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.     

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.     

Experimental constraints on the storage conditions of phonolites from the Kerguelen Archipelago

Phase relations of a phonolite (K1) and a tephri-phonolite (K2) from the Upper Miocene lavas in the Southeast Province of the Kerguelen Archipelago have been investigated in the P/T range 100–500 MPa and 700–900 °C at two fO₂ conditions (~ NNO and ~ NNO+2.3) to clarify the differentiation and pre-eruptive conditions of these magmas. Crystallization experiments were performed in cold seal pressure vessels (CSPV) and internally heated pressure vessels (IHPV) at various X_H2O, under reducing (log fO₂ ~ NNO) and oxidizing conditions (log fO₂ ~ NNO+2.3). Under reducing conditions, the resulting phase assemblage for K1 was: titanomagnetite, nepheline, alkali feldspar, clinopyroxene and biotite; under oxidizing conditions, the assemblage was: magnetite, plagioclase, alkali feldspar, nepheline, titanite (minerals given in the order of appearance with decreasing T at 200 MPa for 4 wt% water in the melt). It is emphasized that an effect of fO₂ on the phase stability of feldspars and feldspathoides was observed. Comparison of the natural and experimental phase assemblages shows that the pre-eruptive conditions for K1 must have been in the log fO₂ range NNO+1–NNO+2, at pressures above 200–250 MPa. Assuming a temperature of 800 °C, the water content of the melt is constrained to be between 4 and 6 wt% H₂O. The pre-eruptive fO₂ conditions for the less evolved sample K2 are more oxidizing with log fO₂ close to NNO+2.3. The experimental results show that the enrichment of alkalis in residual melts during differentiation of tephri-phonolites is enhanced at high fO₂.Editorial responsibility: J. Hoefs     

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.     

O,H, C isotope study of rocks from the KTB pilot hole: crustal profile and constraints on fluid evolution

The pilot hole of the Continental Deep Borehole (KTB) drilling project is located in the Bavarian Oberpfalz at the western margin of the Bohemian Massif. The 4-km deep borehole penetrated various paragneisses and minor orthogneisses with intercalations of amphibolites and metagabbros. The different lithologies have systematically different whole-rock oxygen isotope values and give little evidence for large scale water-rock interaction. Minor fluid interaction is well documented during retrograde metamorphism by non-equilibrium fractionations between refractory minerals (quartz, garnet and hornblende) and altered minerals (chlorite/biolite and feldspar). Ubiquitous vein mineralisation indicates fluid-induced retrogression at temperatures between 150°C and 400°C. The D values of hydroxylbearing minerals are very uniform in all lithologic units. The calculated hydrogen isotope composition of the fluid in equilibrium with matrix and vein minerals increases from -45 for metabasic rocks, to -20 for gneisses, to about -5 for vein minerals. The oxygen isotope composition of the fluid has been buffered by the rock and decreases with decreasing temperature because of increasing fractionations at low temperatures and low water-rock ratios. Modern fluids sampled from open cavities within the borehole have isotopic compositions that suggest a continuous fluid evolution during retrogression in a closed system. The ¹³C values of calcite and graphite also indicate closed system mixing processes.     

Stable isotopic evidence for large-scale seawater infiltration in a regional metamorphic terrane; the Trois Seigneurs Massif,Pyrenees, France

