Oxygen isotope variations in phosphate of biogenic apatites,II. Phosphorite rocks

Phosphorites from sedimentary sequences ranging in age from Archaean to Recent were analysed for δ¹⁸O in both the PO₄ (δ¹⁸O_p) and CO₃ (δ¹⁸O_c) in the apatite lattice. The oxygen isotope record is considerably better preserved in phosphates than in either carbonates or cherts. The use of the Longinelli and Nuti [8] temperature equation yields temperatures for Recent phosphorites that are in good agreement with those measured in the field. The δ¹⁸O_p values of ancient phosphorites decrease with increasing age. These changes with time are not likely to be due to post-depositional exchange. Changes in δ¹⁸O values of seawater and variations of temperature with time can account for the δ¹⁸O_p time trend, but the latter explanation is preferred. In Ancient phosphorites δ¹⁸O_c in structurally bound carbonate in apatite is not a reliable geochemical indicator.     

Oxygen isotope variations in phosphate of biogenic apatites,IV. Mammal teeth and bones

Groups of rats grown from birth to death in identical conditions, but with different δ¹⁸O of drinking water (δ_w), were studied for variations of δ¹⁸O of their body water (δ_BW) and bone phosphate (δ_p). There is a high linear correlation (r = 0.99) between δ_BW and between δ_p and δ_w. The regression lines have similar slope coefficients (0.53 and 0.49). Values of δ_p of different teeth and bones are the same, within the precision of the method (±0.5‰). The isotopic fractionation coefficient between phosphate and body water is 1.0178 and close to the estimated value of 1.0173 derived from the phosphate paleotemperature equation. Deviations from constant fractionation between bone phosphate and environmental drinking water depend primarily on rates of drinking and metabolism. Environment conditions have relatively little effect on oxygen isotope fractionation between water sources and bone phosphate.     

Oxygen isotope variations in phosphate of biogenic apatites,I. Fish bone apatite—rechecking the rules of the game

The major advantage of the oxygen in phosphate isotope paleothermometry is that it is a system which records temperatures with great sensitivity while bone (and teeth) building organisms are alive, and the record is nearly perfectly preserved after death. Fish from seven water bodies of different temperatures (3–23°C) and different δ¹⁸O (values ?16 to +3) of the water were analysed. The δ¹⁸O values of the analysed PO₄ vary from 6 to 25. The system passed the following tests: (a) the temperatures deduced from isotopic analyses of the sequence of fish from Lake Baikal are in good agreement with the temperatures measured in the thermally stratified lake; (b) the isotopic composition of fish bone phosphate is not influenced by the isotopic composition of the phosphate which is fed to the fish, but only by temperature and water composition.Isotopic analysis of fossil fish in combination with analysis of mammal bones should be a useful tool in deciphering continental paleoclimates.     

Oxygen isotope variations in marginal basin and ocean-ridge basalts

Oxygen isotope analyses have been made on 27 tholeiitic basalts from the Lau and Mariana marginal ocean basins and from mid-ocean ridges. The ¹⁸O values are related to the extent of hydration by submarine weathering as indicated by H₂O^? and total water content. Extrapolation to zero H₂O^? content gives a δ¹⁸O value of 5.5‰ on the SMOW scale for unaltered marginal basin basalts, in exact agreement with the oxygen isotope “signature” of ocean-ridge tholeiites. Three alkali basalts from seamount provinces also fit the tholeiite relationship. A Lau Basin gabbro has the tholeiitic ¹⁸O content, but an Indian Ocean gabbro is unusually light (δ¹⁸O = 4.0 for whole rock, plagioclase, and amphibole), and resembles the low -¹⁸O Iceland basalts. The basalt data confirm petrologic and chemical evidence for origin of marginal basins by extensional processes with production of basalts from depleted mantle material isotopically identical to the source of ocean-ridge tholeiites.     

