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.

---

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.

     

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.

---

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.

     

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.     

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     

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.     

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.     

Preliminary investigations of 18O/16O and D/H compositions in rhyo-ignimbrites in the In Hihaou (In Zize) Magmatic Center,central Ahaggar,Algeria

The 620 M.y.-old in Hihaou (In Zize) magmatic complex located at the north-western boundary of the Archaean In Ouzzal block (western Ahaggar), is composed of massive alkaline rhyo-ignimbrites and rhyolitic domes, which are intruded by a granophyric and granitic body. The whole is preserved in a cauldron structure. Extrusive rocks are strongly ¹⁸O-depleted, with -values as low as –1.5/SMOW, while granophyres are less depleted (minimum -¹⁸O value=+2.0/SMOW. The granite has values around + 6/SMOW. D/H compositions are rather low, with D–90 to –110/SMOW. Isotopic zoning of quartz phenocrysts, ¹⁸O/¹⁶O fractionation among coexisting phases, and heterogeneity of the whole-rock -¹⁸O values, suggest that the volcanic rocks have interacted with meteoric water after the eruption. Several mechanisms of isotopic alteration are discussed. The hydrothermal alteration does not seem to have been controlled by the granitic intrusion, but rather seems to have followed the deposition of thick pyroclastic deposits on permeable arkosic sandstones and fluvio-glacial conglomerates. Pervasive circulation of water through the cooling volcanic deposits could have produced the observed ¹⁸O depletion.     

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     

The Hiendelaencina epithermal silver-base metal district,Central Spain: Tectonic and mineralizing processes

The northeastern sector of the Spanish Central System hosts important Stephanian-Permian silver-base metal epithermal mineralizations defining the so-called Hiendelaencina District. The overall geotectonic evolution of this region indicates a major late Variscan extensional period involving the unroofing of dome-shaped metamorphic core complexes, which ultimately led to the radial brittle disruption of these bodies allowing the ascent of andesitic magmas and high-level hydrothermal activity. The deposits are hosted by high-grade metaphorphic rocks belonging to these complexes. Mineralogical and fluid inclusion studies reveal that the mineralizations were formed during two to four hydrothermal stages. These are the result of complex interactions between fluids of contrasted temperatures and salinities. Data on sulphur isotopes suggest that two sources of sulphur existed: magmatic (andesitic derived, with ³⁴S + 6) and metasediment-derived (with initial ³⁴S probably + 25).     

Genesis of copper mineralisation,Myall Creek prospect,South Australia

The Myall Creek copper prospect is in unmetamorphosed carbonaceous dolosiltstone and sandstone at the base of the late Proterozoic (Adelaidean) Tapley Hill Formation. It contains disseminated, fine-grained chalcopyrite, zincian tennanite, bornite, chalcocite, pyrite, sphalerite and galena, and irregular to straight chalcopyrite-rich veinlets. Some ore minerals rim and/or partially replace pyrite or clastic grains. There is no evidence of hydrothermal activity. The ³⁴S_CDT values of pyrite and the other sulfides fall in the wide range –3.6 to +44.2. Dolomite in both mineralised and unmineralised samples has ¹³C_PDB values concentrated around –3, and ¹⁸O_SMOW values around +25. It is concluded that the mineralising fluids were near-neutral brines which leached metals from the basement and early Adelaidean rocks. They entered the Tapley Hill sediments at moderately low temperatures via permeable strata and faults. The metals were precipitated by biogenic H₂S, and also fixed by reaction with iron sulfides and, possibly, organic matter. Continuing ascent of brines into the mineralised strata caused breakdown of detrital feldspars and Fe-Ti oxides, and some solution-remobilisation of early-formed sulfides.     

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.     

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.     

