Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

Geochemistry of lower and middle Keuper sediments in the Central Thuringian Syncline

Cuttings of Lower and Middle Keuper sediments of the INFLUINS-drilling in the central Thuringian Syncline were geochemically analysed. Indications about shifting depositional environments are interpreted from ratios of whole-rock element contents. For the middle part of sandstone cycle S 2 high heavy metal contents imply precipitation of sufidic ores during a short marine interval. Element contents are compared with potential source rocks in the southern part of the Baltic Shield, in the Lausitz Anticline Zone, in the Erzgebirge, in the moldanubian part, in the broad sense, of the Bohemian Massif, in the Münchberg Gneiss Massif and the Fichtelgebirge. The geochemical coincidence of investigated Keuper sediments is highest with grantioid and gabbroic rocks of southern Scandinavia. Granodiorite rocks of the Lausitz are also possible sources, whereas granites of the Fichtelgebirge and the Bohemian Massif are less probable.

(Table T1) Trace-element abundances for igneous basement at ODP Site 206-1256

In this report, I present trace element data for basement samples at Ocean Drilling Program (ODP) Site 1256. The samples analyzed represent a subset of the group ("pool") samples from ODP Leg 206, and these trace element data are part of a more comprehensive data suite for the same samples, with analyses of stable and radiogenic isotopes (e.g., Sr, Li, and O) in progress or recently completed that will be presented elsewhere. The trace element analyses were performed in the GeoAnalytical Lab at Washington State University. The following elements were analyzed: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ba, Th, Nb, Y, Hf, Ta, U, Pb, Rb, Cs, Sr, Sc, and Zr. Trace element data indicate that the igneous basement at Site 1256 is geochemically normal mid-ocean-ridge basalt. A massive ponded flow sampled in both Holes 1256C and 1256D is distinguished by higher abundances of rare earth elements (REE) and most of the other trace elements analyzed. One interval of highly altered basalt has significantly higher concentrations of Cs, Rb, and Ba and lower concentrations of Sr, Pb, Zr, Hf, Sc, and most REE than the samples of background alteration or halos. No correlation is obvious between trace element abundance and macroscopic type of alteration within the background alteration or halos.

Geochemistry of ODP Hole 176-735B igneous and hydrothermal veins

During Legs 118 and 176, Ocean Drilling Program Hole 735B, located on Atlantis Bank on the Southwest Indian Ridge, was drilled to a total depth of 1508 meters below seafloor (mbsf) with nearly 87% recovery. The recovered core provides a unique section of oceanic Layer 3 produced at an ultraslow spreading ridge. Metamorphism and alteration are extensive in the section but decrease markedly downward. Both magmatic and hydrothermal veins are present in the core, and these were active conduits for melt and fluid in the crust. We have identified seven major types of veins in the core: felsic and plagioclase rich, plagioclase + amphibole, amphibole, diopside and diopside + plagioclase, smectite ± prehnite ± carbonate, zeolite ± prehnite ± carbonate, and carbonate. A few epidote and chlorite veins are also present but are volumetrically insignificant. Amphibole veins are most abundant in the upper 50 m of the core and disappear entirely below 520 mbsf. Felsic and plagioclase ± amphibole ± diopside veins dominate between ~50 and 800 mbsf, and low-temperature smectite, zeolite, and prehnite veins are present in the lower 500 m of the core. Carbonate veinlets are randomly present throughout the core but are most abundant in the lower portions. The amphibole veins are closely associated with zones of intense crystal plastic deformation formed at the brittle/ductile boundary at temperatures above 700°C. The felsic and plagioclase-rich veins were formed originally by late magmatic fluids at temperatures above 800°C, but nearly all of these have been overprinted by intense hydrothermal alteration at temperatures between 300° and 600°C. The zeolite, prehnite, and smectite veins formed at temperatures <100°C. The chemistry of the felsic veins closely reflects their dominant minerals, chiefly plagioclase and amphibole. The plagioclase is highly zoned with cores of calcic andesine and rims of sodic oligoclase or albite. In the felsic veins the amphibole ranges from magnesio-hornblende to actinolite or ferro-actinolite, whereas in the monomineralic amphibole veins it is largely edenite and magnesio-hornblende. Diopside has a very narrow range of composition but does exhibit some zoning in Fe and Mg. The felsic and plagioclase-rich veins were originally intruded during brittle fracture at the ridge crest. The monomineralic amphibole veins also formed near the ridge axis during detachment faulting at a time of low magmatic activity. The overprinting of the igneous veins and the formation of the hydrothermal veins occurred as the crustal section migrated across the floor of the rift valley over a period of ~500,000 yr. The late-stage, low-temperature veins were deposited as the section migrated out of the rift valley and into the transverse ridge along the margin of the fracture zone.

