominant effects yielding strong variations in the correlation between the REE-activated CL-intensity and the REE-content. Received December 6, 2001; revised version accepted May 10, 2002     

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.     

Mössbauer study of a California desert celadonite and its pedogenically-related smectite

Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe³⁺ doublet with isomer shift 0.4 mm s^–1 and quadrupole splitting 0.4 mm s^–1, another Fe³⁺ doublet with 0.4, 1.2 mm/s and two Fe²⁺ doublets with 1.1, 1.7, 2.7 mm s^–1 at 300 K were distinguished. The minor Fe³⁺ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M⁺–M²⁺ array. However, about 10% is M1 trans-OH Fe²⁺. Isomer shift vs. T gives Debye temperatures of 570 K for Fe³⁺ in M2 and 380 K for both Fe²⁺ sites, indicating greater vibrational freedom for Fe²⁺. Quadrupole splitting vs. T for Fe²⁺ gives a valence electronic energy splitting of 760 cm^–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe²⁺ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.     

REE-bearing minerals in a Ti-rich vein from the Adamello contact aureole (Italy)

Zirconolite, aeschynite-(Ce), titanite and apatite have been found as minor or accessory minerals in a Ti-rich (TiO₂=2.1–4.5 wt.%) hydrothermal vein occurring in dolomite marbles at the contact with a tonalite intrusion of the Tertiary Adamello batholith (northern Italy). The vein consists of four distinct mineral zones, comprising from margin to center: (1) forsterite+calcite, (2) pargasite+calcite+titanite+sulfides, (3) phlogopite +calcite+titanite+sulfides, and (4) titanian clinohumite +spinel+calcite+sulfides. Zirconolite occurs in two vein zones only: in the phlogopite zone it is invariably anhedral, often corroded, and exhibits complex chemical zonation patterns. In the titanian clinohumite zone zirconolite is idiomorphic and characterized by a pronounced discontinous chemical zoning, but shows no evidence of corrosion. The considerable compositional variation observed for zirconolite (in wt.%: (REE₂O₃)=0.74–16.8, UO₂=0.59–24.0, ThO₂=0.67–17.1) is due to the zoning, and may be attributed to four major substitutions described by the exchange vectors:

Sapphirine I

Microprobe analyses of 26 natural sapphirines from 17 localities indicate that the predominant chemical substitutions in this mineral occur along the solid solution join^VI(Mg,Fe)²⁺+^IVSi⁴⁺=^VI(Al, Fe)³⁺+^IVAl³⁺. Chromium and manganese are minor substituents. Evidence for the substitution SiAl+1/2Mg+1/2 vacancy is absent within the limits of analytical error.A partitioning scheme based on electrostatic charge balance considerations has been devised permitting calculation of Fe²⁺ and Fe³⁺ from total iron content. Results are in good agreement with previous Mössbauer studies which indicate Fe³⁺ is sometimes in octahedral and/or tetrahedral coordination.Distribution coefficients for Fe²⁺-Mg exchange equilibria between sapphirine-spinel and sapphirine-orthopyroxene are similar for most mineral pairs and suggest that most of the assemblages equilibrated at about the same temperature or that the exchange reactions are insensitive to temperature.Compositions of synthetic sapphirines as a function of temperature and pressure are qualitatively predictable from crystal chemical considerations. Changes in sapphirine composition along the MgSi= AlAl solid solution join toward more aluminous compositions stabilize the sapphirine structure at high temperatures and low pressures. The limited extent of MgSi=AlAl solid solution observed in natural sapphirines appears to be related to the requirements of geometrical fit among octahedra and tetrahedra in the almost idealized cubic closest-packed anion framework.     

Contact metamorphism of roof pendants at Hope Valley,Alpine County,California, USA

Calcareous hornfelses and marbles all contain calcite+K-feldspar+quartz+sphene±diopside±plagioclase ±scapolite±clinozoisite. In addition, rocks on one side of a fault contain combinations of biotite, amphibole, and muscovite while those on the other side contain combinations of grossular, wollastonite, and axinite. At bars, mineral-fluid equilibria in biotite and amphibole-bearing rocks record T= 440° C and garnet-bearing rocks record T=540° C and Conventional volumetric fluid-rock ratios were calculated using measured progress of prograde decarbonation reactions and the conditions of metamorphism: marbles, 0–0.4; amphibole-bearing hornfelses, 1.0–1.4; garnet-bearing hornfelses, 2.8–6.7. Decarbonation reactions were driven by pervasive infiltration of rock by reactive aqueous fluids. Differences in fluid-rock ratio between interbedded marble and hornfels and lack of correlation between fluid-rock ratio and whole-rock Cl-content, however, argue for channelized fluid flow along lithologic layers. A new analysis of reaction progress allows estimation of time-integrated fluxes for a specified temperature gradient along the direction of flow. Results are: marbles, 0–0.1×10⁵ cm³/cm²; amphibole-bearing hornfelses, 0.8–1.3×10⁵ cm³/cm²; garnet-bearing hornfelses, 1.2–2.5 × 10⁵ cm³/cm². Fluid flowed from regions of low to regions of high temperature. Using a simple thermal model for the area, the duration of contact metamorphism was estimated as 10⁵ years. Assuming the time of fluid flow was the same as the duration of the thermal event, the first measurements of average metamorphic fluxes (q) and permeabilities (k) are: average marbles, q=0–0.3×10^–8 cm/s and k =2×10^–6 darcy; hornfels, q=3–8×10^–8 cm/s and k =20–53×10^–6 darcy. Estimated premeabilities are within the range of values measured for metamorphic rocks in the laboratory. Fluxes, permeabilities, and whole-system fluidrock ratios are similar to those estimated for the Skaergaard hydrothermal system by Norton and Taylor (1979).     

