Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

Tourmaline mineralization in the Barberton greenstone belt,South Africa: early Archean metasomatism by evaporite-derived boron

Tourmaline-rich rocks are common in the lowgrade, interior portions of the Barberton greenstone belt of South Africa, where shallow-marine sediments and underlying altered basaltic and komatiitic lavas contain up to 50% tourmaline. The presence of tourmaline-bearing rip-up clasts, intraformational tourmalinite pebbles, and tourmaline-coated grains indicates that boron mineralization was a low-temperature, surficial process. The association of these lithologies with stromatolites, evaporites, and shallow-water sedimentary structures and the virtual absence of tourmaline in correlative deep-water facies rocks in the greenstone bels strengthens this model.Five tourmaline-bearing lithologic groups (basalts, komatiites, evaporite-bearing sediments, stromatolitic sediments, and quartz veins) are distinguished based on field, petrographic, and geochemical criteria. Individual tourmaline crystals within these lithologies show internal chemical and textural variations that reflect continued growth through intervals of change in bulk-rock and fluid composition accompanying one or more metasomatic events. Large single-crystal variations exist in Fe/Mg, Al/Fe, and alkali-site vacancies. A wide range in tourmaline composition exists in rocks altered from similar protoliths, but tourmalines in sediments and lavas have similar compositional variations. Boron-isotope analysis of the tourmalines suggest that the boron enrichment in these rocks has a major marine evaporitic component. Sediments with gypsum pseudomorphs and lavas altered at low temperatures by shallow-level brines have the highest ¹¹B values (+2.2 to-1.9); lower ¹¹B values of late quartz veins (-3.7 to-5.7) reflect intermediate temperature, hydrothermal remobilization of evaporitic boron. The ¹¹B values of tourmaline-rich stromatolitic sediments (-9.8 and-10.5) are consistent with two-stage boron enrichment, in which earlier marine evaporitic boron was hydrothermally remobilized and vented in shallow-marine or subaerial sites, mineralizing algal stromatolites. The stromatolite-forming algae preferentially may have lived near the sites of hydrothermal discharge in Archean times.     

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.     

Constraints on the origin of Damaran granites by Rb/Sr and δ18O data

The mean (⁸⁷Sr/⁸⁶Sr) and mean (⁸⁷Rb/⁸⁶Sr) ratios of the intrusive granites from the North and South of the Orogen's Central Zone plot on straight lines. These are interpreted as areal isochrons indicating the time of last Sr isotope homogenization 526 and 571 Ma ago in the respective source rocks.Initial (⁸⁷Sr/⁸⁶Sr) and mean (⁸⁷Rb/⁸⁶Sr) ratios of approximately coeval granites of the main magmatic pulses in the North (470 Ma) and in the South (520 Ma) line up along isochrons suggesting that in both cases 60 Ma passed after the homogenization in the protolith before large scale intrusions took place.The data require that the intrusions have preserved the Rb/Sr ratios of their source rocks permitting only very little assimilation or fractionation.The source rocks in the North and South had rather unradiogenic Sr 526 and 571 Ma ago, respectively. At R_i0.7066 all presently known Damaran metasediments and metavolcanics as well as the basement must be excluded as the protoliths. A hypothetical source with a large proportion of low (⁸⁷Sr/⁸⁶Sr) volcanic material is required. In the center, on the other hand, the Sr isotope ratios are more radiogenic and derivation from common Damaran metasediments is a distinct possibility.The total rock ¹⁸O values show an unusual spread from 7.1 to 15.2, the majority being very heavy. This excludes granulites and requires sediments or heavily altered volcanics as source rocks. A plot of ¹⁸O vs. initial Sr isotope ratios of the granites from the center which could have been derived from Damaran metasediments has a very clear negative slope. No trend is visible for the southern granites. Of the northern granites the older group shows a negative, the younger group a positive correlation. This is interpreted as indicating mainly altered volcanics (perhaps spilites) for the older and a mixture of volcanogenic and metasedimentary rocks as the source for the younger group. The high ¹⁸O values show that the granites are crustal remelts.     