Oxygen isotopic analyses of 95 metamorphic and igneous rocks and minerals from a Hercynian metamorphic sequence in the Trois Seigneurs Massif, Pyrenees, France, indicate that all lithologies at higher metamorphic grades than the andalusite in isograd have relatively homogeneous ¹⁸O values. The extent of homogenization is shown by the similarity of ¹⁸O values in metacarbonates, metapelites and granitic rocks (+11 to +13), and by the narrow range of oxygen isotopic composition shown by quartz from these lithologies. These values contrast with the ¹⁸O values of metapelites of lower metamorphic grade ( ¹⁸O about +15). Homogenization was caused by a pervasive influx of hydrous fluid. Mass-balance calculations imply that the fluid influx was so large that its source was probably high-level groundwaters or connate formation water. Hydrogen isotopic analyses of muscovite from various lithologies are uniform and exceptionally heavy at D=–25 to –30, suggesting a seawater origin. Many lines of petrological evidence from the area independently suggest that metamorphism and anatexis of pelitic metasediment occurred at depths of 6–12 km in the presence of this water-rich fluid, the composition of which was externally buffered. Deep penetration of surface waters in such environments has been hitherto unrecognized, and may be a key factor in promoting major anatexis of the continental crust at shallow depth. Three types of granitoid are exposed in the area. The leucogranites and the biotite granite-quartz diorite are both mainly derived from fusion of local Paleozoic pelitic metasediment, because all these rocks have similar whole-rock ¹⁸O values (+11 to +13). The post-metamorphic biotite granodiorite has a distinctly different ¹⁸O (+9.5 to +10.0) and was probably derived from a deeper level in the crust. Rare mafic xenoliths within the deeper parts of the biotite granite-quartz diorite also have different ¹⁸O (+8.0 to +8.5) and possibly represent input of mantle derived magma, which may have provided a heat source for the metamorphism.Contribution No. 4192, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology     

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

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

Oxygen 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.     

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     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

In pelitic rocks, under conditions of low f _{O 2} and low f _{H 2 O}, the stability of the mineral pair cordierite-garnet is limited by five univariant reactions. In sequence from high pressure and low temperature to high temperature and low pressure these are: cordierite+garnet hypersthene+sillimanite+quartz, cordierite+garnet hypersthene+sapphirine+quartz, cordierite+garnet hypersthene+spinel+quartz and cordierite+garnet olivine+spinel +quartz. In this sequence of reactions the Mg/Mg+Fe²⁺ ratio of all ferro-magnesian minerals involved decreases continuously from the first reaction to the fifth. The five univariant boundaries delimit a wide P-T range over which cordierite and garnet may coexist.Two divariant equilibria in which the Mg/Mg+ Fe²⁺ ratio of the coexisting phases are uniquely determined by pressure and temperature have been studied in detail. P-T-X grids for the reactions cordierite garnet+sillimanite+quartz and cordierite+hypersthene garnet+quartz are used to obtain pressure-temperature estimates for several high grade metamorphic areas. The results suggest temperatures of formation of 700–850° C and load pressures of 5–10 kb. In rare occasions temperatures of 950–1000° C appear to have been reached during granulite metamorphism.On the basis of melting experiments in pelitic compositions it is suggested that Ca-poor garnet xenocrysts found in calc-alkaline magmas derive from admixed pelitic rocks and did not equilibrate with the calc-alkaline magma.     

Transformation of blueschist to greenschist facies rocks as a consequence of fluid infiltration,Sifnos (Cyclades), Greece

The transformation from blueschist to greenschist facies forms a major part of the Alpine regional geodynamic evolution of the Cyclades. The transition in metabasic rocks on Sifnos involves the retrogression of eclogites, blueschists and actinolite-bearing rocks from high-pressure conditions which have been estimated at 460±30° C and 15±3 kb. Petrographically observed parageneses are interpreted by a sequence of hydration and carbonation reactions involving the breakdown of omphacite and glaucophane-bearing assemblages to albite+chlorite±actinolite±calcite assemblages. The retrograde processes are calculated to occur at pressures of 10 to 8 kb during the isothermal uplift of the Sifnos units. Oxygen isotope analyses of different rock types show that interlayered lithologies have experienced a large degree of isotopic equilibration during both metamorphic phases. However, chemically equivalent rocks show systematic increases in ¹⁸O from lowest values (8 to 11 in metabasics) in the unaltered blueschists in the upper stratigraphic levels to higher values (>15 in metabasics) associated with greenschists in the deepest stratigraphic levels. Relict eclogites enclosed within greenschists have the lower ¹⁸O values typical of unaltered blueschist facies rocks. These isotopic gradients and the ¹³C and ¹⁸O compositions of carbonates demonstrate an infiltration mechanism involving the upward movement of ¹⁸O-enriched fluids whose compositions were buffered by exchange with marble units. Calculated minimum fluid/rock ratios for the blueschist-to-greenschist transition decrease from 0.4 in the deepest studied level (Central Sifnos) and 0.2 in the intermediate level (Kamares Bay samples) to an assumed value of zero in unaltered blueschists. These ratios may be lower if recycling of fluids occurred between schists and marbles. Infiltration of fluids became inhibited as the transformation advanced as a consequence of sealing effect of the hydration and carbonation reactions. Although infiltration most probably was a pre-requisite for the regional occurrence of the blueschist-to-greenschist transformation in the Cyclades, the evidence on Sifnos does not suggest the introduction of large quantities of fluid.     

