Shear in the tethys and the Permian paleomagnetism in the Southern Alps, including new results

To verify paleomagnetic proof for megatectonic translation in the Tethys a large collection of samples from a key area, the Bolzano Quartz Porphyry Plateau in the Southern Alps, was examined. Their natural remanent magnetization was analyzed with thermal, and mainly alternating field demagnetization. The result is a well-established paleomagnetic direction of D: 150° and I: −19.5° (₉₅ = 4.9), obtained from 152 samples from 39 sites distributed over 12 volcanic units. It is argued that the inclination of this result is not significantly different from that which can be extrapolated for the Southern Alps from Early Permian paleomagnetic directions of the stable European shield. Consequently it is concluded that a paleomagnetic indication for megatectonic translation of the Southern Alps is virtually absent. But a large counterclockwise deviation of the declination is evident, and is easily explained by a counterclockwise rotation of 50° of the Southern Alps with respect to stable Europe. Since the paleomagnetic direction of the Early Permian volcanics of the Southern Alps fits in reasonably well with the (poorly known) Early Permian paleomagnetic pattern of Africa, a coherence between both regions is presumed.     

Sr, Nd and Pb isotopes in Proterozoic intrusives astride the Grenville Front in Labrador: Implications for crustal contamination and basement mapping

We report Sr, Nd and Pb isotopic compositions of mid-Proterozoic anorthosites and related rocks (1.45-1.65 Ga) and of younger olivine diabase dikes (1.4 Ga) from two complexes on either side of the Grenville Front in Labrador. Anorthositic or diabasic samples from the Mealy Mountains (Grenville Province) and Harp Lake (Nain-Churchill Provinces) complexes have very similar major, minor and trace element compositions, but distinctly different isotopic signatures. All Mealy Mountains samples have I_Sr = 0.7025−0.7033, ε_Nd = +0.6 to +5.6 and Pb isotopic compositions consistent with derivation from a mantle source depleted with respect to Nd/Sm and Rb/Sr. Pb isotopic compositions for the Mealy Mountains samples are slightly more radiogenic than model mantle compositions. All Harp Lake samples have I_Sr = 0.7032−0.7066, ε_Nd = −0.3 to −4.4 and variable, but generally unradiogenic ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb compared to model mantle, suggesting mixing between a mantle-derived component and a U-depleted crustal contaminant. Crustal contaminants are probably a variety of Archean high-grade quartzofeldspathic gneisses with low U/Pb ratios and include a component that must be isotopically similar to the early Archean (>3.6 Ga) Uivak gneisses of Labrador or the Amitsoq gneisses of west Greenland. This would imply that the ancient gneiss complex of coastal Labrador and Greenland is larger than indicated by present surface exposure and may extend in the subsurface as far west as the Labrador Trough. If Harp Lake and Mealy Mountains samples were subjected to the same degree of contamination, as suggested by their chemical similarities, then the Mealy contaminants must be much younger, probably early or middle Proterozoic in age. The Labrador segment of the Grenville Front, therefore, appears to coincide with the southern margin of the Archean North Atlantic craton and may represent a pre mid-Proterozoic suture.     

A mechanism of shape-transformation of quartz inclusions in albite of regional metamorphic rocks

The process of shape-transformation of quartz inclusions from polyhedral to spherical grains in albite single crystals during metamorphism is mainly controlled by the grain boundary diffusion of oxygen along the quartz/albite interface to reduce the interfacial free energy. The rate of the process, which is represented by the growth rate of the curvature of the edge surface of the grain, depends significantly on temperature and on the grain size of the quartz inclusion. The relations between temperature, T, the time, t_r, and the critical radius, R_c, which is equal to the radius of maximum spherical grains, are given by log R_c = −0.11E_b/RT + 0.25log t_r + C, in which E_b is the activation energy of the grain boundary diffusion of oxygen along the quartz/albite interface and C is a material constant.

