(Supplemet S1) Silicon oxide and Potassium + Sodium oxide from the PACManus hydrothermal area

This study presents a systematic analysis and interpretation of autonomous underwater vehicle-based microbathymetry combined with remotely operated vehicle (ROV) video recordings, rock analyses and temperaturemeasurements within the PACManus hydrothermal area located on Pual Ridge in the Bismarck Sea of eastern Manus Basin. The data obtained during research cruise Magellan-06 and So-216 provides a framework for understanding the relationship between the volcanism, tectonismand hydrothermal activity. PACManus is a submarine felsic vocanically-hosted hydrothermal area that hosts multiple vent fields locatedwithin several hundredmeters of one another but with different fluid chemistries, vent temperatures and morphologies. The total area of hydrothermal activity is estimated to be 20,279m**2. Themicrobathymetrymaps combinedwith the ROV video observations allow for precise high-resolution mapping estimates of the areal extents of hydrothermal activity.We find the distribution of hydrothermal fields in the PACManus area is primarily controlled by volcanic features that include lava domes, thick andmassive blocky lava flows, breccias and feeder dykes. Spatial variation in the permeability of local volcanic facies appears to control the distribution of venting within a field.We define a three-stage chronological sequence for the volcanic evolution of the PACManus based on lava flow morphology, sediment cover and lava SiO2 concentration. In Stage-1, sparsely to moderately porphyritic dacite lavas (68-69.8 wt.% SiO2) erupted to form domes or cryptodomes. In Stage-2, aphyric lava with slightly lower SiO2 concentrations (67.2-67.9 wt.% SiO2) formed jumbled and pillowed lava flows. In the most recent phase Stage-3, massive blocky lavaswith 69 to 72.5wt.% SiO2were erupted throughmultiple vents constructing a volcanic ridge identified as the PACManus neovolcanic zone. The transition between these stages may be gradual and related to progressive heating of a silicic magma following a recharge event of hot, mantle-derived melts.

K-Ar age and chemical composition of volcanites from the Sea of Okhotsk

Volcanogenic rocks from the Sea of Okhotsk are divided into seven age complexes: Late Jurassic, Early Cretaceous, Late Cretaceous, Eocene, Late Oligocene, Late Miocene, and Pliocene-Pleistocene. All these complexes are united into two groups - Late Mesozoic and Cenozoic. Each group reflects a certain stage of development of the Sea of Okhotsk region. Late Mesozoic volcanites build the geological basement of the Sea of Okhotsk, and their petrochemical features are similar to those of the volcanic rocks from the Okhotsk-Chukotka Volcanogen. Pliocene-Pleistocene volcanites reflect stages of tectono-magmatic activity; the latter destroyed the continental margin and produced riftogenic troughs. Geochemical features of volcanites from the Sea of Okhotsk indicate influence of the sialic crust on magma formation and testify formation of the Okhotsk Sea Basin on the destructive margin of the Asian continent.

(Table 1) Geochemistry of glass shards at DSDP Site 87-582 and 87-583

In the Leg 87A holes, 45 ash layers were sampled in Recent to upper Pliocene strata. The main volcanogenic deposits came from single eruptions or subcontemporaneous eruptions of cognate volcanoes. Some of them are mixed ashes produced from multiple eruptions and accumulated in reworked sediments. The petrographic and geochemical patterns indicate rhyolitic and dacitic compositions; andesitic glasses are scarce. We infer a magmatic affinity with calc-alkaline sources and a possible origin from the volcanic arc of southwestern Japan. A few samples may originate from the alkaline volcanism of southwestern Japan or the area south of Korea and the Sea of Japan.

(Table 1) K-Ar age determinations on biotite from coarse sand within DSDP Sample 72-516F-76-4,107-115

Qualitative petrographic study of selected clastic horizons within the Eocene section of Hole 516F has revealed the presence of abundant fine-grained lithic fragments, probably volcanic, along with coarser fragments of quartz and feldspar apparently derived from a nearby plutonic terrain. In detail, poor sorting, presence of graded bedding, and an abundance of clay suggest these are turbidite horizons locally derived from a mixed volcanic/plutonic terrain, possibly with some direct contribution from contemporary volcanic ash falls. A progressive increase in plutonic versus volcanic components with time is, however, more consistent with an erosional origin for most of this material. Unusual euhedral dark biotite is abundant in several of the lower clastic horizons; it is most easily interpreted as microphenocrysts weathered in situ out of alkalic volcanic ash. Biotite separated from Sample 516F-76-4,107-115 cm, has been dated by the K-Ar method at about 46 Ma. Alkaline volcanoes active on the Rio Grande Rise in the middle Eocene would be the most probable source of this ash and would be consistent with other evidence for potassic, alkaline volcanism along the Rio Grande Rise and at the Tristan da Cunha hot spot.

