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.

Sand geochemistry on sediment core CRP-3 from the Ross Sea, Antarctica

A total of 167 samples distubuted throughout the CRP-3 drillhole from 5.77 to 787.68 mbsf and representing fine to coarse sandstones have been analysed by X-ray fluorescence spectrometry (XRF) Bulk sample geochemistry (major and trace elements) indicates a dominant provenance of detritus from the Ferrar Supergroup in the uppermost 200 mbsf of the core. A markedly increased contribution from the Beacon sandstones is recognized below 200 mbsf and down to 600 mbsf. In the lower part of CRP-3, down to 787.68 mbsf, geochemical evidence for influxes of Ferrar materials is again recorded. On the basis of preliminary magnetostratigraphic data reported for the lower 447 mbsf of the drillhole, we tentatively evaluated the main periodicities modulating the geochemical records. Our results identify a possible influence of the precession, obliquity and long-eccentricity astronomical components (21, 41, and 400 ky frequency bands) on the deposition mechanisms of the studied glaciomarine sediments.

Geochemical investigations of elements in sediment core CRP-1 from the Ross Sea, Antarctica

Geochemical data are presented for samples from strata, mainly of Miocene age, in the Cape Roberts-1 core (western McMurdo Sound, Antarctica) to assess the sediment provenance. Bulk (major and trace element) chemistry together with bulk mineralogy of fine-grained sandstones, siltstones, mudstones, and diamictites indicate that chemical alteration of source materials, fractionation due to sedimentary sorting, and diagenetic effects were not significant in the Cape Roberts sediment history. Relevant geochemical parameters are consistent with the Cape Roberts sediments being derived mainly from the crystalline basement and the Beacon Supergroup. On the basis of element distributions, an additional contribution from the Ferrar Dolerite and, mainly above about 60 m, influxes of detritus derived from basanitic to intermediate members of the McMurdo Volcanic Group are recognised.

Petrology and geochemistry at DSDP Site 89-462

The 16 samples of Deep Sea Drilling Project (DSDP) Leg 89 basalts that we analyzed for whole rock major and trace elements and for mineralogic compositions are identical to some of the basalts recovered during Leg 61. Leg 89 samples are mostly olivine-plagioclase-clinopyroxene sparsely phyric basalts and exhibit a wide variety of textures. These basalts have lower TiO2 at a given Mg/(Mg+Fe2+)*100 than MORB (midocean ridge basalt). We recognize three major chemical types of basalts in the Nauru Basin. We believe that different degrees of partial melting, modified by fractional crystallization and possibly by magma mixing at shallow depths, can explain the chemical differences among the three groups. This petrogenetic model is consistent with the observed downhole chemical-chronostratigraphic relations of the samples. New 87Sr/86Sr and U3Nd/144Nd analyses of basalt samples from DSDP Site 462 indicate that the Nauru Basin igneous complex is within the Sr-Nd isotopic range of ocean island basalt. Thus the Nauru Basin igneous complex resembles MORB in many aspects of its chemistry, morphology, and secondary alteration patterns (Larson, Schlanger, et al., 1981), but not in its isotopic characteristics. If it were not for the unambiguous evidence that the Nauru Basin complex was erupted off-ridge, the complex could easily be interpreted as normal oceanic layer 2. For this reason, we speculate that the Nauru Basin igneous complex was produced in an oceanic riftlike environment when multiple, fast-propagating rifts were formed during the fast seafloor spreading episode in the Cretaceous.

Composition of sedimentary material from the bottom and the area surrounding the Lake Untersee, East Antarctica

This paper presents data on geographic and geologic conditions of modern sedimentation in the Lake Untersee, the largest lake in the East Antarctica. Geochemical and sedimentation data indicate that the leading mechanism supplying aluminosilicate sedimentary material to the surface layer of bottom sediments is seasonal melting of the Anuchin glacier and the mountain glacier on the southeastern part of the valley hosting the lake. Strongly reduced conditions in the lowermost 25 m of the water column in the smaller of two depressions of the lake bottom were favorable for enrichment of the bottom sediments in bacteriogenic organic matter, Mo, Au, and Pd. H2S-contaminated water results to significant enrichment of the sediments only in redox-sensitive elements that are able to migrate in anionic complexes and precipitate (co-precipitate) as sulfides.