Changes in stable isotope ratios of metapelites and marbles during regional metamorphism,Mount Lofty Ranges,South Australia: implications for crustal scale fluid flow

The Mount Lofty Ranges comprises interlayered marbles, metapsammites, and metapelites that underwent regional metamorphism during the Delamarian Orogeny at 470–515 Ma. Peak metamorphic conditions increased from lowermost biotite grade (350–400°C) to migmatite grade (700°C) over 50–55 km parallel to the lithological strike of the rocks. With increasing metamorphic grade, ¹⁸O values of normal metapelites decrease from 14–16 to as low as 9.0, while ¹⁸O values of calcite in normal marbles decrease from 22–24 to as low as 13.2 These isotopic changes are far greater than can be accounted for by devolatilisation, implying widespread fluid-rock interaction. Contact metamorphism appears not to have affected the terrain, suggesting that fluid flow occurred during regional metamorphism. Down-temperature fluid flow from synmetamorphic granite plutons (¹⁸O=8.4–8.6) that occur at the highest metamorphic grades is unlikely to explain the resetting of oxygen isotopes because: (a) there is a paucity of skarns at granite-metasediment contacts; (b) the marbles generally do not contain low-XCO₂ mineral assemblages; (c) there is insufficient granite to provide the required volumes of water; (d) the marbles and metapelites retain a several permil difference in ¹⁸O values, even at high metamorphic grades. The oxygen isotope resetting may be accounted for by along-strike up-temperature fluid flow during regional metamorphism with time-integrated fluid fluxes of up to 5x10⁹ moles/m² (10⁵ m³/m²). If fluid flow occurred over 10⁵–10⁶ years, estimated intrinsic permeabilities are 10^-20 to 10^-16m². Variations in ¹⁸O at individual outcrops suggest that time-integrated fluid fluxes and intrinsic permeabilities may locally have varied by at least an order of magnitude. A general increase in XCO₂ values of marble assemblages with metamorphic grade is also consistent with the up-temperature fluid-flow model. Fluids in the metapelites may have been derived from these rocks by devolatilisation at low metamorphic grades; however, fluids in the marbles were probably derived in part from the surrounding siliceous rocks. The marble-metapelite boundaries preserve steep gradients in both ¹⁸O and XCO₂ values, suggesting that across-strike fluid fluxes were much lower than those parallel to strike. Up-temperature fluid flow may also have formed orthoamphibole rocks and caused melting of the metapelites at high grades.This paper is a contribution to IGCP Project 304 Lower Crustal Processes     

Oxygen,sulfur, and strontium isotope and fluid inclusion studies of barite deposits from the Iglesiente-Sulcis mining district,Southwestern Sardinia,Italy

This paper deals with barite from stratiform, karst, and vein deposits hosted within Lower Paleozoic rocks of the Iglesiente-Sulcis mining district in southwestern Sardinia. For comparison sulfates from mine waters are studied. Stratiform barite displays ³⁴S=28.8–32.1, ¹⁸O=12.7–15.6, and ⁸⁷Sr/⁸⁶Sr=0.7087, in keeping with an essentially Cambrian marine origin of both sulfate and strontium. Epigenetic barite from post-Hercynian karst and vein deposits is indistinguishable for both sulfur and oxygen isotopes with ³⁴S=15.3–26.4 and ¹⁸O=6.6–12.5; ⁸⁷Sr/⁸⁶Sr ratios vary 0.7094–0.7140. These results and the microthermometric and salinity data from fluid inclusions concur in suggesting that barite formed at the site of mineralization by oxidation of reduced sulfur from Cambrian-Ordovician sulfide ores in warm, sometimes hot solutions consisting of dilute water and saline brine with different ¹⁸O values. The relative proportion of the two types of water may have largely varied within a given deposit during the mineralization. In the karst barite Sr was essentially provided by carbonate host rocks, whereas both carbonate and Lower Paleozoic shale host rocks should have been important sources for Sr of the vein barite. Finally, ³⁴S data of dissolved sulfate provide further support for the mixed seawater-meteoric water composition of mine waters from the Iglesiente area.     

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.     

