Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Nd, Sr and Sm isotopic composition and model ages of rocks from the Anginskaya and Talanchanskaya formations, Lake Baikal

The paper presents data on the Nd-Sr systematics of magmatic rocks of the Khaidaiskii Series of the Anginskaya Formation in the Ol'khon region, western Baikal area, and rocks of the Talanchanskaya Formation on the eastern shore of Lake Baikal. Geochemical characteristics of these rocks are identical and testify to their arc provenance. At the same time, the epsilon(t)Nd of rocks of the Khaidaiskii Series in the Ol'khon area has positive values, and the data points of these rocks plot near the mantle succession line in the epsilon(t)Nd-87Sr/86Sr diagram, whereas the epsilon(t)Nd values of rocks of the Talanchanskaya Formation are negative, and the data points of these rocks fall into the fourth quadrant in the epsilon(t)Nd -87Sr/86Sr diagram. This testifies to a mantle genesis of the parental magmas of the Khaidaiskii Series and to the significant involvement of older crustal material in the generation of the melts that produced the orthorocks on the eastern shore of the lake. These conclusions are corroborated by model ages of magmatic rocks in the Ol'khon area (close to 1 Ga) and of rocks of the Talanchanskaya Formation (approximately 2 Ga). The comparison of our data with those obtained by other researchers on the Nd-Sr isotopic age of granulites of the Ol'khon Group and metavolcanics in various structural zones in the northern Baikal area suggests, with regard for the geochemistry of these rocks, the accretion of tectonic nappes that had different isotopic histories: some of them were derived from the mantle wedge and localized in the island arc itself (magmatic rocks of the Anginskaya Formation) or backarc spreading zone (mafic metamagmatic rocks of the Ol'khon Group), while others were partial melts derived, with the participation of crustal material, from sources of various age (metagraywackes in the backarc basin in the Ol'khon Group and the ensialic basement of the island arc in the Talanchanskaya Formation).

Element contents and isotope composition of sediments and basalts from DSDP Site 78-543

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb (206Pb/204Pb up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and 143Nd/144Nd increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas. Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of "normal" depleted MORB.

Geochemistry and isotopic ratios of samples obtained during R/V Akademik Nikolaj Strakhov cruise ANS24

New petrological and geochemical data were obtained for basalts recovered during cruise 24 of the R/V "Akademik Nikolay Strakhov" in 2006. These results significantly contributed to the understanding of the formation of tholeiitic magmatism at the northern end of the Knipovich Ridge of the Polar Atlantic. Dredging was performed for the first time both in the rift valley and on the flanks of the ridge. It showed that the conditions of magmatism have not changed since at least 10 Ma. The basalts correspond to slightly enriched tholeiites, whose primary melts were derived at the shallowest levels and were enriched in Na and depleted in Fe (Na-TOR type). The most enriched basalts are typical of the earlier stages of the opening and were found on the flanks of the ridge in its northernmost part. Variations in the ratios of Sr, Nd, and Pb isotopes and lithophile elements allowed us to conclude that the primary melts generated beneath the spreading zone of the Knipovich Ridge were modified by the addition of the enriched component that was present both in the Neogene and Quaternary basalts of Spitsbergen Island. Compared with the primitive mantle, the extruding magmas were characterized by positive Nb and Zr anomalies and a negative Th anomaly. The formation of primary melts involved melting of the metasomatized depleted mantle reservoir that appeared during the early stages of opening of the Norwegian-Greenland Basin and transformation of the paleo-Spitsbergen Fault into the Knipovich spreading ridge, which was accompanied by magmatism in western Spitsbergen during its separation from the northern part of Greenland.

Automated Tools for Layer Recognition (BMPix) and Counting (PEAK)

We present tools for rapid and quantitative detection of sediment lamination. The BMPix tool extracts color and gray-scale curves from images at pixel resolution. The PEAK tool uses the gray-scale curve and performs, for the first time, fully automated counting of laminae based on three methods. The maximum count algorithm counts every bright peak of a couplet of two laminae (annual resolution) in a smoothed curve. The zero-crossing algorithm counts every positive and negative halfway-passage of the curve through a wide moving average, separating the record into bright and dark intervals (seasonal resolution). The same is true for the frequency truncation method, which uses Fourier transformation to decompose the curve into its frequency components before counting positive and negative passages. We applied the new methods successfully to tree rings, to well-dated and already manually counted marine varves from Saanich Inlet, and to marine laminae from the Antarctic continental margin. In combination with AMS14C dating, we found convincing evidence that laminations in Weddell Sea sites represent varves, deposited continuously over several millennia during the last glacial maximum. The new tools offer several advantages over previous methods. The counting procedures are based on a moving average generated from gray-scale curves instead of manual counting. Hence, results are highly objective and rely on reproducible mathematical criteria. Also, the PEAK tool measures the thickness of each year or season. Since all information required is displayed graphically, interactive optimization of the counting algorithms can be achieved quickly and conveniently.

