Crystal size distribution (CSD) in rocks and the kinetics and dynamics of crystallization

Crystal-size in crystalline rocks is a fundamental measure of growth rate and age. And if nucleation spawns crystals over a span of time, a broad range of crystal sizes is possible during crystallization. A population balance based on the number density of crystals of each size generally predicts a log-linear distribution with increasing size. The negative slope of such a distribution is a measure of the product of overall population growth rate and mean age and the zero size intercept is nucleation density. Crystal size distributions (CSDs) observed for many lavas are smooth and regular, if not actually linear, when so plotted and can be interpreted using the theory of CSDs developed in chemical engineering by Randolph and Larson (1971). Nucleation density, nucleation and growth rates, and orders of kinetic reactions can be estimated from such data, and physical processes affecting the CSD (e.g. crystal fractionation and accumulation, mixing of populations, annealing in metamorphic and plutonic rocks, and nuclei destruction) can be gauged through analytical modeling. CSD theory provides a formalism for the macroscopic study of kinetic and physical processes affecting crystallization, within which the explicit affect of chemical and physical processes on the CSD can be analytically tested. It is a means by which petrographic information can be quantitatively linked to the kinetics of crystallization, and on these grounds CSDs furnish essential information supplemental to laboratory kinetic studies. In this three part series of papers, Part I provides the general CSD theory in a geological context, while applications to igneous and metamorphic rocks are given, respectively, in Parts II and III.     

内蒙古霍各乞矿区含矿富石榴石岩晶体定量化结构分析及其意义

晶体粒度分布（CSD）是定量化分析火成岩和变质岩结构的重要手段。在变质岩中测量的CSD提供了有关变质过程中晶体成核和生长速率、生长时间的定量信息。文章选取内蒙古霍各乞二号矿床含矿富石榴石岩样品中石榴子石晶体为研究对象，在GIS软件和R语言的支持下，应用空间点模式分析、CSD分析、空间最邻近分析、空间多距离分析、Fry分析等综合方法，探讨了晶体空间数据和点空间数据表征的微结构变化特征，将CSD曲线分段变化记录的信息与地质演化历史联系起来。分段的CSD曲线记录了变质事件的叠加。不同形式的晶体粒度分布直接反映了区域变质岩与接触变质岩演化历史的差异。由于接触变质作用的高温阶段持续时间较短，因此产生的CSD曲线是线性的，不受退火的影响。而区域变质作用涉及长时间升温及其之后的冷却阶段，所以最初的线性CSD后来被退火改造为钟形曲线。含矿富石榴石岩样品的核密度和CSD分析结果显示了两个晶体群密度。分析认为一类晶体群可能与造山过程中的区域变质活动有关，另一类晶体群可能与大面积区域变质期后发生在特定位置的岩体侵入迅速升温的接触热变质事件有关。      

Ostwald ripening of garnet in high P/T metamorphic rocks

This paper presents a theoretical formulation of Ostwald ripening of garnet and discusses the importance of the process during high pressure and low temperature (high P/T) metamorphism. The growth rate of garnet due to Ostwald ripening is formulated for the system consisting of minerals and an intergranular medium. Crystal size distribution (CSD) of garnets are examined and compared with the theoretical distribution for Ostwald ripening. Two types of CSDs are recognized. One is consistent with the theoretical prediction of size distribution while the other is wider than the theoretical distribution. The former CSD applies to samples in which garnets show homogeneous spatial distributions. The latter CSD applies to samples in which garnets show heterogeneous spatial distributions such as in clusters or layers. These relations suggest that the heterogeneity of spatial distributions results in a heterogeneity of concentration of garnet, causing the wide distributions. The mean diameter (dg) has a large variation in samples having narrow distributions. Ostwald ripening explains well the similar patterns of CSD in these samples with different dg because of a scaling law. Compositional profiles of garnets with different size are consistent with Ostwald ripening rather than nucleation and growth kinetics. This suggests that the CSDs result from Ostwald ripening. Magnitude of heating rate will determine which mechanism controls CSD. Nucleation and growth kinetics are dominant when heating rate is large. On the other hand, Ostwald ripening is dominant when heating rate is small. CSDs of garnets in high P/T metamorphic rocks are consistent with the latter case.     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

