Whole rock and Cr-rich spinel geochemistry of ODP Legs 152 and 163 and DSDP Hole 38-338 samples

Coring during Ocean Drilling Program and Deep Sea Drilling Project Legs 163, 152, 104, 81, and 38 recovered sequences of altered basalt from North Atlantic seaward-dipping reflector sequences (SDRS) erupted during the initial rifting of Greenland from northern Europe and likely associated with excessive mantle temperatures caused by an impacting mantle plume head. Cr-rich spinel is found abundantly as inclusions and groundmass crystals within the olivine-rich lavas of Hole 917A (Leg 152) cored into the Southeast Greenland SDRS, but only rarely as inclusions within plagioclase in the lavas of the Vøring Plateau SDRS, and it is absent from other cored SDRS lavas from the Rockall Plateau and Southeast Greenland. Eruptive melt compositions determined from inferred, thermodynamically-defined, spinel-melt exchange equilibria indicate that the most primitive melts represented by Hole 917A basalts have Mg/(Mg + Fe2+) at least as high as 0.70 and approach near-primary mantle melt compositions. In contrast, Cr-rich spinels from Hole 338 (Leg 38) lavas on the Vøring Plateau SDRS give evidence for melt with Mg/(Mg + Fe2+) only as high as 0.64. This study underlines that primitive melts similar to those from Hole 917A comprise only a small fraction of the eruptive North Atlantic SDRS melts, and that most SDRS basalts were, in fact, too evolved to have precipitated Cr-rich spinel, with true melt Mg/(Mg + Fe2+) likely below 0.60. The evolved nature of the SDRS basalts implies large amounts of fractionation at the base of the crust or deep within it, consistent with seismic results that indicate an abnormally thick Layer 3 underlying the SDRS.

Sediment geochemistry of ODP Holes 206-1256B and 206-1256C

We measured the chemical composition of 100 samples from the 250-m sediment sequence retrieved from Ocean Drilling Program Site 1256 in the Guatemala Basin using a newly developed microwave-assisted acid digestion protocol followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis. We compared these data gathered onshore to the results from the flux fusion prepared samples analyzed by shipboard ICP-AES during the leg and published in the Leg 206 Initial Reports volume, as well as to 35 randomly selected samples that were prepared by flux fusion at Boston University and analyzed by ICP-AES. Comparison of the newly developed acid digestion protocol to shore-based flux fusion demonstrates that the microwave-assisted acid technique yields a complete digestion, and because this procedure includes boric acid, it is safe for use with HF acid as boric acid neutralizes excess HF. The precision for nearly all elements in shore-based acid digestions is better than 3% of the measured values, including for elements such as Ni, Cr, and V, which are typically difficult to measure in biogenic-rich sediments. The shore-based flux fusions, while better than shipboard reported precision values (as expected), has precision better than 3% of their respective measured values for all major elements (Si, Al, Ti, Fe, Mn, Ca, Mg, Na, and K) and several trace elements (Ba and Sr). Results for P, Cr, Ni, V, Sc, and Zr are better than 5% of their measured values. Not only does the newly developed acid digestion provide better analytical results than the typical flux fusion method, the shore-based acid procedure also exhibits downhole lithologic and chemical characteristics similar to the shipboard flux fusion prepared results. These results confirm that the current shipboard methods are adequate for first-order geochemical interpretations and that the microwave-assisted acid digestion holds great potential to be the primary technique of preparing sediments on future Integrated Ocean Drilling Program expeditions.

Geochemistry and stable isotope record of black shales and inoceramids from the Demerara Rise

The bulk rock geochemistry and inoceramid isotopic composition from Cenomanian to Santonian, finely laminated, organic-rich black shales, recovered during Ocean Drilling Program Leg 207 on Demerara Rise (western tropical North Atlantic), suggest persistent anoxic (free H2S) conditions within the sediments and short-term variations within a narrow range of anoxic to episodically dysoxic bottom waters over a ~15 Ma time interval. In addition to being organic-rich, the 50-90 m thick sections examined exhibit substantial bulk rock enrichments of Si, P, Ba, Cu, Mo, Ni, and Zn relative to World Average Shale. These observations point to high organic burial fluxes, likely driven by high primary production rates, which led to the establishment of intensely sulfidic pore waters and possibly bottom waters, as well as to the enrichments of Cr, Mo, U, and V in the sediments. At the same time, the irregular presence of benthic inoceramids and foraminifera in this facies demonstrates that the benthic environment could not have been continuously anoxic. The d13C and d15N values of the inoceramid shell organics provide no evidence of chemosymbiosis and are consistent with pelagic rain as being a significant food source. Demerara Rise inoceramids also exhibit well-defined, regularly spaced growth lines that are tracked by d13C and d18O variations in shell carbonate that cannot be simply explained by diagenesis. Instead, productivity variations in surface waters may have paced the growth of the shells during brief oxygenation events suitable for benthic inoceramid settlement. These inferences imply tight benthopelagic coupling and more dynamic benthic conditions than generally portrayed during black shale deposition. By invoking different temporal scales for geochemical and paleontological data, this study resolves recent contradictory conclusions (e.g., sulfidic sedimentary conditions versus dysoxic to suboxic benthic waters) drawn from studies of either sediment geochemistry or fossil distributions alone on Demerara Rise. This variability may be relevant for discussions of black shales in general.

