Oxygen and Carbon Isotope Studies of Contact Metamorphism of Carbonate Rocks

O¹⁸/O¹⁶ and C¹²/C¹³ ratios have been determined for carbonaterocks and coexisting minerals from two contact metamorphic aureolesat Birch Creek, California and Marble Canyon, Texas. The peliticmetasediments and granitic intrusions of the Birth Creek localitywere also analyzed for their O¹⁸/¹⁶ and D/H ratios. Oxygen andcarbon isotope fractionations in coexisting dolomite and calciteare interrelated but show no obvious correlation with sampledistance from the intrusive contact. Small-scale oxygen isotopicexchange effects between rock units are observed within a fewfeet of the intrusive-country rock contacts and the marble-schistcontacts at Birch Creek. Oxygen isotopic temperatures obtainedfrom quartz—biotite fractionations in the biotite schistsof Birch Creek show a systematic decrease with increasing distanceaway from the intrusive contact; the isotopic contact temperatureis calculated to be 535–45°C. Low O¹⁸/¹⁶ and C¹³/¹²ratiosof the contact metamorphic marbles generally correlate wellwith presence of calc-silicate minerals, indicating that theCO₂ liberated during metamorphic decarbonation reactions isenriched in both O¹⁸and C¹² relative to the carbonates. Materialbalance calculations indicate that the liberated CO₂ is about5 per mille richer in O¹⁸ and about 6 per mille richer in C¹³than coexisting calcite.     

Fractionation of carbon and oxygen isotopes and magnesium between coexisting metamorphic calcite and dolomite

Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C $$ \begin{gathered} 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.45 (10^6 T^{ - 2} ) - 0.40 \hfill \\ 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.18 (10^6 T^{ - 2} ) + 0.17. \hfill \\ \end{gathered} $$ These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C¹³ partial exchange experiments of this study. Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO _D ¹⁸ –δO _Ct ¹⁸ values. The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C¹³/C¹² ratios in Grenville and Vermont marbles and O¹⁸/O¹⁶ ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O¹⁸(δO¹⁸=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange. Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O¹⁸ by about 4.9‰ and in C¹³ by about 2.4‰.     

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO₂-H₂O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks.Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed.Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ¹⁸O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences.The range of Adirondack carbonate ¹⁸O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor ¹⁸O and ¹³C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ¹⁸O calcites (25.0 to 27.2), low ¹⁸O wollastonites (–1.3 to 3.5), and sharp gradients in ¹⁸O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn).Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts.     

Oxygen isotope study of metamorphic and granitic rocks of the Yanai district in the Ryoke belt,Japan

¹⁸O/¹⁶O ratios have been obtained for 134 whole-rocks and minerals from metamorphic and granitic rocks of the Yanai district in the Ryoke belt, Southwest Japan. The ¹⁸O/¹⁶O ratios of pelitic rocks of the marginal metamorphic zone decrease progressively with increasing metamorphic grade. In the gneiss-granite complex (zone of migmatite [1]), the most characteristic feature of the rocks is that oxygen isotopic homogenization proceeds on both local and regional scales in parallel with “granitization” or chemical homogenization. Granitic rocks of various origin are fairly uniform in isotopic composition with δ ¹⁸O of quartz of 12 to 14‰ (SMOW) and δ ¹⁸O of biotite of 7 to 9‰ and are about 3 to 4‰ enriched in ¹⁸O compared to other Cretaceous granites of non-metamorphic terranes in Japan. The high ¹⁸O/¹⁶O ratios of granitic rocks of this district were discussed in relation to the ¹⁸O-depletion in metasediments. Oxygen isotopic fractionations among coexisting minerals from various rock-types of the gneiss-granite complex indicate that these minerals were formed under near isotopic equilibrium at a temperature of about 600 to 700° C. Some abnormal fractionations of quartz-biotite pairs also were obtained for rocks which had undergone a progressive ¹⁸O-depletion or ¹⁸O-enrichment. This is due to high resistivity of quartz and contrastive susceptibility of biotite to isotopic exchange during metamorphism and “granitization”.     