Characterisation of a garnet population from the Sikkim Himalaya: insights into the rates and mechanisms of porphyroblast crystallisation

The compositional zoning of a garnet population contained within a garnet-grade metapelitic schist from the Lesser Himalayan Sequence of Sikkim (India) provides insight into the rates and kinetic controls of metamorphism, and the extent of chemical equilibration during porphyroblast crystallisation in the sample. Compositional profiles across centrally sectioned garnet crystals representative of the observed crystal size distribution indicate a strong correlation between garnet crystal size and core composition with respect to major end-member components. Systematic steepening of compositional gradients observed from large to small grains is interpreted to reflect a progressive decrease in the growth rate of relatively late-nucleated garnet as a result of an increase in interfacial energies during progressive crystallisation. Numerical simulation of garnet nucleation and growth using an equilibrium approach accounting for chemical fractionation associated with garnet crystallisation reproduces both the observed crystal size distribution and the chemical zoning of the entire garnet population. Simulation of multicomponent intracrystalline diffusion within the population indicates rapid heating along the pressure–temperature path, in excess of 100 \(^{\circ }\)C Myr\(^{-1}\). Radial garnet growth is correspondingly rapid, with minimum rates of 1.4 mm Myr\(^{-1}\). As a consequence of such rapid crystallisation, the sample analysed in this study provides a close to primary record of the integrated history of garnet nucleation and growth. Our model suggests that nucleation of garnet occurred continuously between incipient garnet crystallisation at \(\sim\)520 \(^{\circ }\)C, 4.5 kbar and peak metamorphic conditions at \(\sim\)565 \(^{\circ }\)C, 5.6 kbar. The good fit between the observed and predicted garnet growth zoning suggests that the departure from equilibrium associated with garnet nucleation and growth was negligible, despite the particularly fast rates of metamorphic heating. Consequently, rates of major element diffusion in the intergranular medium during garnet crystallisation are interpreted to have been correspondingly rapid. It is, therefore, possible to simulate the prograde metamorphic history of our sample as a succession of equilibrium states of a chemical system modified by chemical fractionation associated with garnet crystallisation.     

Oxygen and hydrogen isotope studies of contact metamorphism in the Santa Rosa Range,Nevada and other areas

The O¹⁸/O¹⁶ and D/H ratios have been determined for rocks and coexisting minerals from several granitic plutons and their contact metamorphic aureoles in the Santa Rosa Range, Nevada, and the Eldora area, Colorado, with emphasis on pelitic rocks. A consistent order of O¹⁸/O¹⁶ and D/H enrichment in coexisting minerals, and a correlation between isotopic fractionations among coexisting mineral pairs are commonly observed, suggesting that mineral assemblages tend to approach isotopic equilibrium during contact metamorphism. In certain cases, a systematic decrease is observed in the oxygen isotopic fractionations of mineral pairs as one approaches the intrusive contacts. Isotopic temperatures generally show good agreement with heat flow considerations. Based on the experimentally determined quartz-muscovite O¹⁸/O¹⁶ fractionation calibration curve, temperatures are estimated to be 525 to 625° C at the contacts of the granitic stocks studied.Small-scale oxygen isotope exchange effects between intrusive and country rock are observed over distances of 0.5 to 3 feet on both sides of the contacts; the isotopic gradients are typically 2 to 3 per mil per foot. The degree of oxygen isotopic exchange is essentially identical for different coexisting minerals. This presumably occurred through a diffusion-controlled recrystallization process. The size of the oxygen isotope equilibrium system in the small-scale exchanged zones varies from about 1.5 to 30 cm. A xenolith and a re-entrant of country rock projecting into an intrusive have both undergone much more extensive isotopic exchange (to hundreds of feet); they also show higher isotopic temperatures than the rocks in the aureole. The marginal portions of most plutons have unusually high O¹⁸/O¹⁶ ratios compared to normal igneous rocks, presumably due to large-scale isotopic exchange with metasedimentary country rocks when the igneous rocks were essentially in a molten state. The isotopic data suggest that outward horizontal movement of H₂O into the contact metamorphic aureoles is very minor, but upward movement of H₂O is important. Also, direct influx and absorption of H₂O from the country rock appears to have occurred in certain intrusive stocks. The D/H ratios of biotites in the contact metamorphic rocks and their associated intrusions show a geographic correlation that is similar to that shown by the D/H ratios of meteoric surface waters, perhaps indicating that meteoric waters were present in the rocks during crystallization of the biotites.Except in the exchanged zones, the O¹⁸/O¹⁶ ratios of pelitic rocks do not change appreciably during contact metamorphism, even in the cordierite and sillimanite grades; this is in contrast to regional metamorphic rocks which commonly decrease in O¹⁸ with increasing grade. Thus, contact metamorphic rocks generally do not exchange with large quantities of igneous H₂O, but regional metamorphic rocks appear to have done so.Publications of the Division of Geological Sciences, California Institute of Technology, Contribution No. 1565.     

