Electron microprobe results of clay minerals from samples of the Frankenwald and the Thüringer Wald

Late Devonian (Frasnian) pillow basalts from the Frankenwald and Thüringer Wald within the Saxothuringian zone in Germany were found to contain abundant putative biogenic filaments, indicating that the volcanic rocks once harbored microbial life. The mineralized filaments are found in calcite-filled amygdules (former vesicles), where they started to form on internal surfaces of vesicles after seawater ingress. The filaments postdate an early fibrous carbonate cement but predate later equant calcite spar, revealing syngenetic formation. A biogenic origin of filaments is indicated by their size and morphology resembling modern microorganisms, their independence of crystal faces and cleavage plans, complex branching patterns, and internal segmentation. The filamentous microorganisms represent cryptoendoliths that lived in structural cavities of the basalt. They became preserved upon microbial clay authigenesis similar to the encrustation of modern prokaryotes in iron-rich environments. Filaments consist of clay minerals with the endmember composition berthierine-chamosite and illite-glauconite. Based on the discovery of fossilized filamentous microorganisms in Late Devonian pillow basalts of the Saxothurigian zone that are similar to filaments previously found in Middle Devonian pillow basalts of the Rhenohercynian zone, it is apparent that cryptoendolithic life was more widespread than previously recognized. Structural cavities within seafloor basalt may thus represent a common, perhaps universal niche for life in the oceanic crust.

Electron microprobe investigations of metamorphic reactions and mineral growth histories, Kwoiek area, British Columbia

The Kwoiek Area of British Columbia contains a pendant or screen of metamorphosed sedimentary and volcanic rocks almost entirely surrounded by a portion of the Coast Range Batholith, and intruded by several dozen stocks. The major metamorphic effects were produced by the quartz diorite batholithic rocks, with minor and later effects by the quartz diorite stocks. The sequence of important metamorphic reactions in the metasedimentary and metavolcanic rocks, ranging in grade from chlorite to sillimanite, is:

1. chlorite + carbonate + muscovite → epidote + biotite

2. chlorite + carbonate → actinolite + epidote

3. chlorite + muscovite → garnet + biotite

4. chlorite + epidote → garnet + hornblende

5. chlorite + muscovite → garnet + staurolite + biotite

6. chlorite + muscovite → aluminum silicate + biotite

7. muscovite + staurolite → garnet + aluminum silicate + biotite

8. staurolite → garnet + aluminum silicate

Continuous reactions, occurring between reactions 5 and 7, are:

A. chlorite + (high Ti) biotite + Al₂O₃ (from plagioclase?)→ garnet + staurolite + (low Ti) biotite + O₂

B. muscovite (phengitic) → garnet + staurolite +muscovite (less phengitic) + O₂ (?)

Detailed electron microprobe work on garnet, staurolite, biotite, and chlorite shows that:

(1) The garnet porphyroblasts are zoned according to a depletion model, called the Rayleigh depletion model, which assumes equilibrium between the edge of a growing garnet and the minerals which are unzoned, notably biotite, chlorite, and muscovite, but which assumes disequilibrium within the garnet.

(2) The staurolite porphyroblasts are also zoned, and from their zoning patterns reactions A, B, and 5 are documented. Progressive reduction of iron with increasing grade of metamorphism is also inferred from the staurolite zoning patterns.

(3) During a late period of falling temperature garnet continued to grow and the biotite and chlorite reequilibrated. The biotite, chlorite, and garnet edge compositions can vary from point to point in a given thin section, indicating that the volume of equilibrium at the final stage of metamorphism was only a few cubic microns.

(4) The horizon within the garnet that grew at maximum temperature can be identified. The Mg/Fe ratio of this horizon, if the garnet composition is a limiting composition in the Al₂O₃ - K₂O - FeO - MgO tetrahedron, increases systematically with increasing metamorphic grade. Biotite and chlorite compositions also show a general increase in Mg/Fe ratio with increasing metamorphic grade, but staurolite appears to show the reverse effect.