O18/O16 ratios of the Johnny Lyon granodiorite and Texas Canyon quartz monzonite plutons,Arizona, and their contact aureoles

O¹⁸/O¹⁶ ratios have been measured for 29 quartz samples, 6 whole-rocks, 3 muscovites, and 1 K-feldspar from two adjacent granitic plutons of vastly different age (about 1660 m.y, and 70 m.y.) intruded into the same type of country rock, the Precambrian Pinal schist. Sample traverses were made across 3 different contact zones of these intrusive bodies. Except for 2 quartz veins with O¹⁸=+11.0 and + 12.3, all quartz samples collected more than 15 cm from the margin of the Early Tertiary Texas Canyon pluton are isotopically exceedingly uniform with O¹⁸=9.47±0.11. Four quartz samples collected more than 10 m from the margin of the Precambrian Johnny Lyon pluton have O¹⁸=10.43±0.08. Compared with previous studies of this type, only relatively minor O¹⁸-enrichments have occurred in the border zones of the plutons. This is in part because the original O¹⁸ differences between the metasedimentary rocks and the intrusives are relatively small (only 3 to 6), but is mainly due to the lack of H₂O in the contact zones during intrusion as a result of the general impermeability and prior dehydration of the schist. There is no isotopic evidence for significant influx of external H₂O into either of the plutons during their crystallization and cooling. However, in roof-zones where metasedimentary rocks overlie the plutons there is a strong O¹⁸ lowering in the contact metamorphic aureoles, indicating upward expulsion of low-O¹⁸ magmatic H₂O into these rocks.Contribution No. 2015 of the Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91109.     

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.     

The oxygen isotope geochemistry of igneous rocks

Oxygen isotope analyses have been obtained for 443 igneous rock and mineral samples from various localities throughout the world. Detailed studies were made on the Medicine Lake, Newberry, Lassen, Clear Lake, S. E. Guatemala, Hawaii and Easter I. volcanic complexes and on the Bushveld, Muskox, Kiglapait, Guadalupe, Duluth, Nain, Egersund, Lac St. Jean, Laramie, Skaergaard, Mull, Skye, Ardnamurchan and Alta, Utah plutonic complexes, as well as upon several of the zoned ultramafic intrusions of S. E. Alaska. Basalts, gabbros, syenites and andesites are very uniform in O¹⁸/O¹⁶, commonly with δ-values of 5.5 to 7.0 per mil. Many rhyolite obsidians, particularly those from oceanic areas and the Pacific Coast of the United States, also lie in this range; this indicates that such obsidians are differentiates of basaltic or andesitic magma at high temperatures (about 1,000° C). They cannot represent melted sialic crust. The only plutonic granites with such low δ-values are some of the hypersolvus variety, suggesting that these also might form by fractional crystallization. Obsidians from the continental interior, east of the quartz-diorite line, have higher δ-values. This is compatible with their having assimilated O¹⁸-rich sialic crust. A correlation generally exists between the O¹⁸/O¹⁶ ratios of SiO₂-rich differentiates and the chemical trends in volcanic complexes. High O¹⁸/O¹⁶ ratios accompany those trends having the lower Fe/Mg ratios, while ferrogabbro trends are associated with depletion in O¹⁸. Variations in oxygen fugacity may be responsible for these effects, as abundant early precipitation of magnetite should lead to both O¹⁸-enrichment and Fe-depletion in later differentiates. Plutonic granites have higher O¹⁸/O¹⁶ ratios than their volcanic equivalents, because (a) their differentiation occurred at much lower temperatures, or (b) they are in large part derived from O¹⁸-rich sialic crust by partial melting or assimilation. Also, the oxygen isotope fractionations among coexisting minerals are distinctly larger in plutonic rocks than in volcanic rocks. This is in keeping with their lower crystallization temperatures and their longer cooling history, which promotes post-crystallization oxygen isotope exchange. Hydrated obsidians and perlites have δO¹⁸-values that are much different from their primary, magmatic values. A correlation exists between D/H and O¹⁸/O¹⁶ ratios in hydrated volcanic glass from the western U.S.A., proving that the isotopic compositions are a result of exchange with meteoric waters. The O¹⁸ contents of the glasses appear to be about 25 per mil higher than their associated waters; hence, these hydrated glasses have not simply absorbed H₂O, but they have exchanged with large quantities of it. The igneous rocks from Mull, Skye, Ardnamurchan and the Skaergaard intrusion are all abnormally depleted in O¹⁸ relative to “normal” igneous rocks. This is a result of their having exchanged at high temperatures with meteoric water that was apparently abundant in the highly jointed plateau lavas into which these igneous rocks were intruded. In part, this exchange occurred with liquid magma and in part with the crystalline rock; in the latter case the feldspar was more easily exchanged and has become much more depleted in O¹⁸ than has coexisting quartz or pyroxene. The later differentiates of the Muskox intrusion are markedly O¹⁸-rich, but this is not a result of fractional crystallization. It is in large part a result of deuteric exchange between feldspars and an oxygen-bearing fluid (H₂O ?) that was either O¹⁸-rich or had a relatively low temperature. This phenomenon was also observed in a number of granophyres from other localities, particularly those containing brick-red alkali feldspar. The exchanged feldspars in all these examples are turbid or cloudy, and may be filled with hematite dust. It is concluded that most such feldspar in nature is the result of deuteric exchange and is probably drastically out of oxygen isotopic equilibrium with its coexisting quartz.     