Geochemical and petrological aspects of dike intrusions in the Lycian ophiolites (SW Turkey): a case study for the dike emplacement along the Tauride Belt Ophiolites

Lycian ophiolites located in the Western Taurides, are cut at all structural levels by dolerite and gabbro dikes. The dolerite dikes from this area are both pristine and metamorphosed. The non-metamorphosed dikes are observed both in the peridotites and in the metamorphic sole rocks. Accordingly, the non-metamorphosed dikes cutting the metamorphic sole were generated after cooling of the metamorphic sole rocks. The metamorphosed dolerite dikes are only observed in the peridotites. The physical conditions and timing of the metamorphism for the metamorphosed dolerite dikes are similar to those of the metamorphic sole rocks of the Lycian ophiolites suggesting that the metamorphosed dolerite dikes were metamorphosed together with the metamorphic sole rocks. Therefore, the dike injections in the western part of the Tauride Belt Ophiolites occurred before and after the generation of the metamorphic sole rocks. All metamorphosed and non-metamorphosed dikes are considered to have the same origin and all of them are subduction-related as inferred from whole-rock geochemistry and lead isotopes. Lead isotope compositions of whole rocks of both dike groups cluster in a narrow field in conventional Pb isotope diagrams (²⁰⁶Pb/²⁰⁴Pb = 18.40–18.64; ²⁰⁷Pb/²⁰⁴Pb = 15.56–15.58; ²⁰⁸Pb/²⁰⁴Pb = 38.23–38.56) indicating a derivation from an isotopically homogeneous source. On the ²⁰⁷Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagram, isotope compositions of the dikes plot slightly below the orogen curve suggesting contributions from mantle reservoir enriched by subducted oceanic lithosphere. Such a signature is typical of island arc magmatic rocks and supports the formation of the investigated rocks in a subduction-related environment.     

Carbon isotopic study on coexisting calcite and graphite in the Ryoke metamorphic rocks,northern Kiso district,central Japan

Carbon isotope fractionation between coexisting calcite and grpahite ( ¹³C_cc-gr) has been determined in metamorphosed limestones and calc-silicate rocks from the Ryoke metamorphic belt in the northern Kiso district. In this district, the Ryoke metamorphic rocks, ranging from the lower greenschist facies to the upper amphibolite facies, are widely distributed. The fractionation of ¹³C/¹²C between calcite and graphite decreases regularly with increasing metamorphic grade and is independent of absolute ¹³C values of calcite. This evidence suggests that carbon isotopic exchange equilibrium has been attained during metamorphism even in the greenschist facies and isotopic modification, possibly caused by retrogressive metamorphism, is not distinguished. For T=270–650° C, the fractionation is expressed by the following equation: ¹³C_cc-gr=8.9×10⁶T^–2–7.1 (T in °K).This equation has a slope steeper than the current results on the ¹³C_cc-gr versus 10⁶T^–2 diagram. It can be used as a potential geothermometer for almost the entire temperature range of metamorphism. ¹³C values of carbonaceous matter in unmetamorphosed limestones in this district are approximately –22, due to its biogenic origin. Graphite from metamorphosed limestones is also considered to be of biogenic origin but shows enrichment of ¹³C due to isotopic exchange with calcite. ¹³C values of graphite as well as ¹³C_cc-gr confirm that zone II represents the lowest grade zone of Ryoke metamorphism. The maximum equilibrium fractionation of ¹³C between calcite and graphite is considered to be approximately 23%, which corresponds to 270° C. Below this temperature, it seems that carbon isotopic exchange between the minerals does not occur.Calcite in marble from the higher grade zones has relatively lower ¹³C and ¹⁸O values. The depletion of heavy isotopes is considered to be caused by the loss of ¹³C and ¹⁸O enriched carbon dioxide during decarbonation reactions. For oxygen, it is considered that isotopic exchange with metamorphic fluids plays an important role in lowering the ¹⁸O value of calcite in some higher grade marbles.     