Geochemistry of Cretaceous sills and lava flows of ODP Holes 129-800A and 129-802A

On the basis of their respective eruptive environments and chemical characteristics, alkalic dolerite sills from the northern Pigafetta Basin (Site 800) and tholeiitic pillow lavas from the Mariana Basin (Site 802) sampled during Ocean Drilling Program Leg 129 are considered to represent examples of the widespread mid-Cretaceous volcanic event in the western Pacific. Both groups of basic rocks feature mild, low-grade, anoxic smectite-celadonite-carbonate-pyrite alteration; late-stage oxidation is very limited in extent, with the exception of the uppermost sill unit at Site 800. The aphyric and nonvesicular Site 800 alkalic dolerite sills are all well-evolved mineralogically and chemically, being mainly of hawaiite composition, and are similar to ocean island basalts. They are characterized by high contents of incompatible elements (for example, 300-400 ppm Zr), well-fractionated rare earth element patterns ([La/Yb]N 18-21) and HIMU isotopic characters. They probably represent deep-sea, lateral, intrusive off-shoots from nearby seamounts of similar age. The olivine-plagioclase +/- clinopyroxene phyric tholeiitic pillow lavas and thin flows of Site 802 are nonvesicular and quench-textured throughout. Relative to normal-type mid-ocean ridge basalt, they are enriched in large-ion-lithophile elements, exhibit flat (unfractionated) rare earth element patterns and have distinctive (lower) Zr/Nb, Zr/Ta, La/Ta, and Hf/Th ratios. Overall they are compositionally and isotopically similar to the mid-Cretaceous tholeiites of the Nauru basin and the Ontong-Java and Manihiki plateaus. The Site 802 tholeiites differ from the thickened crustal segments of the oceanic plateaus, however, in apparently representing only a thin veneer over the local basement in an off-axis environment.

Geochemistry and mineralogy at DSDP Holes 61-462, 61-462A and 33-315A

Sedimentary rocks of Barremian through early Maestrichtian age recovered on Deep Sea Drilling Project Leg 61 had their principal source in the complex of igneous rocks with which they are interlayered in the Nauru Basin. Relict textures and primary sedimentary structures show these Cretaceous sediments to be of hyaloclastic origin, in part reworked and redeposited by slumps and currents. The dominant composition now is smectite, but locally iron, titanium, and manganese oxides, plagioclase, pyroxene, analcime, clinoptilolite, chalcedonic quartz, cristobalite, amphibole, nontronite, celadonite, and pyrite are also present. The mineral assemblages and the geochemistry reflect the original basaltic composition and its subsequent alteration by one or more processes of submarine weathering, authigenesis, hydrothermal circulation, and contact metamorphism. Hyaloclastitic sandstone, siltstone, and breccia within the sheet flows below 729 meters sub-bottom depth have Barremian fossils, thus establishing the age of the lower, or extrusive, complex of post-ridge-crest volcanism. Similar hyaloclastites between 564 and 729 meters are invaded by hypabyssal sills of the upper igneous complex, and fossil ages of Albian or Cenomanian set an older limit to the age of that second post-ridge-crest episode. Cenomanian to early Campanian sedimentary rocks between 490 and 564 meters have a substantial contribution of clays of submarine-weathered-basalt origin, as well as hydrothermal and pelagic components. The interval of reworked hyaloclastitic siltstone, sandstone, and breccias between 450 and 490 meters is of late Campanian and early Maestrichtian age. These sediments probably formed from glassy basalt that fragmented upon eruption nearby, when sills were being emplaced. In addition to pelagic elements, these Upper Cretaceous volcanogenic sediments include redeposited material of shallow-water origin, apparently derived from the Marshall Islands.

Geochemistry and oxygen and iron isotope ratios of mafic rocks

Recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes. The oxygen isotope ratios (d18O) of some ocean island basalts (OIB) span values both above and below that of unmetasomatised upper mantle (5.5 ± 0.4 per mil) and provide support for this hypothesis, as it is widely assumed that most variations in d18O are produced by near-surface low-temperature processes. Here we show a significant linear relationship between d18O and stable iron isotope ratios (d57Fe) in a suite of pristine eclogite xenoliths. The d18O values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values. The observed range and correlation between d18O and d57Fe is unlikely to be inherited from oceanic crust, as d57Fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with d18O. It is proposed that the correlated d57Fe and d18O variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out. Fractionation of Fe and O isotopes by removal of partial melt enriched in isotopically heavy Fe and O is supported by negative correlations between bulk sample d57Fe and Cr content and bulk sample and garnet d18O and Sc contents, as Cr and Sc are elements that become enriched in garnet- and pyroxene-bearing melt residues. Melt extraction could take place either during subduction, where the eclogites represent the residues of melted oceanic lithosphere, or could take place during long-term residence within the lithospheric mantle, in which case the protoliths of the eclogites could be of either crustal or mantle origin. This modification of both d57Fe and d18O by melting processes and specifically the production of low-d18O signatures in mafic rocks implies that some of the isotopically light d18O values observed in OIB and eclogite xenoliths may not necessarily reflect near-surface processes or components.