The upper stability limit of the assemblage paragonite + quartz and its natural occurrences

The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al₂SiO₅.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H₂O has been located experimentally. The reversed P _{H 2 O}-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H₂O runs through the following P _{H 2 O}-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H₂O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G _f,298 ⁰ of the Al₂SiO₅ polymorphs may in fact be due to an error of similar magnitude in G _f,298 ⁰ of corundum.A best estimate of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of paragonite based on these considerations yield: S ₂₉₈ ⁰ : 67.61±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ : –1411.4±2.7 kcal gfw^–1 G _f,298 ⁰ : –1320.9±4.0 kcal gfw^–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.     

Sapphirine-kornerupine rocks from the Reynolds Range,central Australia: constraints on the uplift history of a Proterozoic low pressure terrain

Sapphirine-kornerupine-bearing rocks from the Reynolds Range, Northern Territory, Australia preserve spectacular metamorphic reaction textures that provide valuable insights into the regional metamorphic uplift history. The rocks occur in pods that are several meters in diameter within high-temperature, low-pressure (750 to 800°C and 4 to 5 kbar) granulite facies exposures of the early Proterozoic Lander Rock beds, a laterally extensive sequence of folded pelitic and quartzose metasediments. The pods are not associated with large volumes of partial melts and are likely to have formed by metasomatism near the peak of M₂ metamorphism. The rocks in the pods consist of high-temperature Mg- and Al-rich minerals such as boron-free korneurpine, and are coarse-grained (0.5 to >15 cm), non-foliated, and locally nearly monomineralic. The growth of the coarse minerals in the pods largely post-dated the high-grade regional metamorphic D₂ fabric and completely reconstructed the precursor rocks. The retrograde metamorphic reaction textures show that the early retrogression from the M₂ granulite facies conditions was characterized not by isobaric cooling as previously proposed, but by nearly isthermal decompression. These data imply that the Reynolds Range did not follow a simple anticlockwise P-T-t path. Because rocks such as these preserve information from a only restricted portion of the metamorphic history and can preserve evidence of decompression reactions more clearly than many more ordinary lithologies, they can be especially important for discerning metamorphic P-T-t paths.This paper is a contribution to IGCP Project 304, Lower Crustal Processes.     

Silica activity and P total in igneous rocks

The variation of silica activity with temperature and pressure for a variety of silica buffers (mineral pairs) allows P _total to be calculated for a wide range of igneous rocks. The method also depends on evaluating ( log a _{SiO 2}/P)_T and ( log a _{SiO 2}/ T)p; the former is equivalent to the partial molar volume of silica in silicate liquids, while the latter is estimated from published experiments on natural melts. Results for calc-alkaline rhyolites with phenocrysts of quartz, olivine or orthopyroxene, and iron-titanium oxides, range from 3.45 to 9.58 kilobars; a pantellerite is intermediate at 7.53 kilobars. At 1327° C, the silicate inclusions in diamond equilibrated at 63.5 kilobars, and the kimberlite crystallisation path intersected the baddeleyite-zircon reaction at 55.7 kilobars. Two trachybasalts would equilibrate with their lherzolite xenoliths at 17.0 and 21.0 kilobars at surface quenching temperatures. Potassic lavas such as orendites and ugandites at 1300° C would be in equilibrium with mantle olivine-orthropyroxene at 35.1 and 69.0 kilobars respectively. Basalts and basaltic-andesites could equilibrate (at 1100° C) with quartz at between 24.9 and 26.8 kilobars; quartz can therefore be considered a possible high pressure xenocryst in lavas with low Sr⁸⁷/Sr⁸⁶ ratios. Andesites will equilibrate at 1300° C with the mantle at a depth of 75 kilometres; at greater depths andesite will have a basaltic precursor. In general, lavas with low silica activity will equilibrate at greater depths in the mantle than those with higher silica activities.The Apollo 11 basalts contain minerals which suggest equilibration at 37 kilobars; the calculated quenching temperature is 1009° C, from which logf _{O 2} can be derived (–15.2) which in turn indicates approximately 0.10% Fe₂O₃ in these lavas.     

