The formation of columnar fiber texture in wollastonite rims by induced stress and implications for diffusion-controlled corona growth

 The evolution of columnar fiber texture was studied in wollastonite reaction rims synthesized by the reaction calcite + quartz=wollastonite + CO₂. Experiments were performed at 850 to 950 °C at 100 MPa in dry CO₂ and were evaluated by scanning and transmission electron microscopy. Rim growth rates are interpreted as controlled by the diffusion of the SiO₂ component through the rims from the quartz–wollastonite to the wollastonite–calcite interface. The temperature dependence of rim growth rates yields an apparent activation energy of 314 ± 53 kJ mol⁻¹. The columnar fibrous wollastonite crystallizes at the quartz–wollastonite interface and comprises the largest parts of the rims. Ultimately, at the growth front strain contrast centers are present in the quartz. The strained volume extends about 200 nm into the quartz grains. We suggest that this might signify deformation of the quartz lattice due to wollastonite crystallization. Wollastonite fiber thickness was measured from TEM images along traverses that represent intermediate positions of the growth front during the experiments. The average thickness is in the 100–200 nm range. Fiber thickness increases with increasing growth temperature. At a given temperature, the thickness of the fibers at the growth front slightly decreases with time, i.e., the number of fiber tips per unit area in the growth front increases. The decrease of the fiber thickness is well fitted by a parabolic rate law. The generation of the columnar fiber texture is interpreted as an effect of induced stresses at the growth front, resulting from the volume increase due to the local reaction. This volume increase forces SiO₂ to diffuse along the growth front to the grain boundaries between the wollastonite fibers. These serve as fast diffusion pathways through the rims. The fiber thickness monitors the diffusion distances in the growth front and thus the height of the induced stress gradients. Since interface reactions are usually associated with volume changes, growth rates of reaction rims and zones in coronas are not only controlled by the diffusive mobility of the components but also by the volume restraints on the interface reactions. Received: 19 July 2002 / Accepted: 14 February 2003     

Reaction-induced fluid flow in synthetic quartz-bearing marbles

The reaction kinetics and fluid expulsion during the decarbonation reaction of calcite+quartz=wollastonite+CO₂ in water-absent conditions were experimentally investigated using a Paterson-type gas apparatus. Starting materials consisted of synthetic calcite/quartz rock powders with variable fractions of quartz (10, 20, and 30 wt%) and grain sizes of 10 µm (calcite) and 10 and 30 µm (quartz). Prior to reaction, samples were HIPed at 700 °C and 300 MPa confining pressure and varying pore pressures. Initial porosity was low at 2.7–6.3%, depending on pore pressure during HIP and the amount and grain size of quartz particles. Samples were annealed at reaction temperatures of 900 and 950 °C at 150 and 300 MPa confining pressures, well within the wollastonite stability field. Run durations were between 10 min and 20 h. SEM micrographs of quenched samples show growth of wollastonite rims on quartz grains and CO₂-filled pores between rims and calcite grains and along calcite grain boundaries. Measured widths of wollastonite rims vs. time indicate a parabolic growth law. The reaction is diffusion-controlled and reaction progress and CO₂ production are continuous. Porosity increases rapidly at initial stages of the reaction and attains about 10–12% after a few hours. Permeability at high reaction temperatures is below the detection limit of 10^–21 m² and not affected by increased porosity. This makes persistent pore connectivity improbable, in agreement with observed fluid inclusion trails in form of unconnected pores in SEM micrographs. Release of CO₂ from the sample was measured in a downstream reservoir. The most striking observation is that fluid release is not continuous but occurs episodic and in pulses. Ongoing continuous reaction produces increase in pore pressure, which is, once having attained a critical value (P_crit), spontaneously released. Connectivity of the pore space is short-lived and transient. The resulting cycle includes pore pressure build-up, formation of a local crack network, pore pressure release and crack closure. Using existing models for plastic stretching and decrepitation of pores along with critical stress intensity factors for the calcite matrix and measured pore widths, it results that P_crit is about 20 MPa. Patterns of fluid flow based on mineralogical and stable isotope evidence are commonly predicted using the simplifying assumption of a continuous and constant porosity and permeability during decarbonation of the rock. However, simple flow models, which assume constant pore pressure, constant fluid filled porosity, and constant permeability may not commonly apply. Properties are often transient and it is most likely that fluid flow in a specific reacting rock volume is a short-lived episodic process.Editorial responsibility: J. Hoefs     