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.     

The effect of net-transfer reactions on the isotopic composition of minerals

To interpret correctly the isotopic composition of metmorphic rocks and minerals, the effect of nettransfer reactions must be quantitatively evaluated. Such evaluation requires a complete set of linearly independent, net-transfer reactions that fully describe the reacting system. The set of net-transfer reactions is then coupled with mass-balance equations for stable isotopes. Reaction spaces can be contoured with isopleths of °¹⁸O, °¹³C, and D of minerals which allows evaluation of the effect of different reactions and bulk compositions on the stable isotopic composition of minerals and rocks. Using this approach, we examined the effect of fractionation of isotopes due to net-transfer reactions at the biotite and second-sillimanite isograds in northern New England. Our analysis shows that the shift in °¹³C and °¹⁸O at an isograd depends strongly upon the overall net-transfer reaction at the isograd and the bulk composition of the rock. The use of model isograd reactions to determine isotopic shifts, therefore, can lead to serious errors in the interpretation of isotopic data. At the second-sillimanite isograd °¹⁸O _qtz (quartz), °¹⁸O _kspar (K feldsdpar), and °¹⁸O _wr (whole rock) decrease by 0.5, 1.0, and 0.8 per mil, respectively. Quantitative evaluation of the effect of fractionation of isotopes by net-transfer reactions shows that: (1) the relative changes in oxygen isotopes across the isograd could be caused by distillation of fluids during develatilization reactions; (2) the magnitude of the observed isotopic shifts often differs by a factor of 2 from the calculated shifts due to reaction progress alone. The difference between observed and calculated shifts is attributed to either, differences in bulk composition between individual rocks, or, to isotopic exchange between minerals after peak metamorphism. At the biotite isograd the shifts in carbon and oxygen isotope values are different from predicted shifts caused by net-transfer reactions alone. This discrepancy suggests that fluids infiltrated the rocks during the formation of the biotite isograd.     

