Catalysts and processes for next-generation H2 production

The present study is focused on the development of new VIII group metal on CeO2 – ZrO2 (CZO) catalyst to be used in reforming reaction for syngas production. The catalyst are tested in the oxyreforming process, extensively studied by Barbera [44] in a new multistep process configuration, with intermediate H2 membrane separation, that can be carried out at lower temperature (750°C) with respect the reforming processes (900 – 1000°C). In spite of the milder temperatures, the oxy-reforming conditions (S/C = 0.7; O2/C = 0.21) remain critical regarding the deactivation problems mainly deriving from thermal sintering and carbon formation phenomena. The combination of the high thermal stability characterizing the ZrO2, with the CeO2 redox properties, allows the formation of stable mixed oxide system with high oxygen mobility. This feature can be exploited in order to contrast the carbon deposition on the active metal surface through the oxidation of the carbon by means of the mobile oxygen atoms available at the surface of the CZO support. Ce0.5Zr0.5O2 is the phase claimed to have the highest oxygen mobility but its formation is difficult through classical synthesis (co-precipitation), hence a water-in-oil microemulsion method is, widely studied and characterized. Two methods (IWI and bulk) for the insertion of the active metal (Rh, Ru, Ni) are followed and their effects, mainly related to the metal stability and dispersion on the support, are discussed, correlating the characterization with the catalytic activity. Different parameters (calcination and reduction temperatures) are tuned to obtain the best catalytic system both in terms of activity and stability. Interesting results are obtained with impregnated and bulk catalysts, the latter representing a new class of catalysts. The best catalysts are also tested in a low temperature (350 – 500°C) steam reforming process and preliminary tests with H2 membrane separation have been also carried out.

Synthese von grenzflächenaktiven Monomeren zur Herstellung von funktionalen Metall-Chalkogenid,Polymer-Hybridnanopartikeln

