Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Major ion concentrations and chlorine isotope composition of water-soluble chloride and structurally bound chloride in DSDP/ODP serpentinized ultramafic rocks

Eight DSDP/ODP cores were analyzed for major ion concentrations and d37Cl values of water-soluble chloride (d37Clwsc) and structurally bound chloride (d37Clsbc) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition. The average total Cl content of all 86 samples is 0.26±0.16 wt.% (0.19±0.10 wt.% as water-soluble Cl (Xwsc) and 0.09±0.09 wt.% as structurally bound Cl (Xsbc)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl**- site and the water-soluble Cl**- site varies from -1.08? to +1.16?, averaging to +0.21?. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk d37Cl values (+0.05? to +0.36?); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk d37Cl values (-1.26? and -0.54?). The cores with negative d37Cl values also have variable Cl**-/SO4**2- ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ~1? with depth for both the water-soluble and structurally bound Cl fractions. Non-zero bulk d37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive d37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low d37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative d37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.

Geochemistry of ODP Leg 125 peridotites

Trace element analyses (first-series transition elements, Ti, Rb, Sr, Zr, Y, Nb, and REE) were carried out on whole rocks and minerals from 10 peridotite samples from both Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc using a combination of XRF, ID-MS, ICP-MS, and ion microprobe. The concentrations of incompatible trace elements are generally low, reflecting the highly residual nature of the peridotites and their low clinopyroxene content (<2%). Chondrite-normalized REE patterns show extreme U shapes with (La/Sm)n ratios in the range of 5.03-250.0 and (Sm/Yb)n ratios in the range of 0.05-0.25; several samples show possible small positive Eu anomalies. LREE enrichment is common to both seamounts, although the peridotites from Conical Seamount have higher (La/Ce)n ratios on extended chondrite-normalized plots, in which both REEs and other trace elements are organized according to their incompatibility with respect to a harzburgitic mantle. Comparison with abyssal peridotite patterns suggests that the LREEs, Rb, Nb, Sr, Sm, and Eu are all enriched in the Leg 125 peridotites, but Ti and the HREEs exhibit no obvious enrichment. The peridotites also give positive anomalies for Zr and Sr relative to their neighboring REEs. Covariation diagrams based on clinopyroxene data show that Ti and the HREEs plot on an extension of an abyssal peridotite trend to more residual compositions. However, the LREEs, Rb, Sr, Sm, and Eu are displaced off this trend toward higher values, suggesting that these elements were introduced during an enrichment event. The axis of dispersion on these plots further suggests that enrichment took place during or after melting and thus was not a characteristic of the lithosphere before subduction. Compared with boninites sampled from the Izu-Bonin-Mariana forearc, the peridotites are significantly more enriched in LREEs. Modeling of the melting process indicates that if they represent the most depleted residues of the melting events that generated forearc boninites they must have experienced subsolidus enrichment in these elements, as well as in Rb, Sr, Zr, Nb, Sm, and Eu. The lack of any correlation with the degree of serpentinization suggests that low-temperature fluids were not the prime cause of enrichment. The enrichment in the high-field-strength elements also suggests that at least some of this enrichment may have involved melts rather than aqueous fluids. Moreover, the presence of the hydrous minerals magnesio-hornblende and tremolite and the common resorption of orthopyroxene indicate that this high-temperature peridotite-fluid interaction may have taken place in a water-rich environment in the forearc following the melting event that produced the boninites. The peridotites from Leg 125 may therefore contain a record of an important flux of elements into the mantle wedge during the initial formation of forearc lithosphere. Ophiolitic peridotites with these characteristics have not yet been reported, perhaps because the precise equivalents to the serpentinite seamounts have not been analyzed.

Chemical and isotopic compositions of rocks, ores, and hydrothermal minerals from the Rainbow and Logachev-2 hydrothermal fields

The aim of this paper is to analyze and compare mineralogy and geochemistry of copper-zinc sulfide ores from the Logachev-2 and Rainbow hydrothermal fields of the Mid-Atlantic Ridge (MAR) confined to serpentinite protrusions. It was found that Zn(Fe) and Cu, Fe(Zn) sulfides had been deposited in black smokers pipes almost simultaneously from intermittently flowing, nonequilibrium H2S-low solutions of different temperatures. Pb isotope composition confirmed that the deep oceanic crust had been a source of lead. The ores from the Rainbow field are 20-fold higher in Co than ores restricted to basalts and show a high ratio of Co/Ni=46. The ores from the Rainbow field are enriched in 34S isotope (aver. d34S=10 per mil) because of constant flow of cold sea water into the subsurface zone of the hydrothermal system. Ores from the Logachev-2 field are 8 times higher in gold compared to other MAR regions. Sulfide ores from the Rainbow and Logachev-2 fields have no analogues among MAR ore occurrences in terms of enrichment in valuable components (Zn, Cd, Co, and Au).

