(Table 2) Age determination of brock-red sandy mud beds and detrital carbonate beds in the Scotian margin

Piston cores from the continental margin off Nova Scotia show up to four discrete intervals of "brick-red sandy mud", which are up to 20 cm thick. The ages of these intervals are bracketed by several radiocarbon dates, and three fall in the range 12.5-14.1 ka (radiocarbon years with -0.4 kyr reservoir correction). The youngest dates from ~10.4 ka, placing it within the Younger Dryas. The distribution of the beds and their petrographic character indicate a source in the Gulf of Saint Lawrence. The grain size of these beds suggests that they comprise a coarse component transported by ice rafting that diminishes distally and a fine component that represents suspension fallout from a surface plume and resulting nepheloid layers. Graded brick-red beds in some cores were probably redeposited from turbidity currents. The lowermost bed on the Laurentian Fan and East Scotian Rise is immediately overlain by a carbonate-rich interval that can be identified all around the margin of the Grand Banks. This interval is correlated with detrital carbonate bed DC-1 in the Labrador Sea and Heinrich event H1 in the North Atlantic. The sequential occurrence of the two beds suggests that they may be a response to the same trigger, probably sea level rise, but that the Gulf of Saint Lawrence source was more easily destabilized.

Heavy mineral and bulk mineral compositions of cores from Kumano Basin

Coring during Integrated Ocean Drilling Program Expeditions 315, 316, and 333 recovered turbiditic sands from the forearc Kumano Basin (Site C0002), a Quaternary slope basin (Site C0018), and uplifted trench wedge (Site C0006) along the Kumano Transect of the Nankai Trough accretionary wedge offshore of southwest Japan. The compositions of the submarine turbiditic sands here are investigated in terms of bulk and heavy mineral modal compositions to identify their provenance and dispersal mechanisms, as they may reflect changes in regional tectonics during the past ca. 1.5 Myrs. The results show a marked change in the detrital signature and heavy mineral composition in the forearc and slope basin facies around 1 Ma. This sudden change is interpreted to reflect a major change in the sand provenance, rather than heavy mineral dissolution and/or diagenetic effects, in response to changing tectonics and sedimentation patterns. In the trench-slope basin, the sands older than 1 Ma were probably eroded from the exposed Cretaceous-Tertiary accretionary complex of the Shimanto Belt and transported via the former course of the Tenryu submarine canyon system, which today enters the Nankai Trough northeast of the study area. In contrast, the high abundance of volcanic lithics and volcanic heavy mineral suites of the sands younger than 1 Ma points to a strong volcanic component of sediment derived from the Izu-Honshu collision zones and probably funnelled to this site through the Suruga Canyon. However, sands in the forearc basin show persistent presence of blue sodic amphiboles across the 1 Ma boundary, indicating continuous flux of sediments from the Kumano/Kinokawa River. This implies that the sands in the older turbidites were transported by transverse flow down the slope. The slope basin facies then switched to reflect longitudinal flow around 1 Ma, when the turbiditic sand tapped a volcanic provenance in the Izu-Honshu collision zone, while the sediments transported transversely became confined in the Kumano Basin. Therefore, the change in the depositional systems around 1 Ma is a manifestation of the decoupling of the sediment routing pattern from transverse to long-distance axial flow in response to forearc high uplift along the megasplay fault.

(Appendix A) Oxygen and carbon isotope results of detrital carbonate grains of Heinrich layers from HU90-013-028 and IODP Sites 303-U1302/U1303/U1308 in the North Atlantic Ocean