High integrated fluid/rock ratios during metamorphism at Naxos: evidence from carbon isotopes of calcite in schists and fluid inclusions

Calcite in schists of the metamorphic complex at Naxos is depleted both in ¹³C and in ¹⁸O with respect to massive marbles. This effect is attributed to isotope exchange with circulating CO₂-rich fluids, which had an >0.5 according to fluid inclusions. The carbon isotopic composition of the calcites is close to equilibrium with fluid inclusion CO₂ at metamorphic temperatures. Mass balance calculations assuming initial ¹³C values of 0 for calcite and –5 for the fluid, give integrated fluid/rock volume ratios between 0.1 and 2.0. Such high fluid/rock ratios are supported by observations on the distribution of CO₂/H₂O ratios of fluid inclusions, carbon isotopic compositions of fluid inclusion CO₂ and oxygen isotope systematics of silicates.     

Zonal distribution of oxygen isotope ratios in the Hiroshima granite complex,Southwest Japan

¹⁸O/¹⁶O ratios have been obtained for 99 minerals from rocks of the Hiroshima granite complex and adjacent Ryoke granites. Zonal distribution of oxygen isotopes is observed on a regional scale almost parallel to the extension of the Ryoke plutono-metamorphic belt, granites in or around the metamorphic belt being 2–3%₀ richer in ¹⁸O than those farther away from the belt. Isotopic fractionations among coexisting minerals indicate that isotopic zonation existed at a magmatic stage. The zonal enrichment of ¹⁸O in the granite magma in the Ryoke belt and its periphery is a result of isotopic interaction between country rocks and the magma through fluid media. Genetic relationship between granites of the Ryoke and Chugoku belts are discussed with regard to the geological situation of the former belt.     

Oxygen isotope fractionation between calcite and tremolite: an experimental study

Oxygen isotope partitioning between calcite and tremolite was experimentally calibrated in the presence of small amounts of a supercritical CO₂–H₂O fluid at temperatures from 520 to 680° C and pressures from 3 to 10 kbar. The experiments were carried out within the stability field of the calcite-tremolite assemblage based on phase equilibrium relationships in the system CaO–MgO–SiO₂–CO₂–H₂O, so that decomposition of calcite and tremolite was avoided under the experimental conditions. Appropriate proportions of carbon dioxide to water were used to meet this requirement. Large weight ratios of mineral to fluid were employed in order to make the isotopic exchange between calcite and tremolite in the presence of a fluid close to that without fluid. The data processing method for isotopic exchange in a three-phase system has been applied to extrapolate partial equilibrium data to equilibrium values. The determined fractionation factors between calcite (Cc) and tremolite (Tr) are expressed as:10³1n _Cc-Tr=3.80 × 10⁶/T ²-1.67By combining the present data with the experimental calibrations of Clayton et al. (1989) on the calcite-quartz system, we obtain the fractionation for the quartztremolite system: 10³1n _Qz-Tr=4.18 × 10⁶/T ²-1.67Our experimental calibrations are in good agreement with the theoretical calculations of Hoffbauer et al. (1994) and the empirical estimates of Bottinga and Javoy (1975) based on isotopic data from naturall assemblages. At 700 C good agreement also exists between our experimental data and theoretical values calculated by Zheng (1993b). With decreasing temperature, however, an increasing difference between these data appears.Retrograde isotopic reequilibration by oxygen diffusion may be common for amphibole relative to diopside in metamorphic rocks. However, isotopic equilibrium in amphibole can be preserved in cases of rapid cooling.     

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.     

Hydrogen and carbon isotope studies on the graphite-bearing metapelites in the northern Kiso district of central Japan