In dieser Arbeit wurde gezeigt, wie oberflächenfunktionalisierte Polystyrolnanopartikel zur Herstellung von Metallchalkogenid/Polymer-Hybridnanopartikeln eingesetzt werden können. Dazu wurden zunächst phosphonsäure- und phosphorsäurefunktionalisierte Surfmere synthetisiert, die anschließend bei der Miniemulsionspolymerisation von Styrol verwendet wurden. Die Surfmere dienten dabei zugleich zur Stabilisierung und als Comonomer. Die oberflächenfunktionalisierten Polystyrolnanopartikel wurden anschließend als Trägerpartikel für die Kristallisation von Metalloxiden eingesetzt. Dabei wurden Metalloxid/Polymer-Hybridnanopartikel mit einer „himbeerartigen“ Morphologie erhalten. Um die vielseitige Modifizierbarkeit der phosphonat- und phosphat¬funktionalisierten Polystyrolpartikel zu demonstrieren, wurden Cer-, Eisen- sowie Zinkoxid auf der Partikeloberfläche kristallisiert. Dazu wurden sowohl wässrige als auch alkoholische Metalloxid-Präkursorlösungen eingesetzt. Die synthetisierten Metall¬oxid/Polymer-Hybridpartikel wurden detailliert mit REM, TEM und PXRD analysiert. Die Untersuchung des Kristallisationsmechanismus hatte erwiesen, dass die komplexierten Metallkationen auf der Partikeloberfläche als Nukleationszentren wirkten und die Zutropfrate des Fällungsreagenz entscheidend für die Oberflächenkristallisation ist. Durch Mischungsexperimente von Metalloxidnanopartikeln und den oberflächen¬funktionalisierten Polymerpartikeln konnte die Hybridpartikelbildung über Hetero¬koagulation ausgeschlossen werden. Außerdem wurde festgestellt, dass die Polarität der funktionellen Gruppe über die Stärke der Komplexierung der Metalloxid-Präkursor bestimmt. Darüber hinaus wurde ein Modell zur Erklärung der kolloidalen Stabilisierung der Metalloxid/Polymer-Hybridsysteme aufgestellt und ein Zusammenhang zwischen dem gemessenen Zeta-Potential und der Oberflächenbedeckung der Polymerpartikel durch Metalloxid gefunden. Mit der Methode der Oberflächenkristallisation konnten frühe Stadien der Nukleation auf der Partikeloberfläche fixiert werden. Weiterhin wurden die individuellen physikalisch-chemischen Eigenschaften der hergestellten Metall¬oxid/Polymer-Hybridnano¬partikel untersucht. Dabei zeigten die CeO2/Polymer-Hybridpartikel eine hohe katalytische Aktivität bezüglich der photokatalytischen Oxidation von Rhodamin B, die als Modellreaktion durchgeführt wurde. Des Weiteren wurde die Magnetisierung der Magnetit/Polymer-Hybridpartikel gemessen. Die Fe3O4-Hybrid¬partikelsysteme wiesen eine vergleichbare Sättigungsmagnetisierung auf. Die Zinkoxid/Polymer-Hybridsysteme zeigten eine starke Lumineszenz im sichtbaren Bereich bei Anregung mit UV-Licht. Die Metalloxid/Polymer-Hybridpartikel, die mit den phosphonat- oder phosphatfunktion¬alisierten Polystyrolpartikeln hergestellt wurden, zeigten keine signifikanten Unterschiede in ihren physikochemischen Eigenschaften. Im Allgemeinen lässt sich schlussfolgern, dass sowohl Phosphonat- als auch Phosphatgruppen gleichermaßen für die Oberflächenkristallisation von Metalloxiden geeignet sind. Die Zink¬oxid/Polymer-Hybridsysteme stellen eine Ausnahme dar. Die Verwendung der phosphonat¬funktionalisierten Polystyrolpartikel führte zur Entstehung einer Zinkhydroxidphase, die neben der Zinkoxidphase gebildet wurde. Aufgrund dessen zeigten die ZnO/RPO3H2-Hybridpartikel eine geringere Lumineszenz im sichtbaren Bereich als die ZnO/RPO4H2-Hybridsysteme.rnDie Erkenntnisse, die bei der Oberflächenkristallisation von Metalloxiden gewonnen wurden, konnten erfolgreich auf Cadmiumsulfid übertragen werden. Dabei konnte Cadmiumsulfid auf der Oberfläche von phosphonatfunktionalisierten Polystyrolpartikeln kristallisiert werden. Mit Hilfe des RPO3H2-Surfmers konnten phosphonatfunktion¬alisierte Polystyrolpartikel mit superparamagnetischem Kern synthetisiert werden, die zur Herstellung von multifunktionalen CdS/Polymer-Hybridpartikeln mit Magnetitkern verwendet wurden. Die Kristallphase und die Oberflächenbedeckung der multi¬funktionalen Hybridsysteme wurden mit den CdS/Polymer-Hybridsystemen ohne magnetischen Kern verglichen. Dabei konnte nachgewiesen werden, dass in beiden Fällen Cadmiumsulfid in der Greenockit-Modifikation gebildet wurde. Die multifunktionalen CdS/Polymer-Hybridpartikel mit superparamagnetischem Kern konnten sowohl mit einem optischen als auch einem magnetischen Stimulus angeregt werden.rnrn

Reforming dell'etanolo con processo ciclico: studio della reattività di ossidi misti con struttura spinello

This work deals with a study on the feasibility of a new process, aimed at the production of hydrogen from water and ethanol (a compound obtained starting from biomasses), with inherent separation of hydrogen from C-containing products. The strategy of the process includes a first step, during which a metal oxide is contacted with ethanol at high temperature; during this step, the metal oxide is reduced and the corresponding metallic form develops. During the second step, the reduced metal compound is contacted at high temperature with water, to produce molecular hydrogen and with formation of the original metal oxide. In overall, the combination of the two steps within the cycle process corresponds to ethanol reforming, where however COx and H2 are produced separately. Various mixed metal oxides were used as electrons and ionic oxygen carriers, all of them being characterized by the spinel structure typical of M-modified non-stoichiometric ferrites: M0,6Fe2,4O4 (M = Co, Mn or Co/Mn). The first step was investigated in depth; it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation. The new materials were tested in terms of both redox proprieties and catalytic activity to generate hydrogen. Still the problem of coke formation remains the greater challenge to solve.

