Appendix A: LA-ICP-MS results (Laser-ablation inductively coupled plasma mass spectrometer) from monazite Moacir standard

Three samples of garnet-kyanite paragneiss from the Variscan Ulten Zone (Northern Italy) were studied in detail for U-Th-Pb monazite dating. Monazite in these gneisses is abundant, shows highly variable grain size and occupies different textural positions: within the matrix, as inclusion in garnet and kyanite, within apatite aggregates. Monazite shows different deformation features as a function of the textural position: enclosed (shielded) monazite is generally more fractured than matrix (unshielded) monazite. The integration of textural information with deformation features and in situ U-Th-Pb analyses by LA-ICP-MS indicates that there is no direct correlation between textural site and monazite ages. Old ages of 351-343 Ma, determined on portions of large matrix (unshielded) monazite and on rare domains of monazite shielded by garnet, have been related to a prograde stage of the Variscan metamorphic evolution of the Ulten Zone. Ages of 330-326 Ma, which are related to the thermal peak, are recorded by small matrix monazite, external domains of large matrix monazite, and by (domains of) fractured monazite enclosed in garnet and kyanite. Large, old unshielded grains formed as blasts during the prograde metamorphic history and survived the peak metamorphism during which crystallisation/re-crystallisation partially occurred.

Sample locations, CTD data, mean spring and annual temperatures and salinities from World Ocean Atlas (WOA, 2001), and ICP-OES Mg/Ca data

Due to its strong gradient in salinity and small temperature gradient the Mediterranean provides an ideal setting to study the impact of salinity on the incorporation of Mg into foraminiferal tests. We have investigated tests of Globorotalia inflata and Globigerina bulloides in plankton tow and core top samples from the Western Mediterranean using ICP-OES for bulk analyses and LA-ICP-MS for analyses of individual chambers in single specimens. Mg/Ca observed in G. inflata are consistent with existing calibrations, whereas G. bulloides had significantly higher Mg/Ca than predicted, particularly in core top samples from the easterly stations. Scanning Electron Microscopy and Laser Ablation ICP-MS revealed secondary overgrowths on some tests, which could explain the observed high core top Mg/Ca. We suggest that the Mediterranean intermediate and deep water supersaturated with respect to calcite cause these overgrowths and therefore increased bulk Mg/Ca. However, the different species are influenced by diagenesis to different degrees probably due to different test morphologies. Our results provide new perspectives on reported anomalously high Mg/Ca in sedimentary foraminifera and the applicability of the Mg/Ca paleothermometry in high salinity settings, by showing that (1) part of the signal is generated by precipitation of inorganic calcite on the foraminifer test due to increased calcite saturation state of the water and (2) species with high surface-to-volume shell surfaces are potentially more affected by secondary Mg-rich calcite encrustation.

Geochemistry of sediment cores GeoB13820-1 and GeoB13863-1 from the western South Atlantic

Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

Paleoclimate record combinatio of speleothems and of sediment core GeoB3910-2

A substantial strengthening of the South American monsoon system (SAMS) during Heinrich Stadials (HS) points toward decreased cross-equatorial heat transport as the main driver of monsoonal hydroclimate variability at millennial time-scales. In order to better constrain the exact timing and internal structure of HS1 over tropical South America we assessed two precisely dated speleothem records from central-eastern and northeastern Brazil in combination with two marine records of terrestrial organic and inorganic matter input into the western equatorial Atlantic. During HS1 we recognize at least two events of widespread intensification of the SAMS across the entire region influenced by the South Atlantic Convergence Zone (SACZ) at 16.11-14.69 kyr BP and 18.1-16.66 kyr BP (labeled as HS1a and HS1c, respectively), separated by a dry excursion from 16.66-16.11 kyr BP (HS1b). In view of the spatial structure of precipitation anomalies, the widespread increase of monsoon precipitation over the SACZ domain was termed 'Mega-SACZ'.

