Stability Relations of the Ferruginous Biotite, Annite

Annite, KFe₃AISi₃O₁₀(OH)₂ a member of the iron biotites andthe ferrous analogue of phlogopite, has been synthesized andits phase relations have been determined as functions of temperature,fugacity of oxygen (fo₂), and total pressure (P_totalPH₂O+PH₂).A method for controlling fo₂at high total pressures is described,and data for the ‘oxygen buffers’ used are given.Buffers range from quartz+iron+fayalite assemblages (low fo₂)to magnetite-hematite assemblages (high fo₂). Optical propertiesand unit-cell dimensions of synthetic annites depend on theconditions of synthesis. By recalculating published analyses of natural iron-rich biotitesit can be shown that one cannot assume a constant hydrogen contentfor such biotites. Oxidation may have occurred by drying at115?C. Octahedral occupancy therefore cannot be calculated fromsuch data. Phase relations of annite are presented in 2,070 and 1,035 barsections. Depending on fo₂-T values annite was found to decomposeto one of the following assemblages: hematite+ sanidine, magnetite+sanidine,fayalite+leucite+kalsilite, iron+sanidine. All decompositionsare dehydration and redox reactions and are sensitive to changesin fH₂0 and fo₂ (or fH₂0 and fH₂). At 2, 070 bars total pressureannite+magnetite+sanidine can coexist between 425?C and 825?C, depending upon the magnitude of fo₂. In the presence of quartz the stability field of annite is morerestricted. Phase equilibria in the system KAlSiO₄–SiO₂–Fe–O₂–H₂have been summarized schematically. Wherever possible, thermodynamic extrapolations are made totest the internal consistency of the data. Enthalpies of formationare calculated for both annite and phlogopite. Ranges of fo₂values in nature as well as mechanisms for changes in fo₂ areinvestigated. It is useful to distinguish between assemblageswhich are internally buffered with respect to fo₂changes andthose which are not buffered. The applications of individualreactions involving annite to specific geologic problems arediscussed with respect to igneous, metamorphic, and sedimentaryrocks.     

Oxidation During Magmatic Differentiation, Finnmarka Complex, Oslo Area, Norway: Part 2, The Mafic Silicates1

Electron-microprobe analyses are presented for pyroxene, amphibole,and biotite from monzonite, granodiorite, and granite at Finnmarka,Norway. Compositional trends measured in biotite, present inall three rock types, and in amphibole, present in the monzoniteand granodiorite, are markedly atypical and are interpretedas reflecting crystallization under progressively more oxidizingconditions. The average Fe/Fe + Mg for biotites from successivelymore silicic rock types changes from 0.64 0.35 0.28, and foramphiboles changes from 0.58 in the monzonite to 0.29 in thegranodiorite. Analyses of selected areas within amphibole grains in the granodioriteshow marked chemical variations, although single-crystal X-rayphotographs are sharp and do not reveal multiple phases. Onthe basis of 33 such analyses, four coupled substitutions areidentified as operative; the most unusual finding is the relationof 1 Ti cation to 4 Al^IV cations in the unit cell. Variationswithin individual amphibole grains of the granodiorite resemblechanges noted in evolution of amphibole composition from monzoniteto granodiorite and are interpreted as reflecting progressiveoxidation. Consideration of these data for the mafic silicates, data forthe opaque oxides, and the extensive formation of sphene inthe granodiorite, has allowed development of schematic reactionsand an overall picture of magmatic environment and evolutionat Finnmarka. Crystallization apparently took place at PH₂oof 1000 bars or less and a temperature of about 700 °C.The trend of oxidation during differentiation is more extremethan any heretofore reported. Amphiboles, as well as biotites,may participate in oxidation reactions and may reflect the oxidation-reductionprocesses that occurred during magmatic evolution.     

Jurassic aeolian oolite on a palaeohigh in the Sundance Sea, Bighorn Basin, Wyoming

