Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

IRD, benthic foraminifera and stable isotopic record of northern Sargasso Sea sediments

New geochemical proxy data from Bermuda Rise piston cores reveal ocean and climate conditions in the northern Sargasso Sea during marine isotope stage 3. Using ?18O on the planktonic foraminifer Globigerinoides ruber, we can correlate explicitly with every stadial/interstadial change in Greenland ice between ~32 and 58 ka. These data suggest repetitive changes of ~4°C in the annual average sea surface temperature (SST), with maximum cooling comparable to or greater than SST during glacial maximum conditions. The extent of SST depression is about the same for typical stadial events and for Heinrich events 4 and 5, which we have identified on the Bermuda Rise by traces of ice rafting. Benthic foraminiferal d13C decreases during every stadial event, consistent with reduced production of the deepest component of North Atlantic Deep Water and shoaling of its interface with Antarctic Bottom Water. This interpretation is supported by benthic Cd/Ca data from the climate cycle associated with interstadial 8.

Rock magnetic, element, and color data of three sediment cores along the Senegalese continental margin

We present a suite of new high-resolution records (0-135 ka) representing pulses of aeolian, fluvial, and biogenic sedimentation along the Senegalese continental margin. A multiproxy approach based on rock magnetic, element, and color data was applied on three cores enclosing the present-day northern limit of the ITCZ. A strong episodic aeolian contribution driven by stronger winds and dry conditions and characterized by high hematite and goethite input was revealed north of 13°N. These millennial-scale dust fluxes are synchronous with North Atlantic Heinrich stadials. Fluvial clay input driven by the West African monsoon predominates at 12°N and varies at Dansgaard-Oeschger time scales while marine productivity is strongly enhanced during the African humid periods and marine isotope stage 5. From latitudinal signal variations, we deduce that the last glacial ITCZ summer position was located between core positions at 12°26' and 13°40'N. Furthermore, this work also shows that submillennial periods of aridity over northwest Africa occurred more frequently and farther south than previously thought.

Age models of northern North Atlantic sediment cores

Benthic foraminiferal stable isotope records from four high-resolution sediment cores, forming a depth transect between 1237 m and 2303 m on the South Iceland Rise, have been used to reconstruct intermediate and deep water paleoceanographic changes in the northern North Atlantic during the last 21 ka (spanning Termination I and the Holocene). Typically, a sampling resolution of ~100 years is attained. Deglacial core chronologies are accurately tied to North Greenland Ice Core Project (NGRIP) ice core records through the correlation of tephra layers and changes in the percent abundance of Neogloboquadrina pachyderma (sinistral) with transitions in NGRIP. The evolution from the glacial mode of circulation to the present regime is punctuated by two periods with low benthic d13C and d18O values, which do not lie on glacial or Holocene water mass mixing lines. These periods correlate with the late Younger Dryas/Early Holocene (11.5-12.2 ka) and Heinrich Stadial 1 (14.7-16.8 ka) during which time freshwater input and sea-ice formation led to brine rejection both locally and as an overflow exported from the Nordic seas into the northern North Atlantic, as earlier reported by Meland et al. (2008). The export of brine with low ?13C values from the Nordic seas complicates traditional interpretations of low d13C values during the deglaciation as incursions of southern sourced water, although the spatial extent of this brine is uncertain. The records also reveal that the onset of the Younger Dryas was accompanied by an abrupt and transient (~200-300 year duration) decrease in the ventilation of the northern North Atlantic. During the Holocene, Iceland-Scotland Overflow Water only reached its modern flow strength and/or depth over the South Iceland Rise by 7-8 ka, in parallel with surface ocean reorganizations and a cessation in deglacial meltwater input to the North Atlantic.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Radiocarbon measurements and loose-sediment quantification of seafloor sediment samples off northern Mauritania

Heterozoan carbonates are typical for extratropical sedimentary systems. However, under mesotrophic to eutrophic conditions, heterozoan carbonates also form in tropical settings. Nevertheless, such heterozoan tropical sedimentary systems are rare in the modern world and therefore are only poorly understood to date. Here a carbonate depositional system is presented where nutrient-rich upwelling waters push onto a wide shelf. These waters warm up in the shelf, giving rise to the production and deposition of tropical heterozoan facies. The carbonate facies on this shelf are characterized by a mixture of tropical and cosmopolitan biogenic sedimentary grains. Study of facies and taxonomy are the key for identifying and characterizing tropical heterozoan carbonates and for distinguishing them from their coolwater counterparts, in particular in the past where the oceanography cannot be determined directly.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Chemical and isotopic compositions of groundwaters in the Badain Jaran Desert, Northern China

