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1.
Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 18O/16O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in 18O and Sr compared to PLC, and is much more 18O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of 18O-depleted (metamorphic or magmatic) fluid (initial δ18O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10−8 m2, from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼103 to ∼104 years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of 18O/16O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ18O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998  相似文献   

2.
Stable-isotope profiles show that flat-lying marble units acted as impermeable barriers to upward fluid flow in transitional amphibolite-granulite grade rocks of the Kigluaik Mountains, Seward Peninsula, Alaska. The degree of permeability is related to the composition of the marble. The margin of a thick pure dolomite marble chemically reacted with underlying metasyenite (aH2O=0.2) to form a 2 cm boundary layer of calcite + forsterite by introduction of SiO2. No fluid penetrated past this reaction front, although the high temperature of metamorphism (800°C) allowed transport of carbon and oxygen isotopes for an additional 2 cm by diffusion through the solid dolomite. A second marble with a higher silica content underwent more decarbonation, which enhanced porosity and lead to a greater extent of isotope transport (2–3 m) in contact with quartzo-feld-spathic gneiss below. An estimate of total fluid flux across the bottom of this marble layer based on the shape of the isotope profile is 1 cm3/cm2 directed down, out of the marble. At two other marble-gneiss contacts steep isotopic gradients coincide with lithologic contacts, indicating very little cross-lithology fluid flow. The extent of diffusional transport of isotopes in the marbles is limited and interpreted as indicating the transient presence of a pore fluid, generated by thermally driven devolatilization reactions. No wholesale pervasive advection of C-O-H fluid occurred across the thick, continuous, marble units near the exposed base of the Kigluaik Group section during the entire regional metamorphic cycle. Activities of pore-fluid species were controlled by internal processes. Movement of volatiles and stable-isotopes between contrasting rock-types was dominantly diffusive. Channelized fluid pathways through the marble units developed during uplift and cooling but were not present during peak metamorphism. Heating of the section occurred by conduction, probably from an underlying magma source, and not by advection of a C-O-H fluid.  相似文献   

3.
18O/16O ratios vary systematically in the 1,000 m section of interlayered metasediments and granitoids at Lizzies Basin, the deepest structural level exposed in the East Humboldt Range metamorphic core complex. In the lower 300 m of the section (the Lower Zone) 18O is homogeneous and low (+6.6 to +8.8 in silicate rocks, +8.7 to +12.1 in marbles). A detailed oxygen isotope profile across an individual marble layer within the Lower Zone has a similar range in 18O (+9.5 to +11.9) with the highest values preserved in the middle of the layer. In the upper 700 m of the section (the Upper Zone) metasediments have been less strongly 18O depleted. The 18O values are higher and more heterogeneous and in a profile across a marble layer of similar thickness, rise steeply from marginal values of +12 to core values of +23. Quartz from silicate metasediments throughout the Upper Zone ranges from +11 to +13 and is thus fairly homogeneous, particularly where detailed profiles have been measured adjacent to the 18O-rich marble layers. Covariation of 18O/16O and 13C/12C ratios in marbles suggests that the isotopic composition of these elements has been altered by exchange with infiltrating, water-rich, CO2–H2O fluids with mantle-like isotopic composition. In most cases, marble cores preserve protolith 13C values and these vary systematically throughout the section according to structural level, including some exceptionally 13C-rich values up to +12. This range may reflect stratigraphic variation in 13C of the Proterozoic sedimentary protoliths of these rocks. The Upper/Lower Zone boundary, and the contrast in isotope systematics to either side, has been previously explained either as an impermeable barrier to fluid flow, or as an infiltration front (Wickham and Peters 1990). The second alternative has been tested using a numerical model in which low-18O aqueous fluid flows vertically upward through an alternating sequence of monomineralic quartz (18O=+12) and calcite (18O=+22) layers in a regime in which the oxygen isotopic composition is controlled by advection, diffusion (in the fluid), and fluid/solid exchange. Solutions to the relevant transport equations indicate that the abrupt change in the average 18O value of the layers at the Upper/Lower Zone boundary can be reproduced by the model with a uniform porosity throughout the system, but the observed contrast in the shapes of the marble layer profiles in the Upper and Lower Zones cannot be reproduced under these conditions. However, if the calcite layers have two orders of magnitude lower porosity in comparison with the quartz layers and exchange within them is diffusion-dominated (as opposed to advection-dominated in the quartz) the contrasting shapes of the marble profiles in the two zones are reproduced, as well as the Upper/Lower Zone discontinuity. The range of conditions that generates both an infiltration front (at the appropriate scale) and contrasting marble profiles (at the appropriate scale) is quite narrow but requires a volatile flux that could be generated by plausible volumes of mantle-derived magma crystallizing at depth beneath the area, providing support for this mechanism as a viable agent of 18O depletion in the deep-level rocks of this terrane.  相似文献   