We report oxygen and carbon isotope results of detrital carbonate grains from Heinrich layers at three sites in the North Atlantic located along a transect from the Labrador Sea to the eastern North Atlantic. Oxygen isotopic values of individual detrital carbonate grains from six Heinrich layers at all sites average - 5.6 ppm ± 1.5 ppm (1sigma; n = 166), reflecting values of dolomitic limestone derived from source areas in northeastern Canada. The d18O of bulk carbonate at Integrated Ocean Drilling Program (IODP) Site U1308 (re-occupation of Deep Sea Drilling Project (DSDP) Site 609) in the eastern North Atlantic records the proportion of detrital to biogenic carbonate and d18O decreases to - 5 ppm during Heinrich (H) events 1, 2, 4 and 5 relative to a background value of ~ 1 to 2 ppm for biogenic carbonate. Bulk d18O also decreases during H3 and H6 but only attains values of - 1ppm, indicating either a greater proportion of biogenic-to-detrital carbonate or a different source. Because the d18O of detrital carbonate is ~ 9 ppm lower than foraminifer carbonate, any fine-grained detrital carbonate not removed from the inner test chambers will lower foraminifer d18O. We conclude bulk carbonate d18O is a sensitive proxy for detrital carbonate and may be useful for identifying Heinrich layers in cores within and near the margins of the North Atlantic ice-rafted detritus (IRD) belt.

Distribution of heavy minerals in sediment cores from the Laptev Sea continental margin and the central Arctic Ocean

Focussing on heavy-mineral associations in the Laptev-Sea continental margin area and the eastern Arctic Ocean, 129 surface sediment samples, two short and four long gravity cores have been studied. By means of the accessory components, heavy-mineral associations of surface sediment samples from the Laptev-See continental slope allowed the distinction into two different mineralogical provinces, each influenced by fluvial input of the Siberian river Systems. Transport pathways via sea ice from the shallow shelf areas into the Arctic Ocean up to the final ablation areas of the Fram Strait can be reconstructed by heavy-mineral data of surface sediments from the central Arctic Ocean. The shallow shelf of the Laptev Sea seems to be the most important source area for terrigenous material, as indicated by the abundant occurence of amphiboles and clinopyroxenes. Underneath the mixing Zone of the two dominating surface circulation Systems, the Beaufort- Gyre and Transpolar-Drift system, the imprint of the Amerasian shelf regions up to the Fram Strait is detectable because of a characteristical heavy-mineral association dominated by detrital carbonate and opaque minerals. Based On heavy-mineral characteristics of the potential circum-Arctic source areas, sea-ice drift, origin and distribution of ice-rafted material can be reconstructed during the past climatic cycles. Different factors controlling the transport of terrigenous material into the Arctic Ocean. The entrainment of particulate matter is triggered by the sea level, which flooded during highs and lows different regions resulting in the incorporation of sediment from different source areas into the sea ice. Additionally, the fluvial input even at low stands of sea level is responsible for the delivery of material of distinct sources for entrainment into the sea ice. Glacials and interglacials of climate cycles of the last 780 000 years left a characteristical signal in the central Arctic Ocean sediments caused by the ice- rafted material from different sources in the circum-Arctic regions and its change through time. Changes in the heavy-mineral association from an amphibole-dominated into a garnet-epidote-assemblage can be related to climate-related changes in source areas and directions of geostrophic winds, the dominating drive of the sea-ice drift. During Marine Isotope Stage (MIS) 6, the central Arctic Ocean is marked by an heavy-mineral signal, which occurs in recent sediments of the eastern Kara Sea. Its characteristics are high amounts of epidote, garnet and apatite. On the other hand, during the Same time interval a continuous record of Laptev Sea sediments is documented with high contents of amphiboles on the Lomonosov Ridge near the Laptev Sea continental slope. A nearly similar Pattern was detected in MIS 5 and 4. Small-scale glaciations in the Putorana-mountains and the Anabar-shield may have caused changes in the drainage area of the rivers and therefore a change in fluvial input. During MIS 3, the heavy-mineral association of central Arctic sediments show similar patterns than the Holocene mineral assemblage which consists of amphiboles, ortho- and clinopyroxenes with a Laptev Sea source. These minerals are indicating a stable Transpolar-Drift system similar to recent conditions. An extended influence of the Beaufort Gyre is only recognized, when sediment material from the Amerasian shelf areas reached the core location PS2757-718 during Termination Ib. Based On heavy-mineral data from Laptev-Sea continental slope Core PS2458-4 the paleo-sea-ice drift in the Laptev Sea during 14.000 years was reconstructed. During Holocene sea-level rise, the bathymetrically deeper parts of the Western shelf were flooded first. At the beginning of the Atlantic stage, nearly the entire shelf was marine influenced by fully marine conditions and the recent surface circulation was established.