Measurements were made of the hydrogen isotope ratios of hydrous silicates (mica and amphibole) and whole rocks, and the carbon isotope ratios of graphite and carbonaceous matter in the metamorphic rocks from the northern Kiso district in central Japan.D values of hydrous silicates in the graphite-bearing metapelites are always higher than those in graphite-free schists, even though the sample localities of the two rock-types are very close. Hydrogen isotopic equilibrium has been attained between the coexisting minerals.D/H ratios of water in the metamorphic fluids seem to depend strongly on the presence or absence of graphite and seem to be not constant throughout the district. The district is divided into three areas of low (metamorphic zones I, II), medium (zones IIIa–V) and high ¹³C_gr value (zones VIa–VII) areas. In the high ¹³C_gr values area, the carbon contents of the graphite-bearing rocks decrease slightly from zones VIa to VII, whereas the ¹³C_gr values increase sharply from the upper part of zone VIa to VIb. TheD values of biotite in these graphite-bearing rocks are higher than those in the medium ¹³C_gr area. This suggests that methane enriched inH and¹²C is produced and liberated by the devolatilization reactions between muscovite, graphite and water. The fluid produced is composed of water, methane and a subordinate amount of carbon dioxide, and its logfO₂ value is deduced to be about 1.2 lower than that defined by the FMQ buffer. In the medium ¹³C_gr area, the ¹³C values of graphite are nearly constant (–20.8), while the Fe₂O₃/(Fe₂O₃ + FeO) ratio of the graphite-bearing rocks apparently decreases with increasing metamorphic grade.D differences in hydrous silicates between graphite-bearing and graphite-free rocks are observed. These facts are interpreted to mean that methane was produced in addition to water and carbon dioxide, and that its generation ( ratio of the fluid was about 2) had practically no isotope effect on the graphite. In the low ¹³C_gr area, the carbon contents of the rocks decrease clearly from zones I to IIIa. TheD and ¹³C_gr values of the non-metamorphosed shales are much lower than those of the low grade graphite-bearing metapelites. This suggests that methane is produced and liberated from the rocks even at the incipient stage of metamorphism.     

Oxygen isotope studies of early Precambrian granitic rocks from the Giants Range batholith,northeastern Minnesota,U.S.A.

Oxygen isotope studies of granitic rocks from the 2.7 b.y.-old composite Giants Range batholith show that: (1) δ(O¹⁸)_quartz values of 9 to 10 permil characterize relatively uncontaminated Lower Precambrian, magmatic granodiorites and granites; (2) granitic rocks thought to have formed by static granitization have δ(O¹⁸)_quartz values that are 1 to 2 permil higher than magmatic granitic rocks; (3) satellite leucogranite bodies have values nearly identical to those of the main intrusive phases even where they transect O¹⁸-rich metasedimentary wall rocks; (4) oxygen isotopic interaction between the granitic melts and their O¹⁸-rich wall rocks was minimal; and (5) O¹⁸/O¹⁸ ratios of quartz grains in a metasomatic granite are largely inherited from the precursor rock, but during the progression — sedimentary parent → partially granitized parent → metasomatic granite → there is gradual decrease in δ(O¹⁸)_quartz by 1 to 2 permil.     

Timing and origin of midcontinent rift alkaline magmatism,North America: evidence from the Coldwell Complex

The Coldwell Complex represents the largest alkaline intrusion associated with the Midcontinent Rift System in North America. This complex contains a plethora of rock types that have previously been subdivided into three intrusive centers. A detailed U-Pb zircon/baddeleyite age study of five samples indicates that the majority of the complex was emplaced into cold Archean crust at 1108±1 Ma and likely experienced a rapid cooling history. These data, combined with published U-Pb zircon/baddeleyite results for other rift related igneous activity, document the contemporaneous production and emplacement of tholeiitic and alkaline magmas at the onset of rifting. The Sr-Nd-Pb isotopic compositions of selected minerals from different phases of the complex display considerable scatter that is best explained by the presence of magmas with different initial isotopic compositions. The initial Sr and Nd isotopic compositions for clinopyroxene and plagioclase from one of the earliest gabbro phases (_Nd=+0.5 to +1.6; _Sr=+2.4 to +3.1) are identical to published data for primitive olivine tholeiites from the rift and indicate that the majority of magmas, both tholeiitic and alkaline, have a uniform, nearly chondritic isotopic composition. This very reproducible isotopic composition for rift magmatism can be explained by the dominance of a well-mixed mantle plume signature in magma genesis. The shift in isotopic compositions observed for the more evolved granite and syenite samples (_Nd=–4.6 to –6.4; _Sr=+10.2 to +13.8) combined with a less radiogenic Pb isotopic signature is consistent with derivation of these magmas from or interaction with an older granulite facies lower crust. The chondritic isotopic signature typical of most MRS volcanic and plutonic rocks is quite distinct from published results on associated carbonatites (_Nd=+2.1 to +4.5; _Sr=–8.0 to 2212;11.5) indicating the presence of at least two distinct subcontinental mantle isotopic reservoirs in this region.     

