High-pressure experiments on a natural olivine gabbro from ODP Hole 176-735B

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4-9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ~10* greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts.Yaxley-Sobolev

Petrology of basalts from DSDP Hole 66-487

Basaltic rocks recovered at the Middle America Trench area off Mexico are typical plagioclase-olivine phyric abyssal tholeiites containing less than 0.2 wt.% K2O. Phenocrysts of plagioclase and olivine usually make up the aggregate. Plagioclase phenocrysts are Ca-rich and up to An90. Olivine phenocrysts, which are always attached to plagioclase phenocrysts, are magnesian, Fo88 to Fo89, and contain 0.2 to 0.3 wt. % of NiO. Plagioclase phenocrysts contain numerous glass inclusions with the Mg/Mg+Fe atomic ratio of 0.70 to 0.73, which is distinctly higher than the same ratio of the bulk rock (0.62-0.63). Olivine of Fo88 to Fo89 is equilibrated with the liquid with an Mg/Mg+Fe atomic ratio of about 0.7, assuming the KDMg-Fe between liquid and olivine of 0.3. Small droplets of glass within glass inclusions in plagioclase are more enriched in K2O and volatiles than the host glass. This enrichment may have been caused by the extraction of Al2O3 as plagioclase from the trapped liquid and implies its immiscibility. Aggregates of plagioclase with small amounts of olivine may have been floated from more primitive magma with an Mg/Mg+Fe atomic ratio of about 0.7, judging from the chemical characteristics mentioned above. Flotation must have occurred at relatively high pressure. Large crystals of plagioclase and smaller crystals of olivine are xenocryst rather than phenocryst. Parental magma of Leg 66 basalt was high-MgO olivine tholeiite.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Adaptive variability to low-pH river discharges in Acartia tonsa and stress responses to high PCO2 conditions

Environmental transitions leading to spatial physical-chemical gradients are of ecological and evolutionary interest because they are able to induce variations in phenotypic plasticity. Thus, the adaptive variability to low-pH river discharges may drive divergent stress responses [ingestion rates (IR) and expression of stress-related genes such as Heat shock protein 70 (Hsp70) and Ferritin] in the neritic copepod Acartia tonsa facing changes in the marine chemistry associated to ocean acidification (OA). These responses were tested in copepod populations inhabiting two environments with contrasting carbonate system parameters (an estuarine versus coastal area) in the Southern Pacific Ocean, and assessing an in situ and 96-h experimental incubation under conditions of high pressure of CO2 (PCO2 1200 ppm). Adaptive variability was a determining factor in driving variability of copepods' responses. Thus, the food-rich but colder and corrosive estuary induced a traits trade-off expressed as depressed IR under in situ conditions. However, this experience allowed these copepods to tolerate further exposure to high PCO2 levels better, as their IRs were on average 43% higher than those of the coastal individuals. Indeed, expression of both the Hsp70 and Ferritin genes in coastal copepods was significantly higher after acclimation to high PCO2 conditions. Along with other recent evidence, our findings confirm that adaptation to local fluctuations in seawater pH seems to play a significant role in the response of planktonic populations to OA-associated conditions. Facing the environmental threat represented by the inter-play between multiple drivers of climate change, this biological feature should be examined in detail as a potential tool for risk mitigation policies in coastal management arrangements.

