Crustal xenoliths from Calbuco Volcano,Andean Southern Volcanic Zone: implications for crustal composition and magma-crust interaction

Crustal xenoliths in the 1961 andesite flow of Calbuco Volcano, in the southern Southern Volcanic Zone (SSVZ) of the Andes, consist predominantly of pyroxene granulites and hornblende gabbronorites. The granulites contain plagioclase+pyroxene+magnetite±amphibole, and have pronounced granoblastic textures. Small amounts of relict amphibole surrounded by pyroxene-plagioclase-magnetite-glass symplectites are found in some specimens. These and similar textures in the gabbronorites are interpreted as evidence of dehydration melting. Mineral and bulk rock geochemical data indicate that the granulites are derived from an incompatible trace element depleted basaltic protolith that underwent two stages of metamorphism: a moderate pressure, high temperature stage accompanied by melting and melt extraction from some samples, followed by thermal metamorphism after entrainment in the Calbuco andesite lavas. High _Nd ^T values (+4.0 to +8.6), Nd-isotope model ages of 1.7–2.0 Ga, and trace element characteristics like chondrite normalized La/Yb< and La/Nb1 indicate that the protoliths were oceanic basalts. Similar oceanic metabasalts of greenschist to amphibolite facies are found in the Paleozoic metamorphic belt that underlies the Chilean coastal ranges. Mineral and bulk rock compositions of the gabbronorite xenoliths indicate that they are cognate, crystallizing from the basaltic andesite magma at Calbuco. Crystallization pressures for the gabbros based on total Al contents in amphibole are 6–8 kbar. These pressures point to middle to lower crustal storage of the Calbuco magma. Neither granulite nor gabbro xenoliths have the appropriate geochemical characteristics to be contaminants of Calbuco andesites, although an ancient sedimentary contaminant is indicated by the lava compositions. The presence of oceanic metabasaltic xenoliths, together with the sedimentary isotopic imprint, suggests that the lower crust beneath the volcano is analogous to the coastal metamorphic belt, which is an accretionary complex of intercalated basalts and sediments that formed along the Paleozoic Gondwanan margin. If this is the case, the geochemical composition of the lower and middle crust beneath the SSVZ is significantly different from that of most recent SSVZ volcanic rocks.     

Lithological and Structural Controls on Regional 3-D Fluid Flow Patterns during Greenschist Facies Metamorphism of the Dalradian of the SW Scottish Highlands

Greenschist facies metabasite sills enclosed within phyllitesand psammites of the Dalradian Supergroup of the SW ScottishHighlands have been used as quantitative sensors of fluid flow,from which ‘fossil’ fluid flow-paths have been mapped.Infiltration of H₂O–CO₂ fluid caused carbonation of themetabasite assemblage. Consequently, metabasite sills have developeda characteristic asymmetric zonation of reacted (carbonate-bearing)margins and unreacted (carbonate-absent) interiors. Reactionfront advection theory has been used to constrain the time-integratedfluid flux and flow direction in one dimension, for each sill,from the widths of the reacted margins. Three-dimensional fluxesand flow directions have been constrained from one-dimensionalfluxes by geometrical computation, and regional fluid flow patternshave been deduced. On a regional scale, fluid flow was channelled through phyllitesand focused towards the axial zone of major antiformal foldstructures. Fluid flow was channelled through the 6 km thickArdrishaig Phyllites, within which fluid fluxes were found toincrease exponentially with proximity to the axial surface ofthe Ardrishaig Anticline. Fluid flow through the psammites waslimited to narrow zones of intense deformation associated withmetabasic or phyllitic intercalations. Although time-integratedfluid fluxes were locally high (4 10² m³/m²), average fluxes(100 m¹/m²) are compatible with availability of fluid from underlyingdevolatilizing rocks. Complete isotopic homogenization of phyllites,psammites and metabasites within the axial region of the ArdrishaigAnticline is predicted by these high measured fluxes. KEY WORDS: 3-D flow; Dalradian; SW Scotland; greenschist facies; metabasites ^*Corresponding author. Telephone: 0131-650-5885 Fax: 0131-668-3184 E-mail: askelton{at}glg.ed.ac.uk     

Distribution of moderately volatile trace elements in fine-grained chondrule rims in the unequilibrated CO3 chondrite, ALH A77307

