Geochemical analysis of surface sediments along the Portuguese Margin

Twenty-nine surface samples from the Portuguese shelf, recovered offshore from the mouths of the Ave, Douro, Lis and Mira rivers, were analysed using ICP-OES for selected major and trace elements, after total dissolution. Organic carbon, carbonate content and grain size were also determined. Five evaluation tools have been applied in order to compare the three study areas and to evaluate sediment geochemistry and other sediment compositional variability in the acquired samples: (1) empirical methods based on comparison with standard reference criteria, e.g. the NOAA sediment quality guidelines, (2) normalisation ratios using a grain-size proxy element, (3) "Gradient Method", plotting contaminant vs. organic matter or Al, (4) definition of a regional geochemical baseline from a compiled database, and (5) enrichment factors. The evaluation of element and component associations indicates differences related both to the onshore drainage areas and to the environmental shelf setting. Despite the considerable variability in total metal contents indicated by our results, the sediment metal composition is largely of natural origin. Metal enrichments observed in the Mira area are associated with the drainage of mineralised areas rich in Cu, Pb, Zn, Fe and Mn. The near absence of human impact on shelf sediments, despite the vicinity to urban areas with high industrialisation levels, such as the Ave-Douro and Lis areas, is attributed to effective trapping in the estuaries and coastal zones, as well dilution with less contaminated sediments shelf sediments and removal with fine fractions due to grain-size sorting. The character of the contaminated sediments transported to these shelf areas is further influenced by grain-size sorting as well as by dilution with less contaminated marine sediments. The results obtained individually by the different methods complement each other and allow more specific interpretations.

Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.

Chemical analysis of various geological samples from Northern Victoria Land, Antarctica

This paper reports the results of a preliminary palaeomagnetic investigation of the Admiralty Intrusives complex of northern Victoria Land, Antarctica. The samples were collected at Mt. Supernal and Inferno Peak, two pinions mainly formed of granodiorite and minor tonalite and emplaced at ab. 350 Ma at a high crustal level, as shown by amphibole geobarometric data and occurrence of miarolitic cavities. Microprobe and isothermal remanence analyses showed that magnetite. characterized by low coercivity and Curic point in the range 550-570 °C is the only primary ferromagnetic mineral. Stepwise thermaldemagnetization succeeded in isolatingamagnetization component. stable up to 530 °C. The virtual geomagnetic poles (VGPs) of the two plutons are different. That of Inferno Peak is consistent with the Australian palaeopoles of late Devonian-early Carboniferous age, whereas the location of the Mt. Supernal VGP probably results from the tectonic activity which affected the Ross Sea region during the Cenozoic.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Chemical composition of ocean Fe-Mn ores

The monograph includes the study of chemical and mineral compositions of terrestrial and marine manganese ores, methods of their analysis, dependence of manganese crust geochemistry on tectonic position of their formation, problems of manganese genesis and sources of manganese in ocean ores in connection with geohistorical aspects of ocean formation and development. A hypothesis is offered that formation of giant manganese mineral basins on continental margins resulted from a large asteroid fall to the ocean.

Geochemical analysis of nine sections from the Nama Group, Namibia

The first appearance of skeletal metazoans in the late Ediacaran (~550 million years ago; Ma) has been linked to the widespread development of oxygenated oceanic conditions, but a precise spatial and temporal reconstruction of their evolution has not been resolved. Here we consider the evolution of ocean chemistry from ~550 to ~541 Ma across shelf-to-basin transects in the Zaris and Witputs Sub-Basins of the Nama Group, Namibia. New carbon isotope data capture the final stages of the Shuram/Wonoka deep negative C-isotope excursion, and these are complemented with a reconstruction of water column redox dynamics utilising Fe-S-C systematics and the distribution of skeletal and soft-bodied metazoans. Combined, these inter-basinal datasets provide insight into the potential role of ocean redox chemistry during this pivotal interval of major biological innovation. The strongly negative d13C values in the lower parts of the sections reflect both a secular, global change in the C-isotopic composition of Ediacaran seawater, as well as the influence of 'local' basinal effects as shown by the most negative d13C values occurring in the transition from distal to proximal ramp settings. Critical, though, is that the transition to positive d13C values postdates the appearance of calcified metazoans, indicating that the onset of biomineralization did not occur under post-excursion conditions. Significantly, we find that anoxic and ferruginous deeper water column conditions were prevalent during and after the transition to positive d13C that marks the end of the Shuram/Wonoka excursion. Thus, if the C isotope trend reflects the transition to global-scale oxygenation in the aftermath of the oxidation of a large-scale, isotopically light organic carbon pool, it was not sufficient to fully oxygenate the deep ocean. Both sub-basins reveal highly dynamic redox structures, where shallow, inner ramp settings experienced transient oxygenation. Anoxic conditions were caused either by episodic upwelling of deeper anoxic waters or higher rates of productivity. These settings supported short-lived and monospecific skeletal metazoan communities. By contrast, microbial (thrombolite) reefs, found in deeper inner- and mid-ramp settings, supported more biodiverse communities with complex ecologies and large skeletal metazoans. These long-lived reef communities, as well as Ediacaran soft-bodied biotas, are found particularly within transgressive systems, where oxygenation was persistent. We suggest that a mid-ramp position enabled physical ventilation mechanisms for shallow water column oxygenation to operate during flooding and transgressive sea-level rise. Our data support a prominent role for oxygen, and for stable oxygenated conditions in particular, in controlling both the distribution and ecology of Ediacaran skeletal metazoan communities.

