Chemical and mineral compositions of bottom sediments from the East Pacific Rise near 13°N

During underwater photography and sampling of the rift valley bottom in the axial part of the East Pacific Rise, where water transparency is reduced due to hydrothermal input, ore manifestations have been found. The bottom is covered by them as by a jacket on both sides from the EPR axial zone. However, exposed pillow-lavas and clumpy blocks in rift ledges are covered by a thin metal-bearing film. It is supposed that sedimentation results mainly from hydrothermal input of dissolved chemical elements in seawater, their transformation on the geochemical barrier, and subsequent deposition as particulates. Contents of ore components in metalliferous sediments have been measured by atomic-absorption and X-ray radiometry methods. Sediment age has been determined as Middle Pleistocene - Holocene. Maximal hydrothermal activity was at the beginning of Early Holocene, about 10 Ka. A smoker has been found on the western slope of the rift valley.

Geochemical provenance analysis of fine-grained sediment of sediment core AND1-1

Bulk chemical fine-grained sediment compositions from southern Victoria Land glacimarine sediments provide significant constraints on the reconstruction of sediment provenance models in the McMurdo Sound during Late Cenozoic time. High-resolution (~ 1 ka) geochemical data were obtained with a non-destructive AVAATECH XRF Core Scanner (XRF-CS) on the 1285 m long ANDRILL McMurdo Ice Shelf Project (MIS) sediment core AND-1B. This data set is complemented by high-precision chemical analyses (XRF and ICP-OES) on discrete samples. Statistical analyses reveal three geochemical facies which are interpreted to represent the following sources for the sediments recovered in the AND-1B core: 1) local McMurdo Volcanic Group (MVG) rocks, 2) Transantarctic Mountain rocks west of Ross Island (W TAM), and 3) Transantarctic Mountain rocks from more southerly areas (S TAM). Data indicate in combination with other sediment facies analyses (McKay et al., 2009, doi:10.1130/B26540.1) and provenance scenarios (Talarico and Sandroni, 2009, doi:10.1016/j.gloplacha.2009.04.007) that diamictites at the drill site are largely dominated by local sources (MVG) and are interpreted to indicate cold polar conditions with dry-based ice. MVG is interpreted to indicate cold polar condition with dry-based ice. A mixture of MVG and W TAM is interpreted to represent polar conditions and the S TAM facies is interpreted to represent open-marine conditions. Down-core variations in geochemical facies in the AND-1B core are interpreted to represent five major paleoclimate phases over the past 14 Ma. Cold polar conditions with major MVG influence occur below 1045 mbsf and above 120 mbsf. A section of warmer climate conditions with extensive peaks of S TAM influence characterizes the rest of the core, which is interrupted by a section from 525 to 855 mbsf of alternating influences of MVG and W TAM.

Lead and strontium isotopic composition of some metalliferous and pelagic sediments and basalts at DSDP Leg 70 Holes

In recent years, metalliferous sediments have been discovered overlying newly generated oceanic crust in the East Pacific, North Atlantic, Indian Ocean, Red Sea, Gulf of Aden, and elsewhere (e.g., Boström, 1973; Lalou et al., 1977; Bischoff, 1969; Boström and Fisher, 1971; Cann et al., 1977, respectively). Such material has also been recovered by drilling from sediments lying upon older oceanic crust (Boström et al., 1972, 1976; Horowitz and Cronan, 1976). Hydrothermal circulation of seawater at a spreading ridge results in the leaching of Fe, Mn, and possibly other elements from the basaltic volcanic layer and their transport and discharge into ocean bottom waters, whereupon fine-grained Fe-Mn-rich precipitates form and settle into the ambient sediment (cf. Corliss, 1971; Dasch et al., 1971; Spooner and Fyfe, 1973; Bischoff and Dickson, 1975; Heath and Dymond, 1977; Corliss et al., 1979, Edmond et al., 1979). Mn-rich crusts have also been recovered from active ridges and are inferred to have formed in the vicinity of hydrothermal discharge areas (Scott et al., 1974; Moore and Vogt, 1976; Corliss et al., 1978; Hoffert et al., 1978). The source of the trace elements in the metalliferous deposits is generally not clear. They may be derived from seawater by adsorption onto the precipitates or crusts, or from hydrothermal solutions which have leached them from the basalts. Pb, however, can be used as a geochemical tracer because of the known isotopic compositional differences between oceanic basalts and seawater. Isotopic investigations of Pb in ferruginous sediments from the East Pacific have shown that it has been derived partly or mostly from a basaltic source (Bender et al., 1971; Dasch et al., 1971; Dymond et al., 1973). In the present study, Pb isotopic analyses have been made of a suite of metalliferous sediments (nontronite, Mn-oxide crust, Mn-Fe-oxide mud), pelagic sediments, and basalts from the Galapagos mounds area. The main purposes of the Pb study were to determine the source or sources of Pb in the metalliferous sediments, and whether or not stratigraphic variations exist in the isòtopic composition of Pb in the sediments.