The concentrations of Ni, Cu, Zn, Ga, Ge, and Se in five, fine-grained chondrule rims in the highly unequilibrated CO3 chondrite ALH A77307 (3.0) have been determined for the first time by synchrotron X-ray fluorescence (SXRF) microprobe at Brookhaven National Laboratory. These elements are especially useful for tracing the role of condensation and evaporation processes which occurred at moderate temperatures in the solar nebula. Understanding the distribution of moderately volatile elements between matrix and chondrules is extremely important for evaluating the different models for the volatile depletions in chondritic meteorites. The data show that the trace element chemistry of rims on different chondrules is remarkably similar, consistent with data obtained for the major and minor elements by electron microprobe. These results support the idea that rims are not genetically related to individual chondrules, but all sampled the same reservoir of homogeneously mixed dust. Of the trace elements analyzed, Zn and Ga show depletions relative to CI chondrite values, but in comparison with bulk CO chondrites all the elements are enriched by approximately 1.5 to 3.5 x CO. The abundance patterns for moderately volatile elements in ALH A77307 chondrule rims closely mimic those observed in the bulk chondrite, indicating that matrix is the major reservoir for these elements. The close matching of the patterns for the volatile depleted bulk chondrite and enriched matrix is especially striking for Na, which is anomalously depleted in ALH A77307 in comparison with average CO chondrite abundances. The depletion in Na is probably attributable to the effects of leaching in Antarctica. With the exception of Na, the volatile elements show a relatively smooth decrease in abundance as a function of condensation temperature, indicating that their behavior is largely controlled by their volatility.     

A Strontium and Neodymium Isotopic Investigation of the Fongen--Hyllingen Layered Intrusion, Norway

The Fongen—Hyllingen Intrusion, situated 60 km SE of Trondheim,Norway, is a synorogenic layered mafic intrusion of Caledonianage . The intrusion is divided into four evolutionary stages based on cryptic variations: StageI—a basal reversal; Stage II—unchanged mineral chemistryor slight normal evolution; Stage III—a gradual regression;Stage IV— a strong normal fractionation trend Magma replenishmentdominated during most of the crystallization, i.e. during StagesI, II and III Replenishing magma was more dense than resident,evolved magma, and continuing influx eventually caused a compositionallystratified magma column to form. Cryptic lateral variation isan important feature in the southern part of the complex andformed by in situ crystallization from a stratified magma alongan inclined floor, where modal layering formed parallel to thecrystallization front. Initial Sr- and Nd-isotopic ratios inthe cumulates vary as a result of assimilation of country rockand subsequent mixing between uncontaminated, replenishing magmaand contaminated, resident magma. The parental magma had a moderatelydepleted isotope composition, relative to Bulk Earth, with _Nd=584and Sr_i=070308, whereas the main contaminant was a partialmelt of metapelitic country rock with _Nd=-874 and Sr_i=07195(Sr_i is the initial ⁸⁷Sr/⁸⁶Sr). Sr_i in the analysed cumulatewhole-rock samples ranges from 070308 to 070535 and initial_Nd ranges from. 158 to 584. There is a strong correlationbetween mineralogical composition and isotopic trends in mostof the cumulates: the most primitive samples are the least contaminated,as reflected by relatively high ed and low Sr,, and more evolvedsamples have progressively lower eNi and higher Sry A gradualregression of several hundred metres thickness characterizesStage III; stratigraphically upwards mineral compositions becomemore primitive and isotope compositions more depleted (higher_Nd and lower Sr_i), implying a process of. progressive mixing-inof replenishing, primitive and uncontaminated magma. Magma influxin Stage III took place by fountaining, whereas magma additionwas more tranquil in the earlier stages. The fountaining influxentrained resident, relatively evolved and contaminated magma,resulting in a hybrid magma which ponded at the floor. Duringprolonged magma addition with concomitant crystallization, thelowermost magma layer was replaced by progressively more primitivehybrid magma, creating a gradual regression in the crystallizingcumulate sequence. A detailed two-dimensional study revealslateral variations in mineral compositions both at the baseand top of Stage III, whereas lateral variations in Sr- andNd-isotopic compositions are present at the top, but not atthe base. This implies that the lowest crystallizing part ofthe magma column was essentially isotopically homogeneous, butcompositionally stratified, before influx in Stage III. Isotopicgradients in the magma were strong close to the roof, wheremost of the assimilation occurred, and decreased downwards,merging into isotopically homogeneous magma. This stratifiedsystem was destroyed by turbulent mixing between replenishingand resident magma during fountaining influx in Stage III, anda new stratification was established with both an isotopic anda compositional gradient. After the final influx, crystallizationcontinued in an essentially closed system, in which the remainingmagma column eventually became homogenized, as magma layersmixed when their densities converged owing to release of buoyant,residual liquid during fractional crystallization. Corresponding author     

