The distribution of zinc, cadmium, copper and iron in seawater of the Iceland-Faroe Ridge area

During the International ICES Expedition "Overflow '73" a total of 174 samples from 18 stations were collected by R. V. "Meteor" in the waters of the Iceland-Faroe Ridge area. They were filtered on board ship (through 0.4 mym "Nuclepore" filters), then stored in 500 cm**3 quartz bottles (at -20 °C) and analyzed in air-filtered laboratories on land for zinc and cadmium by means of the differential pulse anodic stripping voltammetry technique and copper and iron by flameless atomic absorption spectrometry. The overall averages of 1.9 myg Zn l**-1, 0.07 myg Cd l**-1, 0.5 myg Cu l**-1 and 0.9 myg Fe l**-1 are in good agreement with recent "baseline" studies of open-ocean waters. The mixture of low salinity water masses from the North Iceland Shelf/Arctic Intermediate Waters seem to maintain distinctly lower concentration of Cd, Cu and Fe than the waters from the North Atlantic and the Norwegian Sea where quite similar mean values are found. There is only little evidence for the assumption that overflow events on the ridge are influencing the concentrations of dissolved metals in the near-bottom layers.

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).

Highly dealkylated copper and nickel etioporpyfrins in marine sediments

Copper porphyrins have been recognized as natural constituents of marine sediments only within the past 5 years (Palmer and Baker, 1978, Science201, 49-51). In that report it was suggested that these pigments may derive from and be markers for oxidized terrestrial organic matter redeposited in the marine environment. In the present study we describe the distribution of copper porphyrins in sediments from several north Pacific and Gulf of California DSDP/IPQD sites (Legs 56,63,64). These allochthonous pigments have now been found to be accompanied by identical arrays of highly dealkylated nickel etioporphyrins. Evaluation of data from this and past studies clearly reveals that there is a strong carbon-number distribution similarity betweeen coincident Cu and Ni etioporphyrins. This homology match is taken as reflecting a common source for the tetrapyrrole ligands of this population of Cu and Ni chelates. Predepositional generation of these highly dealkylated etioporphyrins is concluded from the occurrence of these pigments in sediments continuing essentially all stages of in situ chlorophyll diagenesis (cf. Baker and Louda, 1983). That is, their presence is not regulated by the in situ diagenetic continuum. Thus, the highly dealkylated Cu and Ni etioporphyrins represent an 'allochthonous' background over which 'autochthonous' (viz. marine produced) chlorophyll derivatives are deposited and are undergoing in situ diagenesis.

Pollen and non-pollen palynomorph records of the Holocene part of the composite sediment core TMD from lake Tso Moriri (NW India) and of modern surface samples from the Tso Moriri region

The high-altitude lake Tso Moriri (32°55'46'' N, 78°19'24'' E; 4522 m a.s.l.) is situated at the margin of the ISM and westerly influences in the Trans-Himalayan region of Ladakh. Human settlements are rare and domestic and wild animals are concentrating at the alpine meadows. A set of modern surface samples and fossil pollen from deep-water TMD core was evaluated with a focus on indicator types revealing human impact, grazing activities and lake system development during the last ca. 12 cal ka BP. Furthermore, the non-pollen palynomorph (NPP) record, comprising remains of limnic algae and invertebrates as well as fungal spores and charred plant tissue fragments, were examined in order to attest palaeolimnic phases and human impact, respectively. Changes in the early and middle Holocene limnic environment are mainly influenced by regional climatic conditions and glacier-fed meltwater flow in the catchment area. The NPP record indicates low lake productivity with high influx of freshwater between ca. 11.5 and 4.5 cal ka BP which is in agreement with the regional monsoon dynamics and published climate reconstructions. Geomorphologic observations suggest that during this period of enhanced precipitation the lake had a regular outflow and contributed large amounts of water to the Sutlej River, the lower reaches of which were integral part of the Indus Civilization area. The inferred minimum fresh water input and maximum lake productivity between ca. 4.5-1.8 cal ka BP coincides with the reconstruction of greatest aridity and glaciation in the Korzong valley resulting in significantly reduced or even ceased outflow. We suggest that lowered lake levels and river discharge on a larger regional scale may have caused irrigation problems and harvest losses in the Indus valley and lowlands occupied by sedentary agricultural communities. This scenario, in turn, supports the theory that, Mature Harappan urbanism (ca. 4.5-3.9 cal ka BP) emerged in order to facilitate storage, protection, administration, and redistribution of crop yields and secondly, the eventual collapse of the Harappan Culture (ca. 3.5-3 cal ka BP) was promoted by prolonged aridity. There is no clear evidence for human impact around Tso Moriri prior to ca. 3.7 cal ka BP, with a more distinct record since ca. 2.7 cal ka BP. This suggests that the sedimentary record from Tso Moriri primarily archives the regional climate history.