(Table 1) Trace element and isotopic data for ODP Hole 145-887D basalts

Age-progressive, linear seamount chains in the northeast Pacific appear to have formed as the Pacific plate passed over a set of stationary hotspots; however, some anomalously young ages and the lack of an "enriched" isotopic signature in basalts from the seamounts do not fit the standard hotspot model. For example, published ages (28-30 Ma) for basalts dredged from the Patton-Murray seamount platform in the Gulf of Alaska are 2-4 m.y. younger than the time when the platform was above the Cobb hotspot. However, the lowermost basalt recovered by ocean drilling on Patton-Murray yielded a 40Ar-39Ar age of 33 Ma. This age exactly coincides with the time when the seamount platform was above the Cobb hotspot, consistent with a stationary, long-lived mantle plume. A 27 Ma alkalic basalt flow recovered 8 m above the 33 Ma basalt is similar in age and composition to the previously dredged basalts, and may be the alkalic capping phase typical of many hotspot volcanoes. A 17 Ma tholeiitic basalt sill recovered 5 m above the 27 Ma basalt was emplaced long after the seamount platform moved away from the hotspot, and may be associated with a period of intraplate extension. Anomalously young phases of volcanism on this and other hotspot seamounts suggest that they can be volcanically rejuvenated by nonhotspot causes, but this rejuvenation does not rule out the hotspot model as an explanation for the initial creation of the seamount platform. The lack of an "enriched" isotopic signature in any of these basalts shows that enriched compositions are not necessary characteristics of plume-related basalts. The isotopic compositions of the lower basalts are slightly more depleted than the 0-9 Ma products of the Cobb hotspot, despite the fact that the hotspot was closer to a spreading ridge at 0-9 Ma. It appears that this hotspot, like several others, has become more enriched with time.

Age model and elemental data of DSDP Holes 48-401 and 80-549

A growing body of geologic evidence suggests that emplacement of the North Atlantic Igneous Province (NAIP) played a major role in global warming during the early Paleogene as well as in the transient Paleocene-Eocene thermal maximum (PETM) event. A ~5 million year record of major and trace element abundances spanning 56 to 51 Ma at Deep Sea Drilling Project Sites 401 and 549 confirms that the majority of NAIP volcanism occurred as subaerial flows. Thus the trace element records provide constraints on the nature and scope of the environmental impact of the NAIP during the late Paleocene-early Eocene interval. Subaerial volcanism would have injected mantle CO2 directly into the atmosphere, resulting in a more immediate increase in atmospheric greenhouse gas abundances than CO2 input through submarine volcanism. The lack of significant hydrothermalism contradicts recently proposed mechanisms for thermally destabilizing methane hydrate reservoirs during the PETM. Any connection between NAIP volcanism and PETM warming had to occur through the atmosphere.

Mineralogy of Hawaiian Arch sediments

The mineralogy of both bulk- and clay-sized (<2 µm) fractions of sediments from Holes 842A and 842B of Ocean Drilling Program Leg 136 was determined by X-ray diffraction. The sediments consist of a combination of terrigenous (quartz, plagioclase, smectite, illite, kaolinite, and chlorite), volcaniclastic (augite, plagioclase, and volcanic glass), and diagenetic minerals (smectite, phillipsite, clinoptilolite, and opal-CT). Although biogenic silica (radiolarians and diatoms) is common in near-seafloor (<10 mbsf) sediments, biogenic calcite is rare. Variations with depth in abundances of the terrigenous minerals reflect temporal changes in the flux of eolian material to the site. Volcanogenic material derived from the Hawaiian Islands is present in lithologic Unit 1 (0-19.9 meters below seafloor) both as discrete layers and as finely disseminated silt- and clay-sized material. Volcanic glass is present only in the upper 10 m of the sediment column. In Unit 2 (19.9-35.7 mbsf), increased smectite and zeolite abundances with depth as well as indurated, zeolite-rich layers are thought to be the alteration products of volcanogenic material. The source of this older (late Oligocene to middle Miocene) volcanogenic detritus may be continental volcanism. Microfabrics imaged using back-scattered electron imaging reflect the effects of compaction and diagenesis on sediment porosity and matrix structure. As porosity decreases during burial, the matrix changes from an open, floc-like fabric, to an interlocking network of clay mineral domains, and finally to a dense intergrowth of clay minerals and zeolites. Despite the substantial changes in sediment microfabric and mineralogy, correlations between physical and acoustic properties and mineralogy are weak or absent. The sediment has maintained high porosity (>70%), and water content appears to dominate the sediment's physical character and acoustic response.

