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J. R. O’Neil

Publications and source records attributed to J. R. O’Neil.

At least 19 recordsLinked to original sources

Variations in stable- isotope ratios of ground waters in seismically active regions of California

Measurements of D and 18 O concentrations of ground waters in seismically active regions are potentially useful in earthquake prediction and in elucidating mechanisms operative during earthquakes. Principles of this method are discussed and some preliminary data regarding a magnitude 5.7 earthquake at the Oroville Dam in 1975 and a series of events near San Juan Bautista in 1980 are presented to support the utility of such measurements. After earthquakes, the D content of nearby ground waters increased by several permil while the 18 O content remained constant. This increase implies that H 2 O may have either decomposed or reacted to form molecular H 2 at depth. It is emphasized that many areas must be investigated for these effects in order to find a sufficient number of "sensitive" water wells and springs to permit a truly effective program of earthquake research.

Geophysical Research Letters

Petrogenesis of garnet two-mica granites in the Ruby Mountains, Nevada

Garnet-two-mica granites of Jurassic (160 ± 3 m.y.) and Cretaceous (83 ± 1.3 m.y.) ages intrude amphibolite facies metasedimentary rocks of Precambrian age and lower Paleozoic sedimentary rocks in the northern part of the Ruby Mountains, Nevada. High initial 87 Sr/ 86 Sr and high values of δ 18 O for minerals suggest a dominantly sedimentary source for the magmas. Total rare-earth contents are low and less fractionated (Ce N /Yb N = 10) than granitic rocks of similar composition in the Sierra Nevada and show a negative Eu anomaly (Eu/Eu* = 0.57). These data are consistent with melting in the stability field of plagioclase with little contribution to the melt from refractory minerals such as zircon, sphene, and apatite. Minor euhedral garnets are manganese-rich and magnesium-poor (al 60 sp 34 py 3.6 gr 2.8 ) compared to garnet (al 79 sp 6 py 13 gr 2 ) in the intruded metamorphic rocks and show an increase in manganese and a decrease in calcium in the outer few microns. Fractionation of magnesium-iron between garnet and biotite, and of sodium-potassium between K-feldspar and plagioclase in the granites suggest submagmatic equilibration temperatures, in the range of 365° to 505°C, whereas oxygen isotope equilibration temperatures for two granites are higher at 480° and 570°C. The compositions of the granites plot near minimum melting compositions in the water-saturated quartz-albite-orthoclase system. Comparison of muscovite plus quartz stability, the water-saturated granite solidus, and experimental garnet-melt equilibria suggests pressures of crystallization no lower than about 3.5 kbar. This pressure is compatible with that estimated from garnet-plagioclase-sillimanite-quartz equilibria for the intruded metasedimentary rocks.

Nevada

Catastrophic isotopic modification of rhyolitic magma at times of caldera subsidence, Yellowstone Plateau Volcanic Field

The Yellowstone Plateau volcanic field has undergone repeated eruption of rhyolitic magma strongly depleted in 18 O. Large calderas subsided 2.0, 1.3, and 0.6 Ma ago, on eruption of ash flow sheets that represent at least 2500, 280, and 1000 km 3 of zoned magma. More than 60 other rhyolite lavas and tuffs permit reconstruction of the long-term chemical and isotopic evolution of the silicic system. Narrow δ 18 O ranges in the ash flow sheets contrast with wide δ 18 O variations in postcaldera lavas of the first and third caldera cycles. Earliest postcollapse lavas are 3 to 6‰ lighter than the preceding ash flow sheets. The O 18 depletions were short-lived events that immediately followed caldera subsidence; hundreds of cubic kilometers of magma were drastically 18 O depleted and thousands were depleted by 1–2‰. Sequences of postcaldera lavas record partial recovery toward precaldera δ 18 O values; secular trends between collapse events thus reflect gradual reenrichment of the roofmost magma in δ 18 O. Much of the subcaldera reservoir was affected, because lavas that erupted as far apart as 115 km reflect the same pattern of depletion and partial recovery. Contemporaneous extracaldera rhyolites have the highest δ 18 O values in the volcanic field and show no effects of the repeated depletions. Sr and Pb isotope ratios of intracaldera rhyolites jump to more radiogenic values at times of caldera formation and show a longterm zigzag pattern like that of δ 18 O. Although some contamination by foundering roof rocks seenis to be required, water was probably the predominant contaminant. Even if roof rocks had been strongly depleted in O 18 before engulfment, their assimilation would have been far from sufficient to account for the large O 18 shift. The low- O 18 lavas contain no xenocrysts and show no trace element or phenocryst evidence of massive contamination. Their Fe-Ti-oxide temperatures indicate no cooling relative to the caldera-forming ash flow magma, and their whole-rock, glass, and phenoeryst chemistry suggests compositional continuity with the ash flow sequence. Oxygen exchange between the magma and a mass of low-O 18 water greatly exceeding solubility limits may require (1) recurrent explosive activity to sustain access and mixing of water with the magma and (2) convection of the magma reservoir to prevent local saturation.