Hf isotope systematics in granitoids from the central and southern Alps

First initial-Hf isotopic compositions for samples from the Alpine domain are presented and discussed. The results are mainly based on zircons and a few whole rocks with ages between 30 and 450 Ma. Of those so far analyzed, the present-day Hf isotopic compositions of zircons from non-metamorphic and metamorphic granitoid rocks vary between 0.2824 and 0.2829. Zircon populations with concordant U-Pb ages have much higher initial ¹⁷⁶Hf/¹⁷⁷Hf than inversely discordant populations which have been contaminated with older zircons containing less radiogenic Hf. Correlated Nd-Hf crustal-residence ages have been found involving model parameters of Hf/Nd=f(Lu/Hf)/f(Sm/Nd) 1.6 for the depleted mantle and f(Lu/Hf)/f(Sm/Nd) 1.2 for elemental fractionations in the crust. The model implies ¹⁷⁶Lu/¹⁷⁷Hf of 0.017 for the bulk crust. It is suggested that the granitoid rocks are the result of mixing of subcontinental mantle-derived magmas with 1.7 Ga old recycled and partially molten crustal material. The continental/mantle component mass-ratio values for the granitoids range between 0.3 and 2.     

Experimental determination of Mn-Mg mixing properties in garnet,olivine and oxide

We have measured the mixing properties of Mn-Mg olivine and Mn-Mg garnet at 1300° C from a combination of interphase partitioning experiments involving these phases, Pt-Mn alloys and Mn-Mg oxide solid solutions. Activity coefficients of Mn dilute in Pt-Mn alloys at 1300° C/1 atm were measured by equilibrating the alloy with MnO at known f _{O 2}. Assuming that the log f _{O 2} of the Mn-MnO equilibrium under these conditions is-17.80 (Robie et al. 1978), we obtain for _Mn: log_Mn = –5.25 + 3.67 X_Mn + 11.41X² _Mn Mixing properties of (Mn,Mg)O were determined by reversing the Mn contents of the alloys in equilibrium with oxide at known f _{O 2}. Additional constraints were obtained by measuring the maximum extent of immiscibility in (Mn,Mg)O at 800 and 750° C. The data are adequately described by an asymmetric (Mn,Mg)O solution with the following upper and lower limits on nonideality: (a) W_Mn = 19.9kj/Mol; W_Mg = 13.7kj/Mol; (b) W_Mn = 19.9kj/Mol; W_Mg = 8.2kj/Mol; Olivine-oxide partitioning was tightly bracketed at 1300° C and oxide properties used to obtain activity-composition relations for Mn-Mg olivine. Despite strong M2 ordering of Mn in olivine, the macroscopic properties are adequately described by a symmetric model with: W^ol = 5.5 ± 2.5 kj/mol (1-site basis) Using these values for olivine, garnet-olivine partitioning at 27 kbar/1300° C leads to an Mn-Mg interaction parameter in garnet given by: W^gt = 1.5 ± 2.5kJ/mol (1-site basis) Garnet-olivine partitioning at 9 kbar/1000° C is consistent with the same extent of garnet nonideality and the apparent absence of excess volume on the pyrope-spessartine join indicates that any pressure-dependence of W^Gt must be small. If olivine and garnet properties are both treated as unknown and the garnet-olivine partitioning data alone used to derive W^Ol and W^Gt, by multiple linear regression, best-fit values of 6.16 and 1.44 kJ/mol. are obtained. These are in excellent agreement with the values derived from metal-oxide, oxide-olivine and olivine-garnet equilibria.     