A stable isotope study of retrograde alteration in SW Connemara,Ireland

Dalradian metamorphic rocks, Lower Ordovician meta-igneous rocks (MGS) and Caledonian granites of the Connemara complex in SW Connemara all show intense retrograde alteration. Alteration primarily involves sericitization and saussuritization of plagioclase, the alteration of biotite and hornblende to chlorite and the formation of secondary epidote. The alteration is associated with sealed microcracks in all rocks and planes of secondary fluid inclusions in quartz where it occurs, and was the result of a phase of fluid influx into these rocks. In hand specimen K-feldspar becomes progressively reddened with increasing alteration. Mineralogical alteration in the MGS and Caledonian granites took place at temperatures 275±15°C and in the MGS P_fluid is estimated to be 1.5 kbar during alteration. The °D values of alteration phases are:-18 to-29 (fluid inclusions),-47 to-61 (chlorites) and-11 to-31 (epidotes). Chlorite ¹⁸O values are +0.2 to +4.3, while ¹⁸O values for quartz-K-feldspar pairs show both positively sloped (MGS) and highly unusual negatively sloped (Caledonian granites) arrays, diverging from the normal magmatic field on a - plot. The stable isotope data show that the fluid that caused retrogression continued to be present in most rocks until temperatures fell to 200–140°C. The retrograde fluid had D -20 to-30 in all lithologies, but the fluid ¹⁸O varied both spatially and temporally within the range-4 to +7. The fO₂ of the fluid that deposited the epidotes in the MGS varied with its ¹⁸O value, with the most ¹⁸O-depleted fluid being the most oxidizing. The D values, together with low (<0) ¹⁸O values for the retrograde fluid in some lithologies indicate that this fluid was of meteoric origin. This meteoric fluid was probably responsible for the alteration in all lithologies during a single phase of fluid infiltration. The variation in retrograde fluid ¹⁸O values is attributed to the effects of variable oxygen isotope shifting of this meteoric fluid by fluid-rock interaction. Infiltration of meteoric fluid into this area was most likely accomplished by convection of pore fluids around the heat anomaly of the Galway granite soon after intrusion at 400 Ma. However convective circulation of meteoric water and mineralogical alteration could possible have occurred considerably later.     

Corundum,Cr-muscovite rocks at O'Briens,Zimbabwe: the conjunction of hydrothermal desilicification and LIL-element enrichment — geochemical and isotopic evidence

Monomineralic domains of chlorite, corundum and Cr muscovite coexist over a kilometer scale within ultramafic schists of the Harare greenstone belt (2.73 Ga). This exotic lithological association includes the conjunction of some of the most aluminous (Al₂O₃88 wt%) and potassic (K₂O10 wt%) rocks known. The paragenetic sequence developed from chloritecorundumcorundum+ diaspore: Cr muscovite variably overprinted both the corundum and chloritite domains. Terminal stages were marked by sporadic production of andalusite+quartz, and finally margarite.Chlorite (Cr₂O₃=0.31–2.65 wt%), corundum (0.79–2.66 wt%), and diaspore are all Cr-rich varieties. The chromian (Cr₂O₃3.86 wt%) paragonitic muscovite incorporates up to 17% of the paragonite molecule, and significant Mg and Fe substitutions.The suite of rocks are characterized by chondritic Ti/Zr ratios (–x=107), systematically enhanced Cr (up to 14000 ppm) and Ni (up to 1200 ppm) abundances, low levels of the alteration-insensitive incompatible elements Th, Ta, Nb. Chlorite, corundum and Cr muscovite represent progressive stages in the incremental metasomatic alteration of a komatiite precursor. Mass balance calculations, constrained by the isochemical behaviour of Ti, Zr and Hf reveal that the komatiite chloritite transformation involved volumetric contractions of 60% by hydrothermal leaching of Si, Fe, Mn, Ca and Na. Reaction of chloritite to corundum involved further volumetric reductions of 50% due to essentially quantitative loss of Si, Fe, Mn, Mg, K and Ca. Conversion of corundum to muscovite required additions of Si, K, Fe, Mn, Mg, Rb and Ba at 50–200% dilation. K, Rb, Ba, Li and Cs are enriched by up to 2×10³ over background abundances in ultramafic rocks, and the suite is also enriched in B, Se, Te, Bi, As, Sb and Au. REE were extensively leached during chloritite-corundum stages, whereas LREE additions accompany development of muscovite. Ti, Zr, Hf and Al were all concentrated by selective leaching of mobile components, but absolute additions of Al accompanied development of the corundum domains due to Al precipitation in response to depressurization.Corundum ( ¹⁸O=3.5–4.8), muscovite ( ¹⁸O=6.7–7.5) and chlorite (4.5–5.6) are isotopically uniform and formed at 380–520° C from a fluid where ¹⁸O=5.6–6.9. The corundum is ¹⁸O depleted relative to either igneous or anatectic counterparts (O_cor=7.6–8.2), or to gibbsitic laterites ( ¹⁸O=12–17).Previous genetic schemes involving metamorphism of exhalites or bauxite, or Si-undersaturation of magmas, can all be ruled out from the data. The chloritite, corundum, Cr-muscovite association represents sequential alteration products of ultramafic rocks by high temperature, low pH hydrothermal solutions carrying LIL-elements, and in which excursions of pH and/or degree of quartz undersaturation account for the mineralogical transitions. A deep level acid epithermal system, or fluid advection across steep inverted thermal gradients in a thrust regime could account for required hydrothermal conditions.     