Geochemistry of ODP Leg 135 vitrophyric rhyolite samples

In-situ proton-microprobe analyses are presented for glasses, plagioclases, pyroxenes, olivines, and spinels in eleven samples from Sites 834-836, 839, and 841 (vitrophyric rhyolite), plus a Tongan dacite. Elements analyzed are Mn, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Pb, and Sn (in spinels only). The data are used to calculate two sets of partition coefficients, one set based on the ratio of element in mineral/element in coexisting glass. The second set of coefficients, thought to be more robust, is corrected by application of the Rayleigh fractionation equations, which requires additional use of modal data. Data are presented for phenocryst core-rim phases and microphenocryst-groundmass phases from a few samples. Comparison with published coefficients reveals an overall consistency with those presented here, but with some notable anomalies. Examples are relatively high Zr values for pyroxenes and abnormally low Mn values in olivines and clinopyroxenes from Site 839 lavas. Some anomalies may reflect kinetic effects, but interpretation of the coefficients is complicated, especially in olivines from Sites 836 and 839, by possible crystal-liquid disequilibrium resulting from mixing processes.

Chronostratigraphic framework at sites GeoB14403 and GeoB14414 from the Gela Basin, Sicily Channel

A multi-proxy chronological framework along with sequence-stratigraphic interpretations unveils composite Milankovitch cyclicity in the sedimentary records of the Last GlacialeInterglacial cycle at NE Gela Basin on the Sicilian continental margin. Chronostratigraphic data (including foraminifera-based eco-biostratigraphy and d18O records, tephrochronological markers and 14C AMS radiometric datings) was derived from the shallow-shelf drill sites GeoB14403 (54.6 m recovery) and GeoB14414 (27.5 m), collected with both gravity and drilled MeBo cores in 193 m and 146 m water depth, respectively. The recovered intervals record Marine Isotope Stages and Substages (MIS) from MIS 5 to MIS 1, thus comprising major stratigraphic parts of the progradational deposits that form the last 100-ka depositional sequence. Calibration of shelf sedimentary units with borehole stratigraphies indicates the impact of higher-frequency (20-ka) sea level cycles punctuating this 100-ka cycle. This becomes most evident in the alternation of thick interstadial highstand (HST) wedges and thinner glacial forced-regression (FSST) units mirroring seaward shifts in coastal progradation. Albeit their relatively short-lived depositional phase, these subordinate HST units form the bulk of the 100-ka depositional sequence. Two mechanisms are proposed that likely account for enhanced sediment accumulation ratios (SAR) of up to 200 cm/ka during these intervals: (1) intensified activity of deep and intermediate Levantine Intermediate Water (LIW) associated to the drowning of Mediterranean shelves, and (2) amplified sediment flux along the flooded shelf in response to hyperpycnal plumes that generate through extreme precipitation events during overall arid conditions. Equally, the latter mechanism is thought to be at the origin of undulated features resolved in the acoustic records of MIS 5 Interstadials, which bear a striking resemblance to modern equivalents forming on late-Holocene prodeltas of other Mediterranean shallow-shelf settings.

Annotated record and chemical composition of manganese nodules from station VITYAZ 4575, Indian Ocean

Analyses are given for the core and outer colliform shell of a manganese nodule collected at a depth of 5000 m in the Indian Ocean, and for the red clay that encloses the nodules. Trace elements determined include rare earths, Nb, Ta, Th, and V. The cores of the nodules were once composed of basaltic rock, but now are phillipsite and nontronite. The outer shell is composed of manganite, with admixed quartz, phillipsite, and some geothite. The correlations established between the redox potentials and the concentration coefficients for 12 elements indicate that Eh plays a greater role in the formation of the manganiferous shells than coprecipitation properties.