The role of the grain boundary at chemical and isotopic fronts in marble during contact metamorphism

Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (¹⁸O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO₂ and CO₃ ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 10⁶ years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998     

Humite- and scapolite-bearing assemblages in marbles and calcsilicates of Dronning Maud Land, Antarctica: new data for Gondwana reconstructions

This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X _CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X _CO2^fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains f_O2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H₂O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Contrasting fluid flow patterns at the Bufa del Diente contact metamorphic aureole,north-east Mexico: evidence from stable isotopes

Impure limestones with interstratified metachert layers were contact metamorphosed and metasomatized by the Bufa del Diente alkali syenite. Massive marbles exhibit mineralogical and stable isotope evidence for limited fluid infiltration, confined to a 17 m wide zone at the contact. Influx of magmatic brines along most metacherts produced up to 4 cm thick wollastonite rims, according to calcite (Cc)+quartz (Qz)= wollastonite (Wo)+CO₂, and were observed at distances of up to 400 m from the contact. The produced CO₂ exsolved as an immiscible low density CO₂-rich fluid. Chert protolith isotope compositions were ¹⁸O (Qz)=27–30%. and ¹⁸O (Cc)=24–27%.. Many wollastonites in infiltrated metacherts have low ¹⁸O ranging from 11–17 and confirm that decarbonation occurred in presence of a magmatic-signatured fluid. Large gradients in ¹⁸O (Wo) across the rims may reach 6 The ¹⁸O of remaining quartz is often lowered to 15–20 whereas caleites largely retained their original compositions. The isotopic reversals of up to 10 between quartz and calcite along with reaction textures demonstrate non-equilibrium between infiltrating fluid in the aquifer and the assemblage calcite+quartz+wollastonite. This is compatible with the assumption of a down-temperature flow of magmatic fluids that occurred exclusively in the remaining quarzite layer. The ¹³C (Cc) and ¹⁸O (Cc) of marble calcites measured perpendicular to two metachert bands reveal significant isotopic alterations along distances of 4.5 cm and 7.5 cm from the wollastonite-marble boundary only into the hanging wall marble, suggesting an advection process caused by a fluid phase which movel upwards. Covariation trends of ¹³C (Cc) and ¹⁸O (Cc) across the alteration front indicate that this fluid was CO₂-rich. Mass balance calculations show that all CO₂-rich fluid produced by the decarbonation reaction was lost into overlying marble. The metachert aquifers did not leak with respect to water-rich fluids.     

Interdiffusion of H2O and CO2 in metamorphic fluids at ∼490 to 690°C and 1 GPa

Interdiffusion coefficients have been determined for H₂O-CO₂ mixtures by quantifying the flux of CO₂ between two fluid-filled chambers in a specially designed piston-cylinder cell. The two chambers, which are maintained at 1.0 GPa and at temperatures differing by ∼100°C, each contain the X_CO2-buffering assemblage calcite + quartz + wollastonite, in H₂O. The positive dependence of X_CO2 on temperature results in a down-temperature, steady-state flux of CO₂ through a capillary tube that connects the two chambers. This flux drives the wollastonite = calcite + quartz equilibrium to the right in the cooler chamber, producing a measurable amount of calcite that is directly related to CO₂-H₂O interdiffusion rates. Diffusivities calculated from seven experiments range from 1.0 × 10⁻⁸ to 6.1 × 10⁻⁸ m²/s for mean capillary temperatures between ∼490 and 690°C. The data set can be approximated by an Arrhenius-type relation:

     

SHRIMP U-Pb zircon dating from Sulu-Dabie dolomitic marble, eastern China: constraints on prograde, ultrahigh-pressure and retrograde metamorphic ages

Laser Raman spectroscopy and cathodoluminescence (CL) images show that zircon from Sulu‐Dabie dolomitic marbles is characterized by distinctive domains of inherited (detrital), prograde, ultrahigh‐pressure (UHP) and retrograde metamorphic growths. The inherited zircon domains are dark‐luminescent in CL images and contain mineral inclusions of Qtz + Cal + Ap. The prograde metamorphic domains are white‐luminescent in CL images and preserve a quartz eclogite facies assemblage of Qtz + Dol + Grt + Omp + Phe + Ap, formed at 542–693 °C and 1.8–2.1 GPa. In contrast, the UHP metamorphic domains are grey‐luminescent in CL images, retain the UHP assemblage of Coe + Grt + Omp + Arg + Mgs + Ap, and record UHP conditions of 739–866 °C and >5.5 GPa. The outermost retrograde rims have dark‐luminescent CL images, and contain low‐P minerals such as calcite, related to the regional amphibolite facies retrogression. Laser ablation ICP‐MS trace‐element data show striking difference between the inherited cores of mostly magmatic origin and zircon domains grown in response to prograde, UHP and retrograde metamorphism. SHRIMP U‐Pb dating on these zoned zircon identified four discrete ²⁰⁶Pb/²³⁸U age groups: 1823–503 Ma is recorded in the inherited (detrital) zircon derived from various Proterozoic protoliths, the prograde domains record the quartz eclogite facies metamorphism at 254–239 Ma, the UHP growth domains occurred at 238–230 Ma, and the late amphibolite facies retrogressive overprint in the outermost rims was restricted to 218–206 Ma. Thus, Proterozoic continental materials of the Yangtze craton were subducted to 55–60 km depth during the Early Triassic and recrystallized at quartz eclogite facies conditions. Then these metamorphic rocks were further subducted to depths of 165–175 km in the Middle Triassic and experienced UHP metamorphism, and finally these UHP metamorphic rocks were exhumed to mid‐crustal levels (about 30 km) in the Late Triassic and overprinted by regional amphibolite facies metamorphism. The subduction and exhumation rates deduced from the SHRIMP data and metamorphic P–T conditions are 9–10 km Myr^?1 and 6.4 km Myr^?1, respectively, and these rapid subduction–exhumation rates may explain the obtained P–T–t path. Such a fast exhumation suggests that Sulu‐Dabie UHP rocks that returned towards crustal depths were driven by buoyant forces, caused as a consequence of slab breakoff at mantle depth.     

A New LA‐ICP‐MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge

Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti‐in‐quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining ⁴⁸Ti mass fractions in quartz by LA‐ICP‐MS at the 1 μg g^?1 level, relevant to quartz in HP‐LT terranes. We suggest that natural quartz such as the low‐CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g^?1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are insignificant, thus allowing for the use of ⁴⁸Ti as a normalising mass. Average titanium mass fraction from thirty‐three analyses of low temperature quartz from the Czech Erzgebirge is 0.9 ± 0.2 μg g^?1 (2s) using ⁴⁸Ti as a normalising mass and Bishop Tuff quartz rims as a reference material. The 2s average analytical uncertainty for individual analyses of ⁴⁸Ti is 8% for 50 μm spots and 7% for 100 μm spots, which offers much greater accuracy than the 21–41% uncertainty (2s) incurred from using ⁴⁹Ti as an analyte.     