Noble metal abundances in ODP Leg 115 basalts (Table 1)

A comparison of 50 basalts recovered at Sites 706, 707, 713, and 715 along the Reunion hotspot trace during Ocean Drilling Program Leg 115 in the Indian Ocean shows that seafloor alteration had little effect on noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir), determined by inductively coupled plasma-mass spectrometry (ICP-MS), which generally tend to decrease with magma evolution. Their compatible-element behavior may be related to the precipitation of Ir-Os-based alloys, chromite, sulfides, and/or olivine and clinopyroxene in some combination. The simplest explanation indicates silicate control of concentrations during differentiation. Basalts from the different sites show varying degrees of alkalinity. Noble metal abundances tend to increase with decreasing basalt alkalinity (i.e., with increasing percentages of mantle melting), indicating that the metals behave as compatible elements during mantle melting. The retention of low-melting-point Au, Pd, and Rh in mantle sulfides, which mostly dissolve before significant proportions of Ir-Os-based alloys melt, explains increasing Pd/Ir ratios with decreasing alkalinity (increasing melting percentages) in oceanic basalts. High noble metal concentrations in Indian Ocean basalts (weighted averages of Au, Pd, Rh, Pt, Ru, and Ir in Leg 115 basalts are 3.2, 8.1, 0.31, 7.3, 0.22, and 0.11 ppb, respectively), compared with basalts from some other ocean basins, may reflect fundamental primary variations in upper- mantle noble metal abundances

Geological and geochemical characteristics of the Tersang gold deposit, Malaysia: implications for genesis and gold exploration

The Central gold belt of peninsular Malaysia comprises a number of gold deposits located in the east of the N-S striking Bentong-Raub Suture Zone. The Tersang gold deposit is one of the gold deposits in the gold belt and hosted in sandstone, rhyolite and breccia units. The deposit has an inferred resource of 528,000 ounces of gold. The geochronology of the Tersang deposit has been newly constrained by LA ICP-MS U-Pb zircon dating. The maximum depositional age of the host sedimentary rocks ranges from Early Carboniferous to Early Permian (261.5 ± 4.9 Ma to 333.5 ± 2.5 Ma) for the host sandstone and Late Triassic for the rhyolite intrusion (218.8 ± 1.7 Ma). Textural characteristics of pyrite have revealed five types including (1) Euhedral to subhedral pyrite with internal fracturing and porous cores located in the sandstone layers (pyrite 1); (2) Anhedral pyrite overgrowths on pyrite 1 and disseminated in stage 1 vein (pyrite 2); (3) Fracture-filled or vein pyrite located in stages 1 and 2 vein (pyrite 3); (4) Euhedral pyrite with internal fractures also located in stage 2 vein (pyrite 4); and (5) Subhedral clean pyrite located in the rhyolite intrusion (pyrite 5). Based on pyrite mapping and spot analyses, two main stages of gold enrichment are documented from the Tersang gold deposit. Gold in sandstone-hosted pyrite 1 (mean 4.3 ppm) shows best correlation with Bi and Pb (as evidenced on pyrite maps). In addition, gold in pyrite 3 (mean 8 ppm) located in stage 2 vein shows a good correlation with As, Ag, Sb, Cu, Tl, and Pb. In terms of gold exploration, we suggest that elements such as As, Ag, Sb, Cu, Tl, Bi, and Pb associated with Au may serve as vectoring tools in gold exploration. Our new geological, structural, geochemical and isotopic data together with mineral paragenesis, pyrite chemistry and ore fluid characteristics indicate that the Tersang gold deposit is comparable to a sediment-hosted gold deposit. Our new genetic model suggests deposition of the Permo-Carboniferous sediments followed by intrusion of rhyolitic magma in the Late Triassic. At a later stage, gold mineralisation overprinted the rhyolite intrusion and the sandstone.