Composition of noble gases in sediments and metasediments

Solar-type helium (He) and neon (Ne) in the Earth's mantle were suggested to be the result of solarwind loaded extraterrestrial dust that accumulated in deep-sea sediments and was subducted into the Earth's mantle. To obtain additional constraints on this hypothesis, we analysed He, Ne and argon (Ar) in high pressure-low temperature metamorphic rocks representing equivalents of former pelagic clays and cherts from Andros (Cyclades, Greece) and Laytonville (California, USA). While the metasediments contain significant amounts of 4He, 21Ne and 40Ar due to U, Th and K decay, no solar-type primordial noble gases were observed. Most of these were obviously lost during metamorphism preceding 30 km subduction depth. We also analysed magnetic fines from two Pacific ODP drillcore samples, which contain solar-type He and Ne dominated by solar energetic particles (SEP). The existing noble gas isotope data of deep-sea floor magnetic fines and interplanetary dust particles demonstrate that a considerable fraction of the extraterrestrial dust reaching the Earth has lost solar wind (SW) ions implanted at low energies, leading to a preferential occurrence of deeply implanted SEP He and Ne, fractionated He/Ne ratios and measurable traces of spallogenic isotopes. This effect is most probably caused by larger particles, as these suffer more severe atmospheric entry heating and surface ablation. Only sufficiently fine-grained dust may retain the original unfractionated solar composition that is characteristic for the Earth's mantle He and Ne. Hence, in addition to the problem of metamorphic loss of solar noble gases during subduction, the isotopic and elemental fractionation during atmospheric entry heating is a further restriction for possible subduction hypotheses.

Radiocarbon dates of sediments from ODP Site 161-976

Multiproxy paleoenvironmental records (pollen and planktonic isotope) from Ocean Drilling Program Site 976 (Alboran Sea) document rapid ocean and climate variations during the last glacial that follow the Dansgaard-Oeschger climate oscillations seen in the Greenland ice core records, thus suggesting a close link of the Mediterranean climate swings with North Atlantic climates. Continental conditions rapidly oscillated through cold-arid and warm-wet conditions in the course of stadial-interstadial climate jumps. At the time of Heinrich events, i.e., maximum meltwater flux to the North Atlantic, western Mediterranean marine microflora and microfauna show rapid cooling correlated with increasing continental dryness. Enhanced aridity conceivably points to prolonged wintertime stability of atmospheric high-pressure systems over the southwestern Mediterranean in conjunction with cooling of the North Atlantic.

Geochemistry and paleontology of sediment core GeoB3359-3

A geochemical and paleontological reconstruction of paleoproductivity, upwelling intensity and sea surface temperature (SST) off central Chile at 35°S (GeoB3359-3) reveals marked changes from the Last Glacial Maximum (LGM) through the Early Holocene. Surface-water productivity was determined by the interaction between the atmospheric (the Southern Westerlies) and oceanographic (the Antarctic Circumpolar Current, ACC) systems from the LGM through early Termination I (TI). The northward shift of the climate zones during the LGM brought the ACC, as the main macronutrient source, closer to the GeoB3359-3, SST lowered, and surface water productivity and accumulation rates of biogenic components enhanced. With the poleward return of the Southern Westerlies and the ACC, the subtropical high-pressure system became the dominant atmospheric component southward till 35°S during the late TI and Early Holocene and caused surface water productivity to increase through enhanced upwelling.

Petrography, microprobe analyses and isotope composition of ultramafic rock from the northern Haskard Highlands, Shackleton Range, East Antarctica

In the Shackleton Range of East Antarctica, garnet-bearing ultramafic rocks occur as lenses in supracrustal high-grade gneisses. In the presence of olivine, garnet is an unmistakable indicator of eclogite facies metamorphic conditions. The eclogite facies assemblages are only present in ultramafic rocks, particularly in pyroxenites, whereas other lithologies - including metabasites - lack such assemblages. We conclude that under high-temperature conditions, pyroxenites preserve high-pressure assemblages better than isofacial metabasites, provided the pressure is high enough to stabilize garnet-olivine assemblages (i.e. >=18-20 kbar). The Shackleton Range ultramafic rocks experienced a clockwise P-T path and peak conditions of 800-850 °C and 23-25 kbar. These conditions correspond to ~70 km depth of burial and a metamorphic gradient of 11-12 °C/km that is typical of a convergent plate-margin setting. The age of metamorphism is defined by two garnet-whole-rock Sm-Nd isochrons that give ages of 525 ± 5 and 520 ± 14 Ma corresponding to the time of the Pan-African orogeny. These results are evidence of a Pan-African suture zone within the northern Shackleton Range. This suture marks the site of a palaeo-subduction zone that likely continues to the Herbert Mountains, where ophiolitic rocks of Neoproterozoic age testify to an ocean basin that was closed during Pan-African collision. The garnet-bearing ultramafic rocks in the Shackleton Range are the first known example of eclogite facies metamorphism in Antarctica that is related to the collision of East and West Gondwana and the first example of Pan-African eclogite facies ultramafic rocks worldwide. Eclogites in the Lanterman Range of the Transantarctic Mountains formed during subduction of the palaeo-Pacific beneath the East Antarctic craton.