Oxygen isotope measurements of phosphate from fish teeth and bones

In situ measurements of lunar surface brightness temperatures made as a part of the Apollo Lunar Surface Experiments Package at the Apollo 15 Hadley Rille landing site are reported. Data derived from 5 thermocouples of the Heat Flow Experiment, which are lying on or just above the surface, are used to examine the thermal properties of the upper 15 cm of the lunar regolith using eclipse and nighttime cool-down temperatures. Application of finite-difference techniques in modeling the lunar soil shows the thermocouple data are best fit by a model consisting of a low-density and low-thermal conductivity surface layer approximately 2 cm thick overlying a region increasing in conductivity and density with depth. Conductivities on the order of 1 × 10^?5 W/cm-°K are postulated for the upper layer, with conductivity increasing to the order of 1 × 10^?4 W/cm-°K at depths exceeding 20 cm. An increase in mean temperature with depth indicates that the ratio of radiative to conductive transfer at 350°K is 2.7 for at least the upper few centimeters of lunar soil; this value is nearly twice that measured for returned lunar fines. The thermal properties model deduced from Apollo 15 surface temperatures is consistent with earth-based microwave observations if electrical properties measured on returned lunar fines are assumed.     

Oxygen isotope fractionation in mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of¹⁸O-enrichment:pyroxene (Mg, Fe, Ca)₂Si₂O₆>olivine (Mg, Fe)₂SiO₄ > spinel (Mg, Fe)₂SiO₄> ilmenite (Mg, Fe, Ca) SiO₃>perovskite (Mg, Fe, Ca) SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) System are in excellent agreement with the experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth’s interior can be described by the following sequence of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

Neon isotope variations in Mid-Atlantic Ridge basalts

The isotopic composition of neon was measured for seventeen samples of submarine basalt glass from the Mid-Atlantic Ridge between 54° and 73°N. They include the Reykjanes, Kolbeinsey, and Mohns Ridge segments. Neon isotopic anomalies, relative to the atmospheric ratios, exist in both²⁰Ne/²²Ne and²¹Ne/²²Ne. A maximum excess²⁰Ne of 7% was measured in two samples from the Reykjanes Ridge. Samples with lower²⁰Ne excesses (six samples with δ²⁰Ne between 2 and 4%) from all three ridge segments, appear to result from mixing of a mantle component with a δ²⁰Ne of 7% and atmospheric neon.²¹Ne/²²Ne ratios are up to 8% above the atmospheric value, with no apparent correlation with the²⁰Ne excesses. The anomalies in²⁰Ne/²²Ne are difficult to explain by mass fractionation of an atmospheric reservoir since several of the samples have δ²⁰Ne values greater than could be produced by single-stage fractionation. Most likely, the excess²¹Ne results from nuclear reactions in the mantle source, although there is no definite correlation between the δ²¹Ne or the excess²¹Ne (cm³ STP/g) and the uranium concentration. Large variations in the observed⁴He/²⁰Ne ratio (40–12,000) remain unexplained at this time.     

Long-term variations in the biogenic matter runoff of the Dnestr River

Long-term observation data were used to carry out comparative analysis of variations in the biogenic matter runoff of the Dnestr River over a period of fifty years. Based on data of weekly monitoring in 2002–2004, annual dynamics of biogenic matter runoff was analyzed for the Dnestr River and for Dnestr Liman. It was found out that, in spite of the “buffer” role of the latter, the contribution of biogenic substances, finding their way in the sea with the Dnestr River water, to the eutrophication of the northwestern Black Sea remains appreciable (about 60 thousand ton year^?1). Dissolved organic compounds account for 70% of the present-day biogenic matter runoff of the Dnestr River.     

