Eh and pH values in sediments and composition of interstitial waters from the Frolikha Bay, Baikal Lake

Redox conditions and compositions of bottom sediments and sedimentary pore waters in the area of the hydrothermal vent in the Frolikha Bay (Baikal Lake) are under discussion. According to obtained results, the submarine vent and its companion spring nearby on the land originate from a common source. The most convincing evidence for their relation comes from proximity of stable oxygen and hydrogen isotope compositions in the pore waters and spring water. The isotope composition indicates meteoric origin of the pore waters, but their major- and minor element compositions have influence of deep water, which may seep through the permeable faulted crust. Although the pore waters near the submarine vent have specific enrichment in major and minor constituents, hydrothermal discharge at the Baikal bottom causes minor influence on water composition of the Baikal Lake, unlike freshwater lakes in rifts of the East Africa and North America.

Geochemistry of Lau Backarc Basin sediments

Major and minor (Mn, Sr, Ba, V, Cr, Ni, Co, Zn, Cu, Zr, Y, Sc) elements and mineralogic compositions were determined on bulk sediments collected during Ocean Drilling Program Leg 135. Three classes of sediment samples from holes drilled in the Lau Basin are discriminated by mineralogy and major element data. Samples labeled Class 1 are significantly enriched in biogenic calcite and occur predominantly in the northern part of the basin (Sites 834-835), whereas those of Class 3 are mostly enriched in volcanogenic material and are predominant in the central part of the basin (Sites 836-839). The minor element composition records the effects of the hydrothermal activity on the sediments. In the northern area of the basin (Sites 834-835), sedimentation is characterized by higher accumulation rates of the carbonate and hydrothermal fractions. These sediments are probably reworked predominantly, transported in the water column, and then settled locally. Thus, ponded sediments are probably responsible to this high accumulation rates. Diagenetic processes altered the volcanic material to a grade corresponding to the stability of phillipsite. In the central area of the basin (Sites 836-839), sedimentation is characterized by the action of bottom currents preferentially reworking the carbonate and hydrothermal fractions. Volcanogenic accumulation rates are greater at these sites than in the northern Lau Basin. Alteration of volcanic material is more important deeper in the holes and records authigenesis of clay rich in Fe-Mg, most likely smectite. Locally, clay minerals have apparently incorporated Cr and other ore-forming elements.

Chemical composition of phosphorites from the Peru and Chile shelves

Recent and Late Quaternary shelf phosphorites have low Fe, Ti and Al contents. These elements enter the phosphorites with terrigenous impurities and organic detritus. Ti, Al, and some Fe are removed when the phosphorites are lithified, whereas remaining iron settles in the phosphorites as sulfides. Ti/Fe, Al/Fe and Ti/Al ratios are used as examples of difference between behavior of Fe and that of Ti and Al.

Mineralogy and geochemistry of sulfide minerals and bulk rocks from ODP Hole 176-735B

Ocean Drilling Program (ODP) Leg 176 built upon the work of ODP Leg 118 wherein the 500-m section that was sampled represented the most complete recovery of an intact portion of lower oceanic crust ever described. During Leg 176, we deepened Hole 735B to >1500 m below seafloor in an environment where gabbroic rocks have been tectonically exposed at the Southwest Indian Ridge. This new expedition extended the remarkable recovery (>85%) that allowed unprecedented investigations into the nature of the lower oceanic crust as a result of Leg 118. Sulfide mineral and bulk rock compositions were determined from samples in the 1000-m section of oceanic gabbros recovered during Leg 176. The sulfide assemblage of pyrrhotite, chalcopyrite, pentlandite, and troilite is present throughout this section, as it is throughout the 500-m gabbroic section above that was sampled during Leg 118. Troilite is commonly present as lamellae, and the only interval where troilite was not observed is from the uppermost 150 m of the section sampled during Leg 118, which is intensely metamorphosed. The common presence of troilite indicates that much of the sulfide assemblage from Hole 735B precipitated from a magmatic system and subsequently underwent low-temperature reequilibration. Evaluation of geochemical trends in bulk rock and sulfides indicates that the combined effects of olivine accumulation in troctolites and high pentlandite to pyrrhotite ratios account for the sporadic bulk rock compositions high in Ni. Bulk rock and sulfide mineral geochemical indicators that are spatially coincident with structural and physical properties anomalies indicate a heretofore unrecognized lithologic unit boundary in this section. Platinum-group element (PGE) compositions were also determined for 36 samples from throughout the section that were recovered during Leg 176. Whereas most samples had low (<0.4 ppb) PGE concentrations, rare samples had elevated PGE values, but no unique common trend between these samples is evident.