4.
The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (87Sr/86Sr)t and (ɛNd)t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The 87Sr/86Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (87Sr/86Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ18O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ13C and δ18O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ34S of sulfides is 0 to 2‰ (relative to CDT);87Sr/86Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ13C and 87Sr/86Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ13C, δ18O, and 87Sr/86Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.  相似文献   

5.
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  相似文献   

6.
The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ18O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ18O–δ56Fe variations in magnetite is a strong increase in δ18OMt and a mild decrease in δ56Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

7.
The role of silicate and carbonate weathering in contributing to the major cation and Sr isotope geochemistry of the headwaters of the Ganga-Ghaghara-Indus system is investigated from the available data. The contributions from silicate weathering are determined from the composition of granites/ gneisses, soil profiles developed from them and from the chemistry of rivers flowing predominantly through silicate terrains. The chemistry of Precambrian carbonate outcrops of the Lesser Himalaya provided the data base to assess the supply from carbonate weathering. Mass balance calculations indicate that on an average ∼ 77% (Na + K) and ∼ 17% (Ca + Mg) in these rivers is of silicate origin. The silicate Sr component in these waters average ∼40% and in most cases it exceeds the carbonate Sr. The observations that (i) the87Sr/86Sr and Sr/Ca in the granites/gneisses bracket the values measured in the head waters; (ii) there is a strong positive correlation between87Sr/86Sr of the rivers and the silicate derived cations in them, suggest that silicate weathering is a major source for the highly radiogenic Sr isotope composition of these source waters. The generally low87Sr/86Sr (< 0.720) and Sr/Ca (∼ 0.2 nM/ μM) in the Precambrian carbonate outcrops rules them out as a major source of Sr and87Sr/86Sr in the headwaters on a basin-wide scale, however, the high87Sr/86Sr (∼ 0.85) in a few of these carbonates suggests that they can be important for particular streams. The analysis of87Sr/86Sr and Ca/Sr data of the source waters show that they diverge from a low87Sr/86Sr and low Ca/Sr end member. The high Ca/Sr of the Precambrian carbonates precludes them from being this end member, other possible candidates being Tethyan carbonates and Sr rich evaporite phases such as gypsum and celestite. The results of this study should find application in estimating the present-day silicate and carbonate weathering rates in the Himalaya and associated CO2 consumption rates and their global significance.  相似文献   

8.
 Grain boundary diffusion rates of oxygen, potassium and calcium in fine-grained feldspar aggregates were determined experimentally. The starting materials were a natural albite rock from the Tanco pegmatite and aggregates hot-pressed from fragments of Amelia albite or Ab, Or and An composition glasses. The technique employed isotopic tracers (18O, 41K, 42Ca) either evaporated onto the surface or in an aqueous solution surrounding the sample, and depth profiling using an ion microprobe (SIMS). From the depth profiles, the product of the grain boundary diffusion coefficient (D′) and effective boundary width (δ) was calculated using numerical solutions to the appropriate diffusion equation. The experimental reproducibility of D′δ is a factor of 3. A separate determination of D′ independent of δ yields an effective grain boundary width of ∼3 nm, consistent with high resolution TEM observations of a physical grain boundary width <5 nm. Oxygen (as molecular water) grain boundary diffusion rates were determined in the Ab and Or aggregates at 450°–800° C and 100 MPa (hydrothermal), potassium rates in Or aggregates at 450°–700° C both at 0.1 MPa (in air) and at 100 MPa (hydrothermal), and calcium rates in An aggregates at 700°–1100° C and 0.1 MPa (in air). Oxygen grain boundary diffusion rates are similar in all three of the Ab aggregates and in the Or aggregate. Potassium and oxygen depth profiles measured in the same samples yield different D′δ values, confirming a diffusional transport mechanism. Potassium diffusion in the Or aggregate has a greater activation energy (216 vs 78 kJ/mol) than oxygen, and the Arrhenius relations cross at ∼625° C. Potassium D′δ values in Or aggregates are about a factor of five greater in hydrothermal experiments at 100 MPa than in experiments at 0.1 MPa in air. Calcium grain boundary diffusion rates in An aggregates are 4 to 5 orders of magnitude slower than potassium in Or and have a greater (291 kJ/mol) activation energy. This suggests that differences in formal charge and/or size of diffusing species may play an important role in their relative grain boundary diffusion rates. Received: 24 December 1993 / Accepted: 16 June 1994  相似文献   