Oxygen and hydrogen isotope studies of serpentinization in the Troodos ophiolite complex,Cyprus

Oxygen and hydrogen isotopic compositions were measured on 12 serpentine and 2 actinolite samples from the Troodos ophiolite complex, Cyprus. The single analyzed antigorite(δD= ?60, δ¹⁸O= 7.1) is isotopically similar to all previously analyzed antigorites from ultramafic bodies. However, although their D/H ratios are relatively “normal”(δD= ?70to?92), the δ¹⁸O values of most of the Troodos lizardite-chrysotile serpentines (+12.6 to +14.1) are much higher than the 2.0–9.3‰ range typically found in such serpentines. Such high δ¹⁸O values have previously been found only in the serpentine-like mineraloids termed “deweylites”, which apparently formed at Earth-surface temperatures, and in a single sample from Vourinos, Greece that is in contact with high-¹⁸O limestone. The Troodos lizardite-chrysotile samplescannot have formed by reaction with heated ocean waters, but instead must have formed in contact with large amounts of some type of meteoric, metamorphic, or formation water, either (1) at very low temperatures in a near-surface environment, or (2) at about 100°C from waters that were abnormally enriched in¹⁸O(δ¹⁸O ≈ +4 to +8). The latter possibility seems most plausible inasmuch as extensive evaporites were deposited throughout the Mediterranean Sea during the late Miocene, and this would have been accompanied by strong¹⁸O enrichments of the local meteoric waters. Heated ocean waters, however, probably were responsible for the formation of the actinolitic amphiboles(δ¹⁸O= 4.6 to 5.5; δD= ?51to?46) from the gabbro and ultramafic zones in the Troodos complex. The amphiboles must have formed at considerably higher temperatures and at an earlier stage than the lizardite-chrysotile serpentinization.     

Oxygen isotope fractionation in dissolved oxygen in the deep sea

¹⁸O variations in dissolved oxygen have been measured at five stations from the eastern equatorial Pacific, at the GEOSECS-I and -II intercalibration stations in the North Pacific and North Atlantic, and along an Antarctic-South Pacific section from MONSOON expedition. Relative to atmospheric oxygen, dissolved oxygen in the ocean is enriched in¹⁸O up to a maximum of 14‰, the extreme enrichments occurring in the oxygen-minimum region of the eastern Pacific. The vertical diffusion-advection model has been used to determine the isotopic fractionation of deep-water in-situ oxygen consumption ascribed to bacterial metabolism. The single-stage enrichment, ε, in Pacific Deep Water below 1 km is 10‰ (α = 0.99,¹⁶O consumed preferentially). The model calculations show that the isotopic data cannot be fit without the introduction of a fractionation factor, just as the dissolved oxygen data cannot be fit without an in-situ consumption parameter. The consistency of the positive sign for ε and the negative source term for O₂, observed in all deep Pacific profiles analyzed to date, provide strong evidence that vertical transport and in-situ consumption terms dominate the horizontal tracer flux terms, and indicate the presence of a significant “deep metabolism” in abyssal ocean waters.     

Oxygen isotope geochemistry of cherts from the Onverwacht Group (3.4 billion years), Transvaal,South Africa,with implications for secular variations in the isotopic composition of cherts

δ¹⁸O values for 87 chert samples from the 3.4-b.y.-old Onverwacht Group, South Africa, range from +9.4 to +22.1‰. δ-values for cherts representing early silicified carbonates and evaporites, and possible primary precipitates range from +16 to +22‰ and are distinctly richer in¹⁸O than silicified volcaniclastic debris and cherts of problematical origin. The lower δ-values for the latter two chert types are caused by isotopic impurities such as sericite and feldspar, and/or late silicification at elevated temperature during burial. Cherts with δ-values below +16‰ are thus not likely to yield geochemical data relevant to earth surface conditions.Fine-grained chert is less than 0.7‰ depleted in¹⁸O relative to coexisting coarse drusy quartz. Because coarse quartz preserves its isotopic composition with time, the maximum amount of post-depositional lowering of the δ-values of cherts by long-term isotopic exchange with meteoric groundwaters does not exceed 0.7‰ in 3.4 b.y. In response to metamorphism the δ-values of Onverwacht cherts appear to remain unchanged or to have increased by as much as 4‰. Neither metamorphism nor long-term isotopic exchange with groundwaters can explain why Onverwacht cherts are depleted in¹⁸O relative to their Phanerozoic counterparts.Meteoric waters with a δ¹⁸O range of at least 3‰ appear to have been involved in Onverwacht chert diagenesis. δ-values for possible primary cherts or cherts representing silicified carbonates and evaporites are compatible with the depositional and diagenetic environments deduced from field and petrographic evidence. Onverwacht cherts appear to have formed with δ-values at least 8‰ lower than Phanerozoic cherts.The new Onverwacht data combined with all published oxygen isotope data for cherts suggest a secular trend similar to that initially suggested by Perry (1967) in which younger cherts are progressively enriched in¹⁸O. However, Precambrian cherts appear to be richer in¹⁸O than Perry's original samples and can be reasonably interpreted in terms of declining climatic temperatures from ～70°C at 3.4 b.y. to present-day values, as initially suggested by Knauth and Epstein (1976). This surface temperature history is compatible with existing geological, geochemical, and paleontological evidence.     