Chemistry of very young basalts from ODP Hole 106-648B

Basalts in Hole 648B, located in the rift valley of the Mid-Atlantic Ridge at 23°N in crust estimated to be less than 100,000 years old, are mainly fresh, but small amounts of secondary phases are found on fracture surfaces and in alteration halos within the rocks. The halos are defined by dark bands 1-4 mm thick that have developed parallel to fracture surfaces or pillow margins and which in some cases have migrated some centimeters into the rock. The dark bands are the principal locus of secondary phases. The secondary phases are olive-green and yellow protoceladonites, of composition and structure intermediate between celadonite and iron-rich saponite, red (Mn-poor) to opaque (Mn-rich) iron oxyhydroxides, mixtures of protoceladonite and iron oxyhydroxide, and rare manganese oxides. These phases occur mainly as linings or fillings of open spaces in the basalt within the dark bands. Sulfides and intersertal glass are the only primary phases that can be seen to have been altered. Where dark bands have migrated into the rock, the rock behind the advancing band is almost devoid of secondary phases, implying redissolution. The potassium and magnesium in the secondary phases could have been supplied from ambient seawater. The aluminum in the protoceladonites must have been derived from local reaction of intergranular glass. The source of iron and silica could have been intergranular glass or low temperature mineralizing solutions of the type responsible for the formation of deposits of manganese oxides and iron oxyhydroxides and silicates on the seafloor.

Flows with 'Cu-type' characteristics at ODP Hole 104-642E (Table 1)

Native Cu occurs in amygdules, fractures and groundmass of tholeiites from Ocean Drilling Program Site 642 on the Vøring Plateau. Similar occurrences have been reported in other tholeiites of the early Tertiary North Atlantic Volcanic Province drilled at Deep Sea Drilling Project Sites 342 on the Vøring Plateau and 553 on the Rockall Plateau. The flows containing the native Cu have distinctive alteration patterns characterized by the combination of reddened flow tops, distinctive pastel coloration of the upper parts of the flows, relative abundance of celadonite, and the presence of native Cu. These associations suggest that subaerial weathering and subsequent seawater-basalt interaction are related to the occurrence of native Cu. An additional factor may be the increase in compatibility of Cu in silicates and Fe- Ti oxides that may accompany sub-solidus oxidation of basaltic flows. Native Cu occurrences in Site 642 tholeiites have some striking similarities to the large native Cu deposits in the Precambrian basalts of the Keweenaw Peninsula, Michigan, that are suggestive of similar mineralization processes.

Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

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.

Composition of Fe-Mn micronodules, nodules and host bottom sediments from the Northeast Pacific Basin

Authigenic ferromanganese manifestations in bottom sediments from two horizons (0-10 and 240-250 cm) located in the low/high bioproductive transitional zone of the Pacific Ocean were studied. In addition two compositionally different types of micronodules, crusts and ferromanganese nodules were detected in the surface horizon (0-1 cm). Three size fractions (50-100, 100-250, and 250-500 µm) of manganese micronodules were investigated. In terms of surface morphology, color, and shape, the micronodules are divided into dull round (MN1) and angular lustrous (MN2) varieties with different mineral and chemical compositions. MN1 are enriched in Mn and depleted in Fe as compared with MN2. Mn/Fe ratio in MN1 varies from 13 to 14. Asbolane-buserite and birnessite are the major manganese minerals in them. MN2 is mainly composed of vernadite with Mn/Fe ratio from 4.3 to 4.8. Relative to MN1, fraction 50-100 µm of MN2 is enriched in Fe (2.6 times), W (1.8), Mo (3.2), Th (2.3), Ce (5.8), and REE (from 1.2 to 1.8). Relative to counterparts from MN1, separate fractions of MN2 are characterized by greater compositional difference. For example, increase in size of micronodules leads to decrease in contents of Fe (by 10 rel. %), Ce (2 times), W (2.1 times), Mo (2.2 times), and Co (1.5 times). At the same time one can see increase in contents of other elements: Th and Cu (2.1 times), Ni (1.9 times), and REE (from 1.2 to 1.6 times). Differences in chemical and mineral compositions of MN1 and MN2 fractions can be related to alternation of oxidative and suboxidative conditions in the sediments owing to input of labile organic matter, which acts as the major reducer, and allochthonous genesis of MN2.

Composition of Fe-Mn minerals from island arcs of the West Pacific

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kuril, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxyhydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxyhydroxides are todorokite and "Ca-birnessite". The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxyhydroxides.

Chemical composition of Fe-Mn nodules and host bottom sediments along the submeridional profile across the Brazil Basin

Sedimentation and ore formation were studied in sediments from nine stations located along the 24°W profile in the Brazil Basin of the Atlantic Ocean. Bottom sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to bottom sediments from other basins of the Atlantic Ocean, the sediments in study are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to decrease of Ce anomaly and LREE/HREE ratio. In reduced sediments preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crusts and ferromanganese nodules. Judging from contents of iron, manganese, REE, and other trace elements, these formations are ascribed to sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. Extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).