Contents of major components, U, and Th in bones and bone debris

Uranium and thorium contents, as well as their distribution patterns have been studied in biogenic phosphates from the Atlantic and Pacific Oceans. Differently lithified fish remains (bones, scales, teeth) and marine mammal bones (ribs, vertebras, earbones) collected from both reduced shelf sediments and oxidized pelagic ones have been analyzed. U content in the material varies from 0.7 to 700 ppm, and Th content - from <0.5 to 14 ppm. U/Th ratio varies from 0.16 to 400. Contents of both elements increase with lithification of biogenic phosphates. U concentration is more intense on shelves, whereas thorium concentration increases in pelagic areas. Partial positive correlation of U and Th with Fe and negative correlation of U with organic carbon are noted. The latter corresponds to higher lithification of biogenic phosphates. Calcium phosphate transformed from hydroxyapatite to fluorcarbonate-apatite is the main carrier of U, while transformed organic matter is a minor agent. Thorium is mainly bound with Fe.

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.

Paleogene and early Neogene stable isotope record of foraminifera from ODP Leg 119 samples

Oxygen and carbon isotopic records of monogeneric and monospecific benthic and planktonic foraminifer samples from Sites 744 and 738 drilled on the southern end of the Kerguelen Plateau during ODP Leg 119 reveal the evolution of polar Indian Ocean water masses from the early Paleocene to the middle Miocene. Results from Site 738 are from sediments of early Paleocene to late Eocene age and those from Site 744 are late Eocene to middle Miocene. They suggest that intermediate waters at this location did not originate in the high latitudes during the early Eocene. Surface and near-surface waters cooled gradually after the maximum warming at 56 Ma, when surface waters were about 18°C. Intermediate waters cooled after 52 Ma. The highest temperatures (lowest d18O values) of the Cenozoic occurred from 56 to 52 Ma. The records of equatorial Pacific Site 577 and Weddell Sea Site 690 resemble that of the polar Indian Ocean in this interval. The well-documented d13C excursions toward positive values in the late Paleocene and negative values in the early Eocene are represented by foraminifers increases of 1.5 per mil and following decreases of about 3 per mil. Most of the cooling in the Paleogene occurred in the middle and late Eocene. A 2°C decrease of surface water at about 38.4 Ma heralded the beginning of extensive glacial conditions in Antarctica in the early Oligocene. At Site 744, the global d18O shift just above the Eocene/Oligocene boundary is 1.15 per mil, and occurred gradually in sediments dated at 36.5-35.9 Ma. Ice-rafted debris was deposited beginning at 36.1 Ma for about the next 2 m.y. This simultaneous occurrence of the global d18O shift with ice-rafted debris is evidence for early Oligocene glaciation in East Antarctica. Moreover, early and late Oligocene Cibicidoides d18O values between 2 and 2.2 per mil indicate intermediate water cooling and a small ice-volume effect. Production of cold dense bottom water in Antarctica was intensified with continental cooling and glaciation in the early Oligocene. Comparison of Oligocene and early Miocene isotopic data from high-latitude and low-latitude deepsea sites indicates that there were probably at least two sources of bottom waters at this time.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Colimitation of the unicellular photosynthetic diazotroph Crocosphaera watsonii by phosphorus, light, and carbon dioxide

We describe interactive effects of total phosphorus (total P = 0.1-4.0 µmol/L; added as H2NaPO4), irradiance (40 and 150 µmol quanta/m**2/s), and the partial pressure of carbon dioxide (P-CO2; 19 and 81 Pa, i.e., 190 and 800 ppm) on growth and CO2- and dinitrogen (N-2)-fixation rates of the unicellular N-2-fixing cyanobacterium Crocosphaera watsonii (WH0003) isolated from the Pacific Ocean near Hawaii. In semicontinuous cultures of C. watsonii, elevated P-CO2 positively affected growth and CO2- and N-2-fixation rates under high light. Under low light, elevated P-CO2 positively affected growth rates at all concentrations of P, but CO2- and N-2-fixation rates were affected by elevated P-CO2 only when P was low. In both high-light and low-light cultures, the total P requirements for growth and CO2- and N-2-fixation declined as P-CO2 increased. The minimum concentration (C-min) of total P and half-saturation constant (K-1/2) for growth and CO2- and N-2-fixation rates with respect to total P were reduced by 0.05 µmol/L as a function of elevated P-CO2. We speculate that low P requirements under high P-CO2 resulted from a lower energy demand associated with carbon-concentrating mechanisms in comparison with low-P-CO2 cultures. There was also a 0.10 µmol/L increase in C-min and K-1/2 for growth and N-2 fixation with respect to total P as a function of increasing light regardless of P-CO2 concentration. We speculate that cellular P concentrations are responsible for this shift through biodilution of cellular P and possibly cellular P uptake systems as a function of increasing light. Changing concentrations of P, CO2, and light have both positive and negative interactive effects on growth and CO2-, and N-2-fixation rates of unicellular oxygenic diazotrophs like C. watsonii.