Petrology and geochemistry of volcanic rocks from ODP Sites 134-827, 134-829 and 134-830

Igneous rocks recovered from Ocean Drilling Program (ODP) Leg 134 Sites 827, 829, and 830 at the toe of the forearc slope of New Hebrides Island Arc were investigated, using petrography, mineral chemistry, major and trace element, and Sr, Nd, and Pb isotopic analyses. Basaltic and andesitic clasts, together with detrital crystals of plagioclase, pyroxenes, and amphiboles embedded in sed-lithic conglomerate or volcanic siltstone and sandstone of Pleistocene age, were recovered from Sites 827 and 830. Petrological features of these lava clasts suggest a provenance from the Western Belt of New Hebrides Island Arc; igneous constituents were incorporated into breccias and sandstones, which were in turn reworked into a second generation breccia. Drilling at Site 829 recovered a variety of igneous rocks including basalts and probably comagmatic dolerites and gabbros, plus rare ultramafic rocks. Geochemical features, including Pb isotopic ratios, of the mafic rocks are intermediate between midocean ridge basalts and island arc tholeiites, and these rocks are interpreted to be backarc basin basalts. No correlates of these mafic rocks are known from Espiritu Santo and Malakula islands, nor do they occur in the Pleistocene volcanic breccias at Sites 827 and 830. However, basalts with very similar trace element and isotopic compositions have been recovered from the northern flank of North d'Entrecasteaux Ridge at Site 828. It is proposed that igneous rocks drilled at Site 829 represent material from the North d'Entrecasteaux Ridge accreted onto the over-riding Pacific Plate during collision. An original depleted mantle harzburgitic composition is inferred for a serpentinite clast recovered at 407 meters below seafloor (mbsf) in Hole 829A. Its provenance is a matter of speculation. It could have been brought up along a deep thrust fault affecting the Pacific Plate at the colliding margin, or analogous to the Site 829 basaltic lavas, it may represent material accreted from the North d'Entrecasteaux Ridge.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Petrography and geochemistry of lithic clasts in sediments obtained from ODP Leg 180 sites

This report includes the petrographic description and reviews the distribution of lithic clasts in sediments drilled during Leg 180 in the Woodlark Basin (southwest Pacific). The lithic clasts include (1) metamorphic rocks; (2) granites; (3) serpentinites, gabbros, dolerites, and basalts likely derived from the Papuan ophiolite belt; (4) rare alkaline volcanites reworked in middle Miocene sediments; (5) medium- to high-K calc-alkaline island arc volcanites, in part as reworked clasts, and explosive products deposited by fallout or reworked by turbiditic currents; and (6) rare sedimentary fragments. At the footwall sites the clast assemblage evidences the association of dolerites and evolved gabbroic rocks; the serpentinite likely pertaining to the same ophiolitic complex are likely derived from onland outcrops and transported by means of turbidity currents. On the whole, extensional tectonics active at least since the middle Pliocene can be inferred. The calc-alkaline volcanism is in continuity with the arc-related products from the Papua Peninsula and D'Entrecasteaux Islands and with the latest volcanics of the Miocene Trobrian arc. However, the medium- to high-K and shoshonitic products do not display a significant temporal evolution within the stratigraphic setting. Lava clasts, volcanogenic grains, and glass shards are associated with turbidity currents, whereas in the Pliocene of northern margin the increasing frequency of tephra (glass shards and vesicular silicic fragments) suggests more explosive activity and increasing contribution to the sediments from aerial fallout materials. Evidence of localized alkalic volcanism of presumable early to middle Miocene age is a new finding. It could represent a rift phase earlier than or coeval to the first opening of the Woodlark Basin or, less probably, could derive from depositional trajectories diverted from an adjacent basin.