Formation of wollastonite-bearing marbles during late regional metamorphic channelled fluid flow in the Upper Calcsilicate Unit of the Reynolds Range Group,central Australia*

Abstract Granulite facies marbles from the Upper Calcsilicate Unit of the Reynolds Range, central Australia, contain metre-scale wollastonite-bearing layers formed by infiltration of water-rich (X_CO2= 0.1–0.3) fluids close to the peak of regional metamorphism at c. 700° C. Within the wollastonite marbles, zones that contain <10% wollastonite alternate on a millimetre scale with zones containing up to 66% wollastonite. Adjacent wollastonite-free marbles contain up to 11% quartz that is uniformly distributed. This suggests that, although some wollastonite formed by the reaction calcite + quartz = wollastonite + CO₂, the wollastonite-rich zones also underwent silica metasomatism. Time-integrated fluid fluxes required to cause silica metasomatism are one to two orders of magnitude higher than those required to hydrate the rocks, implying that time-integrated fluid fluxes varied markedly on a millimetre scale. Interlayered millimetre -to centimetre-thick marls within the wollastonite marbles contain calcite + quartz without wollastonite. These marls were probably not infiltrated by significant volumes of water-rich fluids, providing further evidence of local fluid channelling. Zones dominated by grandite garnet at the margins of the marl layers and marbles in the wollastonite-bearing rocks probably formed by Fe metasomatism, and may record even higher fluid fluxes. The fluid flow also reset stable isotope ratios. The wollastonite marbles have average calcite (Cc) δ¹⁸O values of 15.4 ± 1.6% that are lower than the average δ¹⁸O(Cc) value of wollastonite-free marbles (c. 17.2 ± 1.2%). δ¹³C(Cc) values for the wollastonite marbles vary from 0.4% to as low as -5.3%, and correlations between δ¹⁸O(Cc) and δ¹³C(Cc) values probably result from the combination of fluid infiltration and devolatilization. Fluids were probably derived from aluminous pegmatites, and the pattern of mineralogical and stable isotope resetting implies that fluid flow was largely parallel to strike.     

Compositional zoning of calcite in a high-pressure metamorphic calc-schist: clues to heterogeneous grain-scale fluid distribution during exhumation

Calcite in former aragonite–dolomite-bearing calc-schists from the ultrahigh-pressure metamorphic (UHPM) oceanic complex at Lago di Cignana, Valtournanche, Italy, preserved different kinds of zoning patterns at calcite grain and phase boundaries. These patterns are interpreted in terms of lattice diffusion and interfacial mass transport linked with a heterogeneous distribution of fluid and its response to a changing state of stress. The succession of events that occurred during exhumation is as follows: As the rocks entered the calcite stability field at T=530–550 °C, P ca. 1.2 GPa, aragonite occurring in the matrix and as inclusions in poikilitic garnet was completely transformed to calcite. Combined evidence from microstructures and digital element distribution maps (Mn-, Mg-, Fe- and Ca–Kα radiation intensity patterns) indicates that transformation rates have been much higher than rates of compositional equilibration of calcite (involving resorption of dolomite and grain boundary transport of Mg, Fe and Ca). This rendered the phase transformation an isochemical process. During subsequent cooling to T ca. 490 °C (where lattice diffusion effectively closed), grains of matrix calcite have developed diffusion-zoned rims, a few hundred micrometres thick, with Mg and Fe increasing and Ca decreasing towards the phase boundary. Composition profiles across concentrically zoned, large grains in geometrically simple surroundings can be successfully modelled with an error function describing diffusion into a semi-infinite medium from a source of constant composition. The diffusion rims in matrix calcite are continuous with quartz, phengite, paragonite and dolomite in the matrix. This points to an effective mass transport on phase boundaries over a distance of several hundred micrometres, if matrix dolomite has supplied the Mg and Fe needed for incorporation in calcite. In contrast, diffusion rims are lacking at calcite–calcite and most calcite–garnet boundaries, implying that only very minor mass transport has occurred on these interfaces over the same T–t interval. From available grain boundary diffusion data and experimentally determined fluid–solid grain boundary structures, inferred large differences in transport rates can be best explained by the discontinuous distribution of aqueous fluid along grain/phase boundaries. Observed patterns of diffusion zoning indicate that fluid was distributed not only along grain-edge channels, but spread out along most calcite–white mica and calcite–quartz two-grain junctions. On the other hand, the inferred non-wetting of calcite grain boundaries in carbonate-rich domains is compatible with fluid–calcite–calcite dihedral angles >60° determined by Holness and Graham (1995) for a wide range of fluid compositions under the P–T conditions of interest. Whereas differential stress has been very low at the stage of diffusion zoning (T > 490 °C), it increased as the rocks were cooling below 440 °C (at 0.3–0.5 GPa). Dislocation creep and the concomitant increase of strain energy in matrix calcite induced migration recrystallisation of high-angle grain boundaries. For that stage, the compositional microstructure of recrystallised calcite grain boundary domains indicates significant mass transport along calcite two-grain junctions, which at the established low temperatures is likely to have been accomplished by ionic diffusion within a hydrous grain boundary fluid film (“dynamic wetting” of migrating grain boundaries). Received: 10 January 2000 / Accepted: 10 April 2000     