Stable isotope constraints on the origin and depth of penetration of hydrothermal fluids associated with Hercynian regional metamorphism and crustal anatexis in the Pyrenees

Late Carboniferous (Hercynian) tectonism in the Pyrenees generated extremely steep thermal gradients at 8–14 km depth in the continental crust, producing andalusite- and sillimanite-grade metamorphism and partial melting of Lower Paleozoic metasediments under water-rich conditions. At the same time, amphibolite- and granulitefacies basal gneisses were equilibrated under dryer conditions at pressures of 4 to 7 kbar (14–25 km depth), beneath these higher-level rocks. We present 95 new oxygen isotopic analyses of samples from the Agly, St. Barthelemy, Castillon and Trois Seigneurs Massifs, highlighting contrasting ¹⁸O/¹⁶O systematics at different structural levels in the Hercynian crust, here termed Zones 1, 2, and 3. The unmetamorphosed, fossiliferous, Paleozoic shales and carbonates of Zone 1 have typical sedimentary ¹⁸O values, mostly in the range +14 to +16 for the pelitic rocks and +20 to +25 for the carbonates. The metamorphosed equivalents of these rocks in Zone 2 all have strikingly uniform and much lower ¹⁸O values; the metapelites mostly have ¹⁸O=+10 to +12, and interlayered metacarbonates from the Trois Seigneurs Massif have ¹⁸O of about +12 to +14. Typically, the Zone 3 basal gneisses are isotopically heterogeneous with variable ¹⁸O values ranging from +6 in mafic lithologies to +22 in carbonate-rich lithologies. Steep gradients in ¹⁸O (as much as 10 per mil over a few cm) are preserved at the margins of some metacarbonate layers. These data indicate that the Zone 3 gneisses were infiltrated by much smaller volumes of metamorphic pore fluids than were the overlying Zone 2 rocks, and that circulation of surface-derived H₂O (either seawater or formation waters, as evidenced by high D values) was mainly confined to the Paleozoic supracrustal sedimentary pile. This is compatible with an overall reduction of interconnected porosity with increasing depth, but perhaps even more important, the extensive partial melting at the base of Zone 2 may have produced a ductile, impermeable barrier to downward fluid penetration.Contribution No. 4287, Publication of the Division of Geological and Planetary Sciences, California Institute of Technology     

Pd-oxide equilibration: a new experimental method for the direct determination of oxide activities in melts and minerals

We have developed a new technique for the experimental determination of the activities of oxide components in melts and minerals using the equilibrium between Pd alloy, oxygen, and the oxide component in the sample of interest. If a melt or mineral sample is equilibrated with Pd metal at fixed P, T, and f _{O 2}, a small amount of each constituent oxide will reduce to metal and dissolve into the Pd, forming an alloy. Due to the extraordinary stability of dilute alloys of Pd with Mg, Al, and Si, these metals dissolve into the Pd in amounts easily measured with the electron microprobe at f _{O 2} s that can be achieved with conventional gas-mixing techniques. We determined the activity-composition relations for Pd–Mg, –Al, and –Si alloys by equilibrating Pd at fixed f _{O 2}and T with periclase, corundum, and cristobalite (a _oxide1). Because Mg, Al, and Si have constant activity coefficients in Pd at low concentrations, the activity of the oxide of each metal is a simple function of the ratio of the concentration of the metal in Pd in equilibrium with the sample to that in Pd in equilibrium with the pure oxide. Therefore, if Pd plus a melt or mineral and Pd plus pure oxide standards are equilibrated simultaneously at fixed T and f _{O 2}, the precision of the analytical technique is the major limitation on the determination of oxide activities. We used Pd-oxide equilibration to explore activities in silicate melts analogous to Type B Ca–Al-rich inclusions (CAIs) from carbonaceous chondrites; the measured activities deviate systematically from model valves but agree to within 1–30%. The activities imply that Type B CAIs did not condense as liquids from a gas of solar composition, and that only very aluminous compositions are potential liquid condensates from the solar nebula. We also used Pd-oxide equilibration to determine the free energy of formation from the oxides, G _f ^/O , of the spinel end-member MgAl₂O₄ at 1150 to 1400°C to a precision of 2–19% (1). Because the technique reflects equilibration at high temperature, the G _f ^/O _s accurately represent the mineral with equilibrium Mg–Al disorder at temperature, a feature not true of drop calorimetric results because of partial reordering during quenching. Our results indicate more negative G _f ^Emphasis>/O and hence higher entropy of formation, S _f ^Emphasis>/O , than given in most compilations of thermodynamic data for spinel.Division of Geological and Planetary Sciences Contribution #5278     