Journal of Geophysical Research Solid Earth

Contrasting serpentinization processes in the eastern Central Alps

Stable isotope compositions have been determined for serpentinites from between Davos (Arosa-Platta nappe, Switzerland) and the Valmalenco (Italy). ??D and ??18O values (-120 to -60 and 6-10???, respectively) in the Arosa-Platta nappe indicate that serpentinization took place on the continent at relatively low temperatures in the presence of limited amounts of metamorphic fluids that contained a component of meteoric water. One sample of chrysotile has a ??18O value of 13??? providing evidence of high W/R ratios and low formation temperature of lizardite-chrysotile in this area. In contrast, relatively high ??D values (-42 to -34???) and low ??18O values (4.4-7.4???) for serpentine in the eastern part of the Valmalenco suggest a serpentinization process that took place at moderate temperatures in fluids that were dominated by ocean water. The antigorite in the Valmalenco is the first reported example of continental antigorite with an ocean water signature. An amphibole sample from a metasomatically overprinted contact zone to metasediments (??D=-36???) indicates that the metasomatic event also took place in the presence of ocean water. Lower ??D values (-93 to -60???) of serpentines in the western part of the Valmalenco suggest a different alteration history possibly influenced by fluids associated with contact metamorphism. Low water/rock ratios during regional metamorphism (and metasomatism) have to be assumed for both regions. ?? 1988 Springer-Verlag.

Contributions to Mineralogy and Petrology

An isotopic study of a fluvial-lacustrine sequence: The Plio-Pleistocene koobi fora sequence, East Africa

Stable isotopic analyses of Plio-Pleistocene and modern sediments in the fluvial-lacustrine system occupying the Turkana Basin, East Africa provide constraints on the paleoenvironmental and diagenetic histories of the Pliocene through the Recent sediments in the basin. The δ 13 C values for carbonates in lacustrine sediments range from −15 to +22‰ relative to PDB, depending on the varying proportions of CO 2 from the atmospheric reservoir and from various metabolic sources. The δ 18 O values of carbonates in lacustrine sediments indicate that the isotopic composition of paleolake water varied by over 10‰ from the Pliocene to the present. The δ 13 C values for pedogenic carbonates record paleoccologic variations and suggest that C 4 plants did not become well established in the preserved depositional parts of the basin until about 1.8 myr ago. The δ 18 O values pedogenic carbonates suggest a range of over 10‰ for the isotopic composition of soil water during this interval. They also suggest a period of major climatic instability from about 3.4 to 3.1 myr and at about 1.8 myr. Together, the δ 13 C and δ 18 O values of pedogenic carbonates indicate that the present conditions are as arid and hot as any that had prevailed during deposition of these Plio-Pleistocene sediments.

Lake Turkana Basin

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6–2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6‰ in 18 O during differentiation is explained by crystallization of 18 O-depleted mafic phases. Silicic glasses have elevated δ 18 O values and relatively low δD values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary δD values of −53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere.