Stability of fluorite and titanite in a calc-silicate rock from the Vizianagaram area, Eastern Ghats Belt, India

In the Vizianagaram area (E 83°29.442′; N 18°5.418′) of the Eastern Ghats Belt, India, a suite of graphite‐bearing calc‐silicate granulites, veined by syenitic rocks, developed wollastonite‐rich veins at 6–7 kbar and > 850 °C. During subsequent near‐isobaric cooling wollastonite was replaced by calcite + quartz and a graphic intergrowth of fluorite + quartz ± clinopyroxene. Titanite with variable Al and F contents is present throughout the rock. Combining the compositional variation of titanite and recent experimental data, it is demonstrated that the mineral assemblage, the composition of coexisting fluids and the mobility of Al exert a far greater control on the composition of titanite than pressure, temperature or the whole rock composition. Thermodynamically computed isothermal–isobaric logf_O2– logf_CO2 and logf_F2– logf_O2 grids in the systems Ca–Fe–Si–O–F (CISOF; calcite‐free) and Ca–Fe–Si–O–F–C–H (CISOFV; calcite‐present) demonstrate the influence of bulk rock and fluid compositions on the stability of the fluorite‐bearing assemblages in diverse geological environments and resolve the problem of the stability of titanite in fayalite + fluorite‐bearing rocks in the Adirondacks. The mineralogy of the studied rocks and the topological constraints tightly fix the logf_O2, logf_F2 and logf_CO2 at ?15.8, ?30.6 and 4.1, respectively, at 6.5 kbar and c. 730 °C. Because of the similarity in the P–T conditions, the compositions of pore fluids in the fluorite‐bearing assemblages of the Adirondacks and the Eastern Ghats Belt have been compared.     

Seasonal temperatures from δ18O in recent Spanish tufa stromatolites: Equilibrium redux!

This study focuses on recent debate over the value of stable isotope‐based environmental proxies recorded in riverine tufa stromatolites. A twelve‐year record (1999 to 2012) of river‐bed tufa stromatolites in the River Piedra (north‐east Spain) was recovered in this study, along with a partly overlapping fifteen‐year record (1994 to 2009) of accumulations in a drainage pipe: both deposits formed in water with near identical physico/chemical parameters. Measured water temperature data and near‐constant δ ¹⁸O_water composition allowed selection of an ‘equilibrium’ palaeotemperature equation that best replicated actual temperatures. This study, as in some previous studies, found that just two published formulas for water temperature calculation from equilibrium calcite δ ¹⁸O compositions were appropriate for the River Piedra, where tufa deposition rates are high, with means between 5·6 mm and 10·8 mm in six months. The δ ¹⁸O_calcite in both the river and the pipe deposits essentially records the full actual seasonal water temperature range. Only the coldest times (water temperature <10°C), when calcite precipitation mass decreased to minimum, are likely to be unrepresented, an effect most noticeable in the pipe where depositional masses are smaller and below sample resolution. While kinetic effects on δ ¹⁸O_calcite‐based calculated water temperature cannot be ruled out, the good fit between measured water temperature and δ ¹⁸O_calcite‐calculated water temperature indicates that temperature is the principal control. Textural and deposition rate variability between the river and pipe settings are caused by differences in flow velocity and illumination. In the river, calcification of growing cyanobacterial mat occurred throughout the year, producing composite dense and porous laminae, whereas in the pipe, discontinuous cyanobacterial growth in winter promoted more abiogenic calcification. High‐resolution δ ¹⁸O_calcite data from synchronous pipe and river laminae show that reversals in water temperature occur within laminae, not at lamina boundaries, a pattern consistent with progressive increase in calcite precipitation rate as cyanobacterial growth re‐established in spring.     