The occurrence and distribution of Mo and molybdenite in unaltered peralkaline rhyolites from Pantelleria,Italy

Small hexagonal and triangular platelets of molybdenite (MoS₂), 5 to 25 m in diameter, were identified in phenocrysts and matrix glass of unaltered felsic volcanic rocks from Pantelleria, Italy. The MoS₂ occurs commonly in pantellerites (peralkaline rhyolites), rarely in pantelleritic trachytes, and never in trachytes. The occurrence of euhedral MoS₂ platelets in all phenocryst phases, in matrix glass, and even in some melt inclusions indicates that MoS₂ precipitated directly from the peralkaline melt. Despite MoS₂ saturation, the melt (glass) contains greater than 95% of the Mo in Pantellerian rocks: X-ray fluorescence analyses of 20 whole rocks and separated glasses show that whole rocks consistently contain less Mo than corresponding matrix glasses, the differences being in proportion to phenocryst abundances. The Mo contents increase with differentiation from trachytes (2–12 ppm) to pantellerites (15–25 ppm) and correlate positively with incompatible elements such as Th, Y, and Nb. The Mo concentrations, as determined by secondary ion mass spectrometry, are essentially the same in matrix glasses and melt inclusions, showing that Mo did not partition strongly into a volatile fluid phase during outgassing. The high Mo contents of the pantellerites (relative to metaluminous magmas with 1–5 ppm) may be due to several factors: (1) the enhanced stability of highly charged cations (such as Mo⁶⁺, U⁴⁺, and Zr⁴⁺) in peralkaline melts; (2) the rarity of Fe-Ti oxides and litanite into which Mo might normally partition; (3) reduced volatility of Mo in low fO₂, H₂O-poor (1–2 wt%) peralkaline magmas. Geochemical modeling indicates that the precipitation of MoS₂ can be explained simply by the drop in temperature during magmatic differentiation. The occurrence of MoS₂ in pantellerites may result from their high Mo concentrations and low redox state (Ni/NiO=-2.5) relative to metaluminous magmas, causing them to reach MoS₂ saturation at magmatic temperatures. The apparent absence of MoS₂ microphenocrysts in more oxidized, metaluminous rhyolites may indicate that Mo is dissolved primarily as a hexavalent ion in those magmas.     

On comparative probabilities for normal confidence intervals by pearson's Types III and VII, and the Edgeworth series models for biotite data

Biotite crystals were counted in standard thin sections which originated from the diamond drill core of the mafic norite formation at Strathcona mine, Sudbury Nickel Irruptive. Pearson's method of moments is suitable to fit Types III and VII to the biotite data and its log ₁₀ transformation values, as the number of samples (thin sections)is large (351).Based on the two models and the Edgeworth series (utilizing the log ₁₀ data)probability values p,that biotite occurrences lie in the interval mean ± Z standard deviations is derived. Results are compared with the usual normal probability values p_Z corresponding to Zand it is shown that the Edgeworth series generated the largest pvalues for intervals when p_Z values are large; for intermediate or lower p_Z s. Types VII and III models produced larger ps, relative to the Normal and the Edgeworth series.