Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

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.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

(Table 2) Integrated concentration, production and dissolution of silica in the water column of the southern Pacific

An intense diatom bloom developed within a strong meridional silicic acid gradient across the Antarctic Polar Front at 61°S, 170°W following stratification of the water column in late October/early November 1997. The region of high diatom biomass and the silicic acid gradient propogated southward across the Seasonal Ice Zone through time, with the maximum diatom biomass tracking the center of the silicic acid gradient. High diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of January 1998 (ca. 70 d) driving the gradient over 500 km to the south of its original position at the Polar Front. The bloom consumed 30 to >40 µM Si(OH)4 in the euphotic zone between about 60 and 66°S leaving near surface concentrations <2.5 µM and occasionally <1.0 µM in its wake. Integrated biogenic silica concentrations within the bloom averaged 410 mmol Si/m**2 (range 162-793 mmol Si/m**2). Average integrated silica production on two consecutive cruises in December 1997 and January 1998 that sampled the bloom while it was well developed were 27.5±6.9 and 22.6±20 mmol Si/m**2/d, respectively. Those levels of siliceous biomass and silica production are similar in magnitude to those reported for ice-edge diatom blooms in the Ross Sea, Antarctica, which is considered to be among the most productive regions in the Southern Ocean. Net silica production (production minus dissolution) in surface waters during the bloom was 16-21 mmol Si/m**2/d, which is sufficient for diatom growth to be the cause of the southward displacement of the silicic acid gradient. A strong seasonal change in silica dissolution : silica production rate ratios was observed. Integrated silica dissolution rates in the upper 100-150 m during the low biomass period before stratification averaged 64% of integrated production. During the bloom integrated dissolution rates averaged only 23% of integrated silica production, making 77% of the opal produced available for export to depth. The bloom ended in late January apparently due to a mixing event. Dissolution : production rate ratios increased to an average of 0.67 during that period indicating a return to a predominantly regenerative system. Our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around Antarctica also occur in the deep ocean near the Polar Front. The bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of Antarctica implying a role for such blooms in the formation of those sediments. Comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the Southern Ocean, which have been corrected for sediment focusing, indicate a burial efficiency of <=4.6% for biogenic silica. That efficiency is considerably lower than previous estimates for the Southern Ocean.

Geochemistry and radiolarian distribution of sediment core MD96-2073

A combination of changes in the species composition of the radiolarian populations, and in the sediment chemical composition (content and mass accumulation rates of carbonate, organic carbon, and selected major and trace elements, with special attention paid to Ba) is used to reconstruct the variations in upwelling activity over the last 250 kyr in the Socotra gyre area (Somali-Socotra upwelling system, NW Indian Ocean). In the Socotra gyre (Core MD 962073 at 10°N), the variations in upwelling intensity are reconstructed by the upwelling radiolarian index (URI) while the thermocline/surface radiolarian index (TSRI) testifies to productivity variations during non-upwelling intervals. Despite an origin related both to marine and terrigenous inputs, the geochemical records of organic carbon, silica, and trace elements (Ba, P, Cu, and Zn) normalized to Al are controlled by the variations in surface paleoproductivity. The data indicate a continuous increase in upwelling intensity during the last 250 kyr with a maximum activity within the MIS 3, while high productivity periods in between the upwelling seasons occurred both during glacial and interglacial intervals. A comparison of our data with published observations from another gyre of the Somalian upwelling area located at 5°N in the Somali gyre area shows differences regarding periods of upwelling activity and their geochemical imprint. Three hypotheses are proposed to explain these differences: (1) changes in the planktonic community, resulting in more silica-rich deposits in the Socotra gyre, and more carbonate-rich deposits in the Somali gyre, that are controlled by differences in the source water of the upwelling; (2) a more important terrigenous input in the southern gyre; and (3) a different location of the sites relative to the geographic distribution of the upwelling gyres and hydrologic fronts.