9.
 In the Klamath Mountains, voluminous tonalite-trondhjemite magmatism was characteristic of a short period of time from about 144 to 136 Ma (Early Cretaceous). It occurred about 5 to 10 m.y. after the ∼165 to 159 Ma Josephine ophiolite was thrust beneath older parts of the province during the Nevadan orogeny (thrusting from ∼155 to 148 Ma). The magmatism also corresponds to a period of slow or no subduction. Most of the plutons crop out in the south-central Klamath Mountains in California, but one occurs in Oregon at the northern end of the province. Compositionally extended members of the suite consist of precursor gabbroic to dioritic rocks followed by later, more voluminous tonalitic and trondhjemitic intrusions. Most plutons consist almost entirely of tonalite and trondhjemite. Poorly-defined concentric zoning is common. Tonalitic rocks are typically of the low-Al type but trondhjemites are generally of the high-Al type, even those that occur in the same pluton as low-Al tonalite. The suite is characterized by low abundances of K2O, Rb, Zr, and heavy rare earth elements. Sr contents are generally moderate (∼450 ppm) by comparison with Sr-rich arc lavas interpreted to be slab melts (up to 2000 ppm). Initial 87Sr/86Sr, δ 18O, and ɛ Nd are typical of mantle-derived magmas or of crustally-derived magmas with a metabasic source. Compositional variation within plutons can be modeled by variable degrees of partial melting of a heterogeneous metabasaltic source (transitional mid-ocean ridge to island arc basalt), but not by fractional crystallyzation of a basaltic parent. Melting models require a residual assemblage of clinopyroxene+garnet±plagioclase±amphibole; residual plagioclase suggests a deep crustal origin rather than melting of a subducted slab. Such models are consistent with the metabasic part of the Josephine ophiolite as the source. Because the Josephine ophiolite was at low T during Nevadan thrusting, an external heat source was probably necessary to achieve significant degrees of melting; heat was probably extracted from mantle-derived basaltic melts, which were parental to the mafic precursors of the tonalite-trondhjemite suite. Thus, under appropriate tectonic and thermal conditions, heterogeneous mafic crustal rocks can melt to form both low- and high-Al tonalitic and trondhjemitic magmas; slab melting is not necessary. Received: 1 September 1994 / Accepted: 28 August 1995  相似文献   

10.
We present the results of a study on gabbroic rocks, syenites, pegmatites, carbonatites, and hydrothermal products of the Oshurkovo apatite-bearing massif. The results include Nd and Sr isotope ratios; the isotope compositions of carbon and oxygen in calcite; oxygen in apatite, magnetite, and silicate minerals (phlogopite, titanite, diopside, amphibole, K-feldspar, and quartz); sulfur in barite; and hydrogen in mica. The isotopic data are close to the EM-1 enriched mantle values and confirm a comagmatic relationship between the gabbros and carbonatites. The binary plot ?Nd vs. 87Sr/86Sr demonstrates strong differentiation between silicate rocks and carbonatites, as is the case with the other Late Mesozoic carbonatite occurrences of southwestern Transbaikalia. The oxygen isotope composition of all comagmatic phases also falls within the range of mantle values. A clear trend toward heavier oxygen and lighter carbon isotope compositions is observed in all successively emplaced phases, which is consistent with a trend defined by hydrothermal products formed under the influence of the parent magma chamber. Carbonates formed during the greenstone alteration of gabbroic rocks are enriched in the light oxygen isotope (δ18O from ?2.8 to ?7.3‰), suggesting a contribution of vadose water.  相似文献   

