Utility of thallium and geochemical analysis of Mariana arc sediments from ODP Hole 129-801A and 129-801B

We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer. In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light epsilon 205Tl (where epsilon 205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (epsilon 205Tl = - 4.4 to 0). The lack of a distinctive epsilon 205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1-2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (epsilon 205Tl = - 3.0 to + 0.4), as previously found in similar sediment types (epsilon 205Tl > + 2.5; Rehkämper et al., 2004). We find a restricted range of epsilon 205Tl = - 1.8 to - 0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with epsilon 205Tl = + 1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of epsilon 205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl. Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.

Toba Tephra across India

A controversy currently exists regarding the number of Toba eruptive events represented in the tephra occurrences across peninsular India. Some claim the presence of a single bed, the 75,000-yr-old Toba tephra; others argue that dating and archaeological evidence suggest the presence of earlier Toba tephra. Resolution of this issue was sought through detailed geochemical analyses of a comprehensive suite of samples, allowing comparison of the Indian samples to those from the Toba caldera in northern Sumatra, Malaysia, and, importantly, the sedimentary core at ODP Site 758 in the Indian Ocean - a core that contains several of the earlier Toba tephra beds. In addition, two samples of Toba tephra from western India were dated by the fission-track method. The results unequivocally demonstrate that all the presently known Toba tephra occurrences in peninsular India belong to the 75,000 yr B.P. Toba eruption. Hence, this tephra bed can be used as an effective tool in the correlation and dating of late Quaternary sedimentary sequences across India and it can no longer be used in support of a middle Pleistocene age for associated Acheulian artifacts.

Major element concentration and radionuclides of equatorial Pacific deep-sea sediments

The (231Pa/230Th)xs,0 records obtained from two cores from the western (MD97-2138; 1°25'S, 146°24'E, 1900 m) and eastern (ODP Leg 138 Site 849, 0°11.59'N, 110°31.18'W, 3851 m) equatorial Pacific display similar variability over the last 85000 years, i.e. from isotopic stages 1 to 5a, with systematically higher values during the Holocene, isotopic stage 3 and isotopic stage 5a, and lower values, approaching the production rate ratio of the two isotopes (0.093), during the colder periods corresponding to isotopic stages 2 and 4. We have also measured the 230Th-normalized biogenic preserved and terrigenous fluxes, as well as major and trace elements concentrations, in both cores. The (231Pa/230Th)xs,0 results combined with the changes in preserved carbonate and opal fluxes at the eastern site indicate lower productivity in the eastern equatorial Pacific during glacial periods. The (231Pa/230Th)xs,0 variations in the western equatorial Pacific (WEP) also seem to be controlled by productivity (carbonate and/or opal). The generally high (231Pa/230Th)xs,0 ratios (>0.093) of the profile could be due to opal and/or MnO2 in the sinking particles. The profiles of (231Pa/230Th)xs,0 and 230Th-normalized fluxes indicate a decrease in exported carbonate, and possibly opal, during isotopic stages 2 and 4 in MD97-2138. Using 230Th-normalized flux, we also show that sediments from the two cores were strongly affected by sediment redistribution by bottom currents suggesting a control of mass accumulation rates by sediment focusing variability.

Grain size, mineral and chemical compositions of modern deposits fron the northern Caspian Sea and the Volga River delta

Comprehensive investigations revealed that modern deposits in the northern Caspian Sea involve terrigenous sands and aleurites with admixture of detritus and intact bivalve shells, including coquina. Generally, these deposits overlay dark grayish viscous clays. Similar geological situation occurs in the Volga River delta; however, local deposits are much poorer in biogenic constituents. Illite prevails among clay minerals. In coarse aleurite fraction (0.100-0.050 mm) heavy transparent minerals are represented mostly by epidotes, while light minerals - mostly by quartz and feldspars. Sedimentary material in the Volga River delta is far from completely differentiated into fractions due to abundant terrigenous inflows. Comparatively better grading of sediments from the northern Caspian Sea is due to additional factors such as bottom currents and storms. When passing from the Volga River delta to the northern Caspian Sea, sediments are enriched in rare earth elements (except Eu), Ca, Au, Ni, Se, Ag, As, and Sr, but depleted in Na, Rb, Cs, K, Ba, Fe, Cr, Co, Sc, Br, Zr, ??, U, and Th. Concentrations of Zn remain almost unchanged. Sedimentation rates and types of recent deposits in the northern Caspian Sea are governed mainly by abundant runoff of the Volga River.