Crystal Size Distribution of Plagioclase and Amphibole from Soufriere Hills Volcano, Montserrat: Evidence for Dynamic Crystallization-Textural Coarsening Cycles

The crystal size distributions (CSDs) of plagioclase and amphibolewere determined from andesites of the Soufrière Hillsvolcano, Montserrat. Plagioclase occurs as separate crystalsand as chadocrysts in large amphibole oikocrysts. The chadocrystsrepresent an earlier stage of textural development, preservedby growth of the oikocryst. Seventeen rock and eight chadocrystplagioclase CSDs are considered together as a series of samplesof textural development. All are curved, concave up, and coincident,differing only in their maximum crystal size. Three amphiboleCSDs have a similar shape and behaviour, but at a differentposition from the plagioclase CSDs. A dynamic model is proposedfor the origin of textures in these rocks. Crystallization ofplagioclase started following emplacement of andesite magmaat a depth of at least 5 km. A steep, straight CSD developedby nucleation and growth. This process was interrupted by theinjection of mafic magma into the chamber, or convective overturnof hotter magma. The magma temperature rose until it was buffered,initially by plagioclase solution and later by crystallization.During this period textural coarsening (Ostwald ripening) ofplagioclase and amphibole occurred: small crystals dissolvedsimultaneously with the growth of large crystals. The CSD becameless steep and extended to larger crystal sizes. Early stagesof this process are preserved in coarsened amphibole oikocrysts.Repetitions of this cycle generated the observed family of CSDs.Textural coarsening followed the ‘Communicating Neighbours’model. Hence, each crystal has its own, unique growth–solutionhistory, without appealing to mixing of magmas that crystallizedin different environments. KEY WORDS: Ostwald ripening; textural coarsening; oikocryst; CSD; texture     

Crystal size distribution (CSD) in rocks and the kinetics and dynamics of crystallization II: Makaopuhi lava lake

Crystal size distribution (CSD) theory has been applied to drill core samples from Makaopuhi lava lake, Kilauea Volcano, Hawaii. Plagioclase and Fe-Ti oxide size distribution spectra were measured and population densities (n)were calculated and analyzed using a steady state crystal population balance equation: n=n ⁰ exp(-L/G). Slopes on ln(n) versus crystal size (L) plots determine the parameter G, a. product of average crystal growth rate (G) and average crystal growth time (). The intercept is J/G where J is nucleation rate. Known temperature-depth distributions for the lava lake provide an estimate of effective growth time (), allowing nucleation and growth rates to be determined that are independent of any kinetic model. Plagioclase growth rates decrease with increasing crystallinity (9.9–5.4×10^–11 cm/s), as do plagioclase nucleation rates (33.9–1.6×10^–3/cm³ s). Ilmenite growth and nucleation rates also decrease with increasing crystallinity (4.9–3.4 ×10^–10 cm/s and 15–2.2×10^–3/cm³ s, respectively). Magnetite growth and nucleation rates are also estimated from the one sample collected below the magnetite liquidus (G =2.9×10^–10 cm/s, J=7.6×10^–2/cm³ s). Moments of the population density function were used to examine the change in crystallization rates with time. Preliminary results suggest that total crystal volume increases approximately linearly with time after 50% crystallization; a more complete set of samples is needed for material with <50% crystals to define the entire crystallization history. Comparisons of calculated crystallization rates with experimental data suggests that crystallization in the lava lake occurred at very small values of undercooling. This interpretation is consistent with proposed thermal models of magmatic cooling, where heat loss is balanced by latent heat production to maintain equilibrium cooling.     