Sulfur isotope ratios of Icelandic rocks

Sulfur isotope ratios have been determined in 27 selected volcanic rocks from Iceland together with their whole rock chemistry. The ³⁴S of analyzed basalts ranges from –2.0 to +0.4 with an average value of –0.8 Tholeiitic and alkaline rocks exhibit little difference in ³⁴S values but the intermediate and acid rocks analyzed have higher ³⁴S values up to +4.2 It is suggested that the overall variation in sulfur isotope composition of the basalts is caused by degassing. The small range of the ³⁴S values and its similarity to other oceanic and continental basalts, suggest that the depleted mantle is homogeneous in its sulfur isotope composition. The ³⁴S of the depleted mantle is estimated to be within the range for undegassed oceanic basalts, –0.5 to +1.0     

Influence of sedimentary environments on sulfur isotope ratios in clastic rocks: a review

Strata-bound sulfide deposits associated with clastic, marine sedimentary rocks, and not associated with volcanic rocks, display distributions of S³⁴ values gradational between two extreme types: 1. a flat distribution ranging from S³⁴ of seawater sulfate to values about 25 lower; and 2. a narrow distribution around value S³⁴ (sulfide)=S³⁴ (seawater sulfate) –50, and skewed to heavier values. S³⁴ (seawater sulfate) is estimated from contemporaneous evaporites. There is a systematic relation between the type of S³⁴ distribution and the type of depositional environment. Type 1 occurs in shallow marine or brackish-water environments; type 2 occurs characteristically in deep, euxinic basins. These distributions can be accounted for by a model involving bacterial reduction of seawater sulfate in systems which range from fully-closed batches of sulfate (type 1) to fully open systems in which fresh sulfate is introduced as reduction proceeds (type 2). The difference in the characteristic distributions requires that the magnitude of the sulfate-sulfide kinetic isotope effect on reduction be different in the two cases. This difference has already been suggested by the conflict between S³⁴ data for modern marine sediments and laboratory experiments. The difference in isotope effects can be accounted for by Rees' (1973) model of steady-state sulfate reduction: low nutrient supply and undisturbed, stationary bacterial populations in the open system settings tend to generate larger fractionations.

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Zusammenfassung Schichtgebundene Sulfid-Lagerstätten in Begleitung von klastischen, marinen Sedimentgesteinen ohne Beteiligung vulkanischer Gesteine zeigen kontinuierliche Verteilungen der S³⁴-Werte zwischen zwei Extremtypen: 1. Eine flache Verteilung im Bereich von S³⁴-Werten des Seewasser-Sulfats bis zu Werten, die etwa 25 niedriger liegen. 2. Eine eng begrenzte Verteilung um den S³⁴ (Sulfid)-Wert=S³⁴ (Seewasser-Sulfat) –50 und asymmetrischer Verteilungskurve mit stärkerer Besetzung bei den schwereren Werten. Das S³⁴ (Seewasser-Sulfat) wird von gleichaltrigen Evaporiten abgeleitet. Es besteht eine systematische Beziehung zwischen der Art der S³⁴-Verteilung und dem Milieu des Ablagerungsraumes. Typ 1 tritt im marinen Flachwasser oder in brackischer Umgebung auf. Typ 2 ist charakteristisch für tiefe euxinische Becken. Diese Verteilungen können erklärt werden mit Hilfe eines Modells mit bakterieller Reduktion von Meerwasser-Sulfat in Systemen, die von völlig abgeschlossenen Sulfat-Mengen (Typ 1) bis zu völlig offenen Systemen reichen, in die bei fortschreitender Reduktion frisches Sulfat zugeführt wird (Typ 2). Der Unterschied in den charakteristischen Verteilungen setzt voraus, daß die Stärke der kinetischen Sulfat-Sulfid-Isotopen-Wirkung auf die Reduktion in beiden Fällen verschieden ist. Dieser Unterschied wurde bereits wegen der Widersprüche zwischen den verschiedenen S³⁴-Werten heutiger mariner Sedimente und Laborexperimente vermutet. Der Unterschied in der Isotopen-Wirkung kann durch das Modell von Rees (1973) für kontinuierlich ablaufende Sulfat-Reduktion erklärt werden. Geringes Nahrungsangebot und ungestörte, gleichbleibende Bakterien-Populationen in offenen Systemen neigen zur Erzeugung stärkerer Fraktionierungen.

     

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.     