Chemical composition of tephra from the Greenland-Iceland-Norwegian-Sea

Explosive ocean island volcanism in the Greenland-Iceland-Norwegian Sea (GIN Sea) is indicated by marine tephra layers at 10-300 ka. Peaks of explosive volcanism occurred in oxygen isotope stages 8, 7, 5 and 1. The depositional age of the tephra was estimated using the oxygen isotope stratigraphy and dating of marine records. Geochemical analyses of the tephra layers show that all originate from Iceland. Here we report the characteristics of tephra from these major Icelandic events in 30 deep-sea cores from the GIN Sea. Our findings provide constraints on the distribution of tephra from the eruption source. For the Vedde Ash (oxygen isotope stage 1) we estimate a minimum fallout area of 2*10**5 km**2, stretching from central Greenland in the west and southern Sweden in the east, to 71°N in the GIN Sea. The magnitude of the eruption and the regional wind conditions controlled the extent and concentrations of these ash fallout events. Oceanic circulation and differential settling may have affected the distribution and final deposition of ash particles such as bubble wall shards.

Bulk density, ash content, humification, peat accumulation and selected lithogenic data of Store Mosse peat bog

This datafile presents chemical and physical as well as age dating information from the Store Mosse peat bog in southern Sweden. This record dates back to 8900 cal yr BP. The aim of the research was to reconstruct mineral dust deposition over time. As such we have only presented the lithogenic element data (Al, Ga, Rb, Sc, Ti, Y, Zr, Th and the REE) as the sample preparation method was tailored to these. This data is supported by parameters describing the deposit including bulk density, humification, ash content and net peat accumulation rates.

Mineral and chemical compositions of a ferromanganese nodule from Station DM41-3911-76

Processes of authigenic manganese ore formation in sediments of the North Equatorial Pacific are considered on the basis of a study of the surface layer (<2 mm) of a ferromanganese nodule and four micronodule size fractions from associated surface sediment (0-7 cm). Inhomogeneity of nodule composition is shown. Mn/Fe ratio is maximal in samples from lateral sectors of the nodule at the water-sediment interface. Compositional differences of nodules are related to preferential accumulation of trace elements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenic component trapped during nodule growth (Ga, Rb, Ba, and Cs). Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by minimal Mn/Fe values. A compositional comparison of manganese micronodules and surface layers of the nodule demonstrates that micronodule material was subjected to more intense reworking during diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe, but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are the least mobile elements during diagenesis. Differences in chemical composition of the micronodules and nodules are related not only to additional input of Mn in the process of diagenesis, but also to transformation of iron oxyhydroxides after removal of Mn from the close association with Fe formed in suspended matter during sedimentation.