Geochemical composition of gabbroic rocks from ODP Hole 179-1105A, southwest Indian Ridge

Oxide-free olivine gabbro and gabbro, and oxide olivine gabbro and gabbro make up the bulk of the gabbroic suite recovered from Ocean Drilling Program (ODP) Leg 179 Hole 1105A, which lies 1.2 km away from Hole 735B on the eastern transverse ridge of the Atlantis II Fracture Zone, Southwest Indian Ridge. The rocks recovered during Leg 179 show striking similarities to rocks recovered from the uppermost 500 m of Hole 735B during ODP Leg 118. The rocks of the Atlantis platform were likely unroofed as part of the footwall block of a large detachment fault on the inside corner of the intersection of the Southwest Indian Ridge and the Atlantis II Transform at ~11.5 Ma. We analyzed the lithologic, geochemical, and structural stratigraphy of the section. Downhole lithologic variation allowed division of the core into 141 lithologic intervals and 4 main units subdivided on the basis of predominance of oxide gabbroic vs. oxide-free gabbroic rocks. Detailed analyses of whole-rock chemistry, mineral chemistry, microstructure, and modes of 147 samples are presented and clearly show that the gabbroic rocks are of cumulate origin. These studies also indicate that geochemistry results correlate well with downhole magnetic susceptibility and Formation MicroScanner (FMS) resistivity measurements and images. FMS images show rocks with a well-layered structure and significant numbers of mappable layer contacts or compositional contrasts. Downhole cryptic mineral and whole-rock chemical variations depict both "normal" and inverse fine-scale variations on a scale of 10 m to <2 m with significant compositional variation over a short distance within the 143-m section sampled. A Mg# shift in whole-rock or Fo contents of olivine of as much as 20-30 units over a few meters of section is not atypical of the extreme variation in downhole plots. The products of the earliest stages of basaltic differentiation are not represented by any cumulates, as the maximum Fo content was Fo78. Similarly, the extent of fractionation represented by the gabbroic rocks and scarce granophyres in the section is much greater than that represented in the Atlantis II basalts. The abundance of oxide gabbros is similar to that in Hole 735B, Unit IV, which is tentatively correlated as a similar unit or facies with the oxide gabbroic units of Hole 1105A. Oxide phases are generally present in the most fractionated gabbroic rocks and lacking in more primitive gabbroic rocks, and there is a definite progression of oxide abundance as, for example, the Mg# of clinopyroxene falls below 73-75. Coprecipitation of oxide at such early Mg#s cannot be modeled by perfect fractional crystallization. In situ boundary layer fractionation may offer a more plausible explanation for the complex juxtaposition of oxide- and nonoxide-bearing more primitive gabbroic rocks. The geochemical signal may, in part, be disrupted by the presence of mylonitic shear zones, which strike east-west and dip both to the south and north, but predominantly to the south away from the northern rift valley where they formed. Downhole deformation textures indicate increasing average strain and crystal-plastic deformation in units that contain oxides. Oxide-rich zones may represent zones of rheologic weakness in the cumulate section along which mylonitic and foliated gabbroic shear zones nucleate in the solid state at high temperature, or the oxide may be a symptom of former melt-rich zones and hypersolidus flow, as predicted during study of Hole 735B.