18O-Enrichment of silicic magmas caused by crystal fractionation at the Galapagos Spreading Center

An extremely differentiated suite of unaltered volcanic rocks dredged from the Galapagos Spreading Center ranges in ¹⁸O from 5.7 to 7.1 At 95°W, low K-tholeiites, FeTi-basalts, andesites and rhyodacites were recovered. Their lithologic and major element geochemical variation can be accounted for by crystal fractionation of plagioclase, pyroxenes, olivine and titanomagnetite in the same proportions and amounts needed to model the ¹⁸O variation by simple Rayleigh fractionation. More complicated behaviour was observed in a FeTi-basalt suite from 85°W. This study shows that 90% fractionation only enriches the residual melt by about 1.2 in ¹⁸O. It also implies that the magma chambers along parts of the Galapagos Spreading Center were static and isolated such that extreme differentiation could occur.     

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 isotopes in mantle related and geothermally altered magmatites of the Transhimalayan (Gangdese) ranges

In closed magma systems SiO₂ approximately measures differentiation progress and oxygen isotopes can seem to obey Rayleigh fractionation only as a consequence of the behaviour of SiO₂. The main role of ¹⁸O is as a sensitive indicator of contamination, either at the start of differentiation ( ¹⁸O_init) or as a proportion of fractionation in AFC. Plots of ¹⁸O vs SiO₂-allow to determine initial ¹⁸O values for different sequences for source comparison. For NBS-28=9.60, the ¹⁸O at 48% SiO₂-varies between a high 6.4 for Kiglapait (Kalamarides 1984), 5.9 for Transhimalaya, 5.8 for Hachijo-Jima (Matsuhisa 1979), 5.6 for Koloula (Chivas et al. 1982) and a low 5.3 for the Darran Complex, New Zealand. The Transhimalayan batholiths (Gangdese belt) were emplaced in the Ladakh-Lhasa terrane, between the present-day Banggong-Nujiang, and Indus-Yarlung Tsangbo suture zones, after its accretion to Eurasia. The gradient of the least contaminated continuous ( ¹⁸O vs SiO₂-igneous trend line is similar to that of Koloula, and AFC calculations suggest a low secondary assimilation rate of less than 0.05 times the rate of crystallisation. Outliers enriched in ¹⁸O are frequent in the Lhasa, and apparently rare in the Ladakh transsect. Low- ¹⁸O (5.0–0) granitoids and andesites on the Lhasa-Yangbajain axis are the result of present day or recent near-surface geothermal activity; their quartzes still trace the granitoids to the Transhimalaya ¹⁸O trend line, but the distribution of low total rock or feldspar ¹⁸O values could be a guide to more recent heat flow and thermally marked tectonic lineaments. Two ignimbrites from Maqiang show hardly any ¹⁸O-contamination by crustal material.     

Isotopic composition of oxygen and hydrogen in mud-volcanic waters from Taman (Russia) and Kakhetia (Eastern Georgia)

The ¹⁸O and D values in mud-volcanic waters of the Taman Peninsula and Kakhetia vary from +0.7 to +10.0 and from –37 to –13 , respectively. These values increase as the Greater Caucasus is approached. The increase in 18O and D also positively correlates with fluid generation temperatures based on hydrochemical geothermometers. This is accompanied by changes in the chemical composition of waters, in which contents of alkali metals, HCO^– ₃ ion, and boron increase, while the content of halogen ions (Cl, Br, J) decreases. Changes in the isotopic composition of water are also accompanied by the increase of ¹³ in methane and decrease of ¹¹ B in clays. Analysis of formal models of the evolution of isotopic composition of mud-volcanic waters showed that mud volcanoes are recharged by freshened water from the Maikop paleobasin with an inferred isotopic composition of D –40 and ¹⁸ O –6. Based on this assumption, the ¹⁸O and D values observed in mud-volcanic waters can be explained not only by processes of distillation and condensation in a closed system, but also by combined processes of isotopic reequilibration in the water-illite-methane system.Translated from Litologiya i Poleznye Iskopaemye, No. 2, 2005, pp. 143–158.Original Russian Text Copyright © 2005 by Lavrushin, Dubinina, Avdeenko.     

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 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.     

Rapports 18O/16O dans les roches du vieux socle catazonal d'In Ouzzal (Sahara algérien)

¹⁸O/¹⁶O ratios have been measured for whole rock samples and mineral separates of granulitic rocks in the very old precambrian shield of In Ouzzal (Sahara). Isotopic fractionations are low and indicate temperatures higher or similar to those found by numerous workers on granitic rocks.The ¹⁸O of whole rock samples are low and homogeneous (5,5<<7.8). As the rocks are clearly of detrital origin, this homogeneity can be explained either by isotopic equilibration with upper mantle material by means of CO₂ rich fluids (Touret, 1971), or by isotopic inertia of minerals during the mainly detrital processes that gave rise to the series. The latter explanation more or less implies that the parent material of the detrital series originated by magmatic differenciation.     