11.
Isotopic compositions of C, O, and Sr in carbonates, as well as Rb-Sr systems in the silicate material from Upper Precambrian and Lower Cambrian rocks exposed by the Chapa River in the northern Yenisei Ridge, are studied. The Late Precambrian part of the section includes the following formations (from the bottom to top): Lopatinskaya (hereafter, Lopatino), Vandadykskaya (hereafter, Vandadyk) or Kar’ernaya, Chivida, Suvorovskaya (hereafter, Suvorovo), Pod”emskaya (hereafter, Podyom), and Nemchanka. They are characterized by alternation of horizons with anomalously high and low δ13C values (such alternation is typical of the ∼700–550 Ma interval). The lower, relatively thin (20 m), positive excursion (δ13C up to 4.3‰) was established in dolomites from the lower subformation of the Vandadyk (Kar’ernaya) Formation (hereafter, lower Vandadyk subformation). The upper positive excursion (δ13C = 2.2 ± 0.6‰) was recorded in the 3-km-thick Nemchanka Formation enriched in terrigenous rocks. The lower negative excursion stands out as uniform, moderately low δ13C values (−2 ± 1‰) and significant thickness. It comprises the upper part of the Vandadyk Formation, as well as Chivida and Podyom formations. The upper negative excursion is related to a thin (∼20 m) marker carbonate horizon of the upper Nemchanka subformation, in which δ13C values fall down to −8.3‰. The lower part of the Lebyazhinskaya (hereafter, Lebyazhino) Formation, which overlies the Nemchanka Formation, shows a step-by-step increase in δ13C from −2.2 to 2.5‰ typical of the Vendianto-Cambrian (Nemakit-Daldyn Horizon/Stage) transitional sequences. The absence of relationships between the carbon and oxygen isotope compositions and other parameters of postsedimentary alterations suggests that the excursions characterized above could form at the sedimentation stage and coincide in general with δ13C fluctuations in seawater. The value of 87Sr/86Sr = 0.7076−0.7078 in limestones of the Podyom Formation points to their early Ediacaran age. Values of 87Sr/86Sr = 0.70841 and 0.70845 in dolomites of the lower Lebyazhino subformation correspond to the Early Cambrian. The Rb-Sr systems of the clay material from the Vandadyk and Chivida formations are approximated by a straight line, parameters of which correspond to the age of 695 ± 20 Ma (87Sr/86Sr0 = 0.7200 ± 0.0013) and probably characterize the epigenetic stage of older sedimentary rocks, which were subjected to very rapid exhumation and “polar” sulfuric acid weathering in the course of glacioeustatic regression.  相似文献   

12.
The relationships between the δ18O of quartz veins and veinlets pertaining to the main stage of gold mineralization at the Sukhoi Log deposit and metasomatically altered host slates are estimated. The oxygen isotopic composition of veined quartz and host slates is not uniform. The δ18O of quartz veins from the Western, Central, and Sukhoi Log areas of the deposit vary from +16 to + 18 ‰. The δ18O range of metasomatically altered slates in the Western and Sukhoi Log areas attains 6 ‰. The δ18O of quartz veins are always higher than those of host slates by 3–7‰. The regular difference in the δ18O between quartz veins and host slates indicates that the oxygen isotopic composition of the ore-bearing fluid forming the system of quartz veins and veinlets at the Sukhoi Log deposit could have formed as a result of interaction with silicate rocks, for instance, terrigenous slates enriched in δ18O. Such interaction, however, took place at deeper levels of the Sukhoi Log deposit. It is suggested that the fluid phase participating in the formation of the vein and veinlet system had initially high δ18O(>+10‰) due to interaction with the rocks enriched in δ18O at a low fluid/rock ratio. The oxygen isotope data indicate that the fluid participating in the formation of gold mineralization at the Sukhoi Log deposit was not in equilibrium with igneous rocks at high temperatures.  相似文献   