Micromass co-culture of human articular chondrocytes and human bone marrow mesenchymal stem cells to investigate stable neocartilage tissue formation in vitro

Cell therapies for articular cartilage defects rely on expanded chondrocytes. Mesenchymal stem cells (MSC) represent an alternative cell source should their hypertrophic differentiation pathway be prevented. Possible cellular instruction between human articular chondrocytes (HAC) and human bone marrow MSC was investigated in micromass pellets. HAC and MSC were mixed in different percentages or incubated individually in pellets for 3 or 6 weeks with and without TGF-beta1 and dexamethasone (±T±D) as chondrogenic factors. Collagen II, collagen X and S100 protein expression were assessed using immunohistochemistry. Proteoglycan synthesis was evaluated applying the Bern score and quantified using dimethylmethylene blue dye binding assay. Alkaline phosphatase activity (ALP) was detected on cryosections and soluble ALP measured in pellet supernatants. HAC alone generated hyaline-like discs, while MSC formed spheroid pellets in ±T±D. Co-cultured pellets changed from disc to spheroid shape with decreasing number of HAC, and displayed random cell distribution. In -T-D, HAC expressed S100, produced GAG and collagen II, and formed lacunae, while MSC did not produce any cartilage-specific proteins. Based on GAG, collagen type II and S100 expression chondrogenic differentiation occurred in -T-D MSC co-cultures. However, quantitative experimental GAG and DNA values did not differ from predicted values, suggesting only HAC contribution to GAG production. MSC produced cartilage-specific matrix only in +T+D but underwent hypertrophy in all pellet cultures. In summary, influence of HAC on MSC was restricted to early signs of neochondrogenesis. However, MSC did not contribute to the proteoglycan deposition, and HAC could not prevent hypertrophy of MSC induced by chondrogenic stimuli.

Nitrogen Oxides in the North Atlantic Troposphere: Impacts of Boreal Wildfire and Anthropogenic Emissions