Geochemistry of volcanic rocks from the Hikurangi and Manihiki Plateaus

Here we present the first radiometric age data and a comprehensive geochemical data set (including major and trace element and Sr-Nd-Pb-Hf isotope ratios) for samples from the Hikurangi Plateau basement and seamounts on and adjacent to the plateau obtained during the R/V Sonne 168 cruise, in addition to age and geochemical data from DSDP Site 317 on the Manihiki Plateau. The 40Ar/39Ar age and geochemical data show that the Hikurangi basement lavas (118-96 Ma) have surprisingly similar major and trace element and isotopic characteristics to the Ontong Java Plateau lavas (ca. 120 and 90 Ma), primarily the Kwaimbaita-type composition, whereas the Manihiki DSDP Site 317 lavas (117 Ma) have similar compositions to the Singgalo lavas on the Ontong Java Plateau. Alkalic, incompatible-element-enriched seamount lavas (99-87 Ma and 67 Ma) on the Hikurangi Plateau and adjacent to it (Kiore Seamount), however, were derived from a distinct high time-integrated U/Pb (HIMU)-type mantle source. The seamount lavas are similar in composition to similar-aged alkalic volcanism on New Zealand, indicating a second wide-spread event from a distinct source beginning ca. 20 Ma after the plateau-forming event. Tholeiitic lavas from two Osbourn seamounts on the abyssal plain adjacent to the northeast Hikurangi Plateau margin have extremely depleted incompatible element compositions, but incompatible element characteristics similar to the Hikurangi and Ontong Java Plateau lavas and enriched isotopic compositions intermediate between normal mid-ocean-ridge basalt (N-MORB) and the plateau basement. These younger (~52 Ma) seamounts may have formed through remelting of mafic cumulate rocks associated with the plateau formation. The similarity in age and geochemistry of the Hikurangi, Ontong Java and Manihiki Plateaus suggest derivation from a common mantle source. We propose that the Greater Ontong Java Event, during which ?1% of the Earth's surface was covered with volcanism, resulted from a thermo-chemical superplume/dome that stalled at the transition zone, similar to but larger than the structure imaged presently beneath the South Pacific superswell. The later alkalic volcanism on the Hikurangi Plateau and the Zealandia micro-continent may have been part of a second large-scale volcanic event that may have also triggered the final breakup stage of Gondwana, which resulted in the separation of Zealandia fragments from West Antarctica.

Trace and rare elements and factors at DSDP Hole 71-511

The distribution of paragenetic assemblages of trace and rare elements, as revealed by factor analysis (R-mode, Q-mode), the ratios of elements to Zr and the interpretation of these data in the context of the known mineralogy, lithology, and geology of the region, provide the bases for the outline of the geochemical history of sedimentation in the study area that forms the subject of this chapter. Two stages may be discerned. 1. Late-Middle Jurassic-Early Cretaceous (160-106? Ma). The sediments that accumulated in relatively shallow water (shelf) were predominantly clay, with dispersed sapropelic organic matter, plant fragments, pyrite, admixtures of acid-medium volcanic glass, and epigenetic crystals of gypsum. The bottom water layers of the basin are notably stagnant. The sediments are characterized by higher amounts of V, Zn, Cu, Cr, Rb, and Be associated with organic matter. Lower Cretaceous sediments, separated from those of the Upper Jurassic by a hiatus, accumulated in a deepened and enlarging basin. These Lower Cretaceous deposits are chemically similar to those of the Upper Jurassic, but contain diagenetic concentrations of Zn, Ni, and La. 2. Early-middle Albian (Unit 5)-middle Maestrichtian (1067-66.6Ma). The prevailing regime was that of an open ocean basin that tended to expand and deepen. During the second half of the early-middle Albian, the biogenic components Ba, Sr, and CaCO3 accumulated. By the end of this interval, Ti/Zr values had increased. In conjunction data on mineral composition, they testify to an outburst of basaltoid volcanism related to tectonic activity before an erosional hiatus (late Albian-Cenomanian). At the end of the Cenomanian-Turonian, residual deposits of predominantly clay sediments with relatively high amounts of Ti and Zr and associated rare alkalis (Li, Rb) accumulated. Clay sediments deposited during the Coniacian-Santonian were characterized by higher concentrations of Ti, Zr, Li, and Rb, by diagenetic carbonate phases of Ni, Zn, and La, and by sulphides and Fe-oxides with an admixture of Ni and Co. The latter half of the interval saw the deposition of fine basaltoid volcanoclastic material, diagenetically altered by zeolitization and carbonatization and enriched with Se, Pb, Ti, Sr, Ba, Y, and Yb. Sediments with a similar chemistry accumulated in the Campanian-middle Maestrichtian. Strong current activity preceding a global hiatus at the Mesozoic/Cenozoic boundary is reflected in both lower sedimentation rates and the presence of higher residual concentrations of Ti, Zr, Ba, Sr, and other elements studied in this chapter.