The mean critical radius of spherical quartz inclusions in albite is 5 μm for the upper chlorite zone and garnet zone, 10 μm for the lower biotite zone, and 20 μm for the upper biotite zone in the Sambagawa metamorphic terrain. The mean values of the critical radii of spherical quartz inclusions in oligoclase of the Ryoke metamorphic rocks is about 5 μm for the chlorite zone and about 10–20 μm for the sillimanite zone.

Assuming temperatures of about 350°C for the upper chlorite and garnet zones, 400°C for the lower biotite zone, 550°C for the upper biotite zone, and 700°C for the sillimanite zone, the activation energy for the grain boundary diffusion of oxygen along the quartz/plagioclase interfase is estimated to be about 30 kcal/mol.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

A palaeomagnetic study of some basaltoids and ores from the Pontic Ranges, Northern Turkey: Palaeogeographic implications

The palaeomagnetism of basic rocks and sulphide ores has been studied in the Küre area, Pontic Ranges, Turkey. Progressive alternating-field demagnetization revealed a characteristic remanent magnetization in all investigated rock types except a dacite. The following virtual geomagnetic poles were obtained:

Basalt and quartz diabase (oldest): D = 59°, I = +66°, ₉₅ = 4.8, pole 49°N, 93°E. Diabase: D = 210°, I = −15°, ₉₅ = 15.0, pole 47°N, 167°E. Massive sulphide ores: D = 107°, I = +63°, ₉₅ = 8.7, pole 18°N, 80°E. Peridotite: D = 131°, I = +54°, ₉₅ = 10.9, pole 2°S, 72°E. Amphibolitized diabase (youngest): D = 293°, I = +59°, ₉₅ = 12.6, pole 40°S, 145°E.

The longidutinal difference in pole positions between the oldest and the youngest rocks is interpreted as being due to a post-Permian counterclockwise rotation of the studied region in relation to the African continent. In addition, there are indications of local rotational movements within the Küre area.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Mantle heterogeneity and crustal recycling in Archean granite-greenstone belts: Evidence from Nd isotopes and trace elements in the Rainy Lake area, Superior Province, Ontario, Canada

The 2685–2752 Ma old granite-greenstone crust in the Rainy Lake area, Ontario, consists of metaigneous and metasedimentary rocks that range in composition from tholeiite to monzogranite and include anorthosite, trachyandesite, monzodiorite and high-silica rhyodacite. Major element, rare earth and other trace element data are the basis for modelling the formation of the crust by melting of large-ionlithophile element enriched and unenriched mantle, by melting of basalt at mantle to crustal levels and by melting of monzodiorite and tonalite at crustal levels.

All metaigneous rocks lie on a ¹⁴³Nd/¹⁴⁴Nd vs. ¹⁴⁷Sm/¹⁴⁴Nd isochron with an age of 2737 ±42 Ma and an initial ¹⁴³Nd/¹⁴⁴Nd of 0.509178 ±33 (ε_Nd = +1.9). This age is consistent with U-Pb zircon ages, which suggests the Nd isotopic system has been unaffected since the crust-forming events. The positive initial ε_Nd's are further evidence for time-averaged depletion in Sm/Nd relative to CHUR for the Archean mantle. The similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks suggests rapid recycling of crustal components, which were previously derived from depleted mantle sources.

Initial ¹⁴³Nd/¹⁴⁴Nd ratios on individual rocks range from ε_Nd = +3.3 to ε_Nd = −0.4. Younger granitoids have lower ε_Nd values (+1.5 to −0.1) relative to tholeiites and monzodiorites crystallized from mantle-derived melts (+3.3 to +1.0). Thus, incorporation of slightly older crust (ca. 100–200 Ma) in some of the granitoid source areas is possible. Mantle-derived rocks form an isochron of 2764 ±58 Ma that represents a minimum age for enrichment processes in the mantle sources for the Rainy Lake area. Consideration of data from the Abitibi belt suggests such enrichment processes in the mantle may have preceded crust-forming events in a wide area of the Superior Province, perhaps by as much as 50–70 Ma.     