Nitrogen oxides play a crucial role in the budget of tropospheric ozone (O sub(3)) and the formation of the hydroxyl radical. Anthropogenic activities and boreal wildfires are large sources of emissions in the atmosphere. However, the influence of the transport of these emissions on nitrogen oxides and O sub(3) levels at hemispheric scales is not well understood, in particular due to a lack of nitrogen oxides measurements in remote regions. In order to address these deficiencies, measurements of NO, NO sub(2) and NO sub(y) (total reactive nitrogen oxides) were made in the lower free troposphere (FT) over the central North Atlantic region (Pico Mountain station, 38 degree N 28 degree W, 2.3 km asl) from July 2002 to August 2005. These measurements reveal a well-defined seasonal cycle of nitrogen oxides (NO sub(x) = NO+NO sub(2) and NO sub(y)) in the background central North Atlantic lower FT, with higher mixing ratios during the summertime. Observed NO sub(x) and NO sub(y) levels are consistent with long-range transport of emissions, but with significant removal en-route to the measurement site. Reactive nitrogen largely exists in the form of PAN and HNO sub(3) ( similar to 80-90% of NO sub(y)) all year round. A shift in the composition of NO sub(y) from dominance of PAN to dominance of HNO sub(3) occurs from winter-spring to summer-fall, as a result of changes in temperature and photochemistry over the region. Analysis of the long-range transport of boreal wildfire emissions on nitrogen oxides provides evidence of the very large-scale impacts of boreal wildfires on the tropospheric NO sub(x) and O sub(3) budgets. Boreal wildfire emissions are responsible for significant shifts in the nitrogen oxides distributions toward higher levels during the summer, with medians of NO sub(y) (117-175 pptv) and NO sub(x) (9-30 pptv) greater in the presence of boreal wildfire emissions. Extreme levels of NO sub(x) (up to 150 pptv) and NO sub(y) (up to 1100 pptv) observed in boreal wildfire plumes suggest that decomposition of PAN to NO sub(x) is a significant source of NO sub(x), and imply that O sub(3) formation occurs during transport. Ozone levels are also significantly enhanced in boreal wildfire plumes. However, a complex behavior of O sub(3) is observed in the plumes, which varies from significant to lower O sub(3) production to O sub(3) destruction. Long-range transport of anthropogenic emissions from North America also has a significant influence on the regional NO sub(x) and O sub(3) budgets. Transport of pollution from North America causes significant enhancements on nitrogen oxides year-round. Enhancements of CO, NO sub(y) and NO sub(x) indicate that, consistent with previous studies, more than 95% of the NO sub(x) emitted over the U.S. is removed before and during export out of the U.S. boundary layer. However, about 30% of the NO sub(x) emissions exported out of the U.S. boundary layer remain in the airmasses. Since the lifetime of NO sub(x) is shorter than the transport timescale, PAN decomposition and potentially photolysis of HNO sub(3) provide a supply of NO sub(x) over the central North Atlantic lower FT. Observed Delta O sub(3)/ Delta NO sub(y) and large NO sub(y) levels remaining in the North American plumes suggest potential O sub(3) formation well downwind from North America. Finally, a comparison of the nitrogen oxides measurements with results from the global chemical transport (GCT) model GEOS-Chem identifies differences between the observations and the model. GEOS-Chem reproduces the seasonal variation of nitrogen oxides over the central North Atlantic lower FT, but does not capture the magnitude of the cycles. Improvements in our understanding of nitrogen oxides chemistry in the remote FT and emission sources are necessary for the current GCT models to adequately estimate the impacts of emissions on tropospheric NO sub(x) and the resulting impacts on the O sub(3) budget.

Effects of Supplementing High or Low Quality Forages with Corn or Corn Processing Co-Products Upon Digestibility of Dry Matter and Energy by Steers

A digestibility trial, utilizing eight crossbred steers weighing initially 741 lbs. was conducted in an 8 x 8 Latin square design. High-fiber corn by-products were compared with corn as energy sources when fed in mixed diets with either lowor high-quality forage. Ground, dry corn stover and ground alfalfa hay were both fed alone or with corn grain, dried corn gluten feed (CGF), and dried corn distillers grains plus solubles (DDG) in a 1:1 ratio (dry basis). Total tract dry matter digestibility (DMD) was increased for both forages when fed with concentrates. Total tract DMD was similar in stover-based and alfalfa-based diets fed with CGF and DDG. However, stover+corn was lower in DMD than either stover+CGF and stover+DDG. Conversely, alfalfa+corn was higher in DMD than alfalfa+CGF or alfalfa+DDG. Feeding stover with corn tended to decrease digestibility of neutral detergent fiber (NDF), while feeding stover with CGF or DDG increased NDFD. There was no effect upon NDF digestion of alfalfa-based diets when fed with any of the concentrates. Feeding either forage with a concentrate increased digestible energy (DE). Stover+CGF and stover+DDG were similar in DE and were both higher in DE than stover+corn. Alfalfa+DDG tended to be higher than alfalfa+CGF and was similar to alfalfa+corn in DE. Alfalfa+CGF was lower in DE compared with alfalfa+corn. Results are interpreted to indicate that stover is more susceptible to negative feed interactions caused by corn grain than is alfalfa. Additionally, highfiber corn co-products fed with stover resulted in a positive associative effect but essentially had no associative effect when fed with alfalfa.

Unique mixed phenotype and unexpected functional effect revealed by novel compound heterozygosity mutations involving SCN5A.