Volcanic ash from the Peru continental margin

During Leg 112 off Peru, volcanic material was recorded from middle Eocene to Holocene time. The petrographical and chemical composition of tephra is consistent with an origin from the Andean volcanic arc. The amount and thickness of ash layers provide valuable evidence for explosive volcanic episodicity. The first indication of volcanism was found in mid-Eocene sediments. Three volcanic pulses date from Miocene time. Two intense episodes took place in upper Pliocene and from Pleistocene to Holocene time. Pliocene-Pleistocene tephra are restricted to the southern upper-slope and shelf sites, indicating a removal of the volcanic arc and the extinction of the northern Peru volcanoes. The Cenozoic tectonic phases of the Andean margin may be correlated with the Leg 112 volcanic records. The explosive supply of evolved magmatic products succeeded the Incaic and Quechua tectonic phases. Acidic glasses are related to both andesitic and shoshonitic series. The calc-alkaline factor (CAF) of these glasses exhibited moderate magmatic variations during middle and late Miocene time. A dramatic change occurred during the Pliocene-Pleistocene, reflected in a strong CAF increase and the appearance of potassium-rich evolved shoshonitic glasses. This took place when the Nazca Ridge subduction began. This change in the magma genesis and/or differentiation conditions is probably related to thickening of the upper continental plate and to a new configuration of the Benioff Zone.

Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Geochemistry of Cenozoic ash layers from the Kerguelen Plateau

Geochemical investigations were conducted on 10 discrete ash layers and 22 samples of dispersed ash accumulations from Sites 747, 749, and 751 of Ocean Drilling Program (ODP) Leg 120 to the Kerguelen Plateau in the southern Indian Ocean. The chemical data obtained from some 400 single-grain glass analyses allow the characterization of two rock series. The first consists of transitional to alkali basalts; the second, mainly of trachytes with subordinated rhyolites, all reflecting the characteristic magmatological evolution of the Kerguelen Plateau as a hotspot-related volcanism. Chemical correlation with possible source areas indicates that the ashes were most probably erupted from the Kerguelen Islands. The investigated ash layers clearly reflect the Oligocene to Quaternary changes in the composition of the volcanic material recorded from the Kerguelen Islands. In addition to the Kerguelen Islands, Heard Island, Crozet Island, and other sources may have contributed to deposition of the tephras. Pleistocene tephras of "exotic" calc-alkaline composition are most probably derived from enhanced magmatic activity during that time span at the South Sandwich island arc. When using data obtained from tephras of the ODP Leg 119 Kerguelen sites, several eruptive periods can be correlated through the composition of the deposited ashes. Some of them are widely distributed over the Kerguelen Plateau and are seen as a first step toward a southern Indian Ocean tephrostratigraphy.

Geochemistry of tephra layers in ODP Site 121-758

A tephrochronology of the past 5 Ma is constructed with ash layers recovered from Neogene sediments during drilling at ODP Leg 121 Site 758 on northern Ninetyeast Ridge. The several hundred tephra layers observed in the first 80 m of cores range in thickness from a few millimeters to 34 cm. Seventeen tephra layers, at least 1 cm thick, were sampled and analyzed for major elements. Relative ages for the ash layers are estimated from the paleomagnetic and d18O chronostratigraphy. The ash layers comprise about 1.7% by volume of the sediments recovered in the first 72 m. The median grain size of the ashes is about 75 ?m, with a maximum of 150 ?m. The ash consists of rhyolitic bubble junction and pumice glass shards. Blocky and platy shards are in even proportion (10%-30%) and are dominated by bubble wall shards (70%-90%). The crystal content of the layers is always less than 2%, with Plagioclase and alkali feldspar present in nearly every layer. Biotite was observed only in the thickest layers. The major element compositions of glass and feldspar reflect fractionation trends. Three groupings of ash layers suggest different provenances with distinct magmatic systems. Dating by d18O and paleomagnetic reversals suggests major marine ash-layer-producing eruptions (marine tephra layers > 1 cm in thickness) occur roughly every approximately 414,000 yr. This value correlates well with landbased studies and dates of Pleistocene Sumatran tuffs (average 375,000-yr eruptive interval). Residence times of the magmatic systems defined by geochemical trends are 1.583, 2.524, and 1.399 Ma. The longest time interval starts with the least differentiated magma. The Sunda Arc, specifically Sumatra, is inferred to be the source region for the ashes. Four of the youngest five ash layers recovered correlate in time and in major element chemistry to ashes observed on land at the Toba caldera.