U-Pb SHRIMP zircon dating of high-grade rocks from the Upper Allochthonous Terrane of Bragança and Morais Massifs (NE Portugal); geodynamic consequences

Bragança and Morais Massifs are part of the mega-klippen ensemble of NW Iberia, comprising a tectonic pile of four allochthonous units stacked above the Central-Iberian Zone autochthon. On top of this pile, the Upper Allochthonous Terrane (UAT) includes different high-grade metamorphic series whose age and geodynamic meaning are controversial. Mafic granulites provided U–Pb zircon ages at 399±7 Ma, dating the Variscan emplacement of UAT. In contrast,U–Pb zircon ages of ky- and hb-eclogites, felsic/intermediate HP/HT-granulites and orthogneisses (ca. 500–480 Ma) are identical to those of gabbros (488 ± 10 Ma) and Grt-pyroxenites (495 ± 8 Ma) belonging to a mafic/ultramafic igneous suite that records upper mantle melting and mafic magma crustal underplating at these times. Gabbros intrude the high-grade units of UAT and did not underwent the HP metamorphic event experienced by eclogites and granulites. These features and the zircon dates resemblance among different lithologies, suggest that extensive age resetting of older events may have been correlative with the igneous suite emplacement/crystallisation. Accordingly, reconciliation of structural, petrological and geochronological evidence implies that the development and early deformation of UAT high-grade rocks should be ascribed to an orogenic cycle prior to ≈500 Ma. Undisputable dating of this cycle is impossible, but the sporadic vestiges of Cadomian ages cannot be disregarded. The ca. 500–480 Ma time-window harmonises well with the Lower Palaeozoic continental rifting that trace the VariscanWilson Cycle onset and the Rheic Ocean opening. Subsequent preservation of the high heat-flowregime, possibly related to the Palaeotethys back-arc basin development (ca. 450–420 Ma), would explain the 461 ± 10 Ma age yielded by some zircon domains in felsic granulites, conceivably reflecting zircon dissolution/ recrystallisation till Ordovician times, long before the Variscan paroxysm (ca. 400–390 Ma). This geodynamic scenario suggests also that UAT should have been part of Armorica before its emplacement on top of Iberia after Palaeotethys closure.

The multistage crystallization of zircon in calc-alkaline granitoids : U-Pb age constraints on the timing of Variscan tectonic activity in SW Iberia

CL imaging and U–Th–Pb data for a population of zircons from two of the Évora Massif granitoids (Ossa-Morena Zone, SW Iberia) show that both calc-alkaline granitoids have zircon populations dominated by grains with cores and rims either showing or not showing differences in Th/U ratio, and having ages in the range ca. 350–335 Ma (Early Carboniferous). Multistage crystallization of zircon is revealed in two main growth stages (ca. 344–342 Ma and ca. 336–335 Ma), well represented by morphologically complex zircons with cores and rims with different ages and different Th/U ratios that can be explained by: (1) crystallization from melts with different compositions (felsic peraluminous to felsic-intermediate metaluminous; 0.001 Th/U ratio < 0.5) and (2) transient temperature fluctuations in a system where anatectic felsic melts periodically underwent injection of more mafic magmas at higher temperatures. The two studied calc-alkaline granitoids do not include inherited zircons (pre-Carboniferous), probably because they were formed at the highest grade of metamorphism (T 837 °C; granulite facies) and/or because they were derived from inheritance-poor felsic and mafic rocks from a previous cycle, as suggested by the internal structures of zircon cores. These Variscan magmatic rocks with crystallization ages estimated at ca. 336–335 Ma are spatially and temporally related to high-temperature metamorphism, anatexis, processes of interaction between crustal- and mantle-derived magmas and intra-orogenic extension that acted in SW Iberia during the Early Carboniferous.