Earth and Planetary Science Letters

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

The Nd, O and Sr isotopic characteristics of Precambrian metasedimentary, metavolcanic and granitic rocks from the Black Hills of South Dakota are examined. Two late-Archean granites (2.5-2.6 Ga) have T dm ages of 3.05 and 3.30 Ga, suggesting that at least one of the granites was derived through the melting of significantly older crust. Early-Proterozoic metasedimentary rocks have T dm ages that range from 2.32 to 2.45 Ga. These model ages, in conjunction with probable stratigraphic ages ranging from 1.9 to 2.2 Ga, indicate that mantle-derived material was added to the continental crust of this region during the early-Proterozoic. Previous studies of the Harney Peak Granite complex have reported U-Pb and Rb-Sr ages of about 1.71 Ga and most granite samples examined in this study have Sr isotopic compositions consistent with that age. Two granite samples taken from the same sill, however, give two-point Rb-Sr and Sm-Nd ages of 2.08 ±0.08 and 2.20 ±0.20Ga (∑ 2200 Nd = −15.5), respectively. In addition, whole-rock and apatite samples of the spatially associated Tin Mountain pegmatite give a Sm-Nd isochron age of 2000 ±100 Ma (∑ 2200 Nd = −5.8 ±1.8). The Sm-Nd, O and Rb-Sr isotopic systematics of these granitic rocks have been complicated to some degree by both crystallization and post-crystallization processes, and the age of the pegmatite and parts of the Harney Peak Granite complex remain uncertain. Processes that probably complicated the isotopic systematics of these rocks include derivation from heterogeneous source material, assimilation, mixing of REE between granite and country rock during crystallization via a fluid phase and post-crystallization mobility of Sr. The Nd isotopic compositions of the pegmatite and the Harney Peak Granite indicate that they were not derived primarily from the exposed metasedimentary rocks.

Geochimica et Cosmochimica Acta

The origin of fluids in the salt beds of the Delaware Basin, New Mexico and Texas

Oxygen and hydrogen isotope analyses have been made of (1) brines from several wells in the salt deposits of the Delaware Basin, (2) inclusion fluids in halite crystals from the ERDA No. 9 site, and (3) local ground waters of meteoric origin. The isotopic compositions indicate that the brines are genetically related and that they probably originated from the evaporation of paleo-ocean waters. Although highly variable in solute contents, the brines have rather uniform isotopic compositions. The stable isotope compositions of brine from the ERDA No. 6 site (826.3 m depth) and fluid inclusions from the ERDA No. 9 site are variable but remarkably regular and show that (1) mixing with old or modern meteoric waters has occurred, the extent of mixing apparently decreasing with depth, and (2) water in the ERDA No. 6 brine may have originated from the dehydration of gypsum. Alternatively, the data may reflect simple evaporation of meteoric water on a previously dry marine flat. Stable isotope compositions of all the waters analyzed indicate that there has been fairly extensive mixing with ground water throughout the area, but that no significant circulation has occurred. The conclusions bear importantly on the suitability of these salt beds and others as repositories for nuclear waste.

New Mexico, Texas

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. ?? 1984 Springer-Verlag.

Contributions to Mineralogy and Petrology

Contrasting fluid/rock interaction between the Notch Peak granitic intrusion and argillites and limestones in western Utah: evidence from stable isotopes and phase assemblages