Oxygen isotope geothermometry and origin of smectites in the Atlantis II Deep,Red Sea

The sediments underlying the hot brine pool of the Atlantis II Deep, a localised area of geothermal activity in the Red Sea, comprise a diversity of facies characterised by combinations of one or more of five species assemblages, sulphide, sulphate, silicate, oxide and carbonate, each including several mineral phases. The silicate mineral assemblage is dominated by geothermal authigenic smectites. Previous studies of these smectites have reported iron-rich varieties only, nontronite in particular, and only one environment of formation. In three cores from the Southwest Basin of the Atlantis II Deep, of the present study, three smectites comprising two species have been distinguished [10,21] evidently from three different environments of formation. Two of these smectites are nontronites, one from sulphide/silicate/amorphous facies, the other from silicate/carbonate/oxide facies. The third is a montmorillonite/beidellite from sulphate/sulphide/silicate/oxide facies.The oxygen isotopic compositions of samples of the three smectites have been determined from which formation temperatures have been calculated. Six samples of the “anoxic” nontronite have formation temperatures in the range 90–140°C. A single sample of the “oxic” nontronite has a formation temperature of about 80°C. Four samples of the montmorillonite/beidellite have formation temperatures in the range 160–200°C.The formation temperature range of the two nontronites is intermediate between the temperature of the brine at or prior to discharge (up to 250°C [12]) and the temperature of the brine pool in the Deep (about 50–60°C [13,14]). The nontronite formation temperature range reflects genesis by combination of isotopically light silica supplied by the incoming brine and isotopically heavier iron oxyhydroxide settling from the upper layers of the brine pool. Evidently, the “anoxic” nontronite forms at greater depth (hotter) in the brine pool than the “oxic” nontronite resulting in a relatively greater contribution from silica but diminished contribution from iron oxyhydroxide in the former compared to the latter. The wide range of the formation temperatures for the “anoxic” nontronite is related to the different actual locations of the samples in the sulphide/silicate/amorphous facies.The formation temperature range of the montmorillonite/beidellite is approaching the estimated temperature of the brine at or prior to discharge. The montmorillonite/beidellite formation temperature range reflects genesis by combination of isotopically light silica and aluminium, both supplied by the incoming brine, at the site of an active discharge vent. The wide range of the formation temperatures for the montmorillonite/beidellite may in part reflect a possible thermal event at the brine source, likely to have occurred during deposition of the sulphate/sulphide/silicate/oxide facies and which, it appears, has contributed to the formation of this facies [10,20].     

Peat deformation and biogenic gas bubbles control seasonal variations in peat hydraulic conductivity