Rare earth elements in standard samples of ocean Fe-Mn nodules and crusts

Contents of rare earth elements (REE) in standard samples of Fe-Mn nodules (SDO-5, 6), Fe-Mn crust (SDO-7), and red clay (SDO-9) have been determined by ICP-MS and instrumental neutron activation analysis. Reproducibility of ICP-MS was 5-6%. These results are discussed and compared with other data. It has been found that distribution of REE in the standard samples of ocean Fe-Mn ores and red clay is highly homogenous.

Speciations of Mn and Fe in Fe-Mn nodules from the western part of the Clarion-Clipperton ore province

Hydrogenic forms of iron and manganese occurrence were studied in samples of ferromanganese nodules sampled within two polygons during Cruise 28 of R/V Dmitry Mendeleeev (1982) in the western part of the Clarion-Clipperton ore province. Contents of labile exchangeable Fe and Mn, amorphous hydroxides and poorly soluble compounds of Fe and Mn were analyzed. In nodules from DM28-2474 Polygon labile exchangeable Fe and Mn and amorphous hydroxides dominated; in nodules from DM28-2483 Polygon poorly soluble compounds dominated. Analysis of contents of labile forms of Fe and Mn occurrence in different morphological types of nodules distinguished predominantly hydrogenous botryoidal nodules, spheroidal and ellipsoidal intergrowth nodules, and hydrogenic-diagenetic discoid nodules.

Iron analysis in bottle profiles off Mauritania

Iron solubility measurements in the Mauritanian upwelling and the adjacent Open Ocean of the Tropical Atlantic show for all stations lower values in the surface mixed layer than at depth below the pycnocline. We attribute this distribution to a combination of loss terms, chiefly photo-oxidation of organic ligands in the surface, and supply terms, predominantly from the release of ligands from the decomposition of organic matter. Significant correlations with pH, oxygen and phosphate for all samples below the surface mixed layer indicate that biogenic remineralisation of organic matter results in the release of iron binding ligands into the dissolved phase. The comparison of the cFeS/PO4**3- ratio with other published data from intermediate and deep waters in the Pacific suggests an enhanced release of iron chelators in the more productive Mauritanian upwelling zone.

Geochemical analysis of sediments from three coring sites in the Mediterranean

In a gravity core from the eastern Mediterranean Sea, a chemically and mineralogically distinct, 5.5-cm-thick layer is present above sapropel S-1 and overlain by hemipelagic marls. Calcite is completely absent in this exotic layer, dolomite is present only in small amounts, and the Cr concentrations are significantly enhanced. The layer was deposited primarily under reducing conditions, but the distributions of redox-sensitive elements show that a large part of the exotic layer is now oxidised by a downward-progressing oxidation front. Sediments from within the nearby anoxic, hypersaline Urania Basin are similar to those from the exotic layer, in particular in S-, C-, and O-isotope distributions of pyrite and dolomite, as well as increased Cr concentrations. Mud expulsion due to expansion of gas-rich mud is proposed to explain the presence of the exotic layer outside the Urania Basin. The deposition of an anoxic layer above S-1 shielded the sapropel from oxidation which resulted in the rare occurrence of a complete preservation of S-1 and provides the first minimum age for the start of anoxic mud accumulation in the Urania Basin.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Analysis of Mn-nodules from Breitgrund, Baltic Sea

The usually high concentrations of Zn, Pb, Cd, and Cu in the most recently accreted portions of ferromanganese nodules from the western Baltic Sea are thought to reflect increased metal input due to anthropogenic mobilization. If so, the point of increase represents a time horizon within the structure of the nodule. Similar trace metal distributions of radiometrically dated sediments from the same area suggest that the ferromanganese nodules have grown in thickness between 0.02 and 0.16 mm yr-1. From this growth rate anthropogenic Zn flux to the nodule surface was calculated to be 80 mg m-2 yr-1.