Tab. 1: Ar40/Ar39 results from Kuyul terrane, northeastern Russia

The Kamchatka Peninsula of northeastern Russia is located along the northwestern margin of the Bering Sea and consists of zones of complexly deformed accreted terranes. Along the northern portion of the peninsula, progressing from then orthwestem Bering Sea inland the Olyutorskiy, Ukelayat, and Koryak superterranes area acreted to the Okhotsk-Chukotsk volcanic-plutonic bell in northern-most Kamchatka. A sedimentary sequence of Albian to Maastrichtian age overlap terranes and units of the Koryak superterrane and constrains their accretion time with this region of the North America plate. Ophiolite complexes, widespread within the Koryak superterrane, are associated with serpentinite melanges and some of the ophiolite terranes include large portions of weakly serpentinized hyperbasites, layered gabbro, sheeted dikes, and pillow basalts outcropping as internally coherent blocks within a sheared melange matrix. Interpretation of magnetic anomalies allow the correlation of the Ukelayat with the West Kamchatka and Sredinny Range superterranes. The Olyutorskiy composite terrane may be correlated with the central and southern Kamchatka Peninsula Litke, Eastern Ranges and Vetlov composite terranes. The most "out-board" of the central and southern Kamchatka Peninsula terranes is the Kronotsky composite terrane, weil exposed along the Kamchatka, Kronotsky and Shipunsky Capes. Using regional geological constraints, paleomagnetism, and plate kinematic models for the Pacific basin a regional model can be proposed in which accretion of the Koryak composite terrane to the North America plate occurs during the Campanian-Maastrichtian, followed by the accretion of the Olyutorskiy composite terrane in the Middle Eocene, and the Late Oligocene-Early Miocene collision of the Kronotsky composite terrane. A revised age estimate of a key overlapping sedirnentary sequence of the Koryak superterrane, calibrated with new Ar40/Ar39 data, supports its Late Cretaceous accretion age.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Mineralogy and geochemistry of weathered serpentinites in DSDP Leg 84 sediments

At Sites 566, 567, and 570 of Leg 84, ophiolitic serpentinite basement was covered by a sequence of serpentinitic mud that was formed by weathering of the serpentinites under sea- or pore-water conditions. Several mineralogical processes were observed: (1) The serpentinitic mud that consists mainly of chrysotile was formed from the lizardite component of the serpentinites by alteration. (2) Slightly trioctahedral smectites containing nonexpandable mica layers, trioctahedral smectites containing nonexpandable chlorite layers, and swelling chlorites were presumably formed from detrital chlorite and/or serpentine. (3) The occurrence of tremolite, chlorite, analcime, and talc can be attributed to reworking of gabbroic ophiolite rocks. (4) Dolomite, aragonite, and Mg-calcite, all authigenic, occur in the serpentinitic mud.

Analysis and compound of carbon sequestration and serpentinization from the Iberian Margin and the Northern Apennine

Fluid circulation in peridotite-hosted hydrothermal systems influences the incorporation of carbon into the oceanic crust and its long-term storage. At low to moderate temperatures, serpentinization of peridotite produces alkaline fluids that are rich in CH4 and H2. Upon mixing with seawater, these fluids precipitate carbonate, forming an extensive network of calcite veins in the basement rocks, while H2 and CH4 serve as an energy source for microorganisms. Here, we analyzed the carbon geochemistry of two ancient peridotite-hosted hydrothermal systems: 1) ophiolites cropping out in the Northern Apennines, and 2) calcite-veined serpentinites from the Iberian Margin (Ocean Drilling Program (ODP) Legs 149 and 173), and compare them to active peridotite-hosted hydrothermal systems such as the Lost City hydrothermal field (LCHF) on the Atlantis Massif near the Mid-Atlantic Ridge (MAR). Our results show that large amounts of carbonate are formed during serpentinization of mantle rocks exposed on the seafloor (up to 9.6 wt.% C in ophicalcites) and that carbon incorporation decreases with depth. In the Northern Apennine serpentinites, serpentinization temperatures decrease from 240 °C to < 150 °C, while carbonates are formed at temperatures decreasing from ~ 150 °C to < 50 °C. At the Iberian Margin both carbonate formation and serpentinization temperatures are lower than in the Northern Apennines with serpentinization starting at ~ 150 °C, followed by clay alteration at < 100 °C and carbonate formation at < 19-44 °C. Comparison with various active peridotite-hosted hydrothermal systems on the MAR shows that the serpentinites from the Northern Apennines record a thermal evolution similar to that of the basement of the LCHF and that tectonic activity on the Jurassic seafloor, comparable to the present-day processes leading to oceanic core complexes, probably led to formation of fractures and faults, which promoted fluid circulation to greater depth and cooling of the mantle rocks. Thus, our study provides further evidence that the Northern Apennine serpentinites host a paleo-stockwork of a hydrothermal system similar to the basement of the LCHF. Furthermore, we argue that the extent of carbonate uptake is mainly controlled by the presence of fluid pathways. Low serpentinization temperatures promote microbial activity, which leads to enhanced biomass formation and the storage of organic carbon. Organic carbon becomes dominant with increasing depth and is the principal carbon phase at more than 50-100 m depth of the serpentinite basement at the Iberian Margin. We estimate that annually 1.1 to 2.7 × 1012 g C is stored within peridotites exposed to seawater, of which 30-40% is fixed within the uppermost 20-50 m mainly as carbonate. Additionally, we conclude that alteration of oceanic lithosphere is an important factor in the long-term global carbon cycle, having the potential to store carbon for millions of years.