The hydraulic conductivity (K) of peat beneath the water table varies over short (annual) periods. Biogenic gas bubbles block pores and reduce K, and seasonal changes in the water table position cause peat deformation, altering peat pore size distribution. Although it has been hypothesized that both processes reduce K during warm dry summer conditions, temporal variations in K under field conditions have been explained previously by peat volume changes (strain) alone. We determine the effect of both controls on K by monitoring changes in gas content (Δγ), strain and K within a poor fen. Over the growing season, K decreased by an order of magnitude. In the near‐surface peat (0.3–0.7 m), this reduction is more strongly correlated with Δγ, providing the first field‐based evidence that biogenic gas bubbles reduce K. In the deeper peat (0.7–1.3 m), K is correlated principally with strain. However, causality is uncertain because of multicollinearity between strain and Δγ. To mitigate for multicollinearity, we took advantage of a peatland drainage experiment where the water table was artificially dropped at the beginning of the growing season, reducing correlations between strain and Δγ. Δγ remained the primary cause of K variations just beneath the water table at a depth of 0.5–0.7 m, although further down through the peat profile (0.7–1.2 m) changes in K were controlled by strain. We suggest that the larger pore structure of the poorly decomposed peat just below the water table is impacted less by volume changes than that of the more decomposed peat at depth. However, within this poorly decomposed peat, K is reduced by the high gas contents that result from higher rates of methane production. Copyright © 2012 John Wiley & Sons, Ltd.     

Oxygen and hydrogen isotope studies of plutonic granitic rocks

The primary δD values of the biotites and hornblendes in granitic batholiths are remarkably constant at about ?50 to ?85, identical to the values in regional metamorphic rocks, marine sediments and greenstones, and most weathering products in temperate climates. Therefore the primary water in these igneous rocks is probably not “juvenile”, but is ultimately derived by dehydration and/or partial melting of the lower crust or subducted lithosphere. Most granitic rocks have δ¹⁸O = +7.0 to +10.0, probably indicating significant involvement of high-¹⁸O metasedimentary or altered volcanic rocks in the melting process; such an origin is demanded for many other granodiorites and tonalites that have δ¹⁸O = +10 to +13. Gigantic meteoric-hydrothermal convective circulation systems were established in the epizonal portions of all batholiths, locally producing very low δ¹⁸O values (particularly in feldspars) during subsolidus exchange. Some granitic plutons in such environments also were emplaced as low-¹⁸O magmas probably formed by melting or assimilation of hydrothermally altered roof rocks. However, the water/rock ratios were typically low enough that over wide areas the only evidence for meteoric water exchange in the batholiths is given by low D/H ratios (δD as low as ?180); for example, because of latitudinal isotopic variations in meteoric waters, as one moves north through the Cordilleran batholiths of western North America an increasingly higher proportion of the granitic rocks have δD values lower than ?120. The lowering of δD values commonly correlates with re-setting of K-Ar ages, and in the Idaho batholith two broad zones (10,000 km²) can be defined where δD biotite <?100 and K-Ar “ages” have all been re-set to values less than 60 m.y., suggesting that the Ar loss was caused by the meteoric-hydrothermal circulation systems. In certain Precambrian batholiths, a much different type of very low-temperature, regional alteration by surface-derived waters took place over an extended period long after emplacement, producing “brick-red” feldspars and markedly discordant Rb-Sr isochron “ages”.     

Oxygen and carbon isotope composition from the UHP Shuanghe marbles, Dabie Mountains, China

Investigations on the oxygen and carbon isotope compositions from the ultrahigh-pressure (UHP)-metamorphosed Shuanghe marbles, that occur as a member of a UHP slab, show that the δ¹⁸ O values range from +11.1% to+20.5% SMOW, and δ¹³ C from+1.0% to+5.7% PDB, respectively. The variations in isotope compositions show a centimeter scale of homogeneity and a heterogeneity of regional scale larger than 1 meter. In contrast to the eclogite marbles from Norway, the Shuanghe marbles have inherited the carbon isotope compositions from their sedimentary precursor. The δ¹³C shows positive correlation to the content of dolomite. The depletion in¹⁸O, compared with the pmtolithic carbonate strata, might result from three possible geological processes: 1) exchanging oxygen isotope with meteoric water before the UHP metamorphism, 2) decarbonation during the UHP metamorphism, and 3) exchanging oxygen isotope with country gneiss at local scale during retrograde metamorphism. It seems that the advection of fluid in the orogenic belt was very limited during subduction and exhumation of UHP rocks. Project supported by a U. S. -China cooperative project led by Prof. Cong Bolin of the Institute of Geology. Chinese Acade-my of Sciences, and Prof. J. G. Liou of the Department of Geological and Environmental Sciences, Stanford University and by the National Natural Science Foundation of china (Grant No. 49794042). Chinese Academy of Sciences (Grant No. KZ951-A1-401r, and National Science Foundation (Grant No. EAR-95-26700).     