Retrievals of a size parameter for phytoplankton and spectral light absorption by colored detrital matter from water-leaving radiances at SeaWiFS channels in a continental shelf region off Brazil

Many efforts are currently oriented toward extracting more information from ocean color than the chlorophyll a concentration. Among biological parameters potentially accessible from space, estimates of phytoplankton cell size and light absorption by colored detrital matter (CDM) would lead to an indirect assessment of major components of the organic carbon pool in the ocean, which would benefit oceanic carbon budget models. We present here 2 procedures to retrieve simultaneously from ocean color measurements in a limited number of bands, magnitudes, and spectral shapes for both light absorption by CDM and phytoplankton, along with a size parameter for phytoplankton. The performance of the 2 procedures was evaluated using different data sets that correspond to increasing uncertainties: ( 1) measured absorption coefficients of phytoplankton, particulate detritus, and colored dissolved organic matter ( CDOM) and measured chlorophyll a concentrations and ( 2) SeaWiFS upwelling radiance measurements and chlorophyll a concentrations estimated from global algorithms. In situ data were acquired during 3 cruises, differing by their relative proportions in CDM and phytoplankton, over a continental shelf off Brazil. No local information was introduced in either procedure, to make them more generally applicable. Over the study area, the absorption coefficient of CDM at 443 nm was retrieved from SeaWiFS radiances with a relative root mean square error (RMSE) of 33%, and phytoplankton light absorption coefficients in SeaWiFS bands ( from 412 to 510 nm) were retrieved with RMSEs between 28% and 33%. These results are comparable to or better than those obtained by 3 published models. In addition, a size parameter of phytoplankton and the spectral slope of CDM absorption were retrieved with RMSEs of 17% and 22%, respectively. If these methods are applied at a regional scale, the performances could be substantially improved by locally tuning some empirical relationships.

Dating minerals by ID-TIMS geochronology at times of in situ analysis: selected case studies from the CPGeo-IGc-USP laboratory

Since 1964, the Center for Geochronological Research - CPGeo, one of the interdepartmental centers of the Instituto de Geociências (IG) of São Paulo University, has developed studies related to several geological processes associated with different rock types. Thermal Ionization Mass Spectrometry Isotopic Dilution (ID-TIMS) has been the technique widely used in the CPGeo U-Pb Laboratory. It provides reliable and accurate results in age determination of superposed events. However, the open-system behavior such as Pb-loss, the inheritance problem and metamictization processes allow and impel us to a much richer understanding of the power and limitations of U-Pb geochronology and thermochronology. In this article, we present the current methodology used at the CPGeo-IGc-USP U-Pb laboratory, the improvements on ID-TIMS method, and report high-precision U-Pb data from zircon, monazite, epidote, titanite, baddeleyite and rutile from different rock types of several domains of the Brazilian south-southeast area, Argentina and Uruguay.

Soil mineralogy of mangrove forests from the state of Sao Paulo, Southeastern Brazil

The minerals of the clay fraction in estuarine plains are mainly detrital being a mixture of marine and continental sediments, but can also be authigenic. Because of the importance of mangrove ecosystems in tropical estuarine areas and the relatively few existing studies of the mineralogical composition of soils in these environments, the aim of this study was to determine the mineralogical assemblage and identify potential contrasts along the coast of the State of Sao Paulo. Soils from I I mangroves distributed along the coastal plain of the State of Sao Paulo were sampled at depths of 0 to 20 and 60 to 80 cm, and samples of suspended sediments from the Ribeira do Iguape River were collected for analysis. Mineralogical analyses were performed on the clay and silt fractions by x-ray diffraction (XRD) and transmission electron microscopy, and fresh soil samples were analyzed by scanning electron microscopy-energy dispersive spectrometry and suspended sediments by XRD. The silt fraction contained quartz, feldspars, gibbsite, kaolinite, illite, and vermiculite, and the clay fraction contained smectite, kaolinite, illite, gibbsite, quartz, and feldspars. Locally, vermiculite, biotite, anatase, halloysite, and goethite may occur because of recent transport of sediments to the system. Pyrite was identified in fresh samples. The allochthonous minerals found either were terrestrial and transported by rivers or had originated from the continental platform by past transgressive events. We suggest that the neoformation of smectite and kaolinite occurs in mangrove soils. Different geomorphological settings along the Sao Paulo coast appear to regulate mineral distribution in mangrove soils.