BACKGROUND Functional characterization of mutations involving the SCN5A-encoded cardiac sodium channel has established the pathogenic mechanisms for type 3 long QT syndrome and type 1 Brugada syndrome and has provided key insights into the physiological importance of essential structure-function domains. OBJECTIVE This study sought to present the clinical and biophysical phenotypes discerned from compound heterozygosity mutations in SCN5A on different alleles in a toddler diagnosed with QT prolongation and fever-induced ventricular arrhythmias. METHODS A 22-month-old boy presented emergently with fever and refractory ventricular tachycardia. Despite restoration of sinus rhythm, the infant sustained profound neurological injury and died. Using polymerase chain reaction, denaturing high-performance liquid chromatography, and direct DNA sequencing, comprehensive open-reading frame/splice mutational analysis of the 12 known long QT syndrome susceptibility genes was performed. RESULTS The infant had 2 SCN5A mutations: a maternally inherited N-terminal frame shift/deletion (R34fs/60) and a paternally inherited missense mutation, R1195H. The mutations were engineered by site-directed mutagenesis and heterologously expressed transiently in HEK293 cells. As expected, the frame-shifted and prematurely truncated peptide, SCN5A-R34fs/60, showed no current. SCN5A-R1195H had normal peak and late current but abnormal voltage-dependent gating parameters. Surprisingly, co-expression of SCN5A-R34fs/60 with SCN5A-R1195H elicited a significant increase in late sodium current, whereas co-expression of SCN5A-WT with SCN5A-R34fs/60 did not. CONCLUSIONS A severe clinical phenotype characterized by fever-induced monomorphic ventricular tachycardia and QT interval prolongation emerged in a toddler with compound heterozygosity involving SCN5A: R34fs/60, and R1195H. Unexpectedly, the 94-amino-acid fusion peptide derived from the R34fs/60 mutation accentuated the late sodium current of R1195H-containing Na(V)1.5 channels in vitro.

Atmospheric CO₂ response to volcanic eruptions: The role of ENSO, season, and variability

Tropical explosive volcanism is one of the most important natural factors that significantly impact the climate system and the carbon cycle on annual to multi-decadal time scales. The three largest explosive eruptions in the last 50�years�Agung, El Chichón, and Pinatubo�occurred in spring/summer in conjunction with El Niño events and left distinct negative signals in the observational temperature and CO2 records. However, confounding factors such as seasonal variability and El Niño-Southern Oscillation (ENSO) may obscure the forcing-response relationship. We determine for the first time the extent to which initial conditions, i.e., season and phase of the ENSO, and internal variability influence the coupled climate and carbon cycle response to volcanic forcing and how this affects estimates of the terrestrial and oceanic carbon sinks. Ensemble simulations with the Earth System Model (Climate System Model 1.4-carbon) predict that the atmospheric CO2 response is �60 larger when a volcanic eruption occurs during El Niño and in winter than during La Niña conditions. Our simulations suggest that the Pinatubo eruption contributed 11�±�6 to the 25�Pg terrestrial carbon sink inferred over the decade 1990�1999 and �2�±�1 to the 22�Pg oceanic carbon sink. In contrast to recent claims, trends in the airborne fraction of anthropogenic carbon cannot be detected when accounting for the decadal-scale influence of explosive volcanism and related uncertainties. Our results highlight the importance of considering the role of natural variability in the carbon cycle for interpretation of observations and for data-model intercomparison.

Slow conduction in mixed cultured strands of primary ventricular cells and stem cell-derived cardiomyocytes