(5) The Mg/Fe ratio at the maximum temperature horizon of the garnet porphyroblasts is a function of its Mn content as evidenced from the study of five garnet-bearing rocks, collected from one outcrop area, with the same assemblage but with differing proportions of minerals.

An important implication of zoned minerals is that the effective composition of a system in a phase lies on the join between the homogeneous minerals (if there are two) and not within three-or- four-phase fields when a zoned mineral, such as garnet or staurolite, is present in the assemblage.

Study of the three aluminum silicates found in the Kwoiek Area showed that a constant pressure change in polymorphs from andalusite to kyanite to sillimanite took place with increasing temperature. This transition series is best explained by the metastable formation of andalusite.

Photographic materials on pages 15, 121, 160, 162, and 164 are essential and will not reproduce clearly on Xerox copies. Photographic copies should be ordered.

Pizgrischite, (Cu,Fe)Cu14PbBi17S35, a new sulfosalt from the Swiss Alps: Description, crystal structure and occurrence

Pizgrischite, (Cu,Fe)Cu14PbBi17S35, is a new mineral species named after the type locality, Piz Grisch Mountain, Val Ferrera, Graubunden, Switzerland. This sulfosalt occurs as thin, striated, metallic lead-grey blades measuring up to I cm in length, embedded in quartz and associated with tetrahedrite, chalcopyrite, pyrite, sphalerite, emplectite and derivatives of the aikinite-bismuthinite series. In plane-polarized light, the new species is brownish grey with no perceptible pleochroism; under crossed nicols in oil immersion, it presents a weak anisotropy with dark brown tints. Minimum and maximum reflectance values (in %) in air are: 40.7-42.15 (470 nm), 41.2-43.1 (546 nm), 41.2-43.35 (589 nm) and 40.7-43.3 (650 nm). Cleavage is perfect along 001 I and well developed on {010}. Abundant polysynthetic twinning is observed on (010). The mean micro-indentation hardness is 190 kg/mm(2) (Mohs hardness 3.3), and the calculated density is 6.58 g/cm(3). Electron-microprobe analyses yield (wt%; mean result of seven analyses): Cu 16.48, Pb 2.10, Fe 0.77, Bi 60.70, Sb 0.35, S 19.16, Se 0.04, total 99.60. The resulting empirical chemical formula is (Cu15.24Fe0.80Pb0.60)(Sigma 16.64)(Bi17.07Sb0.17)(Sigma 17.24)(S35.09Se0.03)(Sigma 35.12), in accordance with the formula derived from the single-crystal refinement of the structure, (Cu,Fe)Cu14PbBi17S35. Pizgrischite is monoclinic, space group C2/m, with the following unit-cell parameters: a 35.054(2), b3.91123(I), c43.192(2) angstrom, beta 96.713(4)degrees, V5881.24 angstrom(3), Z=4. The strongest seven X-ray powder-diffraction lines [d in angstrom (I)(hkl)] are: 5.364(40)((6) over bar 04), 4.080(50)((8) over bar 05), 3.120(40)(118), 3.104(68)((3) over bar 18), 2.759(53) ((9) over bar 11),2.752(44)(910) and 1.956(100)(020). The crystal structure is an expanded monoclinic derivative of kupcikite. Pizgrischite belongs to the cuprobismutite series of bismuth sulfosalts but, sensu stricto, it is not a homologue of cuprobismutite. At the type locality. pizarischite is the result of the Alpine metamorphism under greenschist-facies conditions of pre-Tertiary hydrothermal Cu-Bi mineralization.