The Jurassic Notch Peak granitic stock, western Utah, discordantly intrudes Cambrian interbedded pure limestones and calcareous argillites. Contact metamorphosed argillite and limestone samples, collected along traverses away from the intrusion, were analyzed for ??18O, ??13C, and ??D. The ??13C and ??18O values for the limestones remain constant at about 0.5 (PDB) and 20 (SMOW), respectively, with increasing metamorphic grade. The whole rock ??18O values of the argillites systematically decrease from 19 to as low as 8.1, and the ??13C values of the carbonate fraction from 0.5 to -11.8. The change in ??13C values can be explained by Rayleigh decarbonation during calcsilicate reactions, where calculated {Mathematical expression} is about 4.5 permil for the high-grade samples and less for medium and low-grade samples suggesting a range in temperatures at which most decarbonation occurred. However, the amount of CO2 released was not anough to decrease the whole rock ??18O to the values observed in the argillites. The low ??18O values close to the intrusion suggest interaction with magmatic water that had a ??18O value of 8.5. The extreme lowering of ??13C by fractional devolatilization and the lowering of ??18O in argillites close to the intrusion indicates oxgen-equivalent fluid/rock ratios in excess of 1.0 and X(CO2)F of the fluid less than 0.2. Mineral assemblages in conjunction with the isotopic data indicate a strong influence of water infiltration on the reaction relations in the argillites and separate fluid and thermal fronts moving thru the argillites. The different stable isotope relations in limestones and argillites attest to the importance of decarbonation in the enhancement of permeability. The flow of fluids was confined to the argillite beds (argillite aquifers) whereas the limestones prevented vertical fluid flow and convective cooling of the stock. ?? 1984 Springer-Verlag.

Contributions to Mineralogy and Petrology

Uplift and submarine formation of some Melanesian porphyry copper deposits: Stable isotope evidence

Hydrogen and oxygen isotope analyses of sericites and kaolinites from four young porphyry copper deposits (Ok Tedi (1.2 Ma) and Yandera (6.5 Ma), Papua New Guinea; Koloula (1.5 Ma), Solomon Islands; and Waisoi (<5 Ma), Fiji) indicate that the fluids from which these minerals precipitated were of mixed magmatic and non-magmatic sources. The non-magmatic component of the fluid from the island arc deposits (Koloula, Waisoi) was ocean water. For Ok Tedi, the non-magmatic component was a meteoric water with an isotopic composition different from that of the present meteoric water in the region. The isotopic signature of the former meteoric water is consistent with a surface elevation of 200 m a.s.l. or less at the time of mineralization. The deposit was later exposed and supergene kaolinitization commenced at approximately 1200 m a.s.l. Uplift and erosion has continued to the present at which time the elevation of the exposed deposit is 1800 m a.s.l. This rate of uplift is consistent with that known from other geological evidence. If the rate of uplift were approximately constant during the last 1.2 Ma, the age of supergene enrichment can be dated at approximately 0.4 Ma B.P. Similarly, influx of meteoric water at Yandera occurred when the ground surface above the deposit was at an elevation of approximately 600 m a.s.l. The deposit's present elevation is 1600 m a.s.l. In this case a total uplift of approximately 2.2 km is indicated, with removal of 1.2 km of overburden by erosion.

Earth and Planetary Science Letters

Comment on the International Atomic Energy Agency Report on the Advisory Group Meeting on Stable Isotope Reference Samples for Geochemical and Hydrological Investigation, Vienna, Austria, September 19-21, 1983

According to U.S. Geological Survey records, a report prepared by R. Gonfiantini summarizing the findings and recommendations of the 1983 Advisory Group Meeting on Stable Isotope Reference Samples for Geochemical and Hydrologic Investigations held in Vienna does not accurately represent the consultants ' consensus on three important points. The consultants (1) recommended no value for the C02-H20 oxygen isotope fractionation factor, not the cited value of 1.04115, (2) adopted a value of 1.0309 rather than 1.03086 to relate the PDB and SMOW scales, and (3) adopted a firm 180 value of -2.20% for NBS-19 on the PDB scale rather than agreeing that this would be a tentative value subject to modification when more measurements in selected laboratories are available. (USGS)

Water-Resources Investigations Report

Carbonatite tuffs in the Laetolil Beds of Tanzania and the Kaiserstuhl in Germany