Constraining the conditions of Barrovian metamorphism in Sikkim,India: P–T–t paths of garnet crystallization in the Lesser Himalayan Belt

Garnet crystallization in metapelites from the Barrovian garnet and staurolite zones of the Lesser Himalayan Belt in Sikkim is modelled utilizing Gibbs free energy minimization, multi‐component diffusion theory and a simple nucleation and growth algorithm. The predicted mineral assemblages and garnet‐growth zoning match observations remarkably well for relatively tight, clockwise metamorphic P–T paths that are characterized by prograde gradients of ～30 °C kbar^?1 for garnet‐zone rocks and ～20 °C kbar^?1 for rocks from the staurolite zone. Estimates for peak metamorphic temperature increase up‐structure toward the Main Central Thrust. According to our calculations, garnet stopped growing at peak pressures, and protracted heating after peak pressure was absent or insignificant. Almost identical P–T paths for the samples studied and the metamorphic continuity of the Lesser Himalayan Belt support thermo‐mechanical models that favour tectonic inversion of a coherent package of Barrovian metamorphic rocks. Time‐scales associated with the metamorphism were too short for chemical diffusion to substantially modify garnet‐growth zoning in rocks from the garnet and staurolite zones. In general, the pressure of initial garnet growth decreases, and the temperature required for initial garnet growth was reached earlier, for rocks buried closer toward the MCT. Deviations from this overall trend can be explained by variations in bulk‐rock chemistry.     

U-Pb zircon and Rb-Sr whole-rock dating of low-grade metasediments example: Montagne Noire (Southern France)

Three detrital, Proterozoic zircon suites extracted from siltstones progressively metamorphosed between chlorite- and staurolite-grade independently date the major Caledonian metamorphism within the gneiss dome of the Montagne Noire (Southern France). From this, the following conclusions concerning U-Pb systematics of zircons in low-, medium- and highgrade metamorphic rocks can be drawn:

1. Temperatures of at most 350–400 °C are sufficient to open U-Pb systems of metamict zircons or domains within zircons.
2. The observed open U-Pb system behaviour during metamorphism of the host rocks was found to be due to a low-temperature recrystallisation of highly radiation damaged zircon lattices, probably enhanced by high concentrations of fluid phases in the dehydrating rock volumes.
3. Recrystallisation of metamict zircons under low temperatures causes maximum U-Pb ages for the thermal climax of metamorphism of medium-and high-grade metamorphic rocks, as annealing and accompaning closing of U-Pb systems took place before the maximum temperatures of metamorphism were reached.
4. Low-temperature recrystallisation of old — generally Proterozoic—zircons can readily help to explain the fact that the numerous zircon suites from ancient shield areas yield “lower intercept ages” which are not correlated to any known geological event. Thus, either a weak thermal pulse, not necessarily registered by the mineral assemblage of the host rock, and/or elevated temperatures during burial in the crust might supply enough energy for a structural reordering and simultaneous lead loss of at least the most disordered lattice domains.

In contrast to the U-Pb zircon method, no unambiguous dating of the Caledonian main metamorphism was possible using the Rb-Sr whole-rock technique for phyllites and mica schists sampled in the same metamorphic profile from which the zircon samples were taken. The scatter of data points can best be explained by their rotation around a probable Caledonian isochron. This rotation very probably took place during the later Hercynian orogeny, not significantly affecting the slope of the least square regression line through the scattered data points.     