Geochemistry and petrogenesis of tertiary granitic rocks from the Island of Mull,Northwest Scotland

The anorogenic igneous rocks of Mull consist essentially of a lava pile of predominantly basaltic composition, cut by an intrusive complex. The basement consists of Precambrian metamorphic rocks of the Moine Series underlain by Lewisian gneiss. The intrusive complex contains a significant proportion of granitic intrusions which can be ascribed to three successive centres of activity, Centres 1–3. We report new major and trace element, including rare earth element analyses, ⁸⁷Sr/⁸⁶Sr ratios and ¹⁸O values for a comprehensive collection of granitic rocks from the 3 centres. The ¹⁸O values range from +4 to –6 indicating variable extent of interaction between the rocks and heated meteoric groundwater. However, correlations of ¹⁸O with other major and trace element data and ⁸⁷Sr/⁸⁶Sr ratios are uniformly low, apart from Fe₂O₃. It is thus unlikely that the interaction of the rocks with meteoric water has systematically altered the chemical (including Sr isotope) characteristics. The chemical and Sr isotope data reflect magmatic values and can therefore be used to comment on the petrogenesis of the granitic rocks.These data indicate that there are important differences between granitic rocks of the centres with Centre 1 forming one distinct group and Centres 2 and 3 a different group. For a given SiO₂ value, the Centre 1 granites have higher Na₂O, MgO, P₂O₅, TiO₂, Sr, and V and lower Al₂O₃, MnO, Zn, Zr, and Y than those of Centres 2 and 3. In addition, the Centre 1 granites have lower REE contents and higher Ce_N/Yb_N ratios than those of Centres 2 and 3. Granites from all three centres have Eu anomalies, those of Centre 3 being generally greater (Eu/Eu* = 0.66–0.10). Finally, there are important Sr isotope distinctions between the three Centres; calculated initial ⁸⁷Sr/⁸⁶Sr ratios for the Centre 1 granites (using 58.2Ma) range between 0.71366–0.71646 (average 0.71530) and have a general correlation of ⁸⁷Sr/⁸⁶Sr with ⁸⁷Rb/⁸⁶Sr. The initial ⁸⁷Sr/⁸⁶Sr ratios of the Centre 2 granites range from 0.70663 to 0.70868, but the ⁸⁷Sr/⁸⁶Sr data do not define an isochron. Finally, data for the Centre 3 granites define a Rb-Sr wholerock isochron with an age of 58.2±2.5 Ma and an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.71003 ±36.Both the chemical trends and isotopic data for the Mull granites can be interpreted in terms of contrasted origins for the granitic rocks of the two groups. The relatively primitive chemical composition and high initial ⁸⁷Sr/⁸⁶Sr ratios of the Centre 1 granites indicate a substantial crustal contribution and we consider that these granites formed by a combination of partial melting of Lewisian basement together with some magma derived by fractional crystallization of basaltic magma. In contrast, the chemical and isotope data for the Centre 2 and 3 granites are consistent with formation dominantly by fractional crystallization of basaltic magma, together with a relatively small proportion of crustal contamination. A model is proposed which emphasises that acid magmatism in Mull is a consequence of the rise and crystallization of basic magma into continental crust. Granite magma has formed both by partial melting and by fractional crystallization and both of these events probably occurred under open system conditions.With oxygen isotope analyses by J.J. Durham, Geochemical Division, Institute of Geological Sciences, 64–78 Grays Inn Road, London, WC1X 8NG, England     

Oxygen isotope studies of potassic volcanic rocks of the Roman Province,Central Italy