Characterization of calcium isotopes in natural and synthetic barite

The mineral barite (BaSO₄) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (δ^44/40Ca = −2.01 ± 0.15‰) but are different from hydrothermal and cold seep barite samples (δ^44/40Ca = −4.13 to −2.72‰). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, Δ^44/40Ca = −3.42 to −2.40‰. Temperature, saturation state, , and aCa²⁺/aBa²⁺ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower ⁴⁴Ca/⁴⁰Ca than calcite, by −9‰ at 0 °C and −8‰ at 25 °C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower δ^44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca²⁺ substitution for Ba²⁺ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca²⁺ and other elements in inorganic and biogenic minerals.     

Oxygen and carbon isotope profiles in metasediments from Lizzies Basin,East Humboldt Range,Nevada: constraints on mid-crustal metamorphic and magmatic volatile fluxes

¹⁸O/¹⁶O ratios vary systematically in the 1,000 m section of interlayered metasediments and granitoids at Lizzies Basin, the deepest structural level exposed in the East Humboldt Range metamorphic core complex. In the lower 300 m of the section (the Lower Zone) ¹⁸O is homogeneous and low (+6.6 to +8.8 in silicate rocks, +8.7 to +12.1 in marbles). A detailed oxygen isotope profile across an individual marble layer within the Lower Zone has a similar range in ¹⁸O (+9.5 to +11.9) with the highest values preserved in the middle of the layer. In the upper 700 m of the section (the Upper Zone) metasediments have been less strongly ¹⁸O depleted. The ¹⁸O values are higher and more heterogeneous and in a profile across a marble layer of similar thickness, rise steeply from marginal values of +12 to core values of +23. Quartz from silicate metasediments throughout the Upper Zone ranges from +11 to +13 and is thus fairly homogeneous, particularly where detailed profiles have been measured adjacent to the ¹⁸O-rich marble layers. Covariation of ¹⁸O/¹⁶O and ¹³C/¹²C ratios in marbles suggests that the isotopic composition of these elements has been altered by exchange with infiltrating, water-rich, CO₂–H₂O fluids with mantle-like isotopic composition. In most cases, marble cores preserve protolith ¹³C values and these vary systematically throughout the section according to structural level, including some exceptionally ¹³C-rich values up to +12. This range may reflect stratigraphic variation in ¹³C of the Proterozoic sedimentary protoliths of these rocks. The Upper/Lower Zone boundary, and the contrast in isotope systematics to either side, has been previously explained either as an impermeable barrier to fluid flow, or as an infiltration front (Wickham and Peters 1990). The second alternative has been tested using a numerical model in which low-¹⁸O aqueous fluid flows vertically upward through an alternating sequence of monomineralic quartz (¹⁸O=+12) and calcite (¹⁸O=+22) layers in a regime in which the oxygen isotopic composition is controlled by advection, diffusion (in the fluid), and fluid/solid exchange. Solutions to the relevant transport equations indicate that the abrupt change in the average ¹⁸O value of the layers at the Upper/Lower Zone boundary can be reproduced by the model with a uniform porosity throughout the system, but the observed contrast in the shapes of the marble layer profiles in the Upper and Lower Zones cannot be reproduced under these conditions. However, if the calcite layers have two orders of magnitude lower porosity in comparison with the quartz layers and exchange within them is diffusion-dominated (as opposed to advection-dominated in the quartz) the contrasting shapes of the marble profiles in the two zones are reproduced, as well as the Upper/Lower Zone discontinuity. The range of conditions that generates both an infiltration front (at the appropriate scale) and contrasting marble profiles (at the appropriate scale) is quite narrow but requires a volatile flux that could be generated by plausible volumes of mantle-derived magma crystallizing at depth beneath the area, providing support for this mechanism as a viable agent of ¹⁸O depletion in the deep-level rocks of this terrane.