Geologic setting,genesis and transformation of sulfide deposits in the northern part of Khetri copper belt,Rajasthan, India — an outline

The present study is confined to the northern part of the Khetri copper belt that extends for about 100 km in northern Rajasthan. Mineralization is more or less strata-bound and is confined to the garnetiferous chlorite schist and banded amphibolite quartzite, occurring towards the middle of the Proterozoic Delhi Supergroup. Preserved sedimentary features and re-estimation of the composition of the pre-metamorphic rocks suggest that the latter were deposited in shallow marine environment characterized by tidal activity. Cordierite-orthoamphibole-cummingtonite rock occurring in the neighbourhood of the ores is discussed, and is suggested to be isochemically metamorphosed sediment. The rocks together with the ores were deformed in two phases and metamorphosed in two progressive and one retrogressive events of metamorphism. Study of the host rocks suggests that the maximum temperature and pressure attained during metamorphism are respectively 550–600°C and < 5.5 kb. Principal ore minerals in Madan Kudan are chalcopyrite, pyrrhotite, pyrite and locally magnetite. In Kolihan these are chalcophyrite, pyrrhotite and cubanite. Subordinate phases are sphalerite, ilmenite, arsenopyrite, mackinawite, molybdenite, cobaltite and pentlandite. The last two are very rare. Gangue minerals comprise quartz, chlorite, garnet, amphiboles, biotite, scapolite, plagioclase and graphite. The ores are metamorphosed at temperatures > 491°C. Sulfide assemblages are explained in terms of f_{S 2} during metamorphism. Co-folding of the ore zone with the host rocks, confinement of the ores to the carbonaceous pelites or semi-pelitic rocks, strata-bound and locally even stratiform nature of the orebodies, lack of finite wall rock alteration, metamorphism of the ores in the thermal range similar to that for the host rocks, absence of spatial and temporal relationship with the granitic rocks of the region led the authors to conclude that the entire mineralization was originally sedimentary-diagenetic. Any loss of primitive features and development of incongruency are due to subsequent deformation and metamorphism to which the ores and their hosts were together subjected.     

Sm−Nd dating of multiple garnet growth events in an arc-continent collision zone,northwestern U.S. Cordillera

Integrated petrologic and Sm–Nd isotopic studies in garnet amphibolites along the Salmon River suture zone, western Idaho, delineate two periods of amphibolite grade metamorphism separated by at least 16 million years. In one amphibolite,P–T studies indicate a single stage of metamorphism with final equilibration at 600°C and 8–9 kbar. The Sm–Nd isotopic compositions of plagioclase, apatite, hornblende, and garnet define a precise, 8-point isochron of 128±3 Ma (MSWD=1.2) interpreted as mineral growth at the metamorphic peak. A⁴⁰Ar/³⁹Ar age for this hornblende indicates cooling through 525°C at 119±2 Ma. In a nearby amphibolite, garnets with a two-stage growth history consist of inclusion-rich cores surrounded by discontinuous, inclusion-free overgrowths. Temporal constraints for core and overgrowth development were derived from Sm–Nd garnet — whole rock pairs in which the garnet fractions consist of varying proportions of inclusion-free to inclusion-bearing fragments. Three garnet fractions with apparent ages of 144, 141, and 136 Ma are thought to represent mixtures between late Jurassic (pre-144 Ma) inherited radiogenic components preserved within garnet cores and early Cretaceous (128 Ma) garnet overgrowths. These observations confirm the resilience of garnet to diffusive exchange of trace elements during polymetamorphism at amphibolite facies conditions. Our geochronologic results show that metamorphism of arc-derived rocks in western Idaho was episodic and significantly older than in arc rocks along the eastern margin of the Wrangellian Superterrane in British Columbia and Alaska. The pre-144 Ma event may be an expression of the late Jurassic amalgamation of marginal oceanic arc-related terranes (e.g., Olds Ferry, Baker, Wallowa) during the initial phases of their collision with North American rocks. Peak metamorphism at 128 Ma reflects tectonic burial along the leading edge of the Wallowa arc terrane during its final penetration and suturing to cratonic North America.     