Aeolian limestones are widespread in the Quaternary record and have been identified in outcrops and cores of late Palaeozoic strata. These rocks have been interpreted as a low latitude signal of glacio-eustatic sea level fluctuations and have not been previously reported from the Mesozoic or from other episodes of earth history generally believed to have been non-glacial. Numerous lenticular bodies of cross-stratified oolite lie near the contact between the lower and upper members of the mudstone-dominated lower Sundance Formation (Middle and Upper Jurassic) in the Bighorn Basin of north-central Wyoming, USA. The lenses, up to 12 m thick, contain sedimentary structures diagnostic of aeolian deposition. Inversely graded laminae within thick sets of cross-strata were deposited by climbing wind ripples. Adhesion structures and evenly dispersed lag granules are present in flat-bedded strata at the bases of several of the oolite bodies. Thin sections reveal abundant intergranular micrite of vadose origin. The lenses appear to represent virtually intact, isolated aeolian bedforms that migrated across a nearly sand-free deflation surface. When the Sundance Sea transgressed the dunes, a thin (<1 m thick), wave-rippled, oolite veneer formed on the upper surface of the aeolianite. Previous workers, primarily on the basis of sedimentary structures in the veneer, interpreted the oolite lenses as tidal sand bodies. The dunes provide clear evidence of widespread subaerial exposure on the crest and north flank of the Sheridan Arch. This structural high was delineated by previous workers who demonstrated thinning of pre-upper-Sundance Formation strata and localized development of ooid shoals. Ooids that formed in shoals on the windward (southern) side of the palaeohigh were exposed and deflated during lowstand. Thin, scour-filling ooid grainstone lenses that crop out in the southern part of the study area represent remnants of the marine beds that sourced the aeolianites. Farther north (down-wind), oolitic dunes prograded over thinly laminated lagoonal silts. When relative sea level began to rise, the uncemented dunes were buried under fine-grained marine sediment as the lee side of a low-relief island was inundated.     

Environmental change during the Allerød and Younger Dryas reconstructed from Swiss tree-ring data

Annually resolved tree-ring width variations and radiocarbon ages were measured from a collection of 120 Lateglacial pine stumps excavated on the Swiss Plateau. These data – representing the oldest absolutely dated wood samples worldwide – extend the absolute tree-ring chronology from Central Europe by 183 years back to 12 593 cal. yr BP (10 644 cal. yr BC). They also yield a 1420-year floating chronology covering the entire Allerød and the early Younger Dryas (14 170–12 750 cal. yr BP). Radiocarbon data suggest a 250-year jump in the ¹⁴C reservoir correction around the time of the Allerød to Younger Dryas transition, although calendric dating of the floating chronology – by filling a ∼150 year gap – is necessary for confirmation. Various subgroups, based on the year of germination, were used to assess temporal changes in growth characteristics along the Allerød to Younger Dryas transition. Comparison of these Lateglacial data with a reference data set of living and historic pines from the Swiss Valais (AD 940–2000) revealed differences in both growth trend and level. The generally slower Lateglacial growth was likely influenced by higher geomorphic activity and severe climatic conditions. After removal of the biological age-trend, a strong common signal found in the tree-ring data suggests some skill in estimating interannual to multidecadal Lateglacial climatic variations.     

A reconstruction of Holocene climatic changes from peat bogs in north-west Scotland

Continuous palaeoenvironmental sequences from three peat bogs located in north-west Scotland are presented which reveal palaeoclimatic changes during the Holocene, Peat cores were analysed lor humification. pollen and a range of other physical and palaeoecological data, and chronologies were constructed by radiocarbon dating. Reconstruction of past changes in bog hydrology formed the basis for palaeoclimatic interpretation. Four regional shifts to wetter bog conditions and two regional shifts to drier conditions are inferred. Best estimated aye ranges for the wet shifts span c . 5120 to 5070, 4020 to 3630, 3340 to 3270 and 940 to 800 cal BP, arid dry shifts are estimated at c . 4330 to 4120 and 1480 to 1340 cal BP. The most distinctive feature of the record is the oscillation from wetter to drier conditions around 4300 cal BP, followed by a return to wetter conditions after 4000 cal BP. This oscillation was probably caused by climatic changes which also had an inHuence on the dynamics of Scots pine within the region prior to, and during, its mid-Holocene phase of decline. Later shifts probably also reflect climatic changes, although evidence for human land-use complicates interpretation at c . 3300 cal BP. Potential causes are considered, including changes in the circulation of the North Atlantic Ocean during the mid-Holocene.     