Relations between coal petrology and gas content in the Upper Newlands Seam, central Queensland, Australia

The Upper Newlands Seam in the northern Bowen Basin, Queensland, Australia consists of six benches (A-F) that have different petrographic assemblages. Benches C and E contain relatively abundant inertodetrinite and mineral matter, as well as anomalously high reflectance values; these characteristics support a largely allochthonous, detrital origin for the C and E benches. Fractures and cleats in the seam show a consistent orientation of northeast- southwest for face cleats, and a wide range of orientations for fractures. Cleat systems are well developed in bright bands, with poor continuity in the dull coal. Both maceral content and cleat character are suggested to influence gas drainage in the Upper Newlands Seam. A pronounced positive correlation between vitrinite abundance and gas desorption data suggests more efficient drainage from benches with abundant vitrinite. Conversely, inertinite-rich benches are suggested to have less efficient drainage, and possibly retain gas within pore spaces, which could increase the outburst potential of the coal. (C) 2001 Elsevier Science BN. All rights reserved.

Applications of accurate, high-precision Pb isotope ratio measurement by multi-collector ICP-MS

The isotope composition of Ph is difficult to determine accurately due to the lack of a stable normalisation ratio. Double and triple-spike addition techniques provide one solution and presently yield the most accurate measurements. A number of recent studies have claimed that improved accuracy and precision could also be achieved by multi-collector ICP-MS (MC-ICP-MS) Pb-isotope analysis using the addition of Tl of known isotope composition to Pb samples. In this paper, we verify whether the known isotope composition of Tl can be used for correction of mass discrimination of Pb with an extensive dataset for the NIST standard SRM 981, comparison of MC-ICP-MS with TIMS data, and comparison with three isochrons from different geological environments. When all our NIST SRM 981 data are normalised with one constant Tl-205/Tl-203 of 2.38869, the following averages and reproducibilities were obtained: Pb-207/Pb-206=0.91461+/-18; Pb-208/Ph-206 = 2.1674+/-7; and (PbPh)-Pb-206-Ph-204 = 16.941+/-6. These two sigma standard deviations of the mean correspond to 149, 330, and 374 ppm, respectively. Accuracies relative to triple-spike values are 149, 157, and 52 ppm, respectively, and thus well within uncertainties. The largest component of the uncertainties stems from the Ph data alone and is not caused by differential mass discrimination behaviour of Ph and Tl. In routine operation, variation of sample introduction memory and production of isobaric molecular interferences in the spectrometer's collision cell currently appear to be the ultimate limitation to better reproducibility. Comparative study of five different datasets from actual samples (bullets, international rock standards, carbonates, metamorphic minerals, and sulphide minerals) demonstrates that in most cases geological scatter of the sample exceeds the achieved analytical reproducibility. We observe good agreement between TIMS and MC-ICP-MS data for international rock standards but find that such comparison does not constitute the ultimate. test for the validity of the MC-ICP-MS technique. Two attempted isochrons resulted in geological scatter (in one case small) in excess of analytical reproducibility. However, in one case (leached Great Dyke sulphides) we obtained a true isochron (MSWD = 0.63) age of 2578.3 +/- 0.9 Ma, which is identical to and more precise than a recently published U-Pb zircon age (2579 3 Ma) for a Great Dyke websterite [Earth Planet. Sci. Lett. 180 (2000) 1-12]. Reproducibility of this age by means of an isochron we regard as a robust test of accuracy over a wide dynamic range. We show that reliable and accurate Pb-isotope data can be obtained by careful operation of second-generation MC-ICP magnetic sector mass spectrometers. (C) 2002 Elsevier Science B.V. All rights reserved.

