Appendix A. Whole-rock major, trace and rare earth element analyses of the Ulubey volcanics, Appendix B. Analytical standards and detection limits for analyses

Collisional and post-collisional volcanic rocks in the Ulubey (Ordu) area at the western edge of the Eastern Pontide Tertiary Volcanic Province (EPTVP) in NE Turkey are divided into four suites; Middle Eocene (49.4-44.6 Ma) aged Andesite-Trachyandesite (AT), Trachyandesite-Trachydacite-Rhyolite (TTR), Trachydacite-Dacite (TD) suites, and Middle Miocene (15.1 Ma) aged Trachybasalt (TB) suite. Local stratigraphy in the Ulubey area starts with shallow marine environment sediments of the Paleocene-Eocene time and then continues extensively with sub-aerial andesitic to rhyolitic and rare basaltic volcanism during Eocene and Miocene time, respectively. Petrographically, the volcanic rocks are composed primarily of andesites/trachyandesites, with minor trachydacites/rhyolites, basalts/trachybasalts and pyroclastics, and show porphyric, hyalo-microlitic porphyric and rarely glomeroporphyric, intersertal, intergranular, fluidal and sieve textures. The Ulubey (Ordu) volcanic rocks indicate magma evolution from tholeiitic-alkaline to calc-alkaline with medium-K contents. Primitive mantle normalized trace element and chondrite normalized rare earth element (REE) patterns show that the volcanic rocks have moderate light rare earth element (LREE)/heavy rare earth element (HREE) ratios relative to E-Type MORB and depletion in Nb, Ta and Ti. High Th/Yb ratios indicate parental magma(s) derived from an enriched source formed by mixing of slab and asthenospheric melts previously modified by fluids and sediments from a subduction zone. All of the volcanic rocks share similar incompatible element ratios (e.g., La/Sm, Zr/Nb, La/Nb) and chondrite-normalized REE patterns, indicating that the basic to acidic rocks originated from the same source. The volcanic rocks were produced by the slab dehydration-induced melting of an existing metasomatized mantle source, and the fluids from the slab dehydration introduced significant large ion lithophile element (LILE) and LREE to the source, masking its inherent HFSE-enriched characteristics. The initial 87Sr/86Sr (0.7044-0.7050) and eNd (-0.3 to +3.4) ratios of the volcanics suggest that they originated from an enriched lithospheric mantle source with low Sm/Nd ratios. Integration of the geochemical, petrological and isotopical with regional and local geological data suggest that the Tertiary volcanic rocks from the Ulubey (Ordu) area were derived from an enriched mantle, which had been previously metasomatized by fluids derived from subducted slab during Eocene to Miocene in collisional and post-collisional extension-related geodynamic setting following Late Mesozoic continental collision between the Eurasian plate and the Tauride-Anatolide platform.

(Table 1) Composition of DSDP Hole 37-334 clinopyroxenes

Recent studies of abyssal peridotites (Johnson et al., 1990, doi:10.1029/JB095iB03p02661), mid-ocean-ridge basalts (MORBs) (McKenzie, 1985, doi:10.1016/0012-821X(85)90001-9) and their entrained melt inclusions (Sobolev and Shimizu, 1993, doi:10.1038/363151a0; Humler and Whitechurch, 1988, doi:10.1016/0012-821X(88)90055-6) have shown that fractional melting of the upwelling sub-oceanic mantle produces magmas with a much wider range of compositions than erupted MORBs. In particular, it seems that strongly depleted primary magmas are routinely produced by melting beneath ridges (Johnson et al., 1990, doi:10.1029/JB095iB03p02661). The absence of strongly depleted melts as erupted lavas prompts the question of how long such magmas survive beneath ridges, before their distinctive compositions are concealed by mixing with more enriched magmas. Here we report mineral compositions from a unique suite of oceanic cumulates recovered from DSDP Site 334 (Aumento et al., doi:10.2973/dsdp.proc.37.1977), which indicate that the rocks crystallized from basaltic liquids that were strongly depleted in Na, Ti, Zr, Y, Sr and rare-earth elements relative to any erupted MORB. It thus appears that the magmatic plumbing system beneath the Mid-Atlantic Ridge permitted strongly depleted magmas to accumulate in a magma chamber and remain sufficiently isolated to produce cumulate rocks. Even so, spatial heterogeneity in the compositions of high-calcium pyroxenes suggests that in the later stages of solidification these rocks reacted with infiltrating enriched basaltic liquids.

Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

Geochemistry of the oldest Atlantic oceanic crust

Controversy has surrounded the issue of whether mantle plume activity was responsible for Pangaean continental rifting and massive flood volcanism (resulting in the Central Atlantic Magmatic Province or CAMP, emplaced around 200 Ma) preceding the opening of the central Atlantic Ocean in the Early Mesozoic. Our new Sr-Nd-Pb isotopic and trace element data for the oldest basalts sampled from central Atlantic oceanic crust by deep-sea drilling show that oceanic crust generated from about 160 to 120 Ma displays clear isotopic and chemical signals of plume contamination (e.g., 87Sr/86Sr(i) = 0.7032-0.7036, epsilonNd(t) =+6.2 to +8.2, incompatible element patterns with positive Nb anomalies), but these signals are muted or absent in crust generated between 120 and 80 Ma, which resembles young Atlantic normal mid-ocean ridge basalt. The plume-affected pre-120 Ma Atlantic crustal basalts are isotopically similar to lavas from the Ontong Java Plateau, and may represent one isotopic end-member for CAMP basalts. The strongest plume signature is displayed near the center of CAMP magmatism but the hotspots presently located nearest this location in the mantle reference frame do not appear to be older than latest Cretaceous and are isotopically distinct from the oldest Atlantic crust. The evidence for widespread plume contamination of the nascent Atlantic upper mantle, combined with a lack of evidence for a long-lived volcanic chain associated with this plume, leads us to propose that the enriched signature of early Atlantic crust and possibly the eruption of the CAMP were caused by a relatively short-lived, but large volume plume feature that was not rooted at a mantle boundary layer. Such a phenomenon has been predicted by recent numerical models of mantle circulation.

Geochemistry and oxygen and iron isotope ratios of mafic rocks

Recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes. The oxygen isotope ratios (d18O) of some ocean island basalts (OIB) span values both above and below that of unmetasomatised upper mantle (5.5 ± 0.4 per mil) and provide support for this hypothesis, as it is widely assumed that most variations in d18O are produced by near-surface low-temperature processes. Here we show a significant linear relationship between d18O and stable iron isotope ratios (d57Fe) in a suite of pristine eclogite xenoliths. The d18O values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values. The observed range and correlation between d18O and d57Fe is unlikely to be inherited from oceanic crust, as d57Fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with d18O. It is proposed that the correlated d57Fe and d18O variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out. Fractionation of Fe and O isotopes by removal of partial melt enriched in isotopically heavy Fe and O is supported by negative correlations between bulk sample d57Fe and Cr content and bulk sample and garnet d18O and Sc contents, as Cr and Sc are elements that become enriched in garnet- and pyroxene-bearing melt residues. Melt extraction could take place either during subduction, where the eclogites represent the residues of melted oceanic lithosphere, or could take place during long-term residence within the lithospheric mantle, in which case the protoliths of the eclogites could be of either crustal or mantle origin. This modification of both d57Fe and d18O by melting processes and specifically the production of low-d18O signatures in mafic rocks implies that some of the isotopically light d18O values observed in OIB and eclogite xenoliths may not necessarily reflect near-surface processes or components.