A sulfur isotope study of volcanogenic massive sulfide deposits of the Eastern Black Sea province,Turkey

Kuroko-type massive sulfide deposits of the Eastern Black Sea province of Turkey are related to the Upper Cretaceous felsic lavas and pyroclastic rocks, and associated with clay and carbonate alteration zones in the footwall and hangingwall lithologies. A complete upward-vertical section of a typical orebody consists of a stringer-disseminated sulfide zone composed mainly of pyrite and chalcopyrite; a massive pyrite zone; a massive yellow ore consisting mainly of chalcopyrite and pyrite; a black ore made up mainly of galena and sphalerite with minor amounts of chalcopyrite, bornite, pyrite and various sulfosalts; and a barite zone. Most of the deposits in the province are associated with gypsum in the footwall or hangingwall. The paragenetic sequence in the massive ore is pyrite, sphalerite, chalcopyrite, bornite, galena and various sulfosalts, with some overlap between the mineral phases. Massive, stringer and disseminated sulfides from eight kuroko-type VMS deposits of the Eastern Black Sea province have a ³⁴S range of 0–7 per mil, consistent with the ³⁴S range of felsic igneous rocks. Sulfides in the massive ore at Madenköy (4.3–6.1 per mil) differ isotopically from sulfides in the stringer zone (6.3–7.2 per mil) suggesting a slightly increased input of H₂S derived from marine sulfate with time. Barite and coarse-grained gypsum have a ³⁴S range of 17.7–21.5 per mil, a few per mil higher than the ³⁴S value of contemporaneous seawater sulfate. The deposits may, therefore, have formed in restricted basins in which bacterial reduction of sulfate was taking place. Fine-grained, disseminated gypsum at Kutlular and Tunca has ³⁴S values (2.6–6.1 per mil) overlapping those of ore sulfides, indicating sulfide oxidation during waning stages of hydrothermal activity.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

Mössbauer spectroscopic and x-ray powder diffraction studies of synthetic micas on the join annite KFe3AlSi3O10(OH)2-phlogopite KMg3AlSi3O10(OH)2

Micas of the composition K(Fe_3–x Mg _x )AlSi₃ O₁₀(OH)₂ (x=0.6, 1.2, 1.8, 2.4 and 3.0, corresponding to ann₈₀phl₂₀, ann₆₀phl₄₀, ann₄₀phl₆₀, ann₂₀phl₈₀ and ann₀phl₁₀₀) were synthesized hydrothermally under controlled oxygen fugacity conditions. Lattice parameters a ₀ and b ₀ show a distinct linear decrease with increasing Mg content. With increasing ferric iron content a deviation from this linear trend is observed especially within iron rich samples. The tetrahedral rotation angle increases smoothly from 0° in annite to 9.1° in phlogopite. Mössbauer spectra show Fe²⁺ and Fe³⁺ on the octahedral M1 and M2 sites and partially also Fe³⁺ on the tetrahedral site. There is a smooth increase of the quadrupole splitting on both the M1 and the M2 site going from annite to phlogopite, probably due to changes in the lattice contribution to the electric field gradient, assuming a positive correlation between quadrupole splitting and distortion. Fe³⁺ contents, as determined by Mössbauer spectroscopy, versus oxygen fugacity shows that, depending on the composition of the micas, minimum amounts of Fe³⁺ are present. For ann₈₀phl₂₀ this minimum amount of Fe³⁺ is about 8% decreasing to about 1–2% Fe³⁺ for ann₂₀phl₈₀.The molar volume of each solid solution member has been estimated from the determined relations of the molar volume versus % Fe³⁺ contents, extrapolated back to 0% Fe³⁺. Plotting these volumes as a function of X_phl shows that negative excess volume occur in the annitephlogopite join, with the maximum deviation from ideality around X _phl=0.3. Margules volume parameters have been constrained as: Wv, AnnPhl=0.018±0.016 J/(bar.mol) and Wv, PhlAnn=-0.391±0.025 J(bar.mol) (three site basis).     