First Late Ordovician Paleomagnetic Pole for the Cuyania (Precordillera) Terrane of Western Argentina: a Microcontinent or a Laurentian Plateau

Time and tectonic processes involved in docking of the Argentine Precordillera (Cuyania terrane) against SW Gondwana has been a matter of much debate. A paleomagnetic study on the Early Caradoc Pavón Formation, exposed in the San Rafael block, province of Mendoza, Argentina, is presented. After detailed thermal and alternating field demagnetizations two geologically significant magnetic components were defined. A widespread post-tectonic component (A) is present in most sites of the Pavón Formation, with dual polarities, and is coincident with the characteristic remanence isolated from a Permo-Triassic rhyolitic dome intruding the sediments. Its pole position (83.7°S, 271.0°E, dp = 6.8°, dm = 9.0° N = 11 sites) falls on the Late Permian-Early Triassic South American reference poles suggesting that this component was acquired during the Choiyoi magmatic phase. A second component (B) also shows dual polarities and a positive fold test suggesting a primary origin. Unblocking temperatures and rock magnetic experiments indicate that B is carried either by hematite or magnetite at different sites. Anisotropy of magnetic susceptibility results suggest a depositional fabric and no remanence distortion due to deformation or compaction. A paleomagnetic pole computed from this remanence (PV) falls on 3.6°N, 346.4°E (dp = 2.9°, dm = 4.6° n = 22 samples). It indicates a paleolatitude around 26°S for deposition of Pavón sediments and constrains the paleogeographic evolution of Cuyania during the Ordovician, which was still at subtropical latitudes by the Early Caradoc. PV is consistent with the Laurentian Late Ordovician reference pole if Cuyania remains attached to SE Laurentia for the Early Caradoc, while it shows a significant cw rotation with no paleolatitude anomaly respect to the Gondwana reference pole when kept in its present position in SW South America. These comparisons are interpreted in three possible alternatives for the paleogeographic and tectonic setting of Cuyania in the Late Ordovician.     

Nd, O and Sr isotopic constraints on the origin of Precambrian rocks, Southern Black Hills, South Dakota

The Nd, O and Sr isotopic characteristics of Precambrian metasedimentary, metavolcanic and granitic rocks from the Black Hills of South Dakota are examined. Two late-Archean granites (2.5-2.6 Ga) have T_dm ages of 3.05 and 3.30 Ga, suggesting that at least one of the granites was derived through the melting of significantly older crust. Early-Proterozoic metasedimentary rocks have T_dm ages that range from 2.32 to 2.45 Ga. These model ages, in conjunction with probable stratigraphic ages ranging from 1.9 to 2.2 Ga, indicate that mantle-derived material was added to the continental crust of this region during the early-Proterozoic. Previous studies of the Harney Peak Granite complex have reported U-Pb and Rb-Sr ages of about 1.71 Ga and most granite samples examined in this study have Sr isotopic compositions consistent with that age. Two granite samples taken from the same sill, however, give two-point Rb-Sr and Sm-Nd ages of 2.08 ±0.08 and 2.20 ±0.20 Ga (∑²²⁰⁰_Nd = −15.5), respectively. In addition, whole-rock and apatite samples of the spatially associated Tin Mountain pegmatite give a Sm-Nd isochron age of 2000 ±100 Ma (∑²²⁰⁰_Nd = −5.8 ±1.8).

The Sm-Nd, O and Rb-Sr isotopic systematics of these granitic rocks have been complicated to some degree by both crystallization and post-crystallization processes, and the age of the pegmatite and parts of the Harney Peak Granite complex remain uncertain. Processes that probably complicated the isotopic systematics of these rocks include derivation from heterogeneous source material, assimilation, mixing of REE between granite and country rock during crystallization via a fluid phase and post-crystallization mobility of Sr. The Nd isotopic compositions of the pegmatite and the Harney Peak Granite indicate that they were not derived primarily from the exposed metasedimentary rocks.     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Temperature independent thermal expansivities of sodium aluminosilicate melts between 713 and 1835 K

The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO₂, 0−31 wt% A1203, and 17−33 wt% Na₂O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature (T′_f), and that T′_f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′_f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/dT^liq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm³/mole) for (26.91 ± .04), (37.49 ± .12), (26.48 ± .06) at 1373 K, and (7.64 ± .08 × 10^-3 cm³/mole-K). The results indicate that neither Si02 nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT^liq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/dT^liq can be predicted within 5.6%.     