Boron isotopic variations in hydrous rhyolitic melts: a case study from Long Valley,California

In this paper, we present boron isotope analyses of variably degassed rhyolitic glasses from Long Valley, California. The following results indicate that pre-eruptive boron isotopic signatures were preserved in degassed glasses: (1) averaged secondary ionization mass spectrometry (SIMS) measurements of H₂O-rich (~3 wt%) melt inclusions from late erupted Bishop Tuff pumice are indistinguishable from positive thermal ionization mass spectrometry (PTIMS) analysis of vesiculated groundmass glass (¹¹B=+5.0±0.9 and +5.4±5, respectively); (2) SIMS spot-analyses on H₂O-poor obsidian (~0.15 wt% H₂O) from younger Glass Mountain Dome YA (average ¹¹B=+5.2±1.0) overlap with compositionally similar late Bishop Tuff melt inclusions; and (3) four variably degassed obsidian samples from the 0.6 ka Mono Craters (H₂O between 0.74 and 0.10 wt%) are homogeneous with regard to boron (average ¹¹B=+3.2±0.8, MSWD=0.4). Insignificant variations in ¹¹B between early and late Bishop Tuff melt inclusion glasses agree with published experimental data that predict minor ¹¹B depletion in hydrous melts undergoing gas-saturated fractional crystallization. Melt inclusions from two crystal-rich post-caldera lavas (Deer Mountain and South Deadman Dome) are comparatively boron-rich (max. 90 ppm B) and have lower ¹¹B values (average ¹¹B=+2.2±0.8 and –0.4±1.0 ) that are in strong contrast to the boron isotopic composition of post-caldera crystal-poor rhyolites (27 ppm B; ¹¹B=+5.7±0.8). These variations in ¹¹B are too large to be caused by pre-eruptive degassing. Instead, we favor assimilation of ¹¹B depleted low-temperature hydrothermally altered intrusive rocks subsequent to fresh rhyolite recharge.Editorial responsibility: J. HoefsAn erratum to this article can be found at     

A sulfur isotopic study of alunites from Latium and Tuscany,central Italy

Sulfur isotope analyses were made on 14 alunites from volcanic and sedimentary rocks widely different in chemistry and age from southern Tuscany and northern Latium, central Italy. The ³⁴S values range from +0.7 to +9.6, and appear not to be related to the nature of the host rock. Geological and isotopic evidence suggests that all the alunites formed by supergenic oxidation of sulfides. Sulfides occurring with alunites in the volcanic rocks of Latium can be divided into an isotopically light group of probably magmatic origin (³⁴S=–1.5 to +3.4) and a heavy one with ³⁴S=+6.0 to +10.3, tentatively interpreted as deposited by hydrothermal fluids that leached sulfides of similar ³⁴S/³²S from the deep basement. Such an interpretation is consistent with recent studies indicating that in the perityrrhenian belt of Latium exists a continuation, at depth, of the Tuscan stratigraphic series, rich in sulfides with ³⁴ from +6 to +12.     

Oxygen and hydrogen isotope evidence for meteoric water infiltration during mylonitization and uplift in the Ruby Mountains-East Humboldt Range core complex,Nevada