Seasonal variations of stable isotope in precipitation and moisture transport at Yushu,eastern Tibetan Plateau

Precipitation δ 18O at Yushu, eastern Tibetan Plateau, shows strong fluctuation and lack of clear seasonality. The seasonal pattern of precipitation stable isotope at Yushu is apparently different from either that of the southwest monsoon region to the south or that of the inland region to the north. This different seasonal pattern probably reflects the shift of different moisture sources. In this paper, we present the spatial comparison of the seasonal patterns of precipitation δ 18O, and calculate the moisture transport flux by using the NCAR/NCEP reanalysis data. This allows us to discuss the relation between moisture transport flux and precipitation δ 18O. This study shows that both the southwest monsoon from south and inland air mass transport from north affected the seasonal precipitation δ 18O at Yushu, eastern Tibetan Plateau. Southwest monsoon brings the main part of the moisture, but southwest transport flux is weaker than in the southern part of the Tibetan Plateau. However, contribution of the inland moisture from north or local evaporation moisture is enhanced. The combined effect is the strong fluctuation of summer precipitation δ 18O at Yushu and comparatively poor seasonality.     

Oxygen isotope evidence for submarine hydrothermal alteration of the Del Puerto ophiolite, California

The oxygen isotope compositions and metamorphic mineral assemblages of hydrothermally altered rocks from the Del Puerto ophiolite and overlying volcaniclastic sedimentary rocks at the base of the Great Valley sequence indicate that their alteration occurred in a submarine hydrothermal system. Whole rock δ¹⁸O compositions decrease progressively down section (with increasing metamorphic grade): +22.4‰ (SMOW) to +13.8 for zeolite-bearing volcaniclastic sedimentary rocks overlying the ophiolite; +19.6 to +11.6 for pumpellyite-bearing metavolcanic rocks in the upper part of the ophiolite's volcanic member; +12.3 to +8.1 for epidote-bearing metavolcanic rocks in the lower part of the volcanic member; +8.5 to +5.7 for greenschist facies rocks from the ophiolite's plutonic member; +7.6 to +5.8 for amphibolite facies or unmetamorphosed rocks from the plutonic member.

Modelling of fluid-rock interaction in the Del Puerto ophiolite indicates that the observed pattern of upward enrichment in whole rock δ¹⁸O can be best explained by isotopic exchange with discharging¹⁸O-shifted seawater at fluid/rock mass ratios near 2 and temperatures below 500°C.¹⁸O-depleted plutonic rocks necessarily produced during hydrothermal circulation were later removed as a result of tectonism. Submarine weathering and later burial metamorphism at the base of the Great Valley sequence cannot by itself have produced the zonation of hydrothermal minerals and the corresponding variations in oxygen isotope compositions. The pervasive zeolite and prehnite-pumpellyite facies mineral assemblages found in the Del Puerto ophiolite may reflect its origin near an island arc rather than deep ocean spreading center.     

Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275°C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO₂ which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl₂ and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (10³ ln α) between 1 molal solutions and pure water at 25, 100, and 275°C are: NaCl 0.0, ?1.5, +1.0; KCl 0.0, ?1.0, +2.0; LiCl ?1.0, ?0.6, ?0.5; CaCl₂ ?0.4, ?1.8, +0.8; MgCl₂ ?1.1, ?0.7, ?0.3; MgSO₄ ?1.1, +0.1, ?; NaF (0.8 m) 0.0, ?1.5, ?0.3; and NH₄Cl (0.55 m) 0.0, ?1.2, ?1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required.     