Oxygen and hydrogen isotope compositions as indicators of granite genesis in the New England Batholith,Australia

Oxygen and hydrogen isotope studies of a number of granite suites and mineral separates from the New England Batholith indicate that O¹⁸ can be used to discriminate the major granite protoliths. The granite suites previously subdivided on the basis of mineralogical and geochemical criteria into S-type (sedimentary) and I-type (igneous) have O¹⁸ values consistently higher in the S-type granites (10.4–12.5) than in the spatially related I-type plutons (7.7–9.9). There appears to be a systematic variation in O¹⁸ from the most S-type to the most I-type granites, the dividing point between the two occuring at O¹⁸ equal to 10. A group of leucocratic granites that form about half of the batholith and difficult to classify mineralogically and geochemically is found to have low O¹⁸ values (6.4–8.1), suggesting an affinity to the most I-type granites. A single leucogranite pluton with minor muscovite has a O¹⁸ of 9.6 which is significantly higher than other leucogranites indicating a different origin perhaps involving amphibole fractionation.The behavior of D in the plutonic rocks is much less systematic than O¹⁸. Excluding samples collected adjacent to major faults, the D values show a rough positive correlation with water content similar to, but less pronounced than, the trend previously observed in the Berridale Batholith, southeastern Australia. This relation is considered to reflect an interaction between meteoric water and the granites, the largest effect being observed in samples with the least amount of water. Of note is the generally lower D values of the upper Paleozoic New England Batholith compared with the Silurian Berridale Batholith. This difference may be related to a near equatorial paleolatitude of 22 °S in the Silurian and near polar paleolatitudes in the late Carboniferous that have been inferred for these regions. Granite samples collected from near major faults, and one ignimbrite sample of rhyodacite composition, have very low D values (less than –120) suggesting a much greater degree of interaction with meteoric water.     

Sulphur and sulphate-oxygen isotopes and the origin of the silvermines deposits,Ireland

New sulphur and sulphate-oxygen isotope measurements for the main discordant and stratiform lead-zinc-barite orebodies at Silvermines Co. Tipperary, allow reappraisal of previously offered differing interpretations (Graham, 1970; Greig et al., 1971) of the bearing of sulphur isotopes on the genesis of this important Irish deposit. The following aspects of the data are confirmed: barite ³⁴ S-values range from 17–21, similar to lower Carboniferous seawater sulphate: stratiform sulphide lens pyrites have ³⁴ S-values ranging from –13 to –36; vein sulphide ³⁴ S-values range from –8 to 4; sulphide ³⁴ S-values increase upwards and outwards respectively in the related discordant and stratiform G orebodies; galena-sphalerite isotope palaeotemperatures are not too consistent, ranging from 40 to 430°C (using the calibration of Czamanske and Rye (1974). New facts are as follows: barite ¹⁸O-values range from –13 to –17, stratiform barites ranging from 13 to 14.5; sulphides separated from a single stratiform ore lens hand specimen usually have ³⁴ S_sl > ³⁴ S_ga > ³⁴ S_py; the outward decrease in ³⁴ S-values in the stratiform G orebody is confined to the first few hundred feet only; pyrite ³⁴ S-values progressively increase downwards through one stratiform sulphide orebody; yet variations of 13 occur within a single colloform pyrite structure from another stratiform orebody. It is concluded that there were at least two sources of sulphur, seawater sulphate and deep-seated sulphur. The former was the dominant source of all sulphate and, via biogenic reduction, of the sulphur in the bulk of the stratiform sulphide. The latter was the source of the sulphur in the vein sulphides. There was minimal isotopic interaction between the cool seawater sulphate and the warm unwelling ore fluid sulphur species, even though the latter precipitated under near isotopic equilibrium conditions when the temperature dropped and/or the pH and Eh increased. The lack of isotopic equilibrium between pyrite and ore sulphides in the stratiform ore lenses may result from the latter having precipitated slightly later than the former because of solubility relationships. Overall the present isotopic evidence supports considerable geological evidence favoring a syngenetic origin for the stratiform Silvermines orebodies.     