Carbonatite lava and tephra are now well known. The only modern eruptive carbonatites, from Oldoinyo Lengai, Tanzania, are of alkali carbonatite, whereas all of the pre-modern examples are of calcite or dolomite. Chemical and stable isotope analyses were made of separate phases of Pliocene carbonatite tuffs of the Laetolil Beds in Tanzania and of Miocene carbonatite tuffs of the Kaiserstuhl in Germany in order to understand the reasons for this major difference. The Laetolil Beds contain numerous carbonatite and melilitite-carbonatite tuffs. It is proposed that the carbonatite ash was originally of alkali carbonate composition and that the alkali component was dissolved, leaving a residuum of calcium carbonate. The least recrystallized melilitite-carbonatite tuff contains early-deposited calcite cement and calcite pseudomorphs after nyerereite (?) that have contents of strontium and barium and ??18O and ??13C values suggestive of incomplete chemical and isotopic exchange during alteration and replacement of alkali carbonatite ash. Carbonatite tuffs of the Kaiserstuhl contain globules composed of calcite phenocrysts and microphenocrysts in a groundmass of calcite with a small amount of clay, apatite, and magnetite. The SrO contents of phenocrysts, microphenocrysts, and groundmass calcite average 0.90, 1.42, and 0.59 percent, respectively. The average ??18O and ??13C values of globules (+14.3 and -9.0, respectively) fall between those of coarse-grained intrusive Kaiserstuhl carbonatite (avg. +6.6, -5.8) and those of low-temperature calcite cement in the carbonatite tuffs (+21.8, -14.9). The phenocrysts and microphenocrysts are primary magmatic calcite, but several features indicate that the groundmass has been recrystallized and altered in contact with meteoric water, resulting in weathering of silicate to clay, leaching of strontium, and isotopic exchange. The weight of evidence favors an original high content of alkali carbonatite in the groundmass, with recrystallization following leaching of the alkalies. ?? 1983 Springer-Verlag.

Contributions to Mineralogy and Petrology

Vapor phase exsolution as a controlling factor in hydrogen isotope variation in granitic rocks: the Notch Peak granitic stock, Utah

The Notch Peak granitic stock, western Utah, is comprised of three concentric sequentially intruded rock types, from granite at the rim, to quartz monzonite I, to quartz monzonite II at the core. The δ 18 O values of whole rocks vary about an average of 9.4 (SMOW), irrespective of the rock type and position relative to contact, suggesting that the three magmas had the same parent. The whole rock δD values in the stock range from −100 to −55. δD values increase toward the cores of both quartz monzonite I and quartz monzonite II, resulting in concentric contours. The δD contours of quartz monzonite II cross-cut those of quartz monzonite I, suggesting little isotopic interaction between these bodies and the absence of a late pervasive fluid phase. There is a positive correlation between δD values and water content of the samples, where samples from each body define a distinct field. The positive correlation is explained by isotopic fractionation attendant on vapor exsolution from the crystallizing magma. An observed increase in δD with the degree of chloritization, a trend opposite to that observed in systems where participation of meteoric water has been demonstrated, is the result of subsolidus interaction with the exsolved fluids. These results show that large variations in the hydrogen isotope ratios of a granitoid can arise by exsolution of a vapor phase from the melt on crystallization. In general, magmas with larger modal amount of primary hydrous phases will tend to have higher δD values than those with small amounts of hydrous phases. Furthermore, the relatively high δD values of chlorites at Notch Peak confirm the applicability of classical concepts of closed-system deuteric alteration to some granitoid bodies. Thus, meteoric water interaction need not be always invoked to explain hydrogen isotope variation and deuteric alteration in granitoids.

Earth and Planetary Science Letters

Genetic relations among basic lavas and ultramafic nodules: Evidence from oxygen isotope compositions

??18O values of unaltered basic lavas range from 4.9 to 8.3 but different types of basalts are usually restricted to narrow and distinct ranges of isotopic composition. The average ??18O values for Hawaiian tholeiites, mid-ocean ridge tholeiites, and alkali basalts are 5.4, 5.7, and 6.2 permil, respectively. Potassic lavas and andesites tend to be more 18O rich with ??18O values between 6.0 and 8.0 permil. The differences among the oxygen isotopic compositions of most of these lavas can be attributed to partial melting of isotopically distinct sources. The oxygen isotope compositions of the sources may be a function of prior melting events which produce 18O-depleted partial melts and 18O-enriched residues as a consequence of relatively large isotopic fractionations that exist at high temperatures. It is proposed that lavas with relatively low ??18O values are derived from primitive, 18O-depleted sources whereas 18O-rich basalts are produced from refractory sources that have already produced partial melts. High temperature fractionations among silicate liquids and coexisting minerals can be used in conjunction with the oxygen isotope compositions of ultramafic nodules to place constraints on the genetic relations between some nodules and different types of basic lavas. ?? 1982 Springer-Verlag.