Calc-silicate reactions and bedding-controlled isotopic exchange in the Notch Peak aureole, Utah: implications for differential fluid fluxes with metamorphic grade

Fluid compositions and bedding‐scale patterns of fluid flow during contact metamorphism of the Weeks Formation in the Notch Peak aureole, Utah, were determined from mineralogy and stable isotope compositions. The Weeks Formation contains calc‐silicate and nearly pure carbonate layers that are interbedded on centimetre to decimetre scales. The prograde metamorphic sequence is characterized by the appearance of phlogopite, diopside, and wollastonite. By accounting for the solution properties of Fe, it is shown that the tremolite stability field was very narrow and perhaps absent in the prograde sequence. Unshifted oxygen and carbon isotopic ratios in calcite and silicate minerals at all grades, except above the wollastonite isograd, show that there was little to no infiltration of disequilibrium fluids. The fluid composition is poorly constrained, but X(CO₂)_fluid must have been >0.1, as indicated by the absence of talc, and has probably increased with progress of decarbonation reactions. The occurrence of scapolite and oxidation of graphite in calc‐silicate beds of the upper diopside zone provide the first evidence for limited infiltration of external aqueous fluids. Significantly larger amounts of aqueous fluid infiltrated the wollastonite zone. The aqueous fluids are recorded by the presence of vesuvianite, large decreases in δ¹⁸O values of silicate minerals from c. 16‰ in the diopside zone to c. 10‰ in the wollastonite zone, and extensive oxidation of graphite. The carbonate beds interacted with the fluids only along margins where graphite was destroyed, calcite coarsened, and isotopic ratios shifted. The wollastonite isograd represents a boundary between a high aqueous fluid‐flux region on its higher‐grade side and a low fluid‐flux region on its lower‐grade side. Preferential flow of aqueous fluids within the wollastonite zone was promoted by permeability created by the wollastonite‐forming reaction and the natural tendency of fluids to flow upward and down‐temperature near the intrusion‐wall rock contact.     

Genesis of wollastonite- and grandite-rich skarns in a suite of marble-calc-silicate rocks from Sittampundi, Tamil Nadu: constraints on the P–T–fluid regime in parts of the Pan-African mobile belt of South India