Composition of dissolved, particulate and sinking material in hydrothermal plumes above the TAG and Broken Spur hydrothermal fields

The paper reports data on distribution of dissolved (Mn, Zn, Cu, Pb, and Cd) and particulate (Fe, Mn, Zn, Cu, Pb, Ni, and Co) species of metals in hydrothermal plumes above the active TAG and Broken Spur hydrothermal fields (26° N and 29° N in the MAR rift valley, respectively). Sediment trap data on fluxes of hydrothermal sedimentary material in the areas indicate that (i) the predominant Zn source for metalliferous sediments at the TAG field is material precipitating from the neutrally buoyant plume, and (ii) the predominant source of Fe and Co is re-deposited ore material coming from the area of extensive settling of sulfides.

High-resolution sedimentological and paleontological record of ODP Site 167-1019

Holocene and latest Pleistocene oceanographic conditions and the coastal climate of northern California have varied greatly, based upon high-resolution studies (ca. every 100 years) of diatoms, alkenones, pollen, CaCO3%, and total organic carbon at Ocean Drilling Program (ODP) Site 1019 (41.682°N, 124.930°W, 980 m water depth). Marine climate proxies (alkenone sea surface temperatures [SSTs] and CaCO3%) behaved remarkably like the Greenland Ice Sheet Project (GISP)-2 oxygen isotope record during the Bølling-Allerod, Younger Dryas (YD), and early part of the Holocene. During the YD, alkenone SSTs decreased by >3°C below mean Bølling-Allerod and Holocene SSTs. The early Holocene (ca. 11.6 to 8.2 ka) was a time of generally warm conditions and moderate CaCO3 content (generally >4%). The middle part of the Holocene (ca. 8.2 to 3.2 ka) was marked by alkenone SSTs that were consistently 1-2°C cooler than either the earlier or later parts of the Holocene, by greatly reduced numbers of the gyre-diatom Pseudoeunotia doliolus (<10%), and by a permanent drop in CaCO3% to <3%. Starting at ca. 5.2 ka, coastal redwood and alder began a steady rise, arguing for increasing effective moisture and the development of the north coast temperate rain forest. At ca. 3.2 ka, a permanent ca. 1°C increase in alkenone SST and a threefold increase in P. doliolus signaled a warming of fall and winter SSTs. Intensified (higher amplitude and more frequent) cycles of pine pollen alternating with increased alder and redwood pollen are evidence that rapid changes in effective moisture and seasonal temperature (enhanced El Niño-Southern Oscillation [ENSO] cycles) have characterized the Site 1019 record since about 3.5 ka.

Pleistocene sedimentation in the Benguela Current, southeastern Atlantic

We infer variations in paleoproductivity and eolian input at ODP Site 1082 in the Walvis Basin from stable oxygen isotope compositions of the planktonic foraminifera Globorotalia inflata, total organic carbon mass accumulation rates (TOC MAR), and X-ray fluorescence analyses of Fe content. The most pronounced paleoclimatic changes correspond to the time at about 0.9 Ma, when glacial conditions in the northern hemisphere (NH) led to the onset of pronounced 100-kyr glacial-interglacial cycles. We used Fe intensity as a proxy for eolian terrigenous input, and TOC MAR as a paleoproductivity indicator. Paleoproductivity and eolian input show generally higher-amplitude variations of glacial-interglacial cyclicity from 1.5 to 0.58 Ma, indicating pronounced variations in upwellingfavorable winds in this area. At 0.58 Ma, paleoproductivity and eolian input shifted abruptly to lower-amplitude variations with a periodicity of 100 kyr while delta18O values show a trend toward more negative isotope values for the past 0.65 Myr. Especially during glacial periods, oxygen isotope values indicate increasingly warmer sea-surface temperatures toward the end of the Pleistocene. To evaluate the relative influences of NH glaciation and southern hemisphere (SH) insolation as potential forcing mechanisms for variations of eolian input and productivity in the northern Benguela system, we filtered our proxy records at orbital frequencies. The filtered records of Fe intensity and TOC MAR indicate a strong influence of the 100-kyr and 41-kyr frequency bands, supporting our assumption that strong ice buildup in the NH is the dominant trigger for climate changes on the continent and probably in trade-wind intensity. SH insolation and low-latitude precession-related insolation changes were important for paleoproductivity variations in the northern Benguela system, modifying the nutrient supply by southern ocean intermediate waters and the zonal direction of upwelling-inducing trades by the African monsoon system, respectively.