Episode 49 of the Pu'u 'O'o-Kupaianaha eruption of Kilauea volcano-breakdown of a steady-state eruptive era

The Pu'u 'O'o-Kupaianaha eruption (1983-present) is the longest lived rift eruption of either Kilauea or neighboring Mauna Loa in recorded history. The initial fissure opening in January 1983 was followed by three years of episodic fire fountaining at the Pu'u 'O'o vent on Kilauea's east rift zone 19km from the summit (episodes 4–47). These spectacular events gave way in July 1986 to five and a half years of nearcontinuous, low-level effusion from the Kupaianaha vent, 3km to the cast (episode 48). A 49th episode began in November 1991 with the opening of a new fissure between Pu'u 'O'o and Kupaianaha. this three week long outburst heralded an era of more erratic eruptive behavior characterized by the shut down of Kupaianaha in February 1992 and subsequent intermittent eruption from vents on the west flank of Pu'u 'O'o (episodes 50 and 51). The events occurring over this period are due to progressive shrinkage of the rift-zone reservoir beneath the eruption site, and had limited impact on eruption temperatures and lava composition.     

Geochronology and geochemistry of eclogites from the Mariánské Lázně Complex,Czech Republic: Implications for Variscan orogenesis

The Mariánské Lázn complex (MLC) is located in the Bohemian Massif along the north-western margin of the Teplá-Barrandian microplate and consists of metagabbro, amphibolite and eclogite, with subordinate amounts of serpentinite, felsic gneiss and calcsilicate rocks. The MLC is interpreted as a metaophiolite complex that marks the suture zone between the Saxothuringian rocks to the north-west and the Teplá-Barrandian microplate to the south-east. Sm-Nd geochronology of garnet-omphacite pairs from two eclogite samples yields ages of 377±7, and 367±4 Ma. Samples of eclogite and amphibolite do not define a whole rock Sm-Nd isochron, even though there is a large range in Sm/Nd ratio, implying that the suite of samples may not be cogenetic. Eclogites do not have correlated _Nd values and initial ⁸⁷Sr/⁸⁶Sr ratios. Five of the eight eclogite samples have high _Nd values (+10.2 to +7.1) consistent with derivation from a MORB-like source, but variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7059) which probably reflect hydrothermal seawater alteration. Three other eclogite samples have lower _Nd values (+ 5.4 to –0.8) and widely variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7096). Such low _Nd values are inconsistent with derivation from a MORB, source and may reflect a subduction or oceanic island basalt component in their source. The MLC is an important petrotectonic element in the Bohemian Massif, providing evidence for Cambro-Ordovician formation of oceanic crust and interaction with seawater, Late Devonian (Frasnian-Famennian) high- and medium-pressure metamorphism related to closure of a Saxothuringian ocean basin, Early Carboniferous (Viséan) thrusting of the Teplá terrane over Saxothuringian rocks and Late Viséan extension.     

The age of the Kagenfels granite (northern Vosges) and its bearing on the intrusion scheme of late Variscan granitoids

In the Saxothuringian part of the Vosges (France), a first series of Variscan plutonic rocks (diorites to granites) has been intruded by several younger granites. Rocks of both the older generations have been cross-cut by the late orogenic Kagenfels granite. The averages of the hitherto published mineral ages of the earlier rock generations are 331 and 334 Ma, respectively, whereas Rb-Sr and K-Ar dates around 290 Ma have been reported for the Kagenfels granite. Because of the unlikely large age hiatus, a redetermination of the intrusion age of the Kagenfels granite formation appeared to be irrevocable. The newly obtained mineral ages on the Kagenfels granite (K-Ar and ⁴⁰Ar/³⁹Ar biotite ages as well as single zircon radiogenic ²⁰⁷Pb/²⁰⁶Pb data: 331 ± 5 Ma) are about 40 Ma older than the previous results. They are interpreted as giving the time of emplacement of the Kagenfels granite during the latest Visan. The mineral ages of the earlier plutonic rocks in this part of the Variscan Orogeny in all probability are not significantly different from their ages of intrusion. Therefore the age concordance of all three granitoid generations constrains a rather narrow time interval of orogenic magmatism close to the Lower-Upper Carboniferous boundary.