Modern concepts for the treatment of myocardial diseases focus on novel cell therapeutic strategies involving stem cell-derived cardiomyocytes (SCMs). However, functional integration of SCMs requires similar electrophysiological properties as primary cardiomyocytes (PCMs) and the ability to establish intercellular connections with host myocytes in order to contribute to the electrical and mechanical activity of the heart. The aim of this project was to investigate the properties of cardiac conduction in a co-culture approach using SCMs and PCMs in cultured cell strands. Murine embryonic SCMs were pooled with fetal ventricular cells and seeded in predefined proportions on microelectrode arrays to form patterned strands of mixed cells. Conduction velocity (CV) was measured during steady state pacing. SCM excitability was estimated from action potentials measured in single cells using the patch clamp technique. Experiments were complemented with computer simulations of conduction using a detailed model of cellular architecture in mixed cell strands. CV was significantly lower in strands composed purely of SCMs (5.5 ± 1.5 cm/s, n = 11) as compared to PCMs (34.9 ± 2.9 cm/s, n = 21) at similar refractoriness (100% SCMs: 122 ± 25 ms, n = 9; 100% PCMs: 139 ± 67 ms, n = 14). In mixed strands combining both cell types, CV was higher than in pure SCMs strands, but always lower than in 100% PCM strands. Computer simulations demonstrated that both intercellular coupling and electrical excitability limit CV. These data provide evidence that in cultures of murine ventricular cardiomyocytes, SCMs cannot restore CV to control levels resulting in slow conduction, which may lead to reentry circuits and arrhythmias.

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.

The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

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 on manganese nodules from Loch Fyne, Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10-15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180-200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5-8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments. The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn. The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice. Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.

Geochemistry of mafic clasts of ODP Holes 125-778A and 125-779A

Clasts of metamorphosed mafic igneous rock of diverse composition were recovered in two drill sites on a serpentine mud volcano in the outer Mariana forearc during Ocean Drilling Program Leg 125. These clasts are xenolithic fragments that have been entrained in the rising serpentine mud, and make up less that 9% of the total rock recovered at Sites 778 and 779. Most samples are metabasalt or metadiabase, although one clast of possible boninite and one cumulate gabbro were recovered. On the basis of trace element signatures, samples are interpreted to represent both arc-derived and mid-ocean ridge-derived compositions. Rocks with extremely low TiO2 (<0.3 wt%) and Zr (<30 ppm) are similar to boninite series rocks. Samples with low TiO2 (<0.9 wt%) and Zr (<50 ppm) and extreme potassium enrichment (K2O/Na2O >3.9) may represent island arc rocks similar to shoshonites. However, the K2O/Na2O ratios are much higher than those reported for shoshonites from modem or ancient arcs and may be the result of metamorphism. Samples with moderate TiO2 (1.4 to 1.5 wt%) and Zr (72 to 85 ppm) are similar to rocks from mid-ocean ridges. A few samples have TiO2 and Zr intermediate between island arc and mid-ocean ridge basalt-like rocks. Two samples have high iron (Fe2O3* = >12.8 to 18.5 wt%) (Fe2O3* = total iron calculated as Fe2O3) and TiO2 (>2.3 wt%) and resemble FeTi basalt recovered from mid-ocean ridges. Metamorphism in most samples ranges from low-temperature zeolite, typical of ocean floor weathering, to prehnite-pumpellyite facies and perhaps lower greenschist. Blue amphibole and lawsonite minerals are present in several samples. One diabase clast (Sample 9) exhibits Ca enrichment, similar to rodingite metamorphism, typical of mafic blocks in serpentinized masses. The presence of both low-grade (clays and zeolites) and higher grade (lawsonite) metamorphism indicates retrograde processes in these clasts. These clasts are fragments of the forearc crust and possibly of the subducting plate that have been entrained in the rising serpentine and may represent the deepest mafic rocks ever recovered from the Mariana forearc. The variable compositions and degree of metamorphism of these clasts requires at least two tectonic origins. The recovery of clasts with mid-ocean ridge and arc chemical affinities in a single drill hole requires these clasts to have been "mixed" on a small scale either (1) in the forearc crustal sequence, or (2) after inclusion in the rising serpentine mud. The source of the MORB-like samples and an explanation for the presence of both MORB-like and arc-like rocks in close proximity is critical to any model of the evolution of the Mariana forearc. The source of the MORB-like samples likely will be one (or more) of the following: (1) accretion of Pacific plate lithosphere, (2) remnants of original forearc crust (trapped plate), (3) volcanism in the supra-subduction zone (arc or forearc) environment, or (4) derivation from the subducting slab by faulting along the dÈcollement.