Grain size analyses, Ca/Ti and other selected elemental ratios from XRF core scanning of sediment cores from the Apulian Margin

An extensive, high-resolution, sedimentological-geochemical survey was done using geo-acoustics, XRF-core scans, ICP-AES, AMS 14C-dating and grain size analyses of sediments in 11 cores from the Gulf of Taranto, the southern Adriatic Sea, and the central Ionian Sea spanning the last 16 cal. ka BP. Comparable results were obtained for cores from the Gallipoli Shelf (eastern Gulf of Taranto), and the southern Adriatic Sea suggesting that the dominant provenance of Gallipoli Shelf sediments is from the western Adriatic mud belt. The 210Pb and 14C-dated high-accumulation-rate sediments permit a detailed reconstruction of climate variability over the last 16 cal. ka BP. Although, the Glacial-Interglacial transition is generally dry and stable these conditions are interrupted by two phases of increased detrital input during the Bølling-Allerød and the late Younger Dryas. The event during the Younger Dryas period is characterized by increased sediment inputs from southern Italian sources. This suggests that run-off was higher in southern- compared to northern Italy. At approximately ~ 7 cal. ka BP, increased detrital input from the Adriatic mud belt, related to sea level rise and the onset of deep water formation in the Adriatic Sea, is observed and is coincident with the end of sapropel S1 formation in the southern Adriatic Sea. During the mid-to-late Holocene we observed millennial-scale events of increased detrital input, e.g. during the Roman Humid Period, and of decreased detrital input, e.g., Medieval Warm Period. These dry/wet spells are consistent with variability in the North Atlantic Oscillation (NAO). A negative state of the NAO and thus a more advanced penetration of the westerlies into the central Mediterranean, that result in wet conditions in the research area concord with events of high detrital input e.g., during the Roman Humid Period. In contrast, a positive state of the NAO, resulting in dry conditions in the Mediterranean, dominated during events of rapid climate change such as the Medieval Warm Period and the Bronze Age.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Description, geochemistry and mineral composition of ODP Site 193-1189 jasperoids, PACMANUS field

Bright red "jasperoids" were recovered at three positions during Leg 193 drilling below Roman Ruins (Site 1189) in the PACMANUS hydrothermal field. These do not represent fossil exhalative oxide deposits equivalent to those associated with sulfide chimneys at the Roman Ruins seafloor. Rather, they constitute an integral, relatively early stage involving oxidized fluids in the development of veins and breccias that characterize the mostly sulfidic stockwork zone intersected below Roman Ruins in Hole 1189B. They formed by growth of quartz in open spaces created by hydrofracturing, the characteristic feature being mostly euhedral cores dusted by tiny hematite flakes. In one occurrence there are also frondlike aggregates and possible earlier cavity linings of hematite, overgrown by quartz, that potentially formed by maturation of ferruginous gels first deposited in the openings. The trace element geochemistry of the jasperoids, apart from minor enrichment in uranium, provides no indication that they represent subsurface conduits for fluids that deposit Fe-Mn-Si at the seafloor, though this remains a possibility for some such deposits.

Mg/Ca ratios of Cenozoic benthic foraminifera from the Indian and South Atlantic Ocean

We investigate the evolution of Cenozoic climate and ice volume as evidenced by the oxygen isotopic composition of seawater (delta18Osw) derived from benthic foraminiferal Mg/Ca ratios to constrain the temperature effect contained in foraminiferal delta18O values. We have constructed two benthic foraminiferal Mg/Ca records from intermediate water depth sites (Ocean Drilling Program sites 757 and 689 from the subtropical Indian Ocean and the Weddell Sea, respectively). Together with the previously published composite record of Lear et al. (2002, doi:10.1126/science.287.5451.269) and the Neogene record from the Southern Ocean of Billups and Schrag (2002, doi:10.1029/2000PA000567), we obtain three, almost complete representations of the delta18Osw for the past 52 Myr. We discuss the sensitivity of early Cenozoic Mg/Ca-derived paleotemperatures (and hence the delta18Osw) to assumptions about seawater Mg/Ca ratios. We find that during the middle Eocene (~ 49-40 Ma), modern seawater ratios yield Mg/Ca-derived temperatures that are in good agreement with the oxygen isotope paleothermometer assuming ice-free conditions. Intermediate waters cooled during the middle Eocene reaching minimum temperatures by 40 Ma. The corresponding delta18Osw reconstructions support ice growth on Antarctica beginning by at least 40 Ma. At the Eocene/Oligocene boundary, Mg/Ca ratios (and hence temperatures) from Weddell Sea site 689 display a well-defined maximum. We caution against a paleoclimatic significance of this result and put forth that the partitioning coefficient of Mg in benthic foraminifera may be sensitive to factors other than temperature. Throughout the remainder of the Cenozoic, the temporal variability among delta18Osw records is similar and similar to longer-term trends in the benthic foraminiferal delta18O record. An exception occurs during the Pliocene when delta18Osw minima in two of the three records suggest reductions in global ice volume that are not apparent in foraminiferal delta18O records, which provides a new perspective to the ongoing debate about the stability of the Antarctic ice sheet. Maximum delta18Osw values recorded during the Pleistocene at Southern Ocean site 747 agree well with values derived from the geochemistry of pore waters (Schrag et al., 1996, doi:10.1126/science.272.5270.1930) further highlighting the value of the new Mg/Ca calibrations of Martin et al. (2002, doi:10.1016/S0012-821X(02)00472-7) and Lear et al. (2002, doi:10.1016/S0016-7037(02)00941-9) applied in this study. We conclude that the application of foraminiferal Mg/Ca ratios allows a refined view of Cenozoic ice volume history despite uncertainties related to the geochemical cycling of Mg and Ca on long time scales.

