Paleoceanographic and paleoclimatic evolution of the Aegean Sea since the last interglacial (~130 ka BP) with special emphasis on sapropel formation

Five long piston cores collected from different subbasins of the Aegean Sea constitute the primary source of data for this PhD thesis. This study is the first to document a continuous paleoceanographic and paleoclimatic record of the Aegean Sea since the last interglacial. The chronostratigraphic reconstructions of the cored sediments based on organic carbon contents, stratigraphic position of known ash layers and oxygen isotopic curve matching collectively demonstrate the presence of sapropel S1 and MISS sapropels S3, S4 and S5 in the Aegean Sea subbasins. Generally, the organic carbon (TOC wt%) contents in sapropels range between 0.8% and 2% with highest concentrations of 9-13% in sapropels S4 and S5. Average sedimentation rates range between 4.7 and 11.8 cmlka with highest rates being observed in Euboea and North Ikaria basins (9.8 and 11.8 cm lka, respectively). The timing of the onset of sapropels S4 and S5 mostly predate those in the eastern Mediterranean with ages ranging from 106.4-105.6 and 128.6-128.4 ka BP, respectively. On the other hand, the initiation of the onset of sapropel S3 (i.e., 83.2-80.4 ka BP) seems to agree with its Mediterranean counterparts, which highlights the heterogeneity of the Aegean Sea subbasins in terms of rapid vs. lagged response to changing climatic conditions. The sapropel initiations appear to be synchronous across the Aegean Sea; whereas, the terminations display a wider temporal variability implying that the cessation of sapropels is controlled both by the amplitude of paleoclimatic changes and the physiography/location ofthe subbasins. Quantitative variations in the planktonic faunal assemblages exhibit a sequence of bioevents during the last -130,000 years which allow identification of four major biozones. The distributional patterns of the most significant taxa demonstrate similar trends among all core localities suggesting that the major changes in the planktonic foraminifera assemblages have taken place rather synchronously in the Aegean Sea. Sapropels S3, S4 and S5 were deposited under similar hydrographic conditions during which a distinct deep chlorophyll maximum (DCM) layer was established. This situation points to a stratified water column and increased export productivity during times of sapropel formation. On the other hand, the faunal contrast between Sl and older sapropels indicates that the former was developed in the absence of a DCM layer, lacking a deep phytoplankton assemblage. Under such conditions, oxygen advection via intermediate water flow must have been significantly reduced which implies significant stagnation. Sapropels are interpreted to have been deposited under normal marine conditions with temporary establishment of semi-euxinic bottom water conditions. Both marine and terrestrial organic matter contributed equally to MISS sapropels. In addition, organic carbon isotopic values across sapropels are more depleted than those in the eastern Mediterranean which, in tum, suggests enhanced riverine input during their deposition. Primary productivity calculations show that, particularly for sapropels with very high TOC values, both preservation and increased productivity are imperative in order to deposit sapropels with very high organic carbon contents (i.e., up to 13%).

Derivation of base-line geochemistry, petrography, and isotopic data for the host rocks to the Lucky Strike deposit and comparison with data from other alteration zones, Buchans Mining Camp, Newfoundland