Geochemistry and 40Ar/39Ar geochronology of pseudotachylyte associated with UHP whiteschists from the Dora Maira massif, Italy

In situ UV-Iaser ablation Ar-40/(39) Ar geochronological and geochemical data, together with rock and mineral compositional data, have been determined from pseudotachylyte and surrounding mylonitic gneiss associated with the UHP whiteschists of the Dora Maira Massif, Italy. Several generations of fresh pseudotachylyte occur as irregular veins up to a few cur thick both parallel and at high angles to the foliation. Whole rock XRF data collected from representative lithologies of mylonitic gneiss are uniformly consistent with a mildly alkalic granitic protolith. Minimal compositional variation is observed between the pseudotachylyte and its surrounding mylonitic gneiss. The pseudotachylyte contains newly crystallized grains of biotite and K-feldspar in a matrix of glass with partially fused grains of quartz, zircon, apatite, and titanite. Electron microprobe analyses of the glass show significant compositional variation that is probably strongly influenced by micrometer-scale changes in mineralogy. UV-Iaser ablation ICP-MS traverses across the mylonitic gneiss-pseudotachylyte contact are consistent with cataclastic communition of REE carriers such as epidote, monazite, allanite, zircon, and apatite before melting as an efficient mechanism of REE homogenization in the pseudotachylyte. The 40Ar/39Ar data from one band of pseudotachylyte indicate formation at 20.1 +/- 0.5 Ma, when the mylonitic gneisses were already in a near surface position. The variable effects of top-to-the-west shear deformation within outcrops of the coesite-bearing unit are reflected in localized zones of protomylonite, cataclasite, ultracataclasite, and pseudotachylyte. Preservation of several generations of pseudotachylyte suggests that seismic events may have played a significant role in triggering late unroofing of the UHP rocks. It is speculated that deeper crustal seismic events potentially played a role in the unroofing of the UHP rocks at earlier stages in their exhumation history. (c) 2005 Elsevier B.V. All rights reserved.

THE PYROCHLORE SUPERGROUP OF MINERALS: NOMENCLATURE

A new scheme of nomenclature for the pyrochlore supergroup, approved by the CNMNC-IMA, is based on the ions at the A, B and Y sites. What has been referred to until now as the pyrochlore group should be referred to as the pyrochlore supergroup, and the subgroups should be changed to groups. Five groups are recommended, based on the atomic proportions of the B atoms Nb, Ta, Sb, Ti, and W. The recommended groups are pyrochlore, microlite, romite, betafite, and elsmoreite, respectively. The new names are composed of two prefixes and one root name (identical to the name of the group). The first prefix refers to the dominant anion (or cation) of the dominant valence [or H(2)O or rectangle] at the Y site. The second prefix refers to the dominant cation of the dominant valence [or H(2)O or rectangle] at the A site. The prefix "" keno-"" represents "" vacancy"". Where the first and second prefixes are equal, then only one prefix is applied. Complete descriptions are missing for the majority of the pyrochlore-supergroup species. Only seven names refer to valid species on the grounds of their complete descriptions: oxycalciopyrochlore, hydropyrochlore, hydroxykenomicrolite, oxystannomicrolite, oxystibiomicrolite, hydroxycalcioromite, and hydrokenoelsmoreite. Fluornatromicrolite is an IMA-approved mineral, but the complete description has not yet been published. The following 20 names refer to minerals that need to be completely described in order to be approved as valid species: hydroxycalciopyrochlore, fluornatropyrochlore, fluorcalciopyrochlore, fluorstrontiopyrochlore, fluorkenopyrochlore, oxynatropyrochlore, oxyplumbopyrochlore, oxyyttropyrochlore-(Y), kenoplumbopyrochlore, fluorcalciomicrolite, oxycalciomicrolite, kenoplumbomicrolite, hydromicrolite, hydrokenomicrolite, oxycalciobetafite, oxyuranobetafite, fluornatroromite, fluorcalcioromte, oxycalcioromite, and oxyplumboromite. For these, there are only chemical or crystalstructure data. Type specimens need to be defined. Potential candidates for several other species exist, but are not sufficiently well characterized to grant them any official status. Ancient chemical data refer to wet-chemical analyses and commonly represent a mixture of minerals. These data were not used here. All data used represent results of electron-microprobe analyses or were obtained by crystal-structure refinement. We also verified the scarcity of crystal-chemical data in the literature. There are crystalstructure determinations published for only nine pyrochlore-supergroup minerals: hydropyrochlore, hydroxykenomicrolite, hydroxycalcioromite, hydrokenoelsmoreite, hydroxycalciopyrochlore, fluorcalciopyrochlore, kenoplumbomicrolite, oxycalciobetafite, and fluornatroromite. The following mineral names are now discarded: alumotungstite, bariomicrolite, bariopyrochlore, bindheimite, bismutomicrolite, bismutopyrochlore, bismutostibiconite, calciobetafite, ceriopyrochlore-(Ce), cesstibtantite, ferritungstite, jixianite, kalipyrochlore, monimolite, natrobistantite, partzite, plumbobetafite, plumbomicrolite, plumbopyrochlore, stannomicrolite, stetefeldtite, stibiconite, stibiobetafite, stibiomicrolite, strontiopyrochlore, uranmicrolite, uranpyrochlore, yttrobetafite-(Y), and yttropyrochlore-(Y).