Improving the ionic conductivity of yttria-stabilised zirconia electrolyte materials

Low-temperature anneals (1200 degreesC for 40 h) of 8 mol% yttria-stabilised zirconia, prior to the samples being sintered at 1500 degreesC, had the effect of improving the ionic conductivity of the specimens. The presence Of SiO2 in the specimens was shown to be detrimental, however. Irrespective of the SiO2 content, this type of heat treatment also leads to improvements in conductivity. Extensive microstructural analysis provided indication of the mechanism of this phenomenon. This included selective formation of zircon, relief of sintering strain leading to the formation of coherent grain boundaries and segregation effects. (C) 2002 Elsevier Science B.V All rights reserved.

Stratigraphy, facies architecture and tectonic implications of the Upper Devonian to Lower Carboniferous Campwyn Volcanics of the northern New England Fold Belt

Upper Devonian to Lower Carboniferous strata of the Campwyn Volcanics of east central Queensland preserve a substantial sequence of first-cycle volcaniclastic sedimentary and coeval volcanic rocks that record prolonged volcanic activity along the northern New England Fold Belt. The style and scale of volcanism varied with time, producing an Upper Devonian sequence of mafic volcano-sedimentary rocks overlain by a rhyolitic ignimbrite-dominated sequence that passes upward into a Lower Carboniferous limestone-bearing sedimentary sequence. We define two facies associations for the Campwyn Volcanics. A lower facies association is dominated by mafic volcanic-derived sedimentary breccias with subordinate primary mafic volcanic rocks comprising predominantly hyaloclastite and peperite. Sedimentary breccias record episodic and high energy, subaqueous depositional events with clastic material sourced from a mafic lava-dominated terrain. Some breccias contain a high proportion of attenuated dense, glassy mafic juvenile clasts, suggesting a syn-eruptive origin. The lower facies association coarsens upwards from a lithic sand-dominated sequence through a thick interval of pebble- to boulder-grade polymict volcaniclastic breccias, culminating in facies that demonstrate subaerial exposure. The silicic upper facies association marks a significant change in eruptive style, magma composition and the nature of eruptive sources, as well as the widespread development of subaerial depositional conditions. Crystal-rich, high-grade, low- to high-silica rhyolite ignimbrites dominate the base of this facies association. Biostratigraphic age controls indicate that the ignimbrite-bearing sequences are Famennian to lower-mid Tournaisian in age. The ignimbrites represent extra-caldera facies with individual units up to 40 m thick and mostly lacking coarse lithic breccias. Thick deposits of pyroclastic material interbedded with fine-grained siliceous sandstone and mudstone (locally radiolarian-bearing) were deposited from pyroclastic flows that crossed palaeoshorelines or represent syn-eruptive, resedimented pyroclastic material. Some block-bearing lithic-pumice-crystal breccias may also reflect more proximal subaqueous silicic explosive eruptions. Crystal-lithic sandstones interbedded with, and overlying the ignimbrites, contain abundant detrital volcanic quartz and feldspar derived from the pyroclastic deposits. Limestone is common in the upper part of the upper facies association, and several beds are oolitic (cf. Rockhampton Group of the Yarrol terrane). Overall, the upper facies association fines upward and is transgressive, recording a return to shallow-marine conditions. Palaeocurrent data from all stratigraphic levels in the Campwyn Volcanics indicate that the regional sediment-dispersal direction was to the northwest, and opposed to the generally accepted notion of easterly sediment dispersal from a volcanic arc source. The silicic upper facies association correlates in age and lithology to Early Carboniferous silicic volcanism in the Drummond (Cycle 1) and Burdekin Basins, Connors Arch, and in the Yarrol terranes of eastern Queensland. The widespread development of silicic volcanism in the Early Carboniferous indicates that silicic (rift-related) magmatism was not restricted to the Drummond Basin, but was part of a more substantial silicic igneous province.