Paleomagnetic evidence for a stationary Marion hotspot: Additional paleomagnetic data from Madagascar

The island of Madagascar experienced widespread magmatism at ca. 90 Ma due to its interaction with the Marion hotspot. Previous paleomagnetic data from igneous rocks in the southwestern and northwestern regions of the island indicated that the Marion hotspot has remained fixed for the past 90 Ma. We report paleomagnetic data from northeastern Madagascar (d'Analava Complex). Samples were collected from basalts, rhyolites, gabbros and a dolerite dyke. Sixty samples from 5 sites yield a paleomagnetic pole at 66.7°S, 43.5°E (A95 = 10.7°) and a grand mean pole (GMP) calculated from 10 different studies covering the entire island of Madagascar falls at 68.9°S, 49.0°E (A95 = 4.4°). This pole translates to a paleolatitude for the Volcan de l'Androy (focal point of the hotspot) at 45.2° + 6°/− 5°S compared to the current location of the Marion hotspot at  46°S. Our results confirm, and expand upon, previous studies that argue for the fixity of the Marion hotspot for the past 90 Ma.     

Paleomagnetism of Permo-Triassic Redbeds from the Asturias and Cantabric Chain (northern Spain): evidence for strong lower Tertiary remagnetizations

The paleomagnetic analysis of the Permo-Triassic redbeds outcropping in the western part of the Cantabric Chain and the small Mesozoic basin from the Asturias shows that these formations have a history of complex magnetization. Only a few sites did not experience the remagnetization processes and retained original directions. The most reliable results yield a paleomagnetic pole located at: lat. 49° N, long. 217° E (n = 11, ₉₅ = 3.7°), which is suggested as reliable Permo-Triassic data for the Iberian plate. Two remagnetization phases are recognized: a moderate phase predating the folding gave rise to a first overprinting. It is connected with the distension which occurred in the Pyreneo-Cantabrian region during the upper Jurassic-lower Cretaceous. The main remagnetization phase which occurred after the folding is dated from the lower Tertiary, and can be related to the compression induced on the northern boundary of Iberia from upper Cretaceous onwards. In some cases this phase led to a complete replacement of the primary magnetization.

Previously published data, which were at the time interpreted as being European-like in direction, are attributed to this phase. Hence, our results do not support the hypothesis of a micro-plate called “le Danois block”, which was suggested in order to explain these results. We believe that there is no paleomagnetic evidence supporting the existence of a complicated boundary between Europe and Iberia during the mid-Cretaceous opening of the Bay of Biscay.     

Strontium diffusion in sanidine and albite, and general comments on strontium diffusion in alkali feldspars

Strontium chemical diffusion has been measured in albite and sanidine under dry, 1 atm, and QFM buffered conditions. Strontium oxide-aluminosilicate powdered sources were used to introduce the diffusant and Rutherford Backscattering Spectroscopy (RBS) used to measure diffusion profiles. For the 1 atm experiments, the following Arrhenius relations were obtained:

Sanidine (Or₆₁), temperature range 725–1075°C, diffusion normal to (001): D=8.4 exp(−450±13 kJ mol⁻¹/RT) m²s⁻¹. Albite (Or₁), temperature range 675–1025°C, diffusion normal to (001): D=2.9 × exp(−224±11 kJ mol⁻¹/RT) m²s⁻¹.