Petrology and geochronology of "muscovite age standard" B4M

Muscovite B4M, distributed in 1961 as an age standard, was ground under ethanol. Five grain size fractions were obtained and characterized by X-ray diffraction. They display a mixing trend between a phengitic (enriched in the fraction <0.2 µm) and a muscovitic component (predominant in the fraction >20 µm). High-pressure phengite is preserved as a relict in retrograde muscovite. Electron microprobe analyses of the distributed mineral separate reveal at least four white mica populations based on Si, Al, Mg, Na, Fe and F. Rb/K ratios vary by one order of magnitude. Rb–Sr analyses link the mineralogical heterogeneity to variable Rb/Sr and 87Sr/86Sr ratios. The grain size fractions define no internal isochron. Relict fine-grained phengite gives older ages than coarse-grained retrograde greenschist facies muscovite. The inverse grain size–age relationship also characterizes 39Ar/40Ar analyses. Cl/K anticorrelates with step ages: Cl-rich coarse muscovite is younger than Cl-poor fine relict phengite. Sr and Ar preserve a similar isotopic inheritance despite peak metamorphism reaching 635±20 °C. A suitable mineral standard requires that its petrological equilibrium first be demonstrated. Relicts and retrograde reaction textures are a guarantee of isotopic disequilibrium and heterogeneous ages within single crystal at the micrometre scale.

Holtite and Dumortierite from the Szklary Pegmatite, Lower Silesia, Poland

The Szklary holtite is represented by three compositional varieties: (I) Ta-bearing (up to 14.66 wt.% Ta(2)O(5)), which forms homogeneous crystals and cores within zoned crystals; (2) Ti-bearing (up to 3.82 wt.% TiO(2)), found as small domains within the core; and (3) Nb-bearing (up to 5.30 wt.% Nb(2)O(5),) forming the rims of zoned crystals. All three varieties show variable Sb+As content, reaching 19.18 wt.% Sb(2)O(3) (0.87 Sb a.p.f.u.) and 3.30 wt.% As(2)O(3) (0.22 As a.p.f.u.) in zoned Ta-bearing holtite, which constitutes the largest Sb+As content reported for the mineral. The zoning in holtite is a result of Ta-Nb fractionation in the parental pegmatite-forming melt together with contamination of the relatively thin Szklary dyke by Fe, Mg and Ti. Holtite and the As- and Sb-bearing dumortierite, which in places overgrows the youngest Nb-bearing zone, suggest the following crystallization sequence: Ta-bearing holtite -> Ti-bearing holtite -> Nb-bearing holtite -> As- and Sb-bearing, (Ta,Nb,Ti)-poor dumortierite -> As- and Sb-dominant, (Ta,Nb,Ti)-free dumortierite-like mineral (16.81 wt.% As(2)O(3) and 10.23 wt.% Sb(2)O(3)) with (As+Sb) > Si. The last phase is potentially a new mineral species, Al(6)rectangle B(Sb,As)(3)O(15). or Al(5)rectangle(2)B(Sb,As)(3)O(12)(OH)(3), belonging to the dumortierite group. The Szklary holtite shows no evidence of clustering of compositions around 'holtite I' and 'holtite II'. Instead, the substitutions of Si(4+) by Sb(3+)+As(3+) at the Si/Sb sites and of Ta(5+) by Nb(5+) or Ti(4+) at the Al(l) site suggest possible solid solutions between: (1) (Sb,As)-poor and (Sb,As)-rich holtite; (2) dumortierite and the unnamed (As+Sb)-dominant dumortierite-like mineral; and (3) Ti-bearing dumortierite and holtite, i.e. our data provide further evidence for miscibility between holtite and dumortierite, but leave open the question of defining the distinction between them. The Szklary holtite crystallized from the melt along with other primary Ta-Nb-(Ti) minerals such as columbite-(Mn), tantalite-(Mn), stibiotantalite and stibiocolumbite as the availability of Ta decreased. The origin of the parental melt can be related to anatexis in the adjacent Sowie Mountains complex, leading to widespread migmatization and metamorphic segregation in pelitic-psammitic sediments metamorphosed at similar to 390-380 Ma.