Pb-Pb single-zircon ages of granitoid boulders from the Vendian tillite of Wahlenbergfjorden, Nordaustlandet, Svalbard

There are three areas in eastern Svalbard where Vendian tillites are exposed: eastern Ny Friesland, western Nordaustlandet (north and south of Murchisonfjorden) and further east in inner Wahlenbergfjorden, near Aldousbreen. Clasts within the massive unmetamorphosed clay-mica-carbonate matrix of the tillites include carbonates, sandstones, siltstones, metavolcanics, schists and different granitoids, the metamorphic and igneous rock types being more frequent in the upper levels of the formation. Large granite boulders, up to 1 m in diameter, are known from the easternmost outcrop at Aldousbreen. Three granitoid boulders from the Aldousbreen outcrop, differing in petrography and chemistry. have been dated by the Pb-Pb singlezircon method. They yield ages of 2830 ± 5 Ma, 1802 ± 4 Ma and 1497 ± 26 Ma. These clasts also differ in petrography, chemistry and age from all known granitic rocks on Nordaustlandet, which have recently yielded Grenvillian (950-960 Ma) and Caledonian (ca. 410 Ma) ages. The concentration of large granitic clasts in the easternmost known tillite outcrops suggests derivation from the east and/or south. Possible areas include those beneath the ice of Austfonna and below the Carboniferous strata of southeastem Nordaustlandet. The apparent lack of a significant Grenvillian overprint suggests the possibility of a more distant source.     

Petrology of Submarine Lavas from Kilauea's Puna Ridge, Hawaii

We have studied 30 quenched tholeiitic lava flows recoveredby 20 dredge hauls and one submersible dive along Puna Ridge,the submarine part of the East Rift Zone of Kilauea Volcano,Hawaii Glass grains from numerous additional flows were recoveredin turbidite sands cored in the Hawaiian Trough. These quenchedlavas document variable primary magma compositions; olivineand multiphase crystallization and fractionation; degassing;wall-rock stoping and assimilation; mixing in the crustal reservoirand the rift zone; entrainment of olivine xenocrysts from ahot, ductile, olivine cumulate body; and disruption of gabbrowallrocks in the rift zone. Glass grains in turbidite sands contain up to 15•0wt% MgO,in contrast to < 7•0wt% MgO for the sampled glass rindson lavas. The most forsteritic olivine phenocryst (F0₉₀₇) isin equilibrium with primary Kilauea liquid containing an average16•5 wt% MgO, but ranging from 13•4 to 18•4%.Lavas and glass grains have more restricted P₂O₅/K₂O and TiO₂/K₂Othan glass inclusions in olivine, because more diverse liquidstrapped as glass inclusions are mixed and homogenized beforeeruption. Variable trace element compositions in glass grainsand whole rocks indicate that the primary liquids form by partialmelting of mantle sources retaining clinopyroxene and garnet. Orthopyroxene xenocrysts formed at moderate pressures provideevidence for a sub-crustal staging zone. Chromite and olivinecrystallize in the crustal magma reservoir as the liquid coolsfrom an average 1346C to 1170C. Low viscosities of the primaryliquids (04 Pas) facilitate olivine settling, and the crystallizedolivine forms an olivine cumulate body at the base of the reservoir.Olivine is deformed as the hot ductile dunite body flows downand away from the summit. This flow drives instability of theHilina landslide on Kilauea. Dikes intrude the dunite, and magmaflowing through the dikes disaggregates and entrains olivinexenocrysts in Puna Ridge magmas. Primary liquids pond at or near the base of Kilauea's crustalreservoir because they are denser than more fractionated liquidsthat occupy the upper parts of the reservoir. The sulfur andwater contents of glass rinds indicate that fractionated liquidsnear the top of the reservoir degas at low pressure, a processthat increases their density and causes them to sink to levelswhere they mix with resident undegassed, near-primary liquid.The fractionated liquids near the top of the magma reservoiracquire excess Cl, owing to assimilation of hydrothermally alteredroofrocks. Magma flowing into the rift zone encounters and mixes with low-temperature,multiphase-fractionated melt. The mixed magmas typically containrare orthopyroxene, plagioclase as sodic as andesine, olivineas fayalitic as F0₇₅ and Fe-rich augite derived from the fractionatedmagma. Magma flowing through dikes also dislodged fragmentsof gabbroic wallrocks that occur as xenoliths. The interrelations in the Kilauean submarine lavas between hostglass and glass inclusion compositions, volatile contents andmineral chemistry reveal an extraordinarily complex sequenceof petrogenetic processes and events that are difficult or impossibleto determine in subaerial Kilauea lavas because of crystallization,reequilibration and degassing during or after their eruption. KEY WORDS: submarine lavas; petrology; Kilauea; Hawaii; magma mixing ^*Corresponding authorPresent address: Rosentiel School of Marine and Atmospheric Science, Division of Marine Geology and Geophysics, University of Miami, 4600 Rickenbacker Causeway, Miami, FL 33149-1098, USA