Chemical composition of bottom sediments from the Deryugin Basin, Sea of Okhotsk

This paper reports data including new analyses of contents of Ni, Co, V, Mo, Fe, Mn, Zn, Ba, Sc, Y, Cd, Rb, Cs, and W in bottom sediments of the Deryugin Basin. Features of chemical element distribution in the bottom area were identified and zones of maximum accumulation of major and trace elements were allocated. A correlation between the elements was shown.

Documentation, profile descriptions and analytical results of loes profiles from Bavaria, southern Germany

This study investigates the landscape evolution and soil development in the loess area near Regensburg between approximately 6000-2000 yr BP (radiocarbon years), Eastern Bavaria. The focus is on the question how man and climate influenced landscape evolution and what their relative significance was. The theoretical background concerning the factors that controlled prehistoric soil erosion in Middle Europe is summarized with respect to rainfall intensity and distribution, pedogenesis, Pleistocene relief, and prehistoric farming. Colluvial deposits , flood loams, and soils were studied at ten different and representative sites that served as archives of their respective palaeoenvironments. Geomorphological, sedimentological, and pedological methods were applied. According to the findings presented here, there was a high asynchronity of landscape evolution in the investigation area, which was due to prehistoric land-use patterns. Prehistoric land use and settlement caused highly difIerenciated phases of morphodynamic activity and stability in time and space. These are documented at the single catenas ofeach site. In general, Pleistocene relief was substantially lowered. At the same time smaller landforms such as dells and minor asymmetric valleys filled up and strongly transformed. However, there were short phases at many sites, forming short lived linear erosion features ('Runsen'), resulting from exceptional rainfalls. These forms are results of single events without showing regional trends. Generally, the onset of the sedimentation of colluvial deposits took place much earlier (usually 3500 yr BP (radiocarbon) and younger) than the formation of flood loams. Thus, the deposition of flood loams in the Kleine Laaber river valley started mainly as a consequence of iron age farming only at around 2500 yr BP (radiocarbon). A cascade system explains the different ages of colluvial deposits and flood loams: as a result of prehistoric land use, dells and other minor Pleistocene landforms were filled with colluvial sediments. After the filling of these primary sediment traps , eroded material was transported into flood plains, thus forming flood loams. But at the moment we cannot quantify the extent ofprehistoric soil erosion in the investigation area. The three factors that controlled the prehistoric Iandscapc evolution in the Ioess area near Regensburg are as follows: 1. The transformation from a natural to a prehistoric cultural landscape was the most important factor: A landscape with stable relief was changed into a highly morphodynamic one with soil erosion as the dominant process of this change. 2. The sediment traps of the pre-anthropogenic relief determined where the material originated from soil erosion was deposited: either sedimentation took place on the slopes or the filled sediment traps of the slopes rendered flood loam formation possible. Climatic influence of any importance can only be documented as the result of land use in connection with singular and/or statistic events of heavy rainfalls. Without human impact, no significant change in the Holocene landscape would have been possible.