The triplite–triploidite supergroup: structural modulation in wagnerite, discreditation of magniotriplite, and the new mineral hydroxylwagnerite

Electron-microprobe analysis, single-crystal X-ray diffraction with an area detector, and high-resolution transmission electron microscopy show that minerals related to wagnerite, triplite and triploidite, which are monoclinic Mg, Fe and Mn phosphates with the formula Me2+ 2PO4(F,OH), constitute a modulated series based on the average triplite structure. Modulation occurs along b and may be commensurate with (2b periodicity) or incommensurate but generally close to integer values (∼3b, ∼5b, ∼7b, ∼9b), i.e. close to polytypic behaviour. As a result, the Mg- and F-dominant minerals magniotriplite and wagnerite can no longer be considered polymorphs of Mg2PO4F, i.e., there is no basis for recognizing them as distinct species. Given that wagnerite has priority (1821 vs. 1951), the name magniotriplite should be discarded in favour of wagnerite. Hydroxylwagnerite, end-member Mg2PO4OH, occurs in pyrope megablasts along with talc, clinochlore, kyanite, rutile and secondary apatite in two samples from lenses of pyrope–kyanite–phengite–quartz-schist within metagranite in the coesite-bearing ultrahigh-pressure metamorphic unit of the Dora-Maira Massif, western Alps, Vallone di Gilba, Val Varaita, Piemonte, Italy. Electron microprobe analyses of holotype hydroxylwagnerite and of the crystal with the lowest F content gave in wt%: P2O5 44.14, 43.99; SiO2 0.28, 0.02; SO3 –, 0.01; TiO2 0.20, 0.16; Al2O3 0.06, 0.03; MgO 48.82, 49.12; FeO 0.33, 0.48; MnO 0.01, 0.02; CaO 0.12, 0.10; Na2O 0.01, –; F 5.58, 4.67; H2O (calc) 2.94, 3.36; –O = F 2.35, 1.97; Sum 100.14, 99.98, corresponding to (Mg1.954Fe0.007Ca0.003Ti0.004Al0.002Na0.001)Σ=1.971(P1.003Si0.008)Σ=1.011O4(OH0.526F0.474)Σ=1 and (Mg1.971Fe0.011Ca0.003Ti0.003Al0.001)Σ=1.989(P1.002Si0.001)Σ=1.003O4(OH0.603F0.397)Σ=1, respectively. Due to the paucity of material, H2O could not be measured, so OH was calculated from the deficit in F assuming stoichiometry, i.e., by assuming F + OH = 1 per formula unit. Holotype hydroxylwagnerite is optically biaxial (+), α 1.584(1), β 1.586(1), γ 1.587(1) (589 nm); 2V Z(meas.) = 43(2)°; orientation Y = b. Single-crystal X-ray diffraction gives monoclinic symmetry, space group P21/c, a = 9.646(3) Å, b = 12.7314(16) Å, c = 11.980(4) Å, β = 108.38(4) , V = 1396.2(8) Å3, Z = 16, i.e., hydroxylwagnerite is the OH-dominant analogue of wagnerite [β-Mg2PO4(OH)] and a high-pressure polymorph of althausite, holtedahlite, and α- and ε-Mg2PO4(OH). We suggest that the group of minerals related to wagnerite, triplite and triploidite constitutes a triplite–triploidite super-group that can be divided into F-dominant phosphates (triplite group), OH-dominant phosphates (triploidite group), O-dominant phosphates (staněkite group) and an OH-dominant arsenate (sarkinite). The distinction among the three groups and a potential fourth group is based only on chemical features, i.e., occupancy of anion or cation sites. The structures of these minerals are all based on the average triplite structure, with a modulation controlled by the ratio of Mg, Fe2+, Fe3+ and Mn2+ ionic radii to (O,OH,F) ionic radii.