Despite its extreme aridity the Badain Jaran Desert is rich in groundwater. In the southeastern part of this desert it is characterized by coexistence of high megadunes and a great number of lakes. Deuterium and oxygen 18 isotope compositions as well as hydrochemistry of groundwater, lake water, soil water and river water were investigated in detail to gain an insight into their relationships and the origin of the groundwater. The results show that the groundwater and the lake water are genetically related, but unrelated to local precipitation and the leakage of Heine River at the northern slope of the Qilian mountain. dD and d18O values of deep soil water (deeper than 40 cm) and groundwater plot on the same evaporation line E11, which shows that they have the same recharge source. The point of intersection between E11 and LMWL suggests that the groundwater originates from a water resource, which has a weighted mean value that is lighter by some 6 per mil d18O than local precipitation in Badain Jaran Desert. 3H data of water samples show that the groundwater in the Badain Jaran Desert originates from water recharged after the nuclear test. The deep fault zone underground maybe a water circulation channel based on helium analysis of groundwater. The result has guiding significance to rational exploitation and utilization of the local groundwater.

Lithology and palynology of profiles from three low mountain ranges in northern Germany

Im Fichtelgebirge, im Harz und in der Rhön wurden die spätglazialen und frühpostglazialen Ablagerungen von vier Mooren in 625-805 m Meereshöhe pollenanalytisch hinsichtlich von Makrofossilien (Samen, Früchte) und stratigraphisch untersucht. 1. Nur im Fichtelgebirge konnte in 625 m Höhe ein vollständiger Spätglazialablauf aufgedeckt werden. Es handelt sich dabei um einen ehemaligen kleinen See südlich Fichtelberg, der wahrscheinlich durch Tieftauen eines begrabenen Firn- oder Schneefeldes entstand. Betula pubescens wurde kontinuierlich vom Ende der Älteren Tundrenzeit bis zum Boreal nachgewiesen. Auf nahe Vorkommen von Kiefern darf man seit IIb (Jüngere Allerödzeit) schließen, sie wurden aber durch die Jüngere Tundrenzeit, während der es noch zu Solifluktionserscheinungen kam, von ihren höher gelegenen Standorten wieder verdrängt. Die allerödzeitlichen Birken- bzw. Birkenkiefernwälder müssen in diesen Höhen noch licht oder parkartig gewesen sein. Verbreitet waren Rasengesellschaften, die hauptsächlich aus Gramineen und Artemisia bestanden. Auch Beutla nana und Pollen von Ephedra cf. distachya wurden nachgewiesen. In der Seelohe (770-780 m) ist nur der Ausklang einer waldarmen Zeit, offensichtlich der Jüngeren Tundrenzeit, erfaßt. Großreste von Bäumen fehlen. 2. Im Oberharz (Radauer Born, 800 m) wurde nur ein kurzes Stück der Jüngeren Tundrenzeit aufgedeckt. Großreste von Bäumen fehlen hier ebenfalls. Aus dem Praeboreal stammt der erst fossile Nachweis von Betuala nana im Oberharz. Die Zwergbirke wächst auf dem Moor noch heute und gilt hier als Eiszeitrelikt. 3. Eine Datierung der spätglazialen Ablagerungen vom Roten Moor in der Rhön ist zur Zeit nur mit Vorbehalt möglich. Zwar wurde hier der Laacher Bimstuff gefunden, er ist jedoch umgelagert und unmittelbar über dem Tuffhorizont befindet sich eine Schichtlücke. Wahrscheinlich zeigt die Bimsstuffschicht aber doch noch den Allerödhorizont an. 4. Während der Jüngeren Tundrenzeit dürfte im Fichtelgebirge die Waldgrenze bei etwas 600 m gelegen haben. Das bedeutet gegenüber der heutigen Waldgrenze eine Erniedrigung um rund 700 m. Am Schluß der Älteren Tundrenzeit lag die Waldgrenze wahrscheinlich wie in der Allerödzeit höher als 600-650 m, aber unter 800 m. 5. Pollenkörner der Ericalen sind in den Ablagerungen aus dem Harz wesentlich häufiger als in den anderene Gebieten. Häufungen von Ericalen-pollen sind besonders für Spätglazialablagerungen solcher Gebiete charakteristisch, die heute im subozeanischen oder ozeanischen Klimabereich liegen (Niederlande, Irland). 6. Während sich die Bodengegensätze in der heutigen Vegetation der drei Untersuchungsgebiete sehr deutlich bemerkbar machen, wurden keine nennenswerten Unterschiede im spätglazialen Pollenniederschlag der drei Mittelgebirge gefunden. Vermutlich erfolgte die Auswaschung der Nährstoffe aus den an sich nährstoffkräftigen Granitverwitterungsböden während der Späteiszeit nicht so rasch, wie es heute der Fall ist. Die Niederschlagsmengen dürften geringer und das Klima weniger humid gewesen sein. 7. In der Liste der spätglazialen Pflanzen überwiegen die Arten mit borealzirkumpolarer Verbreitung. Arktisch-alpine Arten treten zurück. Kontinentale und subatlantische bzw. subozeanische Arten sind etwa gleich stark vertreten.