Grain size composition and age of ODP Hole 167-1017E sediments

Siliciclastic sedimentation at Ocean Drilling Program Site 1017 on the southern slope of the Santa Lucia Bank, central California margin, responded closely to oceanographic and climatic change over the past ~130 ka. Variation in mean grain-size and sediment sorting within the ~25-m-thick succession from Hole 1017E show Milankovitch-band to submillenial-scale variation. Mean grain size of the "sortable silt" fraction (10-63 µm) ranges from 17.6 to 33.9 µm (average 24.8 µm) and is inversely correlated with the degree of sorting. Much of the sediment has a bimodal or trimodal grain-size distribution that is composed of distinct fine silt, coarse silt to fine sand, and clay-size components. The position of the mode and the sorting of each component changes through the succession, but the primary variation is in the presence or abundance of the coarse silt fraction that controls the overall mean grain size and sorting of the sample. The occurrence of the best-sorted, finest grained sediment at high stands of sea level (Holocene, marine isotope Substages 5c and 5e) reflect the linkage between global climate and the sedimentary record at Site 1017 and suggest that the efficiency of off-shelf transport is a key control of sedimentation on the Santa Lucia Slope. It is not clear what proportion of the variation in grain size and sorting may also be caused by variations in bottom current strength and in situ hydrodynamic sorting.

Rare earth and other element contents and speciations in samples from Core AKO26-35, Pacific Ocean, Southwest Basin

Ferromanganese micro- and macronodules in eupelagic clays at Site AKO26-35 in the Southwest Pacific Basin were studied in order to check REE distribution during ferromanganese ore formation in non-productive zones of the Pacific Ocean. Host sediments and their labile fraction, ferromanganese micronodules (in size fractions 50-100, 100-250, 250-500, and >500 ?m) from eupelagic clays (horizons 37-10, 105-110, 165-175, and 189-190 cm), and buried ferromanganese micronodules (horizons 64-68, 158-159, and 165-166 cm) were under study. Based on partition analysis data anomalous REE enrichment in eupelagic clays from Site AKO26-35 is related to accumulation of rare earth elements in iron hydroxophosphates. Concentration of Ce generally bound with manganese oxyhydroxides is governed by oxidation of Mn and Ce in ocean surface waters. Micronodules (with Mn/Fe from 0.7 to 1.6) inherit compositional features of the labile fraction of bottom sediments. Concentrations of Ce, Co, and Th depend on micronodule sizes. Enrichment of micronodules in hydrogenic or hydrothermal matter is governed by their sizes and by a dominant source of suspended oxyhydroxide material. The study of buried ferromanganese micronodules revealed general regularities in compositional evolution of oxyhydroxide matrices of ferromanganese micro- and macronodules. Compositional variation of micro- and macronodules relative to the labile fraction of sediments in the Pacific non-productive zone dramatically differs from the pattern in bioproductive zones where micronodule compositions in coarser fractions are similar to those in associated macronodules and labile fractions of host sediments due to more intense suboxidative diagenesis.

Hydrocarbons in particulate matter and bottom sediments from the north Caspian Sea shelf

Data are presented on content and composition of hydrocarbons (HC) (aliphatic AHC and polyaromatic PAH) in filtered particulate matter and in the surface layer of bottom sediments from the northern shelf of the Caspian Sea and related to data on their contents in the Volga River estuary. Because of transformation and precipitation of anthropogenic and natural compounds, HC composition in particulate matter and bottom sediments undergoes transformations caused by mixing of fresh and saline waters (in bottom sediments, within concentration ranges 70.4-4557.9 µg/g for AHC and 3.8-4800 ng/g for PAH). It was found that the greatest concentrating of HC proceeds in the region of the avalanche sedimentation, and their contents are independent of grain-size types of bottom sediments. Anthropogenic HC (oil and pyrogenous) do not get over the marginal filter of the Volga River and do not pass to the open part of the sea.