Description, geochemistry, mineralogy and isotopes of sulfides from ODP Site 193-1189, PACMANUS field

Chemical and isotopic data for rare massive and semimassive sulfide samples cored at Site 1189 (Roman Ruins, PACMANUS) suggest their genetic relationship with sulfide chimneys at the seafloor. Sand collected from the hammer drill after commencement of Hole 1189B indicates that at least the lower section of the cased interval was occupied by material similar to the stockwork zone cored from 31 to ~100 meters below seafloor (mbsf) in this hole, but with increased content of barite, sphalerite, and lead-bearing minerals. Fractional crystallization of ascending hydrothermal fluid involving early precipitation of pyrite may explain vertical mineralogical and chemical zoning within the stockwork conduit and the high base and precious metal contents of Roman Ruins chimneys. A mineralized volcaniclastic unit cored deep in Hole 1189A possibly represents the lateral fringe of the conduit system. Lead isotope ratios in the sulfides differ slightly but significantly from those of fresh lavas from Pual Ridge, implying that at least some of the Pb within the Roman Ruins hydrothermal system derived from a deeper, more radiogenic source than the enclosing altered volcanic rocks.

Nd isotopes of sediments, foraminifera and fish debris of the western North Atlantic

Understanding changes in ocean circulation during the last deglaciation is crucial to unraveling the dynamics of glacial-interglacial and millennial climate shifts. We used neodymium isotope measurements on postdepositional iron-manganese oxide coatings precipitated on planktonic foraminifera to reconstruct changes in the bottom water source of the deep western North Atlantic at the Bermuda Rise. Comparison of our deep water source record with overturning strength proxies shows that both the deep water mass source and the overturning rate shifted rapidly and synchronously during the last deglacial transition. In contrast, any freshwater perturbation caused by Heinrich event 1 could have only affected shallow overturning. These findings show how changes in upper-ocean overturning associated with millennial-scale events differ from those associated with whole-ocean deglacial climate events.

Chemical composition of ferromanganese concretions and host bottom sediments from the Black Sea

Ferromanganese concretions spread out on the bottom of the shallow northwest part of the Black Sea are mainly represented by Fe and Mn nodules on shells and substituted worm tubes. Element composition of these formations was measured by methods of chemical, atomic absorbtion, neutron activation, and ICP-MS analyses. It was established that Fe and Mn contents and Mn/Fe ratio in the concretions varied considerably and which controlled occurrence of several associated metals and minor elements; some of them have not been studied in Black Sea concretions before.

Composition of phosphorites from continental margins, seamounts, and islands

Behavior of molybdenum and manganese is studied in phosphorite samples from shelves, seamounts, and islands of the ocean. In shelf phosphorites molybdenum and manganese contents are 2-128 and 12-1915 ppm, respectively, while the Mo/Mn ratio varies from 0.004 to 4.5. Phosphorites from ocean seamounts impregnated with ferromanganese oxyhydroxides contain 0.84-14.5 ppm Mo and 0.1-17% Mn. The Mo/Mn ratio varies within 0.0008-0.004. Phosphate bearing ferromanganese crusts overlying seamount phosphorites contain 54-798 ppm Mo and 10-20% Mn; the Mo/Mn ratio varies within 0.002-0.005. Corresponding values for most island phosphorites are 0.44-11.2 ppm, 27-287 ppm, and 0.008-0.20. Phosphorites from reduced environment are characterized by relative enrichment in Mo and depletion in Mn, whereas the Mo/Mn ratio reaches maximum values. The ratio decreases with transition to suboxic and oxic conditions. Molybdenum content in recent shelf sediments is commonly higher than that in authigenic phosphorites from these sediments. Recent phosphorite nodules from the Namibian shelf become depleted in Mo and Mn during their lithification, but Pliocene-Pleistocene nodules of similar composition and origin from the same region are enriched in Mo and characterized by variable Mn content. Higher Mo contents in phosphate bearing ferromanganese crusts result from coprecipitation of Mo and Mn from seawater. Unweathered phosphorites on continents and phosphorites from ocean shelves are largely enriched in Mo with the Mo/Mn ratio varying from 0.01 to 1.0. This is an evidence of their formation in reduced conditions.

Chemical and isotopic compositions of basaltic glasses and crusts from the Mid-Atlantic Ridge rift valley

Data presented in the paper suggest significant differences between thermodynamic conditions, under which magmatic complexes were formed in MAR at 29°-34°N and 12°-18°N. Melts occurring at 29°-34°N were derived by melting of a mantle source with homogeneous distribution of volatile components and arrived at the surface without significant fractionation, likely, due to their rapid ascent. The MAR segments between 12° and 18°N combine contrasting geodynamic environments of magmatism, which predetermined development of a large plume region with widespread mixing of melting products of geochemically distinct mantle sources. At the same time, this region is characterized by conditions favorable for origin of localized zones of anomalous plume magmatism. These sporadic magmatic sources were spatially restricted to MAR fragments with the Hess crust, whose compositional and mechanical properties were, perhaps, favorable for focusing and localization of plume magmatism. The plume source between 12° and 18°N beneath MAR may be geochemically heterogeneous.

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.