The Buchans ore bodies of central Newfoundland represent some of the highest grade VMS deposits ever mined. These Kuroko-type deposits are also known for the well developed and preserved nature of the mechanically transported deposits. The deposits are hosted in Cambro-Ordovician, dominantly calc-alkaline, bimodal volcanic and epiclastic sequences of the Notre Dame Subzone, Newfoundland Appalachians. Stratigraphic relationships in this zone are complicated by extensively developed, brittledominated Silurian thrust faulting. Hydrothermal alteration of host rocks is a common feature of nearly all VMS deposits, and the recognition of these zones has been a key exploration tool. Alteration of host rocks has long been described to be spatially associated with the Buchans ore bodies, most notably with the larger in-situ deposits. This report represents a base-line study in which a complete documentation of the geochemical variance, in terms of both primary (igneous) and alteration effects, is presented from altered volcanic rocks in the vicinity of the Lucky Strike deposit (LSZ), the largest in-situ deposit in the Buchans camp. Packages of altered rocks also occur away from the immediate mining areas and constitute new targets for exploration. These zones, identified mostly by recent and previous drilling, represent untested targets and include the Powerhouse (PHZ), Woodmans Brook (WBZ) and Airport (APZ) alteration zones, as well as the Middle Branch alteration zone (MBZ), which represents a more distal alteration facies related to Buchans ore-formation. Data from each of these zones were compared to those from the LSZ in order to evaluate their relative propectivity. Derived litho geochemical data served two functions: (i) to define primary (igneous) trends and (ii) secondary alteration trends. Primary trends were established using immobile, or conservative, elements (i. e., HFSE, REE, Th, Ti0₂, Al₂0₃, P₂0₅). From these, altered volcanic rocks were interpreted in terms of composition (e.g., basalt - rhyodacite) and magmatic affinity (e.g., calc-alkaline vs. tholeiitic). The information suggests that bimodality is a common feature of all zones, with most rocks plotting as either basalt/andesite or dacite (or rhyodacite); andesitic senso stricto compositions are rare. Magmatic affinities are more varied and complex, but indicate that all units are arc volcanic sequences. Rocks from the LSZ/MBZ represent a transitional to calc-alkalic sequence, however, a slight shift in key geochemical discriminants occurs between the foot-wall to the hanging-wall. Specifically, mafic and felsic lavas of the foot-wall are of transitional (or mildly calc-alkaline) affinity whereas the hanging-wall rocks are relatively more strongly calc-alkaline as indicated by enriched LREE/HREE and higher ZrN, NbN and other ratios in the latter. The geochemical variations also serve as a means to separate the units (at least the felsic rocks) into hanging-wall and foot-wall sequences, therefore providing a valuable exploration tool. Volcanic rocks from the WBZ/PHZ (and probably the APZ) are more typical of tholeiitic to transitional suites, yielding flatter mantlenormalized REE patterns and lower ZrN ratios. Thus, the relationships between the immediate mining area (represented by LSZ/MBZ) and the Buchans East (PHZ/WBZ) and the APZ are uncertain. Host rocks for all zones consist of mafic to felsic volcanic rocks, though the proportion of pyroclastic and epiclastic rocks, is greatest at the LSZ. Phenocryst assemblages and textures are common in all zones, with minor exceptions, and are not useful for discrimination purposes. Felsic rocks from all zones are dominated by sericiteclay+/- silica alteration, whereas mafic rocks are dominated by chlorite- quartz- sericite alteration. Pyrite is ubiquitous in all moderately altered rocks and minor associated base metal sulphides occur locally. The exception is at Lucky Strike, where stockwork quartzveining contains abundant base-metal mineralization and barite. Rocks completely comprised of chlorite (chloritite) also occur in the LSZ foot-wall. In addition, K-feldspar alteration occurs in felsic volcanic rocks at the MBZ associated with Zn-Pb-Ba and, notably, without chlorite. This zone represents a peripheral, but proximal, zone of alteration induced by lower temperature hydrothermal fluids, presumably with little influence from seawater. Alteration geochemistry was interpreted from raw data as well as from mass balanced (recalculated) data derived from immobile element pairs. The data from the LSZ/MBZ indicate a range in the degree of alteration from only minor to severe modification of precursor compositions. Ba tends to show a strong positive correlation with K₂0, although most Ba occurs as barite. With respect to mass changes, Al₂0₃, Ti0₂ and P₂0₅ were shown to be immobile. Nearly all rocks display mass loss of Na₂O, CaO, and Sr reflecting feldspar destruction. These trends are usually mirrored by K₂0-Rb and MgO addition, indicating sericitic and chloritic alteration, respectively. More substantial gains ofK₂0 often occur in rocks with K-feldspar alteration, whereas a few samples also displayed excessive MgO enrichment and represent chloritites. Fe₂0₃ indicates both chlorite and sulphide formation. Si0₂ addition is almost always the case for the altered mafic rocks as silica often infills amygdules and replaces the finer tuffaceous material. The felsic rocks display more variability in Si0₂. Silicic, sericitic and chloritic alteration trends were observed from the other zones, but not K-feldspar, chloritite, or barite. Microprobe analysis of chlorites, sericites and carbonates indicate: (i) sericites from all zones are defined as muscovite and are not phengitic; (ii) at the LSZ, chlorites ranged from Fe-Mg chlorites (pycnochlorite) to Mg-rich chlorite (penninite), with the latter occurring in the stockwork zone and more proximal alteration facies; (iii) chlorites from the WBZ were typical of those from the more distal alteration facies of the LSZ, plotting as ripidolite to pycnochlorite; (iv) conversely, chlorite from the PHZ plot with Mg-Al-rich compositions (chlinochlore to penninite); and (v) carbonate species from each zone are also varied, with calcite occurring in each zone, in addition to dolomite and ankerite in the PHZ and WBZ, respectively. Lead isotope ratios for galena separates from the different various zones, when combined with data from older studies, tend to cluster into four distinctive fields. Overall, the data plot on a broad mixing line and indicate evolution in a relatively low-μ environment. Data from sulphide stringers in altered MBZ rocks, as well as from clastic sulphides (Sandfill prospect), plot in the Buchans ore field, as do the data for galena from altered rocks in the APZ. Samples from the Buchans East area are even more primitive than the Buchans ores, with lead from the PHZ plotting with the Connel Option prospect and data from the WBZ matching that of the Skidder prospect. A sample from a newly discovered debris flow-type sulphide occurrence (Middle Branch East) yields lead isotope ratios that are slightly more radiogenic than Buchans and plot with the Mary March alteration zone. Data within each cluster are interpreted to represent derivation from individual hydrothermal systems in which metals were derived from a common source.