Geochemistry of ODP Sites 128-798 and 128-799 sediments

Nineteen trace elements, including seven rare earth elements (REE's), and 10 major and minor elements in 76 sediment samples from Sites 798 (Oki Ridge) and 799 (Yamato Trough) were determined by means of instrumental neutron activation analysis and X-ray fluorescence spectrometry. Most REE patterns (chondrite-normalized) of the sediments from both sites were nearly identical to the patterns of terrigenous materials. The cerium anomaly (slightly positive) frequently appeared in REE patterns of the sediments (200-750 mbsf) from Site 799. Cerium may be selectively incorporated into the sediments with hydrogenous manganese precipitation. However, the degree of the anomaly was not well correlated with manganese content, suggesting that cerium may behave as a trivalent REE (like the other REE's) during diagenesis while manganese is transported in the sediment column accompanied by reduction to a lower oxidation state. The Th/Sc ratio of the sediments from Sites 798 and 799 tended to decrease with penetration depth. Such a depth profile may indicate a decrease in basic volcanism activities from the Pliocene (Site 798) and Miocene (Site 799). The La/Yb ratio and degree of europium anomaly also varied with depth, which may imply that two or more components with different REE patterns were supplied throughout sedimentation at sites in the Japan Sea.

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.

Mineralogical composition, copper and d18O at DSDP Site 59-448

Alteration in a submarine remnant volcanic arc should leave an important record of (1) the mineralogy of sea water-volcanic arc rock interaction; (2) the chemistry of solid reaction products; (3) the isotopic characteristics of such reactions (Muehlenbachs and Clayton, 1972; Spooner, Beckinsale, et al , 1977; Spooner, Chapman, et al., 1977); (4) the metallogenesis within such a sequence (Mitchell and Bell, 1973); and (5) the geothermal gradient during the alteration. The volcaniclastic breccias, tuffs, and igneous units of Sites 448 (993 m) and 451 (930.5 m) on the Palau-Kyushu and West Mariana ridges, respectively, are particularly suited for such studies because the thick sequences have remained submarine throughout their history, seemingly unaffected by magmatic or hydrothermal events after cessation of volcanic activity. Also, shipboard observations indicated a change in alteration products with depth. At both sites the igneous units and volcaniclastic rocks were altered to brownish clays and zeolites near the top of the volcanic sequence; to bright blue green clays and zeolites at moderate depths; and to very dark, nearly opaque, forest green clays and zeolites at still greater depths. Native copper occurs both as disseminated pockets in the volcaniclastic breccias and vesicular basalts and as veins in the breccias; native copper is restricted to stratigraphic levels characterized by the absence of sulfides or oxides of copper and iron. Although some native copper is found in vesicles of basalts and may be orthomagmatic, most of it is clearly secondary. Near dikes and sills, higher sulfur fugacity conditions caused the precipitation of iron and copper sulfides with an absence of native copper (Garrels and Christ, 1965). The occurrence of native copper may be an initial stage of Cu metallogenesis that forms porphyry coppers in island arcs (Mitchell and Bell, 1973). This study will address primarily the possibility that hydrothermal sea water interaction with volcanic arc rocks has created the mineralogical and isotopic zonation in Leg 59 cores. Hydrothermal activity can be expected in a rapidly growing island arc and is probably the result of a high geothermal gradient prevalent during arc magmatic activity. The chemical character of the alteration is further discussed by Hajash (1981).

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.

Chemical composition of ferromanganese nodules from the Black Sea

Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied by transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese oxyhydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. Oxyhydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Concentrations of Mn, As, and Mo are 12-18 times higher relative to sediments, while concentrations of Fe, P, Ni, and Co increase 5-7 times during nodule formation.

