Geochemistry of basalts from the Caribbean Large Igneous Province

Oceanic flood basalts are poorly understood, short-term expressions of highly increased heat flux and mass flow within the convecting mantle. The uniqueness of the Caribbean Large Igneous Province (CLIP, 92-74 Ma) with respect to other Cretaceous oceanic plateaus is its extensive sub-aerial exposures, providing an excellent basis to investigate the temporal and compositional relationships within a starting plume head. We present major element, trace element and initial Sr-Nd-Pb isotope composition of 40 extrusive rocks from the Caribbean Plateau, including onland sections in Costa Rica, Colombia and Curaçao as well as DSDP Sites in the Central Caribbean. Even though the lavas were erupted over an area of ~3*10**6 km**2, the majority have strikingly uniform incompatible element patterns (La/Yb=0.96+/-0.16, n=64 out of 79 samples, 2sigma) and initial Nd-Pb isotopic compositions (e.g. 143Nd/144Ndin=0.51291+/-3, epsilon-Nd i=7.3+/-0.6, 206Pb/204Pbin=18.86+/-0.12, n=54 out of 66, 2sigma). Lavas with endmember compositions have only been sampled at the DSDP Sites, Gorgona Island (Colombia) and the 65-60 Ma accreted Quepos and Osa igneous complexes (Costa Rica) of the subsequent hotspot track. Despite the relatively uniform composition of most lavas, linear correlations exist between isotope ratios and between isotope and highly incompatible trace element ratios. The Sr-Nd-Pb isotope and trace element signatures of the chemically enriched lavas are compatible with derivation from recycled oceanic crust, while the depleted lavas are derived from a highly residual source. This source could represent either oceanic lithospheric mantle left after ocean crust formation or gabbros with interlayered ultramafic cumulates of the lower oceanic crust. High 3He/4He in olivines of enriched picrites at Quepos are ~12 times higher than the atmospheric ratio suggesting that the enriched component may have once resided in the lower mantle. Evaluation of the Sm-Nd and U-Pb isotope systematics on isochron diagrams suggests that the age of separation of enriched and depleted components from the depleted MORB source mantle could have been <=500 Ma before CLIP formation and interpreted to reflect the recycling time of the CLIP source. Mantle plume heads may provide a mechanism for transporting large volumes of possibly young recycled oceanic lithosphere residing in the lower mantle back into the shallow MORB source mantle.

Geochemical composition of minerals obtained from ODP Sites 180-1109, 180-1117 and 180-1118

During the last 8 m.y. the Papuan Peninsula region of Papua New Guinea has been affected by extension which opened the Woodlark Basin. The present-day spreading tip is located at the foot of the Moresby Seamount, a crustal block whose northern flank is an active low-angle normal fault related to this extension. During Ocean Drilling Program Leg 180 (7 June-11 August 1998), 11 sites (1108-1118) were drilled along a north-south-trending transect across the Woodlark Basin just ahead of the spreading tip. Four of these sites (1118, 1109, 1114, and 1117) reached the crystalline basement, which is composed of diabase and gabbro. Sites 1118 and 1109, located on the Woodlark Rise, belong to the hanging wall block, and Sites 1114 and 1117, located on the crest of the Moresby Seamount, belong to the footwall block and the fault zone itself. Most of the basalt, diabase, and gabbro that were recovered show a well-preserved magmatic texture. The diabase, which is the most abundant rock type, has a coarse-grained ophitic texture composed of poikilitic clinopyroxene including radiating, locally skeletal plagioclase laths with interstitial iron oxide grains. Secondary mineralogy consists of chlorite, zeolite, calcite, albite, and quartz. The gabbro shows a medium-grained granular texture. The magmatic mineralogy consists of euhedral laths of plagioclase and anhedral interstitial clinopyroxene. Secondary mineralogy consists of a magnesio to actinolitic hornblende, chlorite, clinozoisite, zeolite, quartz, and calcite. The retrograde metamorphic evolution of both gabbro and diabase occurred under low amphibolite to subgreenschist facies conditions associated mainly with brittle deformation and the development of a local low-temperature shear zone. This shows no evidence for high thermal gradient in the crust during the continental rifting.