Isotope analysis, age calculation and calcite concentration from IODP Hole 310-M0005D

We present uranium-thoriumchronology for a 102 mcore through a Pleistocene reef at Tahiti (French Polynesia) sampled during IODP Expedition 310 "Tahiti Sea Level". We employ total and partial dissolution procedures on the older coral samples to investigate the diagenetic overprint of the uranium-thoriumsystem. Although alteration of the U-Th system cannot be robustly corrected, diagenetic trends in the U-Th data, combined with sea level and subsidence constraints for the growth of the corals enables the age of critical samples to be constrained to marine isotope stage 9. We use the ages of the corals, together with d18O based sea-level histories, to provide maximum constraints on possible paleo water-depths. These depth constraints are then compared to independent depth estimates based on algal and foraminiferal assemblages, microbioerosion patterns, and sedimentary facies, confirming the accuracy of these paleo water-depth estimates. We also use the fact that corals could not have grown above sea level to place amaximumconstraint on the subsidence rate of Tahiti to be 0.39 m ka**-1,with the most likely rate being close to the existing minimum estimate of 0.25m ka**-1.

Chemistry of minerals from amphibole-chlorite veins of ODP Site 209-1270

We examined small-scale shear zones in drillcore samples of abyssal peridotites from the Mid-Atlantic Ridge. These shear zones are associated with veins consisting of chlorite + actinolite/tremolite assemblages, with accessory phases zircon and apatite, and they are interpreted as altered plagiogranite melt impregnations, which originate from hydrous partial melting of gabbroic intrusion in an oceanic detachment fault. Ti-in-zircon thermometry yields temperatures around 820°C for the crystallization of the evolved melt. Reaction path modeling indicates that the alteration assemblage includes serpentine of the adjacent altered peridotites. Based on the model results, we propose that formation of chlorite occurred at higher temperatures than serpentinization, thus leading to strain localization around former plagiogranites during alteration. The detachment fault represents a major pathway for fluids through the oceanic crust, as evidenced by extremely low d18O of altered plagiogranite veins (+3.0-4.2 per mil) and adjacent serpentinites (+ 2.6-3.7 per mil). The uniform oxygen isotope data indicate that fluid flow in the detachment fault system affected veins and adjacent host serpentinites likewise.

Geochemistry of minerals in CRP sediment cores from the Ross Sea, Antarctica

Sixty-four volcanic chists, sandstones and tephras between 5.95 and 618.19 meters below sea floor (mbsf) in the Cape Roberts Project cores 2 and 2A cores (CRP-2/2A) were examined for Cenozoic and Mesozoic volcanic components, using optical and Scanning Electron Microscopy. Minerals and glass shards in a selection of samples were analysed by electron microprobe fined with an EDAX detector. Laser-Ablation ICP-Mass-Spectrometry (ICP-MS) was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to pin-point the onset of McMurdo Volcanic Group (MVG) activity in the stratigraphic column. Pumices in tephra layers of peralkaline phonolite composition in Unit 7.2 -between 108 and 114 mbsf - were also analysed for trace elements by ICP-MS. This tephra unit is not reworked and its isotopic age (21.44 ± 0.05 Ma) is the age of deposition. The height of the eruptive column responsible for the deposition of the tephra was probably less than 8 km; the source was local, probably within 30 km from the drill site. Phonolite of unit 7.2 of CRP-2/2A has no direct petrogenetic relation with the peralkaline trachyte in the tephra-enriched layer of CRP-1 at 116.55 mbsf. Volcanic clasts and sand grains (glass shards, aegirine-augite, anorthoclase) related to Cenozoic activity of MVG were observed only starting from Unit 9.8, where they are dated at 24.22 ± 0.06 Ma at c. 280 mbsf. In this unit the lowest- occurring basaltic glass shard is found at 297.54 mbsf. Sampled McMurdo volcanics are generally vesicular and vary in composition from alkali basalt to trachyte and peralkaline phonolite. By contrast, below 320 mbsf, aphyric or slightly-porphyritic volcanic clasts become more abundant but they are all non-vesiculated, pigeconite and ilmenite-bearing basalts and dolerite of tholeiitic affinity. These rocks are considered to be related to lava flows and associated intrusions of Jurassic age (Kirkpatrick basalts and Ferrar dolerite). As in CRP-1, McMurdo volcanics appear to derive from a variety of lithologics. Besides glaciers, a dominant role of wind transportation from exposed volcanic rocks may be inferred from the contemporary occurrence of glass shards of different compositions at depths above 297.54 mbsf. These data confirm that the onset of magmatic activity in southern Victoria Land is considerably delayed (by about 24 Ma) with respect to northern Victoria Land.