The Pan-African tectonothermal activities in areas near Sittampundi, south India, are characterized by metamorphic changes in an interlayered sequence of migmatitic metapelites, marble and calc-silicate rocks. This rock sequence underwent multiple episodes of folding, and was intruded by granite batholiths during and subsequent to these folding events. The marble and the calc-silicate rocks develop a variety of skarns, which on the basis of mineralogy; can be divided into the following types: Type I: wollastonite?+?clinopyroxene (mg#?=?71–73)?+?grandite (16–21 mol% Adr)?+?quartz?±?calcite, Type II: grandite (25–29 mol% Adr )?+?clinopyroxene (mg#?=?70)?+?calcite?+?quartz, and Type III: grandite (36–38 mol% Adr)?+?clinopyroxene (mg#?=?55–65)?+?epidote?+?scapolite?+?calcite?+?quartz. Type I skarn is 2–10 cm thick, and is dominated by wollastonite (>70 vol%) and commonly occurs as boudinaged layers parallel to the regional foliation Sn₁ related to the Fn₁ folds. Locally, thin discontinuous lenses and stringers of this skarn develop along the axial planes of Fn₂ folds. The Type II skarn, on the other hand, is devoid of wollastonite, rich in grandite garnet (40–70 vol%) and developed preferentially at the interface of clinopyroxene-rich calc-silicates layers and host marble during the later folding event. Reaction textures and the phase compositional data suggest the following reactions in the skarns: 1. calcite?+?SiO₂?→?wollastonite?+?V, 2. calcite?+?clinopyroxene?+?O₂?→?grandite?+?SiO₂?+?V, 3. scapolite?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V and 4. epidote?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V Textural relations and composition of phases demonstrate that (a) silica metasomatism of the host marble by infiltration of aqueous fluids (X_CO2?<?0.15) led to production of large volumes of wollastonite in the wollastonite-rich skarn whereas mobility of FeO, SiO₂ and CaO across the interface of marble and calc-silicate and infiltration of aqueous fluids (X_CO2?<?0.35) were instrumental for the formation of grandite skarns. Composition of minerals in type II skarn indicates that Al₂O₃ was introduced in the host marble by the infiltrating fluid. Interpretation of mineral assemblages observed in the interlayered metapelites and the calcareous rocks in pseudosections, isothermal P-X_CO2 and isobaric T-X_CO2 diagrams tightly bracket the “peak” metamorphic conditions at c.9?±?1 kbar and 750°?±?30°C. Subsequent to ‘peak’ metamorphic conditions, the rocks were exhumed on a steeply decompressive P–T path. The estimated ‘peak’ P–T estimates are inconsistent with the “extreme” metamorphic conditions (>11 kbar and >950°C) inferred for the Pan-African tectonothermal events from the neighboring areas. Field and petrological attributes of these skarn rocks are consistent with the infiltration of aqueous fluid predominantly during the Fn₁ folding event at or close to the ‘peak’ metamorphic conditions. Petrological features indicate that the buffering capacity of the rocks was lost during the formation of type I and II skarns. However, the host rock could buffer the composition of the permeated fluids during the formation of type III skarn. Aqueous fluids derived from prograde metamorphism of the metapelites seem to be the likely source for the metasomatic fluids that led to the formation of the skarn rocks.     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high X_CO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO₂ fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low X_H2O.     

Grain boundary diffusion in enstatite

We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg_0.90Fe_0.10)₂SiO₄ at controlled oxygen fugacities in the range 10^?5.7 to 10^?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg_0.92Fe_0.08)₂Si₂O₆. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10^?9f0.0O₂e^?400±65/RT?m³s^?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.     

Silicon and oxygen self diffusion in enstatite polycrystals: the Milke et al. (2001) rim growth experiments revisited