Palliser Rockslide cosmogenic 36Cl exposure ages (raw data) and erosion effect on the cosmogenic

This paper presents the results of a combined study, using cosmogenic 36Cl exposure dating and terrestrial digital photogrammetry, of the Palliser Rockslide located in the southeastern Canadian Rocky Mountains. This site is particularly well-suited to demonstrate how this multi-disciplinary approach can be used to differentiate distinct rocksliding events, estimate their volume, and establish their chronology and recurrence interval. Observations suggest that rocksliding has been ongoing since the late Pleistocene deglaciation. Two major rockslide events have been dated at 10.0 ± 1.2 kyr and 7.7 ± 0.8 kyr before present, with failure volumes of 40 Mm3 and 8 Mm3, respectively. The results have important implications concerning our understanding of the temporal distribution of paraglacial rockslides and rock avalanches; they provide a better understanding of the volumes and failure mechanisms of recurrent failure events; and they represent the first absolute ages of a prehistoric high magnitude event in the Canadian Rocky Mountains.

Geochemical investigations of sediment profiles in the Norwegian-Greenland Sea

High-, i.e. 15-140-yr-resolution climate records from sediment cores 23071, 23074, and PS2644 from the Nordic Seas were used to recon:;truct changes in the surface and deep water circulation during marine isotope stages 1-5.1, i.e. the last 82 000 yr. From this the causal links between the paleoceanographic signals and the Dansgaard-Oeschger events 1-21 revealed in 0180-ice-core records from Greenland were determined. The stratigraphy of the cores is based on the planktic 0180 curves, the minima of which were directly correlated with the GISP2-0180 record, numerous AMS 14C ages, and some ash layers. The planktic d18O and dl3C curves of all three cores reveal numerous meltwater events, the most pronounced of which were assigned to the Heinrich events 1-6. The meltwater events, among other things also accompanied by cold sea surface temperatures and high IRD concentration, correlate with the stadial phases of the Dansgaard-Oeschger cycles and in the western Iceland Sea also to colder periods or abrupt drops in 0180 within a few longer interstadials. Besides being more numerous, the meltwater events also show isotope values lighter in the Iceland Sea than in the central Norwegian Sea, especially if compared to core 23071. This implies a continuous inflow of relative warm Atlantic water into the Norwegian Sea and a cyclonic circulation regime.

Description of Mn deposits and chemical composition of altered pelagic sediments of sites surveyed by R/V Vityaz in the Southern Basin of the Pacific Ocean

The object of the detailed investigations was an unusual material collected in the region of the Southern Basin of the Pacific Ocean floor, with features of intense manifestation of volcanic processes and subsequent hydrothermal alterations. These processes to a significant degree transformed the ferromanganese nodules and the pelagic sediments, causing the development of a new type of oceanic manganese mineralization.

Geochemistry, and Nd- and Pb-isotopic composition of basalts from the upper oceanic crust of the Costa Rica Rift

The DSDP/ODP Hole 504B, drilled in the 5.9 Ma southern flank of the Costa Rica Rift, represents the deepest section through modern ocean floor basaltic basement. The hole penetrates a 570 m thick volcanic zone, a 210 m thick transition zone of volcanic rocks and dykes, and 1056 m of dykes. A representative selection of these basalt types has been investigated with respect to Nd and Pb isotopes. The epsilonNd of the basalts varies from 7.62 to 11.16. This range in the Nd-isotope composition represents about 67% of the total range reported for Pacific MORB. The Pb-isotope composition also shows significant variation, with 206Pb/204Pb varying from 17.90 to 18.82. The isotopic data show that a small volume of enriched mantle existed in the source. The large ranges in isotopic composition in a single drill hole demonstrate the importance of small-scale mantle heterogeneities in the petrogenesis of MORB. Fractional melting and extraction of small magma batches by channelled flow, and small, short-lived crustal magma reservoirs, with limited potential for mixing of the mantle derived magmas, are favored by these isotopic data.

Chemical composition of rocks and minerals from DSDP holes

The book summarizes materials obtained by Soviet scientists during participation in legs of D/S Glomar Challenger and in post-cruise studies. Results on stratigraphy and lithology of the sedimentary cover, petrography and geochemistry of magmatic rocks of the oceanic crust are discussed in the book. A modern analysis of the geophysical structure of the oceanic crust and of the tectonic structure of the ocean floor is given.