Non-isoprenoidal intact polar lipids, isoprenoidal and non-isoprenoidal core lipids, isoprenoidal intact polar lipids of the Black Sea site GeoB15105 sampled during Meteor cruise M84/1 in February 2011

This PhD thesis focused on the analysis and application of microbial membrane lipids as biomarkers in marine sediments. Existing protocols for lipid extraction from marine sediments and biomass were modified. In addition, recent protocols based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) as well as state-of-the-art mass spectrometric analysis by quadrupole time-of-flight (MSqTOF) and the triple quadrupole (MSQQQ) mass spectrometer were used to investigate matrix effects and evaluate the reliability of quantitative analysis in marine environmental samples. The improved lipid extraction and quantification were used to analyze Black Sea water column and sediments samples to a depth of 8 meters from site GeoB 15105 taken during cruise M84/1 (DARCSEAS) with R/V Meteor to apply lipid analysis in benthic bio systems. With this component specific differentiation between planktonic and benthic lipid signature we assessed possible lipid sources. Here, this high detail lipid fingerprinting allowed us to observe changes in the head group and lipid core structures of the intact polar lipids according to the geochemical zonation.

Dioxin-like and non-dioxin like contaminants in the herring Clupea harengus in the Norwegian and North Sea

The Norwegian spring spawning (NSS) herring is an ecologically important fish stock in the Norwegian Sea, and with a catch volume exceeding one million tons a year it is also economically important and a valuable food source. In order to provide a baseline of the levels of contaminants in this fish stock, the levels of organohalogen compounds were determined in 800 individual herring sampled at 29 positions in the Norwegian Sea and off the coast of Norway. Due to seasonal migration, the herring were sampled where they were located during the different seasons. Concentrations of dioxins and dioxin-like PCBs, non-dioxin-like PCBs (PCB7) and PBDEs were determined in fillet samples of individual herring, and found to be relatively low, with means (min-max) of 0.77 (0.24-3.5) ngTEQ/kg wet weight (ww), 5.0 (1.4-24) µg/kg ww and 0.47 (0.091-3.1) µg/kg ww, respectively. The concentrations varied throughout the year due to the feeding- and spawning cycle: Starved, pre-spawning herring caught off the Norwegian coast in January-February had the highest levels and those caught in the Norwegian Sea in April-June, after further starvation and spawning, had the lowest levels. These results show that the concentrations of organohalogen compounds in NSS herring are relatively low and closely tied to their physiological condition, and that in the future regular monitoring of NSS herring should be made in the spawning areas off the Norwegian coast in late winter.

Seawater carbonate chemistry and growth, reproduction of calcifying and non-calcifying epibionts of a brown macroalga in a laboratory experiment

Seaweeds are key species of the Baltic Sea benthic ecosystems. They are the substratum of numerous fouling epibionts like bryozoans and tubeworms. Several of these epibionts bear calcified structures and could be impacted by the high pCO2 events of the late summer upwellings in the Baltic nearshores. Those events are expected to increase in strength and duration with global change and ocean acidification. If calcifying epibionts are impacted by transient acidification as driven by upwelling events, their increasing prevalence could cause a shift of the fouling communities toward fleshy species. The aim of the present study was to test the sensitivity of selected seaweed macrofoulers to transient elevation of pCO2 in their natural microenvironment, i.e. the boundary layer covering the thallus surface of brown seaweeds. Fragments of the macroalga Fucus serratus bearing an epibiotic community composed of the calcifiers Spirorbis spirorbis (Annelida) and Electra pilosa (Bryozoa) and the non-calcifier Alcyonidium hirsutum (Bryozoa) were maintained for 30 days under three pCO2 conditions: natural 460±59 µatm, present-day upwelling1193±166 µatm and future upwelling 3150±446 µatm. Only the highest pCO2 caused a significant reduction of growth rates and settlement of S. spirorbis individuals. Additionally, S. spirorbis settled juveniles exhibited enhanced calcification of 40% during daylight hours compared to dark hours, possibly reflecting a day-night alternation of an acidification-modulating effect by algal photosynthesis as opposed to an acidification-enhancing effect of algal respiration. E. pilosa colonies showed significantly increased growth rates at intermediate pCO2 (1193 µatm) but no response to higher pCO2. No effect of acidification on A. hirsutum colonies growth rates was observed. The results suggest a remarkable resistance of the algal macro-epibionts to levels of acidification occurring at present day upwellings in the Baltic. Only extreme future upwelling conditions impacted the tubeworm S. spirorbis, but not the bryozoans.