Contributions to Mineralogy and Petrology

Stable isotope systematics in mesozoic granites of Central and Northern California and Southwestern Oregon

18O, D, and H2O+ contents were measured for whole-rock specimens of granitoid rocks from 131 localitics in California and southwestern Oregon. With 41 new determinations in the Klamath Mountains and Sierra Nevada, initial strontium isotope ratios are known for 104 of these samples. Large variations in ??18O (5.5 to 12.4), ??D (-130 to -31), water contents (0.14 to 2.23 weight percent) and initial strontium isotope ratios (0.7028 to 0.7095) suggest a variety of source materials and identify rocks modified by secondary processes. Regular patterns of variation in each isotopic ratio exist over large geographical regions, but correlations between the ratios are generally absent except in restricted areas. For example, the regular decrease in ??D values from west to east in the Sierra Nevada batholith is not correlative with a quite complex pattern of ??18O values, implying that different processes were responsible for the isotopic variations in these two elements. In marked contrast to a good correlation between (87Sr/86Sr)o and ??18O observed in the Peninsular Ranges batholith to the south, such correlations are lacking except in a few areas. ??D values, on the other hand, correlate well with rock types, chemistry, and (87Sr/86Sr)o except in the Coast Ranges where few of the isotopic signatures are primary. The uniformly low ??D values of samples from the Mojave Desert indicate that meteoric water contributed much of the hydrogen to the rocks in that area. Even so, the ??18O values and 18O fractionations between quartz and feldspar are normal in these same rocks. This reconnaissance study has identified regularities in geochemical parameters over enormous geographical regions. These patterns are not well understood but merit more detailed examination because they contain information critical to our understanding of the development of granitoid batholiths. ?? 1981 Springer-Verlag.

Contributions to Mineralogy and Petrology

13C 12C exchange between calcite and graphite: A possible thermometer in Grenville marbles

The fractionation of 13 C between calcite and graphite, Δ(Cc-Gr). is consistently small (2.6–4.8 permil) in 34 assemblages from upper amphibolite- and granulite-facies marbles of the Grenville Province. In 25 samples from the Adirondack Mountains, New York, it decreases regularly with increasing metamorphic temperature. The fractionations are independent of absolute δ 13 C values of calcite (−2.9 to +5.0). For T = 600–800° C , the Adirondack data are described by Δ ( Cc - Gr ) = −0.00748 T (° C ) + 8.68. This good correlation between Δ and T suggests that carbon isotope equilibrium was attained in these high-grade marbles and that the theoretical calculations of this fractionation by Bottinga are approximately 2 permil too large in this temperature range. Because of the relatively high temperature sensitivity suggested by these results and by Bottinga's calculations, and the pressure independence of isotope fractionation, Δ(Cc-Gr) may provide a very good thermometer for high-grade marbles. Comparison of this field calibration for Δ(Cc-Gr) vs temperature with results from other terranes supports the utility of Δ(Cc-Gr) for geothermometry and suggests that graphite is much more sluggish to exchange than calcite, that exchange between calcite and graphite occurs at temperatures as low as 300°C, and that equilibrium may normally be attained only when peak metamorphic temperatures are greater than 500–600°C. Because 13 C exchange is an unavoidable metamorphic process at temperatures above 300°C, high values of δ 13 C(Gr) in moderate- to high-grade carbonate-bearing rocks do not provide a sufficient criterion to infer an abiogenic origin for the graphite.

Geochimica et Cosmochimica Acta