The ¹⁸O/¹⁶O ratios of rocks and coexisting minerals were measured for 93 samples of leucite-bearing lavas, pyroclastics, and related volcanic rocks from the Quaternary Roman Co-Magmatic Province, Italy. The ¹⁸O values were found to generally increase northward in the sequence: Ischia (5.8 to 7.0); Somma-Vesuvius and Phlegrean Fields (7.3 to 8.3); Alban Hills (7.3 to 8.7); M. Sabatini (7.3 to 9.7); Vico Volcano (7.4 to 10.2); and M. Vulsini (8.1 to 11.7). The northward increase in ¹⁸O parallels a similar increase in ⁸⁷Sr/⁸⁶Sr, and these data indicate that the Roman magmas have interacted strongly with high-¹⁸O continental crust. A marked increase in ¹⁸O occurs just north of Rome where the Roman Province begins to overlap the calc-alkaline, oversaturated Tuscan Magmatic Province. Therefore, some of the observed ¹⁸O/¹⁶O and ⁸⁷Sr/⁸⁶Sr enrichments in the Roman magmas may have been facilitated by direct mixing with the high-¹⁸O Tuscan magmas or because the high-¹⁸O country rocks underwent widespread heating during a couple of million years of Tuscan igneous activity. Although many of the Roman magmas underwent fractional crystallization without appreciable change in ¹⁸O, contamination has produced a correlation between ¹⁸O and SiO₂ content at several of the volcanic centers; thus the trachytes are typically higher in ¹⁸O than the undersaturated rocks. The major features of the oxygen isotope data can be explained in terms of a simple two-component mixing model in which one end-member was a primary, strongly undersaturated magma derived from the upper mantle, with ¹⁸O+6, ⁸⁷Sr/⁸⁶Sr0.704 to 0.705, and SiO₂<44wt.%. However, none of the analyzed samples have these values, as they have all been contaminated to some extent. The closest approach is found in some of the leucitepyroxenite ejecta from the Alban Hills. The second end-member, derived from the continental crust, had a variable composition with ¹⁸O+12 to +20, ⁸⁷Sr/⁸⁶Sr0.712 to 0.720, and SiO₂65wt.%, and it mixed in much greater proportions in the volcanoes north of Rome than in those of the Alban Hills or the Naples area. The widespread interactions between the Roman magmas and the continental crust are probably due to (1) the fact that such low-SiO₂ magmas always have a very strong tendency to interact with quartz-bearing rocks of the continental crust, and (2) in Italy, these magmas were emplaced into a tectonically very active area containing poorly consolidated sedimentary rocks, and in the northern part of the belt there had been a prior history of extensive calc-alkaline igneous activity.Publication of the Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, Contribution Number 2501.     

Silicate oxygen isotope geochemistry: History,principles, techniques,and application to petrological problems

The importance of oxygen isotope geochemistry in studies of terrestrial and extra-terrestrial silicate rocks was recognized nearly sixtyeight years ago soon after the discovery of O¹⁸ and O¹⁷. As early as 1934, the significance of oxygen isotope variations in rocks and minerals was stressed by Russian geochemists who also pioneered the discipline of silicate oxygen isotope geochemistry. It is now known that processes involving isotopic interaction between rock and water, magmatic differentiation, and metamorphic recrystallization fractionate oxygen isotopes in the lithosphere. δO¹⁸ (the conventional notation for reporting O¹⁸/O¹⁶ ratios in rocks and minerals) is highest in sedimentary rocks (17 to 35 ‰) and lowest in igneous rocks (4 to 12‰). Metamorphic rocks have intermediate values. δO¹⁸ in mafic minerals (1 to 8‰) is lower than in felsic minerals (8 to 16‰). In igneous and metamorphic rocks, quartz is most enriched in O¹⁸ (10 to 16‰) and magnetite the least (1 to 2‰). An important application of O¹⁸/O¹⁶ techniques is in geothermometry, where these are capable of elucidating several petrological processes.