Oxygen and hydrogen isotopic composition of Alpine and pre-Alpine minerals of the Swiss Central Alps

The rocks of the Swiss Central Alps consist of pre-Mesozoic and Mesozoic rocks which were metamorphosed during the Alpine orogeny. Eightysix samples from this area have been analyzed for their isotopic composition (310 mineral phases for their ¹⁸O values and 99 mineral phases for their D values).The mineral phases of pre-Mesozoic and Mesozoic rocks differ significantly in their stable isotope composition. The minerals in pre-Mesozoic rocks display a rather uniform oxygen and hydrogen isotope composition indicative of large-scale homogenization with magmatic fluids. The mineral phases of Mesozoic rocks, on the other hand, show a large variation in their isotopic composition, their ¹⁸O values are heavier, and their D values are isotopically lighter than the pre-Mesozoic phases. These data indicate the lack of a large-scale water supply to the gneissic cores of the Penninic nappes during Alpine metamorphism.Equilibrium conditions, as indicated by concordant oxygen isotope temperatures, are attained in several samples; disequilibrium, however, is more frequently observed, mainly in the central part of the Lepontin area. The pre-Mesozoic rocks recrystallized during Alpine metamorphism. This process was accompanied by partial reequilibration of the oxygen isotopes, and took place in a closed system. In the pre-Mesozoic rocks, the oxygen isotope fractionations, therefore, reflect the temperatures at the time of this recrystallization which, in many cases, is not the maximum temperature of Alpine metamorphism. There is strong evidence that oxygen isotope ratios are frozen during the progressive phase of a metamorphic event.Oxygen isotope fractionations indicate temperatures of Alpine metamorphism ranging from 500 ° C near Andermatt to 700 ° C near the Bergell granite.     

A mechanism for preferential H2O leakage from fluid inclusions in quartz,based on TEM observations

Preferential leakage of H₂O from fluid inclusions containing multiple gas components has been suspected in natural metamorphic rocks and has been demonstrated experimentally for synthetic H₂O-CO₂-rich inclusions in natural quartz. Knowledge of the physical and chemical characteristics of the leakage mechanism, which may be very complex, increases the value of natural fluid inclusions to metamorphic geology. It is proposed that crystal defects play a major role in nondecrepitative preferential H₂O leakage through quartz, and remain effective during metamorphism. Inclusions with either an internal overpressure or underpressure produce strain in the adjacent quartz crystal via the nucleation of many dislocations and planar defects (like Dauphiné twin boundaries). These defects allow preferential loss of H₂O from H₂O-CO₂-rich inclusions at supercritical conditions. The transport capacity of this leakage mechanism is enhanced by nucleation of small bubbles on defect structures. The nucleation of these bubbles seems to be a recovery process in strained crystals. Solubility gradients of quartz in water in a crystal with internally underpressurized inclusions may result in optical visible implosion halos in a three dimensional spatial arrangement, caused by the growth of small bubbles at the expense of the larger original fluid inclusion. Natural fluid inclusions from Naxos (Greece) are always associated with numerous interlinked dislocations. These dislocations may have been produced by plastic derormation or by crystal growth related processes (e.g. crack healing). The presence of small bubbles on these dislocations indicates that a similar leakage mechanism for H₂O must have occurred in these rocks.     

The significance of intergranular diffusion to the mechanisms and kinetics of porphyroblast crystallization