The alkali feldspars in this and earlier work display a broad range of activation energies for Sr diffusion, which may be a consequence of the thermodynamic non-ideality of the alkali feldspar system and/or the mixed alkali effect.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Magma–host interactions during differentiation and emplacement of a shallow-level, zoned granitic pluton (Tarçouate pluton, Morocco): implications for magma emplacement

The Tarçouate pluton (Anti-Atlas, Morocco) is an inversely zoned laccolith emplaced 583 Ma ago into low-grade metasediments, with the following succession: leucocratic granites, biotite–granodiorites (±monzodiorites), hornblende–granodiorites (±monzodiorites) and monzodiorites syn-plutonic dykes. These rocks form two distinct, chemically coherent, units:

(1) A main unit consists of layered (572<59 wt.%) and homogeneous (632<67%) hornblende–granodiorites, biotite–granodiorites (672<72%) and aplites (702<76%). All these rocks are metaluminous to peraluminous and display fractionated HREE depleted patterns (La/Yb_N=14–61; Yb_N=0.7–6.8). Initial ⁸⁷Sr/⁸⁶Sr ratios (0.7072 to 0.7080) increase, whereas _Nd(t) values (−1.7 to −2.8) decrease from the hornblende– to the biotite–granodiorites. Monzodiorites occur as mafic microgranular enclaves or syn-plutonic dykes.

(2) A subordinate unit consists of leucocratic, distinctly peraluminous, muscovite-bearing granites (722<75%) occurring at the northern edge of the pluton and as dykes in the surrounding schists towards the top of the pluton. These rocks are free of monzodioritic enclaves. They display less fractionated patterns with higher HREE contents (La/Yb_N=2–19; Yb_N=11–18), a distinct _Nd(t) value (−11.8) and a ⁸⁷Sr/⁸⁶Sr initial ratio (0.7480) within those of the surrounding schists (0.7393–0.7819).

Magma–host interactions are closely related to differentiation and occurred at different levels, but mainly before emplacement. Field relationships and petrogenetic modelling show that the bt–granodiorites formed at levels deeper than the level of emplacement, by fractional crystallisation (0.65

These data preclude any significant material transfer process for the emplacement of the Tarçouate pluton, but rather suggest assembly of successive pulses of variably differentiated crystal-poor magmas. These shallow level granitic plutons can be considered as an end-member of magma emplacement with minimum interactions with the country rocks.     

Antimony in hydrothermal processes: solubility, conditions of transfer, and metal-bearing capacity of solutions

Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H₂S–H₂O describing the formation of these deposits.

We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (m_HS⁻ = 0.0001−0.1) and chloride (m_Cl⁻ = 0.1−5) solutions and the joint dissolution of Sb_(s)⁰ and Sb₂S_3(s) in sulfide-chloride solution (m_HS⁻ = 0.01; m_Cl⁻ = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions.

The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions.     

Fluid inclusions in Scourian granulites from the Lewisian complex of NW Scotland: evidence for CO2-rich fluid in Late Archaean high-grade metamorphism

In this paper the first fluid-inclusion data are presented from Late Archaean Scourian granulites of the Lewisian complex of mainland northwest Scotland. Pure CO₂ or CO₂-dominated fluid inclusions are moderately abundant in pristine granulites. These inclusions show homogenization temperatures ranging from − 54 to + 10 °C with a very prominent histogram peak at − 16 to − 32 °C. Isochores corresponding to this main histogram peak agree with P-T estimates for granulite-facies recrystallization during the Badcallian (750–800 °C, 7–8 kbar) as well as with Inverian P-T conditions (550–600 °C, 5 kbar). The maximum densities encountered could correspond to fluids trapped during an early, higher P-T phase of the Badcallian metamorphism (900–1000 °C, 11–12 kbar). Homogenization temperatures substantially higher than the main histogram peak may represent Laxfordian reworking (≤ 500 °C, < 4 kbar). In the pristine granulites, aqueous fluid inclusions are of very subordinate importance and occur only along late secondary healed fractures. In rocks which have been retrograded to amphibolite facies from Inverian and/or Laxfordian shear zones, CO₂ inclusions are conspicuously absent; only secondary aqueous inclusions are present, presumably related to post-granulite hydration processes. These data illustrate the importance of CO₂-rich fluids for the petrogenesis of Late Archaean granulites, and demonstrate that early fluid inclusions may survive subsequent metamorphic processes as long as no new fluid is introduced into the system.