Oxygen isotope fractionation in decarbonation metamorphism: the Mottled Zone event

Calculated univariant equilibria and oxygen isotope compositions of silicates and carbonates support the proposal that the “Mottled Zone Event” is a low-pressure (1–25 atm), high-temperature (200° < T < 1300°C) metamorphism of calcareous siliceous sediments in which the thermal energy is provided by combustion of organic matter. δ¹⁸O of silicates decreases systematically with increasing metamorphic grade from averages of 18.1‰ in protolith shales, to 16.6‰ in grossular-diopside-zeolite rocks, 15.6‰ in wollastonite and anorthite-diopside-gehlenite-grossular fels, 14.1‰ in spurrite-brownmillerite marbles and 11.7‰ in the highest-grade larnite-gehlenite-brownmillerite assemblages. Decarbonation is the principal mechanism influencing the oxygen isotope compositions. The progressive decrease of δ¹⁸O in silicates can be modelled as a Rayleigh distillation of CO₂ approximately 16‰ enriched in ¹⁸O relative to whole rock assemblages i.e., of initial isotopic composition 8.5‰ heavier than the parent carbonates. The mineral assemblage of one sample with an unusual granoblastic texture is in apparent isotopic equilibrium at a temperature of 540°C.     

Oxygen isotope evidence for past and present hydrothermal regimes of Long Valley caldera, California

Whole-rock oxygen isotope compositions of cores and cuttings from Long Valley exploration wells show that the Bishop Tuff has been an important reservoir for both fossil and active geothermal systems within the caldera. The deep Clay Pit-1 and Mammoth-1 wells on the resurgent dome penetrate mildly to strongly altered Bishop Tuff with δ¹⁸O_WR values as low as −2.6% (vs V-SMOW). The idfu 44-16 well intercepts a thinner Bishop Tuff section with δ¹⁸O_WR values of +0.4 to +2.3%. in the western caldera moat, where milder and more sporadic ¹⁸O depletions occur in Tertiary volcanic rocks of the western caldera floor (δ¹⁸O_WR = +2.2 to +6.4‰). Bishop Tuff samples from deeper parts of the 715 m rdo-8 (Shady Rest) well in the SW moat are also strongly depleted in ¹⁸O (δ¹⁸O_WR = −1.5 to +0.6‰). Four shallow thermal gradient wells (469–715 m td drilled in the western moat did not penetrate Bishop Tuff, but Early Rhyolites from two of these holes are depleted in ¹⁸O (δ¹⁸O_WR = −1.2 to +6.0‰ inplv-1 +4.6 to +5.3%. inmlgrap-1), compared to lithologic equivalents from the other two holes (δ¹⁸O_WR = +6.3 to +8.0‰ inplv-2 andmlgrap-2).Whole-rock oxygen isotope profiles for the resurgent dome wells are unlike profiles calculated assuming alkali feldspar-H₂O fractionation behavior and total O-isotopic equilibration with −14.3‰ fluids at measured temperatures. The sense of this divergence implies an earlier hydrothermal episode within the central caldera driven by one or more shallow intrusions. Geochemical similarities between an intrusive granophyre at the bottom of the Clay Pit-1 well and a nearby Moat Rhyolite dome with a K/Ar cooling age of 0.5 Ma suggest that vigorous hydrothermal activity beneath the central resurgent dome may have occurred as much as 0.5 m.y. ago. Calculated and measured O-isotope profiles are similar for deep wells that penetrate the western moat of the caldera, where steep temperature gradients and low δ¹⁸O_WR values in Early Rhyolites from plv-1 are attributed to an active hydrothermal aquifer that has descended slightly from earlier, shallower elevations. Similarly, severe ¹⁸O depletions in Bishop Tuff samples from the idfu 44-16 and rdo-8 wells reflect active convection beneath the western moat, whereas milder ¹⁸O depletions in Early Rhyolites from mlgrap-1 were apparently caused by hydrothermal alteration at lower temperatures. The O-isotope profiles imply that surface discharge within and around the resurgent dome results from shallow, eastward-directed outflow from a zone of higher enthalpy hydrothermal upflow beneath the western caldera moat. Intrusive magmatic heat source(s) are inferred to exist beneath the western moat, perhaps beneath Mammoth Mountain.