Major element compositions, minerals and trace elements at DSDP Leg 67 Holes

Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 18 samples of volcanic rocks from the Guatemala Trench area (Deep Sea Drilling Project Leg 67). Typical fresh oceanic tholeiites occur in the trench itself (Hole 500) and in its immediate vicinity on the Cocos Plate (Site 495). Several samples (often reworked) of "spilitic" oceanic tholeiites are also described from the Trench: their mineralogy (greenschist facies association - actinolite + plagioclase + chlorite) and geochemistry (alteration, sometimes linked to manganese and zinc mineralization) are shown to result from high-temperature (300°-475°C) hydrothermal sea water-basalt interactions. The samples studied are depleted in light rare-earth elements (LREE), with the exception of the slightly LREE-enriched basalts from Hole 500. The occurrence of such different oceanic tholeiites in the same area is problematic. Volcanic rocks from the Guatemala continental slope (Hole 494A) are described as greenschist facies metabasites (actinolite + epidote + chlorite + plagioclase + calcite + quartz), mineralogically different from the spilites exposed on the Costa Rica coastal range (Nicoya Peninsula). Their primary magmatic affinity is uncertain: clinopyroxene and plagioclase compositions, together with titanium and other hygromagmaphile element contents, support an "active margin" affinity. The LREE-depleted patterns encountered in the present case, however, are not frequently found in orogenic samples but are typical of many oceanic tholeiites.

The molecular structure of matioliite – NaMgAl5(PO4)4(OH)6·2(H2O) : a pegmatite mineral from Minas Gerais, Brazil

Detailed spectroscopic and chemical investigation of matioliite, including infrared and Raman spectroscopy, scanning electron microscopy and electron probe microanalysis has been carried out on homogeneous samples from the Gentil pegmatite, Mendes Pimentel, Minas Gerais, Brazil. The chemical composition is (wt.%): FeO 2.20, CaO 0.05, Na2O 1.28, MnO 0.06, Al2O3 39.82, P2O5 42.7, MgO 4.68, F 0.02 and H2O 9.19; total 100.00. The mineral crystallize in the monoclinic crystal system, C2/c space group, with a = 25.075(1) Å, b = 5.0470(3) Å, c = 13.4370(7) Å, β = 110.97(3)°, V = 1587.9(4) Å3, Z = 4. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of matioliite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of matioliite.

Phase-relations in the system CAO-SIO2-ZRO2 AT 1573-K

Zirconia-based solid electrolytes with zircon (ZrSiO4) as the auxiliary electrode have been suggested of sensing silicon concentrations in iron and steel melts. A knowledge of phase relations in the ternary system MO-SiO2-ZrO2 (M = Ca, Mg) is useful for selecting an appropriate auxiliary electrode. In this investigation, an isothermal section for the phase diagram of the system CaO-SiO2ZrO2 at 1573 K has been established by equilibrating mixtures of component oxides in air, followed by quenching and phase identification by optical miroscopy, energy disperse analysis of X-rays (EDAX) and X-ray diffraction analysis (XRD). The equilibrium phase relations have also been confirmed by computation using the available thermodynamic data on condensed phases in the system. The results indicate that zircon is not in thermodynamic equilibrium with calcia-stabilized zirconia or calcium zirconate. The silica containing phase in equilibrium with stabilized zirconia is Ca3ZrSi2O9. Calcium zirconate can coexist with Ca3ZrSi2O9 and Ca2SiO4.

Mass spectrometric and electrochemical studies of thermodynamic properties of liquid and solid phases in the CaO Al2O3 system

The activities of CaO and Al2O3 in lime-alumina melts were studied by Knudsen cell-mass spectrometry at 2060 K. Emf of solid state cells, with CaF2 as the electrolyte, was measured from 923 to 1223 K to obtain the free energies of formation of the interoxide compounds. The results are critically evaluated in the light of data reported in the literature on phase equilibria, activities in melts, and stabilities of compounds. A coherent set of data is presented, including the previously unknown free energy of formation of CaO.6Al2O3 and the temperature dependence of activities in the liquid phase.

Revision of thermodynamic data on MnO Al2O3 melts

The high temperature region of the MnO-A1203 phase diagram has been redetermined to resolve some discrepancies reported in the literature regarding the melting behaviour of MnA1,04. This spinel was found to melt congruently at 2108 (+ 15) K. Theactivity of MnOin MnO-Al,03 meltsand in the two phase regions, melt + MnAI,04 and MnAI2O4 + A1203, has been determined by measuring the manganese concentration in platinum foils in equilibrium under controlled oxygen potentials. The activity of MnO obtained in this study for M ~ O - A I ,m~el~ts is in fair agreement with the results of Sharma and Richardson.However. the alumina-rich melt is found to be in equilibrium with MnAl,04 rather than AI2O3. as suggested by ~ha rmaan d Richardson. The value for the acthity of MnO in the M~AI ,O,+ A1,03 two phaseregion permits a rigorous application of the Gibbs-Duhem equation for calculating the activity of A1203 and the integral Gibbs' energy of mixing of MnO-A1203 melts, which are significantly different from those reported in the literature.