Analysis of Manganese nodules from Sonne cruises SO06/1 and /2, "Hawaii-Tahiti-Transect", Teilprojekt ICIME

Manganese nodules research has focused on the area between the Clarion Fracture Zone to the North and the Clipperton Fracture Zone to the South where significant concentrations were found ni Ni-Cu. During the CCOP/SOPAC-IOC/IDOE International workshop on the "Geology Mineral Resources and Geophysics of the South Pacific" held in Fiji in September 1975, a working group on manganese nodules was formed by scientists from: CNEXO, Brest, the Institute of Oceanography, New Zealand, Imperial College, London and the Technical University of Aachen. A draft project was presented in July 1976 by J. Andrews, University of Hawaii and G. Pautot, Cnexo on a joint survey under the name of: "Hawaii-Tahiti Transect program". Further details were worked on in September 1976 during the International Geological Congress in Sydney with the participation of D. Cronan, Imperial College, Glasby, New Zealand Geological Survey and G. Friedrich, Aachen TU. The scientific final program was established in July 1977, planning on the participation of three research vessels: the Suroit (CNEXO), the Kana Keoki (U. of Hawaii) and the Sonne (Aachen TU). Several survey areas were selected across the Pacific Ocean (Areas A, B, C, D, E, F, G and H) with about the same crustal age (about 40 million years) and a similar water depths. Being near large fault zones, the ares would be adequate to study the influences of biological productivity, sedimentation rate and possibly volcanic activity on the formation and growth of manganese nodules. The influnece of volcanic activity study would particularly apply to area G being situated near the Marquesas Fracture Zone. The cruise from R/V Sonne started in August 1978 over areas C, D, F, G K. The R/V suroit conducted a similar expedition in 1979 over areas A, B, C, D, E, H and I. Others cruises were planned during the 1979-1980 for the R/V Kana Keoki. The present text relates the R/V Sonne Cruises SO-06/1 and SO-06/2 held within the frame work of this international cooperative project.

Bulk chemical analysis of sediments ODP Hole 110-671B and 110-672A

Chemical analyses for calcium carbonate, organic carbon, and major constituents (Al, Ti, Ca, Mg, K, Fe) of bulk sediments collected in Hole 671B have been carried out. Organic carbon contents in Pleistocene through middle Miocene sediments above the zone of decollement are very low (<0.1%); below the decollement considerably higher concentrations of organic carbon occur (up to 1 %). Changes in Ti/Al and Fe/Al ratios are minor, but K/Al and Mg/Al ratios show clear trends with the age of the sediments. Preliminary comparisons of these ratios with mineralogic information on clays indicate good correspondence with clay abundances. Calculations of the mass flux of magnesium from the overlying ocean into the pore fluids suggest that addition of magnesium to the sediments is difficult to detect, especially in the absence of a background reference concentration.

Uranium and radioactive isotopes in bottom sediments and Fe-Mn nodules and crusts of seas and oceans

The main stages of the sedimentary cycle of uranium in modern marine basins are under consideration in the book. Annually about 18 thousand tons of dissolved and suspended uranium enters the ocean with river runoff. Depending on a type of a marine basin uranium accumulated either in sediments of deep-sea basins, or in sediments of continental shelves and slopes. In the surface layer of marine sediments hydrogenic uranium is predominantly bound with organic matter, and in ocean sediments also with iron, manganese and phosphorus. In diagenetic processes there occurs partial redistribution of uranium in sediments, as well as its concentration in iron-manganese, phosphate and carbonate nodules and biogenic phosphate detritus. Concentration of uranium in marine sediments of various types depending on their composition, as well as on forms of its entering, degree of differentiation and of sedimentation rates, on hydrochemical regime and water circulation, and on intensity of diagenetic processes.