Sulphur isotope compositions in the Åmmeberg Zn-Pb ore deposit,south-central Sweden: Genetic implications

The distribution of sulphur isotope compositions in the Åmmeberg sulphide ore deposit is discussed. The ³⁴S values for various sulphides show a complex pattern of fluctuations between isotopic equilibrium and non-equilibrium conditions. This feature as well as the observed variations in the ³⁴S values of galena and sphalerite are interpreted to have originated from successive pulses of sulphide-forming solutions. On the basis of geological field criteria and sulphur isotope data, the Ammeberg deposit is considered to be a typical distal mineralization, belonging to the volcanic-exhalative group of ore deposits. The banded structure of the ore, the spatial separation of Pb and Zn and the presence of discrete, persistant ore layers probably relate to the type of convective system that created the mineral-forming solutions and to the various processes taking place when the brines were expelled onto the sea floor.

---

Zusammenfassung Es wird die Verteilung von Schwefelisotopenzusammensetzungen in der Åmmeberg Sulfidlagerstätte diskutiert. Die ³⁴S-Werte für verschiedene Sulfide zeigt ein kompliziertes Schwankungsmuster zwischen Isotopengleichgewichts- und Isotopenungleichgewichtsbedingungen. Dieses Merkmal zusammen mit den beobachteten ³⁴S Schwankungen von Bleiglanz und Zinkblende werden dahingehend interpretiert, daß sie ihren Ursprung im anhaltenden Zustrom von sulfidhaltigen Lösungen hatten. Auf der Basis von geologischen Geländebefunden und Schwefelisotopendaten wird die Åmmeberg Lagerstätte als eine typische distale Mineralisation eingestuft, welche zur vulkanisch-exhalativen Lagerstättengruppe gehört. Die gebänderte Struktur des Erzes, die räumliche Trennung von Blei und Zink und die Anwesenheit von gesondert durchziehenden Erzlagen sind zum konvektiven System in Beziehung zu setzen, welches die mineralformenden Lösungen lieferte. Ebenfalls zeigt sich ein Zusammenhang zu den verschiedenen Prozessen, welche abliefen als die Sole auf den Meeresboden ausgestoßen wurde.

---

Résumé L'auteur discute la distribution des compositions du soufre dans le gisement de sulfure d'Åmmeberg. Les valeurs de ³⁴S pour divers sulfures présentent des fluctuations complexes entre les conditions d'équilibre et de non-équilibre isotopique.Cette distribution, ainsi que les variations observées de ³⁴S de la galène et de la blende sont interprétées comme résultant d'arrivées successives de solutions sulfurantes. Sur la base de critères géologiques de terrain et des données relatives aux isotopes du soufre, le gisement d'Åmmeberg est considéré comme une minéralisation typiquement distale, appartenant au groupe volcanique exhalatif. La structure rubanée du minerai, la séparation spatiale du Pb et du Zn et la présence de couches de minerai discrètes et continues doivent vraisemblablement être mises en relation avec le type de système convectif qui a engendré les solutions minéralisantes et avec les divers processus qui sont entrés en jeu lorsque les saumures se sont répandues sur le fond de la mer.

---

Åmmeberg. d³⁴S . d³⁴S, , , . Åmmeberg , , . , , . , , .