Magnetic mineralogy and geochemistry of ODP Holes 137-504B and 140-504B samples

Leg 140 of the Ocean Drilling Program deepened Hole 504B to a total depth of 2000.4 m below seafloor (mbsf), making it the deepest hole drilled into ocean crust. Site 504, south of the Costa Rica Rift, is considered the most important in-situ reference section for the structure of shallow ocean crust. We present the results of studies of magnetic mineralogy and magnetic properties of Hole 504B upper crustal rocks recovered during Legs 137 and 140. Results from this sample set are consistent with those discussed in Pariso et al. (this volume) from Legs 111, 137, and 140. Coercivity (Hc) ranges from 5.3 to 27.7 mT (mean 12 mT), coercivity of remanence (HCR) ranges from 13.3 to 50.6 mT (mean 26 mT), and the ratio HCR/HC ranges from 1.6 to 3.19 (mean 2.13). Saturation magnetization (JS) ranges from 0.03 to 5.94 * 10**-6 Am**2, (mean 2.52 * 10**-6 Am**2), saturation remanence (JR) ranges from 0.01 to 0.58 * 10**-6 Am2 (mean 0.37 * 10**-6 Am**2), and the ratio JR/JS ranges from 0.08 to 0.29 (mean 0.16), consistent with pseudo-single-domain behavior. Natural remanent magnetization (NRM) intensity ranges from 0.029 to 7.18 A/m (mean 2.95 A/m), whereas RM10 intensity varies only from 0.006 to 4.8 A/m and has a mean of only 1.02 A/m. Anhysteretic remanent magnetization (ARM) intensity ranges from 0.04 to 6.0 A/m, with a mean of 2.46 A/m, and isothermal remanent magnetization (IRM) intensity ranges from 0.5 to 1683 A/m, with a mean of 430.7 A/m. Volume susceptibility ranges from 0.0003 to 0.043 SI (mean 0.011 SI). In all samples examined, high-temperature oxidation of primary titanomagnetite has produced lamellae or pods of magnetite and ilmenite. Hydrothermal alteration has further altered the minerals in some samples to a mixture of magnetite, ilmenite, titanite, and a high-titanium mineral (either rutile or anatase). Electron microprobe analyses show that magnetite lamellae are enriched in the trivalent oxides Cr2O3, Al2O3, and V2O5, whereas divalent oxides (MnO and MgO) are concentrated in ilmenite lamellae.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Mineral chemistry of basalts from DSDP Holes 65-483 and 65-483B

During DSDP Leg 65, a series of holes was drilled into the oceanic basement across the mouth of the Gulf of California to study the composition of the crust and the nature of its construction at a young spreading center. In Holes 483 and 483B, two of the deepest basement holes drilled on this leg, the basement is characterized by an upper sequence of interlayered massive basalts and sediments underlain by a lower sequence of interlayered pillow and massive basalts. Electron microprobe analyses were performed on pyroxene, plagioclase, olivine, spinel, and glass from 14 representative samples of 10 of the 16 major lithologic units. These analyses along with petrographic results can be used to interpret the detailed crystallization history of the basalts. We believe from the results of this study that the basalts were formed by at least a three-stage cooling process, followed by eruption and formation of quench phases. Our data do not support magma mixing.