Stable isotope analyses of rocks and minerals associated with the detachment fault and underlying mylonite zone exposed at Secret Creek gorge and other localities in the Ruby-East Humboldt Range metamorphic core complex in northeastern Nevada provide convincing evidence for meteoric water infiltration during mylonitization. Whole-rock ¹⁸O values of the lower plate quartzite mylonites (95% modal quartz) have been lowered by up to 10 per mil compared with structurally lower, compositionally similar, unmylonitized material. Biotite from these rocks has D values ranging from -125 to -175, compared to values of -55 to-70 in biotite from unmylonitized rocks. Mylonitized leucogranites have large disequilibrium oxygen isotope fractionations ( ^{quartz-feldspar} up to 8 per mil) relative to magmatic values ( ^{quartz-feldspar}1 to 2 per mil)). Meteoric water is the only major oxygen and hydrogen reservoir with an isotopic composition capable of generating the observed values. Fluid inclusion water from unstrained quartz in silicified breccia has a D value of-119 which provides a plausible estimate of the D of the infiltrating fluid, and is similar to the isotopic composition of present-day and Tertiary local meteoric water. The quartzite mylonite biotites would have been in equilibrium with such a fluid at temperatures of 480–620° C, similar to independent estimates of the temperature of mylonitization. The relatively high temperatures required for isotopic exchange between quartz and water, the occurrence of fluid inclusion trails and deformed veins in quartzite mylonites, and the spatial association of the low-¹⁸O, low-D rocks with the shear zone all constrain isotopic exchange to the mylonitic (plastic) deformation event. These observations suggest thata significant amount of meteoric water infiltrated the shear zone during mylonitization to depths of at least 5 to 10 km below the surface. The depth of penetration of meteoric fluids into the lower plate mylonites was at least 70 meters below the detachment fault. In contrast, the upper-plate unmylonitized fault slices are dominated by brittle fracture and are often intensely veined (carbonates) or silicified (volcanic rocks and breccias). The fluids associated with the veining and silicification were also meteoric as evidenced by low ¹⁸O values of the veins, which are often 10 per mil lower than the adjacent carbonate matrix, and the exceptionally low ¹⁸O values (down to-4.4) of the breccias. Several previous studies have documented the infiltration of meteoric fluids into the brittley deformed upper plate rocks of core complexes, but this study provides convincing evidence that surface fluids have penetrated lower plate rocks undergoing plastic deformation. It is proposed that infiltration took place as the shear zone began the transition from plastic flow to brittle fracture while the lower plate rocks were being uplifted. During this period, plastic flow and brittle fracture were operating simultaneously, perhaps allowing upper plate meteoric fluids to be seismically pumped down into the lower plate mylonites.     

Sea water basalt interaction in spilites from the Iberian Pyrite Belt

Low grade hydrothermally metamorphosed mafic rocks from the Iberian Pyrite Belt are enriched in ¹⁸O relative to the oxygen isotopic ratio of fresh basalt (+6.5±1). The observed ¹⁸O whole rock values range from +0.87 to +15.71 corresponding to positive isotopic shifts of +5 to +10, thus requiring isotopic exchange with fluids under conditions of high water:rock ratios at low temperatures. The lowest ¹⁸O observed corresponds to an albitized dolerite still and is compatible with independent geochemical data suggesting lower water: rock ratios for the alteration of these rocks.The isotope data are consistent with the hypothesis that the spilites from the Pyrite Belt were produced by interaction of basaltic material with sea water.Significant leaching of transition metals from the mafic rocks during alteration coupled with available sulphur isotopic data for the sulphide ores also suggest that sea water may have played an important role in the formation of ore deposits in the Iberian Pyrite Belt.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

Modification of δD values in eastern Nevada granitoid rocks spatially related to thrust faults

Stable isotope data have been determined for 13 Mesozoic and Tertiary plutons in eastern Nevada and nearby Utah. In the southern Snake Range of eastern Nevada, where relations are best exposed and have been most intensively studied, D, ¹⁸O, and apparent K-Ar ages depend on proximity to the Snake Range decollement. Where stresses resulting from late movement on the decollement have caused cataclasis of Oligocene (37 Ma) granitoid rock, ¹⁸O, D, and K-Ar age values as low as –2.5, –155, and 18 Ma, respectively, have been determined. Where there has been no cataclasis, ¹⁸O values of Jurassic, Cretaceous, and Oligocene granitoid rocks are apparently unaffected, but both D values and K-Ar ages have been modified for distances of tens of meters below the decollement.Results similar to those in the southern Snake Range have been observed in other eastern Nevada granitoid rocks spatially related to regional thrust faults, as in the Kern Mountains, the Toana Range, and the northern Egan Range. In each of these areas cataclasis or deformation of granitoid rocks has resulted in lowered ¹⁸O, D, and K-Ar age values. Where there has been no cataclasis or deformation, ¹⁸O values are unaffected, but both D and K-Ar age values have been lowered by stresses resulting from postcrystallization movement along overlying thrust faults.Many of the plutons discussed have not been deeply eroded, and spatially related thrust faults crop out. Where thrust faults are not in evidence and the granitoid rocks give D values lower than about –130 along with spuriously low K-Ar age results, modification of the D and K-Ar age values may have been caused by stresses related to late movement along an overlying (now eroded) thrust fault.