The spatial disposition, compositional zoning profiles, and size distributions of garnet crystals in 11 specimens of pelitic schist from the Picuris Range of New Mexico (USA) demonstrate that the kinetics of intergranular diffusion controlled the nucleation and growth mechanisms of porphyroblasts in these rocks. An ordered disposition of garnet centers and a significant correlation between crystal radius and near-neighbor distances manifest suppressed nucleation of new crystals in diffusionally depleted zones surrounding pre-existing crystals. Compositional zoning profiles require diffusionally controlled growth, the rate of which increases exponentially as temperature increases with time; an acceleration factor for growth rate can be estimated from a comparison of compositional profiles for crystals of different sizes in each specimen. Crystal size distributions are interpreted as the result of nucleation rates that accelerate exponentially with increasing temperature early in the crystallization process, but decline in the later stages because of suppression effects in the vicinity of earlier-formed nuclei. Simulations of porphyroblast crystallization, based upon thermally accelerated diffusionally influenced nucleation kinetics and diffusionally controlled growth kinetics, quantitatively replicate textural relations in the rocks. The simulations employ only two variable parameters, which are evaluated by fitting of crystal size distributions. Both have physical significance. The first is an acceleration factor for nucleation, with a magnitude reflecting the prograde increase during the nucleation interval of the chemical affinity for the reaction in undepleted regions of the rock. The second is a measure of the relative sizes of the porphyroblast and the diffusionally depleted zone surrounding it. Crystal size distributions for the Picuris Range garnets correspond very closely to those in the literature from a variety of other localities for garnet and other minerals. The same kinetic model accounts quantitatively for crystal size distributions of porphyroblastic garnet, phlogopite, sphene, and pyroxene in rocks from both regional and contact metamorphic occurrences. These commonalities indicate that intergranular diffusion may be the dominant kinetic factor in the crystallization of porphyroblasts in a wide variety of metamorphic environments.     

Oxygen isotopic study of the Cretaceous granitic rocks in Japan

The ( ¹⁸O values of nine Cretaceous granitic rocks from the low P/T type regional metamorphic zone of Japan are +10.0 to +13.2 relative to SMOW, while ten Cretaceous granitic rocks from the non-metamorphic zone are +7.9 to +9.8. The ¹⁸O-enrichment in the former rocks is mainly attributed to oxygen isotopic exchange between the granitic magma and the surrounding metamorphic rocks during regional metamorphism. The assimilation of ¹⁸O-rich country rocks is also possible in the cases such as gneissose granite and migmatite.The oxygen isotopic ratios of quartz-biotite pairs in the granitic rocks indicate that they are isotopically in near-equilibrium with each other. The quartz-biotite isotopic equilibrium temperatures estimated for these rocks range from 550° to 670° C. Feldspar is occasionally isotopically in disequilibrium with other minerals. This may be caused by exchange of oxygen isotopes between feldspar and hydrothermal or meteoric water after crystallization.     

Granulite facies metamorphism, palaeo-isotherms and disturbance of the U-Pb systematics of zircon in anorogenic plutonic rocks from the Adirondack Highlands

Abstract In the Adirondack Highlands of New York State, the effect of granulite facies metamorphism on the physical and isotopic characteristics of zircon from anorogenic plutonic rocks has a distinct geographical pattern. The location of zircon populations which appear to have been altered describes a roughly circular area where metamorphic palaeotemperatures have been determined to be in excess of 750° C. Zircons from anorogenic plutonic rocks outside this area were undisturbed during metamorphism and yield well constrained ages. Granitic, charnockitic and mangeritic anorogenic plutonic rocks peripheral to the Marcy anorthosite massif have large, euhedral, prismatic zircons that display fine, internal, magmatic growth zonations and abundant, randomly orientated, mineral inclusions. Co-genetic zircon fractions yield linear discordant arrays and well constrained upper intercepts of 1125–1157 Ma. Metamorphic zircon is limited to sporadically developed and volumetrically insignificant, clear, low-U overgrowths or protuberances. In marked contrast, zircons from petrographically and geochemically identical rocks adjacent to, or within, the Marcy anorthosite massif are typically large, limpid, anhedral to subhedral crystals or crystal fragments lacking internal features except for tubular cavities and CO-₂-rich inclusions. Co-genetic zircon fractions yield nearly concordant, non-linear clusters with ²⁰⁷Pb/²⁰⁶Pb minimum ages of 1073–1095 Ma. Metamorphic overgrowths cannot be readily identified by optical or cathodoluminscence techniques; however, many grains show complex and unusual external boundaries suggestive of post-crystallization modification. These data indicate that temperatures as low as 750° C, in combination with other factors, may have been sufficient to facilitate recrystallization, and diffusion of radiogenic Pb from the zircon crystal structure, during the complex, protracted metamorphism of the Adirondack Highlands.