13.
 Quartz grains in hydrothermally altered granites from the Isle of Skye are highly heterogeneous and not equilibrated in oxygen isotope ratio at the 20 μm scale. Ion microprobe analysis of one grain shows a gradient of 13‰ over 400 μm and a greater range in δ 18O than all quartz previously analyzed on the Isle of Skye. Other crystals from the same outcrop are homogeneous. Digitized cathodoluminescence images reveal patterns of magmatic zoning and brittle fracturing not otherwise detectable. The ion probe analysis correlates low δ 18O values on a micro-scale to one set of healed cracks. Thus, quartz exchanges oxygen isotopes primarily by solution and reprecipitation along fractures, in contrast to more reactive feldspar that appears to exchange from the grain boundary inward. Macroscopic models of isotope exchange are not realistic for these rocks; the flow of hydrothermal fluids was heterogeneous, anisotropic and crack controlled. Received: 23 October 1995/Accepted: 9 April 1996  相似文献   

14.
Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ18O values decrease down to values of 12‰ towards the contact with dolostones. This 18O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from 87Sr/86Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with 87Sr/86Sr = 0.7094 near dolomitization fronts. Dolostones have δ18O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (87Sr/86Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ18O values close to dolostones but substantially lower δ13C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with 87Sr/86Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ18O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.  相似文献   

15.
 Previous stable isotope studies at Lizzies Basin revealed that metasedimentary rocks are 18O-depleted relative to protolith values, particularly in the lower parts of the section (Lower Zone) where the rocks are also isotopically homogeneous on a scale of hundreds of meters (quartz δ18O=+9.0 to +9.6 per mil). In contrast, metasedimentary rocks at higher levels at Lizzies Basin (Upper Zone) are less 18O-depleted and more heterogeneous in δ18O. In order to understand more fully the isotopic evolution of this terrane, a series of detailed, meter-scale traverses across various metamorphic and igneous lithologies were completed at Lizzies Basin, and at the structurally higher Angel Lake locality. Traverses in the Lizzies Basin Lower Zone and in the lower parts of Angel Lake (Angel Lake Lower Sequence) across various silicate lithologies, including abundant granitoids, reveal similar degrees of homogeneity, although the average δ18O values are higher at Angel Lake. In contrast, traverses which include substantial thicknesses of marble and calc-silicate gneiss and very little granitoid have more heterogeneous quartz δ18O values (+11.9 to +13.4 per mil), and also have a higher average δ18O (+12.9 per mil), than observed elsewhere. The scale of 18O/16O homogeneity in quartz observed at Lizzies Basin and Angel Lake (meters to hundreds of meters) requires fluid-mediated isotope exchange, which accompanied Tertiary metamorphism. There is a correlation between the degree of 18O-depletion in metasedimentary rocks, 18O/16O homogenization between lithologies, and the proportion of granitoids (leucogranites in particular) within any part of the section, and a corresponding anticorrelation with the proportion of marble. This points to a causal relationship, whereby the leucogranites (as well as the Tertiary hornblende diorite and biotite monzogranite) acted as both a relatively low-18O reservoir and a source of fluids to enhance exchange, while the marbles hindered isotope depletion and homogenization by acting as relatively high-18O reservoirs and impermeable layers. Material balance calculations help delineate the plausible mechanisms of exchange between granitoids and metasediments. Single-pass infiltration of magmatic fluids from the granitoids is not capable of reproducing all of the observations. Fluid-mediated exchange by convective recirculation of magmatic fluids on a scale of meters is the mechanism which explains all of the observations. The generalized model for the isotopic evolution of the East Humboldt Range core complex provides an excellent opportunity to establish the main causes and controlling factors of 18O-depletion and 18O/16O homogenization during regional metamorphism. Received: 27 July 1993 / Accepted: 1 July 1994  相似文献   

16.
Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ18O and ±0.71‰ for δ13C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ18O and 0.10-0.29‰ for δ13C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ13C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ13C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ18O (up to 9.4‰), intercrystalline inhomogeneity in δ18O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ18O and δ13C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ18O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ18O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.  相似文献   

17.
The oxygen isotope ratios (δ18O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ18O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ18O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ18O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ18O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ18O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ18O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ18O source for the high δ18O zircons. Predicted equilibrium values of Δ18O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ18O marble will have high δ18O. The high δ18O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ18O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid(external)/rock); the lower δ18O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ18O. High δ18O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ18O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ18O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.  相似文献   