Phase equilibria in the system NiO-CaO-SiO2 and Gibbs energy of formation of CaNiSi2O6

Phase relations in the pseudoternary system NiO-CaO-SiO2 at 1373 K are established. The coexisting phases are identified by X-ray diffraction and energy-dispersive X-ray analysis of equilibrated samples. There is only one quaternary oxide CaNiSi2O6 with clinopyroxene structure. The Gibbs energy of formation of CaNiSi2O6 is measured using a solid state galvanic cell incorporating stabilized zirconia as the solid electrolyte in the temperature range of 1000 to 1400 K:Pt, Ni + SiO2 + CaSiO3 + CaNiSi2O6 \ (Y2O3)ZrO2 \ Ni + NiO, Pt From the electromotive force (emf) of the cell, the Gibbs energy of formation of CaNiSi2O6 from NiO, SiO2, and CaSiO3 is obtained. To derive the Gibbs energy of formation of the quaternary oxide from component binary oxides, the free energy of formation of CaSiO, is determined separately using a solid state cell based on single crystal CaF2 as the electrolyte: Pt, O-2, CaO + CaF2 \ CaF2 \ CaSiO3 + SiO2 + CaF2, O-2, Pt The results can be expressed by the following equations: NiO (r.s) + CaO (r.s) + 2SiO(2) (qz) --> CaNiSi2O6 (pyr) Delta G degrees = -115,700 + 10.63T (+/-100) J mol(-1) CaO (r.s) + SiO2 (qz) --> CaSiO3 (wol) Delta G degrees = -90,030 -0.61T (+/-60) J mol(-1).

Phase Equilibria in the System Al2O3-CaO-CoO and Gibbs Energy of Formation of Ca3CoAl4O10

An isothermal section of the system Al2O3-CaO-CoO at 1500 K has been established by equilibrating 22 samples of different compositions at high temperature and phase identification by optical and scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy after quenching to room temperature. Only one quaternary oxide, Ca3CoAl4O10, was identified inside the ternary triangle. Based on the phase relations, a solid-state electrochemical cell was designed to measure the Gibbs energy of formation of Ca3CoAl4O10 in the temperature range from 1150 to 1500 K. Calcia-stabilized zirconia was used as the solid electrolyte and a mixture of Co + CoO as the reference electrode. The cell can be represented as: ( - )\textPt,\textCaAl 2 \textO 4 + \textCa 1 2 \textAl 1 4 \textO 3 3 + \textCa 3 \textCoAl 4 \textO 10 + \textCo//(CaO)ZrO 2 \text// \textCoO + \textCo,\text Pt ( + ). (−)PtCaAl2O4+Ca12Al14O33+Ca3CoAl4O10+Co//(CaO)ZrO2//CoO+Co Pt (+) From the emf of the cell, the standard Gibbs energy change for the Ca3CoAl4O10 formation reaction, CoO + 3/5CaAl2O4 + 1/5Ca12Al14O33 → Ca3CoAl4O10, is obtained as a function of temperature: \Updelta Gr\texto Unknown control sequence '\Updelta'/J mol−1 (±50) = −2673 + 0.289 (T/K). The standard Gibbs energy of formation of Ca3CoAl4O10 from its component binary oxides, Al2O3, CaO, and CoO is derived as a function of temperature. The standard entropy and enthalpy of formation of Ca3CoAl4O10 at 298.15 K are evaluated. Chemical potential diagrams for the system Al2O3-CaO-CoO at 1500 K are presented based on the results of this study and auxiliary information from the literature.

Nano Al2O3-Pb AND SiO2-Pb cermets by sol-gel technique and the phase transformation study of the embedded Pb particles

Sol-gel processing followed by H2 reduction is used to produce dispersions of nanosized Pb in amorphous SiO2 and ultrafine γ Al2O3 matrices. A depression of 3–5K in Pb melting point is reported. The size and shape of these metastable particles in molten and solid state are discussed in the light of the experimental observations and expectations from the intersection group theory for equilibrium shape.