Chemical and isotopic composition of carbonate veins from ODP Leg 209

Carbonate veins hosted in ultramafic basement drilled at two sites in the Mid Atlantic Ridge 15°N area record two different stages of fluid-basement interaction. A first generation of carbonate veins consists of calcite and dolomite that formed syn- to postkinematically in tremolite-chlorite schists and serpentine schists that represent gently dipping large-offset faults. These veins formed at temperatures between 90 and 170 °C (oxygen isotope thermometry) and from fluids that show intense exchange of Sr and Li with the basement (87Sr/86Sr = 0.70387 to 0.70641, d7Li L-SVEC = + 3.3 to + 8.6 per mil). Carbon isotopic compositions range to high d13C PDB values (+ 8.7 per mil), indicating that methanogenesis took place at depth. The Sr-Li-C isotopic composition suggests temperatures of fluid-rock interaction that are much higher (T > 350-400 °C) than the temperatures of vein mineral precipitation inferred from oxygen isotopes. A possible explanation for this discrepancy is that fluids cooled conductively during upflow within the presumed detachment fault. Aragonite veins were formed during the last 130 kyrs at low-temperatures within the uplifted serpentinized peridotites. Chemical and isotopic data suggest that the aragonites precipitated from cold seawater, which underwent overall little exchange with the basement. Oxygen isotope compositions indicate an increase in formation temperature of the veins by 8-12 °C within the uppermost ~ 80 m of the subseafloor. This increase corresponds to a high regional geothermal gradient of 100-150 °C/km, characteristic of young lithosphere undergoing rapid uplift.

Geochemistry of lower sheeted dike complex samples of ODP Holes 137-504B and 140-504B

Rocks of the lower sheeted dike complex of Hole 504B sampled during Leg 140 were analyzed for major and trace element compositions to investigate the effects of igneous processes and hydrothermal alteration on the compositions of the rocks. The rocks are relatively uniform in composition and similar to the shallower dikes. They are moderately evolved mid-ocean-ridge basalts (MORB) with relatively high MgO (7.9-10 wt%) and Mg# (0.60-0.70), and have unusually low incompatible element contents (TiO2 = 0.42-1.1 wt%, Zr = 23-62 ppm). Discrete compositional intervals in the hole reflect varying degrees of differentiation, and olivine and plagioclase accumulation in the rocks, and may be related to injection of packets of dikes having similar compositions. Systematic depletions of total REE, Zr, Y, TiO2, and P2O5 in centimeter-size patches are most likely attributed to exclusion of highly differentiated, late-stage interstitial liquids from small portions of the rocks. The rocks exhibit increased H2O+ reflecting hydrothermal alteration. Replacement of primary plagioclase by albite and oligoclase led to local gains of Na2O, losses of CaO, and slightly positive Eu anomalies. Some mobility of P2O5 led to minor increases and decreases in P2O5 contents, and some local mobility of Ti may have occurred during alteration of titanomagnetite to titanite. Higher temperatures of alteration in the lower sheeted dikes led to breakdown of pyroxene and sulfide minerals and losses of Zn, Cu, and S to hydrothermal fluids. Later addition of anhydrite to the rocks in microfractures and replacing plagioclase caused local increases in sulfur contents. The lower sheeted dikes are a major source of metals to hydrothermal fluids for the formation of metal sulfide deposits on and within the seafloor.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

(Table 3) Geochemistry of borehole fluids of ODP Hole 137-504B

Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (>160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.

Geochemistry of ODP Hole 108-658C sediments

During the African Humid Period (AHP), much of the modern hyperarid Saharan desert was vegetated and covered with numerous lakes. In marine sediments off northwestern Africa, the AHP is represented by markedly reduced siliciclastic sediment flux between ~ 12.3 and 5.5 ka. Changes in the origin of this terrigenous sediment fraction can be constrained by sediment chemistry and radiogenic isotope tracers. At Ocean Drilling Program (ODP) Site 658, Hole C (20°44.95'N, 18°34.85'W, 2263 mbsl), the neodymium (Nd) isotope composition of terrigenous detritus shows little variability throughout the last 25 kyr, indicating that the contributing geological terranes have not changed appreciably since the last glacial period. In contrast, there were large and abrupt changes in strontium (Sr) isotope ratios and chemical compositions associated with the AHP, during which 87Sr/86Sr ratios were markedly less radiogenic, and sediments show higher chemical indices of alteration. We show that sediment geochemical changes during the AHP cannot be attributed to changes in the source terranes, physical sorting, or intensity of chemical weathering. The low 87Sr/86Sr and high Sr concentrations of AHP-age samples also conflict with the interpretation of increased fine-grained, fluvially derived sediments. We propose that the most significant compositional changes at ODP 658C are due to the addition of an aluminosilicate component that has a highly altered major element signature but is enriched in soluble elements like Sr and magnesium (Mg) compared to aluminum (Al) and has low 87Sr/86Sr relative to local terrigenous source areas. We interpret these characteristics to reflect authigenic sediment supply from extensive North African paleolake basins that were prevalent during the AHP.