Agricultural pesticide in sediment cores from the Lac de Saint-André, France

Agricultural pesticide use has increased worldwide during the last several decades, but the long-term fate, storage, and transfer dynamics of pesticides in a changing environment are poorly understood. Many pesticides have been progressively banned, but in numerous cases, these molecules are stable and may persist in soils, sediments, and ice. Many studies have addressed the question of their possible remobilization as a result of global change. In this article, we present a retro-observation approach based on lake sediment records to monitor micropollutants and to evaluate the long-term succession and diffuse transfer of herbicides, fungicides, and insecticide treatments in a vineyard catchment in France. The sediment allows for a reliable reconstruction of past pesticide use through time, validated by the historical introduction, use, and banning of these organic and inorganic pesticides in local vineyards. Our results also revealed how changes in these practices affect storage conditions and, consequently, the pesticides' transfer dynamics. For example, the use of postemergence herbicides (glyphosate), which induce an increase in soil erosion, led to a release of a banned remnant pesticide (dichlorodiphenyltrichloroethane, DDT), which had been previously stored in vineyard soil, back into the environment. Management strategies of ecotoxicological risk would be well served by recognition of the diversity of compounds stored in various environmental sinks, such as agriculture soil, and their capability to become sources when environmental conditions change.

Geochemistry of evaporite in the Red Sea

One of the major shipboard findings during Leg 23 drilling in the Red Sea was the presence of late Miocene evaporites at Sites 225, 227, and 228. The top of the evaporite sequence correlates with a strong reflector (Reflector S) which has been mapped over much of the Red Sea (Ross et al., 1969, Phillips and Ross, 1970). This indicates that the Red Sea appears to be extent. Miocene sediments, including evaporites, are known from a few outcrops along the coastal plains of the Gulf of Suez to lat 14°N (Sadek, 1959, cited in Friedman, 1972; Heybroek, 1965; Friedman, 1972). Along the length of the Red Sea, the presence of Miocene salt is indicated by seismic reflection studies (Lowell and Genik, 1972) and confirmed by drilling. The recently published data from deep exploratory wells (Ahmed, 1972) demonstrate the great thickness of elastics and evaporites which were deposited in the Red Sea depression during Miocene time. The Red Sea evaporites are of the same age as the evaporites found by deep sea drilling (DSDP Leg 13) in the Mediterranean Sea. Therefore, Reflector S in the Red Sea is comparable to Reflector M in the Mediterranean. It is assumed that during Miocene time a connection between these two basins was established (Coleman, this volume) resulting in a similar origin for the evaporites deposited in the Red Sea and in the Mediterranean Sea. The origin of the Mediterranean evaporites has been discussed in great detail (Hsü et al., 1973; Nesteroff, 1973; Friedman, 1973). The formation of evaporites may be interpreted by three different hypotheses. 1) Evaporation of a shallow restricted shelf sea or lagoon which receives inflows from the open ocean. 2) Evaporation of a deep-water basin which is separated from the open ocean by a shallow sill (Schmalz, 1969). 3) Evaporation of playas or salt lakes which are situated in desiccated deep basins isolated from the open ocean (Hsü et al., 1973). The purpose of this study is to show whether one of these models might apply to the formation and deposition of the Red Sea evaporites. Therefore, a detailed petrographic and geochemical investigation was carried out.

Salinity and SO4 and Br enrichment of seawater and frost flowers near Barrow, Alaska

Frost flowers have been proposed to be the major source of sea-salt aerosol to the atmosphere during polar winter and a source of reactive bromine during polar springtime. However little is known about their bulk chemical composition or microstructure, two important factors that may affect their ability to produce aerosols and provide chemically reactive surfaces for exchange with the atmosphere. Therefore, we chemically analyzed 28 samples of frost flowers and parts of frost flowers collected from sea ice off of northern Alaska. Our results support the proposed mechanism for frost flower growth that suggests water vapor deposition forms an ice skeleton that wicks brine present on newly grown sea ice. We measured a high variability in sulfate enrichment factors (with respect to chloride) in frost flowers and seawater from the vicinity of freezing sea ice. The variability in sulfate indicates that mirabilite precipitation (Na2SO4 x 10 H2O) occurs during frost flower growth. Brine wicked up by frost flowers is typically sulfate depleted, in agreement with the theory that frost flowers are related to sulfate-depleted aerosol observed in Antarctica. The bromide enrichment factors we measured in frost flowers are within error of seawater composition, constraining the direct reactive losses of bromide from frost flowers. We combined the chemical composition measurements with temperature observations to create a conceptual model of possible scenarios for frost flower microstructure development.