Milke et al. (Contrib Mineral Petrol 142:15–26, 2001) studied the diffusion of Si, Mg and O in synthetic polycrystalline enstatite reaction rims. The reaction rims were grown at 1,000°C and 1 GPa at the contacts between forsterite grains with normal isotopic compositions and a quartz matrix extremely enriched in ¹⁸O and ²⁹Si. The enstatite reaction rim grew from the original quartz-forsterite interface in both directions producing an inner portion, which replaced forsterite and an outer portion, which replaced quartz. Here we present new support for this statement, as the two portions of the rim are clearly distinguished based on crystal orientation mapping using electron backscatter diffraction (EBSD). Milke et al. (Contrib Mineral Petrol 142:15–26, 2001) used the formalism of LeClaire (J Appl Phys 14:351–356, 1963) to derive the coefficient of silicon grain boundary diffusion from stable isotope profiles across the reaction rims. LeClaires formalism is designed for grain boundary tracer diffusion into an infinite half space with fixed geometry. A fixed geometry is an undesired limitation in the context of rim growth. We suggest an alternative model, which accounts for simultaneous layer growth and superimposed silicon and oxygen self diffusion. The effective silicon bulk diffusivity obtained from our model is approximately equal within both portions of the enstatite reaction rim: D _Si,En ^eff =1.0–4.3×10^–16 m² s^–1. The effective oxygen diffusion is relatively slow in the inner portion of the reaction rim, D _O,En ^eff =0.8–1.4×10^–16 m² s^–1, and comparatively fast, D _O,En ^eff =5.9–11.6×10^–16 m² s^–1, in its outer portion. Microstructural evidence suggests that transient porosity and small amounts of fluid were concentrated at the quartz-enstatite interface during rim growth. This leads us to suspect that the presence of an aqueous fluid accelerated oxygen diffusion in the outer portion of the reaction rim. In contrast, silica diffusion does not appear to have been affected by the spatial variation in the availability of an aqueous fluid.

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Bimetasomatic zoning in the CaO-MgO-SiO2-H2O-CO2 system: Experiments with the use of natural rock samples

Experiments reproducing the development of bimetasomatic zoning in the CaO-MgO-SiO₂-H₂O-CO₂ system were conducted at elevated P-T parameters with the use of samples of naturally occurring quartzdolomite and calcite-serpentinite rocks. In order to maintain mass transfer exclusively via the diffusion-controlled mechanism, we used the method of the ensured compaction of the cylindrical sample surface with a thin-walled gold tube. In the course of the experiments, a single diopside zone ～2.5 × 10^?5 m thick was obtained at the quartz-dolomite interface at T = 600°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.5 for 25–40 days and a succession of metasomatic zones at T = 750°C, $P_{H_2 O + CO_2 } $ = 300 MPa, and $X_{CO_2 } $ = 0.4 for 48 days. The metasomatic zones were as follows (listed in order from quartz to dolomite): wollastonite ‖ diopside ‖ tremolite ‖ calcite + forsterite; with the average width of the diopside zone equal to ～1.3 × 10^?5 m and the analogous part of the wollastonite zone equal to ～2.6 × 10^?5 m. Two zones (listed in order from calcite to serpentine) diopside and diopside-forsterite (the average widths of these zones were ～6 × 10^?4 and ～8 × 10^?4 m, respectively) were determined to develop at contact between serpentine and calcite during experiments that lasted 124 days at T = 500°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.2–0.4. In the former and latter situations, the growth rate of the zoning ranged between 3.1 × 10^?12 and 1.2 × 10^?11 m/s and between 5.6 × 10^?11 and 7.5 × 10^?11 m/s, respectively. The higher growth rate in the latter case can be explained by the higher water mole fraction in the fluid, with this water released during serpentinite decomposition in the experiments. The development of the only diopside zone in the experiments modeling the interaction of quartz and dolomite at T = 600–650°C and $P_{H_2 O + CO_2 } $ = 200 MPa is in conflict with theoretical considerations underlain by the Korzhinskii-Fisher-Joesten model. The interaction of quartz and dolomite in the CaO-MgO-SiO₂-CO₂-H₂O system at the P-T- $X_{CO_2 } $ parameters specified above should be attended by the origin of a number of reaction zones consisting of various proportions of talc, forsterite, tremolite, diopside, and calcite. The saturation of the fluid with respect to these minerals was likely not reached, and this resulted in the degeneration of the respective stability fields in the succession of zones. Conceivably, this was related to the insufficient rates of quartz and dolomite dissolution and the relatively low diffusion rates of the dissolved species in the low-permeable medium. In the experiments with interacting calcite and serpentine, the zoning calcite ‖ diopside ‖ diopside + forsterite ‖ serpentine developed in its complete form, in agreement with the theory. Equilibrium was likely achieved in these experiments due to the higher diffusion coefficients.