Geochemistry and isotopic ratios of Neogene basalts from Spitzbergen Island, Svalbard archipelago

Petrological and geochemical data obtained on Neogene magmatism restricted to a deep fault in Andree Land at Spitsbergen Island, which was related to the overall restyling of the Arctic territory at 25-20 Ma, indicate that the derivation of the Neogene magmas was significantly affected by the continental pyroxenite mantle. The Neogene basalts are noted for a radiogenic isotopic composition of Pb (207Pb/204Pb= 15.5-15.55, 206Pb/204Pb = 18.4-18.6, 208Pb/204Pb = 38.4-38.6) and Sr (87Sr/86Sr = 0.7038-0.7048) at low 143Nd/144Nd = 0.5129. Melts of this type are the extremely enriched end member of the isotopic mixing of a depleted and enriched sources and determine a geochemical trend that passes through the compositions of alkaline magmas from Quaternary volcanoes at Spitsbergen and weakly enriched tholeiites of the Knipovich Ridge, which started to develop simultaneously with the onset of Neogene magmatism in the western part of Spitsbergen. The composition of the liquidus olivine (which is rich in NiO) indicates that melting occurred in the olivine-free mantle. Our data thus testify that a significant role in the genesis of the Neogene magmas was played by continental pyroxenite mantle.

Composition of sedimentary rocks from the Burun-Tas Formation, Bol'shoi Lyakhov Island (New Siberian Islands)

Graywackes and shales of the Bol'shoi Lyakhov Island originally attributed to Mesozoic were subsequently considered based on microfossils as Late Proterozoic in age. At present, these sediments in the greater part of the island are dated back to Permian based on palynological assemblages. In the examined area of the island, this siliciclastic complex is intensely deformed and tectonically juxtaposed with blocks of oceanic and island-arc rocks exhumed along the South Anyui suture. The complex is largely composed of turbidites with members displaying hummocky cross-stratification. Studied mineral and geochemical charac¬teristics of the rocks defined three provenances of clastic material: volcanic island arc, sedimentary cover and/or basement of an ancient platform, and exotic blocks of oceanic and island-arc rocks such as serpentinites and amphibolites. All rock associations represent elements of an orogenic structure that originated by collision of the New Siberian continental block with the Anyui-Svyatoi Nos island arc. Flyschoid sediments accumu¬lated in a foredeep in front of the latter structure in the course of collision. Late Jurassic volcanics belonging to the Anyui-Svyatoi Nos island arc determine the lower age limit of syncollision siliciclastic rocks. Presence of Late Jurassic zircons in sandstones of the flyschoid sequence in the Bol'shoi Lyakhov Island is confirmed by fission-track dating. The upper age limit is determined by Aptian-Albian postcollision granites and diorites intruding the siliciclastic complex. Consequently, the flyschoid sequence is within stratigraphic range from the terminal Late Jurassic to Neocomian. It appears that Permian age of sediments suggested earlier is based on redeposited organic remains. The same Late Jurassic-Neocomian age and lithology are characteristic of fossiliferous siliciclastic sequences of the Stolbovoi and Malyi Lyakhov islands, the New Siberian Archipelago, and of graywackes in the South Anyui area in the Chukchi Peninsula. All these sediments accumulated in a spacious foredeep that formed in the course the late Cimmerian orogeny along the southern margin of the Arctic conti¬nental block.