Chemical composition of basalts from the Atlantic Ocean

Basalt recovered beneath Jurassic sediments in the western Atlantic at Deep Sea Drilling Project sites 100 and 105 of leg 11 has petrographic features characteristic of water-quenched basalt extruded along modern ocean ridges. Site 100 basalt appears to represent two or three massive cooling units, and an extrusive emplacement is probable. Site 105 basalt is less altered and appears to be a compositionally homogeneous pillow lava sequence related to a single eruptive episode. Although the leg 11 basalts are much more closely related in time to the Triassic lavas and intrusives of eastern continental North America, their geochemical features are closely comparable to those of modern Mid-Atlantic Ridge basalts unrelated to postulated "mantle plume" activity. Projection of leg 11 sites back along accepted spreading "flow lines" to their presumed points of origin shows that these origins are also outside the influence of modern" plume" activity. Thus, these oldest Atlantic seafloor basalts provide no information on the time of initiation of these "plumes". The Triassic continental diabases show north to south compositional variations in Rb, Ba, La, and Sr which lie within the range of " plume "-related basalt on the Mid-Atlantic Ridge (20° - 40° N) This suggests that these diabases had mantle sources similar in composition to those beneath the present Mid-Atlantic Ridge. "Plumes" related to deep mantle sources may have contributed to the LIL-element enrichment in the Triassic diabase and may also have been instrumental in initiating the rifting of the North Atlantic. Systematically high values for K and Sr87/Sr86 in the Triassic diabases may reflect superimposed effects of crustal contamination in the Triassic magmas.

Major element composition of phenocrysts from the volcanic basement of ODP Hole 125-786B, Izu forearc region, Philippine Sea

Early arc volcanism during Eocene to Oligocene in the Izu forearc region was investigated during ODP Legs 125 and 126 in 1989, and effusive and intrusive volcanics were recovered from Leg 125 Site 786. These rocks were all classified into boninites and associated rocks by Leg 125 Shipboard Scientific Party, and they concluded that boninitic volcanism had occurred before 40 Ma, and arc tholeiitic volcanism began after 40 Ma. In this study, lava flows and breccias that classified into boninite series are divided into two groups, tholeiite and boninite, based on petrographical and petrological properties. Both series are also distinguished by bulk rock composition. It is considered that the sources of both rock types have similar depleted compositions because of their similar, very low bulk HFSE concentrations. We suggest that boninitic and tholeiitic volcanism occurred closely in time and space, and reflected different temperature and water condition.

Element abundances and Nd isotopic composition in boninite and tholeiite from DSDP Hole 60-458

Boninites are unusual high MgO-high SiO2 volcanic rocks found in several western Pacific island arcs. Their high Mg/(Mg + total Fe) (0.55-0.83) and compatible element contents (Ni = 70-450 ppm, Cr = 200-1800 ppm) indicate equilibration with mantle peridotite, but their low TiO2 contents (0.1-0.5%) indicate severe depletion of this source. K, Rb, Sr and Ba abundances in boninites are typical of primitive arc basalts, but ratios such as Ti/Zr and La/Yb are variable (Ti/Zr = 23-67, (La/Yb)e.f. = 0.6-4.7). Evidence for both enrichment and depletion of incompatible elements suggests that boninites are derived from refractory peridotite which has been metasomatically enriched in LREE, Zr, Sr, Ba and alkalis. Wide variations in 143Nd/144Nd (0.51262-0.51296) are correlated with La/Sm, Sm/Nd and Ti/Zr, which enables identification of components in the boninite source. Possible LREE depleted components have relative REE and Ti abundances like those in depleted peridotites and high 143Nd/144Nd ratios which reach MORB-like values. Possible LREE enriched components have relative REE abundances similar to those in metasomatized mantle peridotite nodules, and low 143Nd/144Nd ratios which indicate either sedimentary sources or mantle sources with recent to ancient LREE enrichment. Relative abundances of Ba and Sr in boninites decrease with increasing LREE enrichment and suggest a non-sedimentary source for the LREE enriched material. Enrichment in Ba, Sr and alkalis may result from a third component derived from subducted oceanic crust. Two models can account for the successive generation of boninites and arc tholeiites within a single area: 1) boninites can be derived from the peridotite residue of earlier arc tholeiite generation which is metasomatically enriched in LREE before boninite volcanism, or 2) arc tholeiites and boninites can be derived from a variably depleted peridotite source which has been pervasively enriched in LREE. Areas of fertile peridotite would yield tholeiites while refractory areas would yield boninites.

Occurrence and geochemistry of lake-bottom manganiferous deposits in Canadian lakes

It is the purpose of this paper to record information concerning the distribution and occurrence of manganiferous concretions and other manganese oxide deposits that develop on certain lake bottoms. During the summer of 1935 several days were devoted to a study of this type of lake bottom deposit in various parts of Nova Scotia. Lake studies in Ontario have extended the known distribution from lakes on or near the Atlantic coast to lakes in southern Ontario. During the writer's first work on lacustrine manganiferous deposits the concretions of manganese oxide which were found were almost entirely limited to the relatively shallow parts of the lakes examined. Other lakes are now known where the manganese oxide appears to occur only in the maximum depths.