18.
In order to reconstruct the formation and exhumation mechanisms of UHP metamorphic terrains, the Chinese Continental Scientific Drilling Program (CCSD) has been carried out in Donghai of the Dabie-Sulu ultrahigh-pressure (UHP) metamorphic belt, East China. Eclogite, gneiss, amphibolite (retrograded from eclogite), ultramafic rocks, and minor schist and quartzite have been drilled. Aiming to reveal the fluid behaviour in a vertical sequence of an UHP slab, we investigated fluid inclusion and oxygen isotope characteristics of selected drillcores from the main hole and the pilot-holes PP2 and ZK 703 of the CCSD. More than 540 laser-ablation oxygen isotope analyses on garnet, omphacite, quartz, kyanite, amphibole, phengite, rutile, epidote, amphibole, plagioclase, and biotite from various rocks in the depth range of 0–3,000 m (mainly eclogite and gneiss) show that the investigated rocks can be divided into two groups: 18O-depleted rocks (as low as δ18O = −7.4‰ for garnet) indicate interaction with cold climate meteoric waters, whereas 18O-normal rocks (with bulk δ18O > +5.6‰) have preserved the O-isotopic compositions of their protoliths. Meteoric water/rock interaction has reached depths of at least 2,700 m. Oxygen isotope equilibrium has generally been achieved. Isotopic compositions of mineral phases are homogeneous on a mm to cm scale regardless of lithology, but heterogeneous on the scale of a few metres. Oxygen isotope distributions in the vertical sections favour an “in situ” origin of the UHP metamorphic rocks. The very negative δ18O eclogites usually have higher hydroxyl-mineral contents than the normal δ18O rocks, indicating higher water content during UHP metamorphism. Fluid inclusion data suggest that rocks with depleted 18O compositions have had different fluid histories compared to those with normal δ18O values. Rocks with depleted 18O mainly have primary medium-to-high salinity inclusions in omphacite, kyanite and quartz, and abundant secondary low-salinity or pure water inclusions in quartz, indicating a high-salinity-brine-dominated fluid system during peak UHP metamorphism; no carbonic inclusions have been identified in these rocks. By contrast, primary very high-density CO2 inclusions are commonly found in the rocks with normal δ18O values. These observations suggest that fluid and oxygen isotope composition of minerals are related and reflect variable degrees of alterations of the Dabie-Sulu UHP metamorphic rocks.  相似文献   

19.
Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial 87Sr/86Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest 143Nd/144Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial 87Sr/86Sr ratios (maximum 0.7105) and lower initial 143Nd/144Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have 143Nd/144Nd and 87Sr/86Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The 143Nd/144Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.  相似文献   

20.
The Brandberg West region of NW Namibia is dominated by poly-deformed turbidites and carbonate rocks of the Neoproterozoic Damara Supergoup, which have been regionally metamorphosed to greenschist facies and thermally metamorphosed up to mid-amphibolite facies by Neoproterozoic granite plutons. The meta-sedimentary rocks host Damaran-age hydrothermal quartz vein-hosted Sn–W mineralization at Brandberg West and numerous nearby smaller deposits. Fluid inclusion microthermometric studies of the vein quartz suggests that the ore-forming fluids at the Brandberg West mine were CO2-bearing aqueous fluids represented by the NaCl–CaCl2–H2O–CO2 system with moderate salinity (mean=8.6 wt% NaClequivalent).Temperatures determined using oxygen isotope thermometry are 415–521°C (quartz–muscovite), 392–447°C (quartz–cassiterite), and 444–490°C (quartz–hematite). At Brandberg West, the oxygen isotope ratios of quartz veins and siliciclastic host rocks in the mineralized area are lower than those in the rocks and veins of the surrounding areas suggesting that pervasive fluid–rock interaction occurred during mineralization. The O- and H-isotope data of quartz–muscovite veins and fluid inclusions indicate that the ore fluids were dominantly of magmatic origin, implying that mineralization occurred above a shallow granite pluton. Simple mass balance calculations suggest water/rock ratios of 1.88 (closed system) and 1.01 (open system). The CO2 component of the fluid inclusions had similar δ 13C to the carbonate rocks intercalated with the turbidites. It is most likely that mineralization at Brandberg West was caused by a combination of an impermeable marble barrier and interaction of the fluids with the marble. The minor deposits in the area have quartz veins with higher δ 18O values, which is consistent with these deposits being similar geological environments exposed at higher erosion levels.  相似文献   

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