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.

(Table 2) Geochemistry of glasses at DSDP Leg 54 Holes

The compositions of 45 natural basalt glasses from nine dredge stations and six Deep Sea Drilling Project Leg 54 sites near 9°N on the East Pacific Rise have been determined by electron microprobe. These comprise 19 distinct chemical groups. Seventeen of these fall in the range of the eastern Pacific tholeiite suite, which is characterized by marked enrichment in FeO*, TiO2, K2O, and P2O5 as CaO, MgO, and Al2O3 all decrease. Based on trace elements, an estimated 50-75 per cent fractionation of plagioclase, clinopyroxene, and olivine is required to produce ferrobasalts from parental olivine tholeiites. Additional chemical variations occur which require source heterogeneities, differences in the degree of melting, different courses of shallow fractionation, or magma mixing to explain. Glass compositions from within the Siqueiros fracture zone are mostly less fractionated than those from the flanks of the Rise, and show chemical differences which require variations in the depth of melting or highpressure fractionation to explain. Some of them could not be parental to East Pacific Rise flank ferrobasalts. Two remaining glass groups, from dredge hauls atop a ridge and a seamount, respectively, have distinctly higher K2O, P2O5, and TiO2 as well as lower CaO/Al2O3 and SiO2 at corresponding values of MgO than the tholeiite suite. These abundances, and whole-rock Y/Zr, Ce/Y, Nb/Zr, and isotopic abundances indicate that these basalts had a deeper, less depleted mantle source than the Rise tholeiite suite. Trace element abundances preclude the "ridge" basalt type from being a hybrid between the "seamount" basalt type and any East Pacific Rise tholeiite so far analyzed. The East Pacific Rise glasses from 9°N compare very closely to glasses dredged and drilled elsewhere on the East Pacific Rise. However, glass compositions from Site 424 on the Galapagos Rift drilled during Leg 54, as well as glasses and basalts dredged from the Galapagos and Costa Rica rifts, indicate that a greater degree of melting prevailed along much of the Galapagos Spreading Center than anywhere along the East Pacific Rise.