Grain size, mineral and chemical compositions of modern deposits fron the northern Caspian Sea and the Volga River delta

Comprehensive investigations revealed that modern deposits in the northern Caspian Sea involve terrigenous sands and aleurites with admixture of detritus and intact bivalve shells, including coquina. Generally, these deposits overlay dark grayish viscous clays. Similar geological situation occurs in the Volga River delta; however, local deposits are much poorer in biogenic constituents. Illite prevails among clay minerals. In coarse aleurite fraction (0.100-0.050 mm) heavy transparent minerals are represented mostly by epidotes, while light minerals - mostly by quartz and feldspars. Sedimentary material in the Volga River delta is far from completely differentiated into fractions due to abundant terrigenous inflows. Comparatively better grading of sediments from the northern Caspian Sea is due to additional factors such as bottom currents and storms. When passing from the Volga River delta to the northern Caspian Sea, sediments are enriched in rare earth elements (except Eu), Ca, Au, Ni, Se, Ag, As, and Sr, but depleted in Na, Rb, Cs, K, Ba, Fe, Cr, Co, Sc, Br, Zr, ??, U, and Th. Concentrations of Zn remain almost unchanged. Sedimentation rates and types of recent deposits in the northern Caspian Sea are governed mainly by abundant runoff of the Volga River.

Age determination and faunal composition of sediments off northern Greenland

We present a record encompassing marine isotope stages 7-1 from a hitherto unexplored and heavily ice-covered area of the Arctic Ocean, the Lomonosov Ridge off the northern Greenland-Canada continental margin, using nannofossil and benthic foraminifera stratigraphy. Planktic foraminifera assemblages are used as a key paleoceanographic proxy, and a surprisingly large variability is found for an interior Arctic Ocean site. Abundant small (63-125 µm) subpolar Turborotalita quinqueloba occur in two sections, possibly representing substages 5e (last interglacial) and 5a (warm interstadial). However, the present-day circulation pattern and the very distant location of high productive regions cannot explain such high abundances of subpolar specimens in the interior, perennially sea ice-covered Arctic Ocean. Hence our proxy record indicates that last interglacial sea ice concentrations were reduced off some areas of northern Greenland-Canada. Whether this was part of a larger regional pattern or it represents the influence of polynya areas with locally increased productivity remains to be solved. With respect to glacial conditions, increased ice-rafted debris (IRD) deposition in the area appears to be associated with glacial stages 6, 4, and late 3. Stage 2 sediments (including the Last Glacial Maximum) are condensed with a sparse IRD content only.

Composition of drilled sediments and pore waters from the continental slope of the Northern Gulf of Mexico

Pore waters were analyzed from 6 holes drilled from M.V. "Eureka" as a part of the Shell Oil Co. deeper offshore study. The holes were drilled in water depths of 600-3000 ft. (approximately 180-550 m) and penetrated up to 1000 ft. (300 m) of Pliocene-Recent clayey sediments. Salt and anhydrite caprock was encountered in one diapiric structure on the continental slope. Samples from holes drilled near diapiric structures showed systematic increases of pore-water salinity with depth, suggestive of salt diffusion from underlying salt plugs. Anomalous concentrations of K and Br indicate that at least one plug contains late-stage evaporite minerals. Salinities approaching halite saturation were observed. Samples from holes away from diapiric structures showed little change in pore-water chemistry, except for loss of SO4 and other variations attributable to early-stage diagenetic reactions with enclosing sediments. Thus, increased salt concentrations in even shallow sediments from this part of the Gulf appear to provide an indicator of salt masses at depth.

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.

Orbital control on carbonate-lignite cycles on sediment core KAP-107 in the Ptolemais Basin, northern Greece

Time control is essential for the reconstruction of geological processes. We use a combination of relative and absolute methods to establish the chronology and related paleoclimatic processes for Late Neogene lacustrine sediment from the Ptolemais Basin, northern Greece. We determined changes in magnetic polarity and correlated them to the global magnetic polarity time scale, which again is calibrated by radiometric methods, to provide a low-resolution age model for the Upper Miocene to Lower Pliocene (7 - 3 Ma). Sedimentary successions show rhythmic alterations of lignites, clays, and marls. Using photospetrometry we measured this variability at 1-cm resolution, and correlated the pattern to known changes in earth's orbital parameters, namely to eccentricity and precession. For 230-m long borehole KAP-107 from the Amynteon Sub-Basin we obtained a high-resolution age model that spans 2 myr from 5.1 to 3.1 Ma, with age control points at insolation maxima (20-kyr resolution). We recommend using photospectrometry as reliable tool to establish orbital-based chronologies and to reconstruct paleoclimate variability at high resolution.