Chronostratigraphic framework at sites GeoB14403 and GeoB14414 from the Gela Basin, Sicily Channel

A multi-proxy chronological framework along with sequence-stratigraphic interpretations unveils composite Milankovitch cyclicity in the sedimentary records of the Last GlacialeInterglacial cycle at NE Gela Basin on the Sicilian continental margin. Chronostratigraphic data (including foraminifera-based eco-biostratigraphy and d18O records, tephrochronological markers and 14C AMS radiometric datings) was derived from the shallow-shelf drill sites GeoB14403 (54.6 m recovery) and GeoB14414 (27.5 m), collected with both gravity and drilled MeBo cores in 193 m and 146 m water depth, respectively. The recovered intervals record Marine Isotope Stages and Substages (MIS) from MIS 5 to MIS 1, thus comprising major stratigraphic parts of the progradational deposits that form the last 100-ka depositional sequence. Calibration of shelf sedimentary units with borehole stratigraphies indicates the impact of higher-frequency (20-ka) sea level cycles punctuating this 100-ka cycle. This becomes most evident in the alternation of thick interstadial highstand (HST) wedges and thinner glacial forced-regression (FSST) units mirroring seaward shifts in coastal progradation. Albeit their relatively short-lived depositional phase, these subordinate HST units form the bulk of the 100-ka depositional sequence. Two mechanisms are proposed that likely account for enhanced sediment accumulation ratios (SAR) of up to 200 cm/ka during these intervals: (1) intensified activity of deep and intermediate Levantine Intermediate Water (LIW) associated to the drowning of Mediterranean shelves, and (2) amplified sediment flux along the flooded shelf in response to hyperpycnal plumes that generate through extreme precipitation events during overall arid conditions. Equally, the latter mechanism is thought to be at the origin of undulated features resolved in the acoustic records of MIS 5 Interstadials, which bear a striking resemblance to modern equivalents forming on late-Holocene prodeltas of other Mediterranean shallow-shelf settings.

Geochemical composition of the Trincheira Complex in the southwestern Amazon craton, Brazil

We document the first-known Mesoproterozoic ophiolite from the southwestern part of the Amazon craton, corresponding to the Trincheira Complex of Calymmian age, and propose a tectonic model that explains many previously enigmatic features of the Precambrian history of this key craton, and discuss its role in the reconstruction of the Columbia supercontinent. The complex comprises extrusive rocks (fine-grained amphibolites derived from massive and pillowed basalts), mafic-ultramafic intrusive rocks, chert, banded iron formation (BIFs), pelites, psammitic and a smaller proportion of calc-silicate rocks. This sequence was deformed, metasomatized and metamorphosed during the development of the Alto Guaporé Belt, a Mesoproterozoic accretionary orogen. The rocks were deformed by a single tectonic event, which included isoclinal folding and metamorphism of the granulite-amphibolite facies. Layered magmatic structures were preserved in areas of low strain, including amygdaloidal and cumulate structures. Metamorphism was pervasive and reached temperatures of 780-853°C in mafic granulites and 680-720°C in amphibolites under an overall pressure of 6.8 kbar. The geochemical composition of the extrusive and intrusive rocks indicates that all noncumulus mafic-ultramafic rocks are tholeiitic basalts. The mafic-ultramafic rocks display moderately to strongly fractionation of light rare earth elements (LREE), near-flat heavy rare earth elements (HREE) patterns and moderate to strong negative high field strength elements (HFSE) anomalies (especially Nb), a geochemical signature typical of subduction zones. The lowest units of mafic granulites and porphyroblastic amphibolites in the Trincheira ophiolite are similar to the modern mid-ocean ridge basalt (MORB), although they locally display small Ta, Ti and Nb negative anomalies, indicating a small subduction influence. This behavior changes to an island arc tholeiites (IAT) signature in the upper units of fine-grained amphibolites and amphibole rich-amphibolites, characterized by progressive depletion in the incompatible elements and more pronounced negative Ta and Nb anomalies, as well as common Ti and Zr negative anomalies. Tectono-magmatic variation diagrams and chondrite-normalized REE and primitive mantle normalized patterns suggest a back-arc to intra-oceanic island arc tectonic regime for the eruption of these rocks. Therefore, the Trincheira ophiolite appears to have originated in an intraoceanic supra-subduction setting composed of an arc-back-arc system. Accordingly, the Trincheira Complex is a record of oceanic crust relics obducted during the collision of the Amazon craton and the Paraguá block during the Middle Mesoproterozoic. Thus, the recognition of the Trincheira ophiolite and suture significantly changes views on the evolution of the southern margin of the Amazon craton, and how it can influence the global tectonics and the reconstruction of the continents.