Tab.1: Representative bulk-rock and trace element chemistry

High-pressure/low-temperature metabasites occupy a definite geological position within the structure of the Polar Urals and have a very important bearing on the understanding of the early history of the Ural Mountains. Recently obtained geological, petrographic, geochemical and isotope data allow some conclusions on this history. The metabasites of the Khord"yus and Dzela complexes contain relics of a Neoproterozoic (578 ±8 Ma) oceanic crust. This crust formed part of the base of the early Paleozoic (500 Ma) ensimatic island arc and experienced Ca-Al-Si±Na metasomatism and, probably, partial melting with the formation of boninite melts. However, so far no boninite volcanics have been found. The metabasites at the base of the island arc took part in the collision and as a consequence experienced glaucophane schist and greenschist facies metamorphism during the collision and obduction over the passive Baltic margin 350 ±11 Ma ago.

Chemistry of orthopyroxenes, clinopyroxenes, and spinels of ODP Hole 103-637A peridotites

Mineral compositions of the plagioclase-bearing ultramafic tectonites dredged and cored seaward of the continental slope of the Galicia margin (Leg 103, Site 637) were compared to mineral compositions from onshore low-pressure ultramafic bodies (southeastern Ronda, western Pyrenees, and Lizard Point), on the basis of standardized (30-s counting time) probe analyses. The comparison was extended to some plagioclase-free harzburgites related to ophiolites (Santa Elena in Costa Rica, north Oman, and the Humboldt body in New Caledonia) on the basis of new analytical data and data from the literature. The behavior of Cr, Na, Al, Mg, Fe, Ni, and Ti in olivine, pyroxenes, and spinel was examined in order to distinguish between the effects of partial melting and mineral facies change, from the spinel to plagioclase stability fields. The peridotite from the Galicia margin appears slightly depleted in major incompatible elements and experienced a minor partial melting. However, it experienced large scale but heterogeneous recrystallization in the plagioclase field. These features are very similar to those observed in Ronda, whereas in the western Pyrenees the minerals exemplify a very minor partial-melting event (or none at all) and have retained compositions corresponding to those of the relatively high-pressure Seiland sub facies. The minerals from the Lizard Point peridotite have characteristics (low Mg/(Mg + Fe) ratio; high Cr/(Cr + Al) ratio in spinel) more related to cumulate from a differentiated tholeiitic melt than related to ophiolitic tectonite. Diffusion profiles of Al and Cr across pyroxenes and spinel show that recrystallization features occurred at different speeds or temperatures in the different bodies. The pyroxenes from Ronda would have experienced recrystallization about 14 times faster than the peridotite from the Galicia margin. The western Pyrenean lherzolites also experienced rapid recrystallization; nevertheless, because they are of a different mineral facies, the data are not directly comparable to that from Ronda and Galicia. The harzburgite at Santa Elena as well as a xenolith from alkali basalt exemplify rapid cooling characterized by very weak re-equilibration. Recrystallization speed is related to emplacement speed in the present geological environment. The slow-rising Galicia margin peridotite was emplaced by thinning of the lithospheric subcontinental mantle near an incipient mid-oceanic ridge. The fast-rising peridotites from Ronda and the western Pyrenees were hot diapirs emplaced from the asthenosphere along transcurrent faults, possibly related to the opening of the Atlantic Ocean.

A late Quaternary planktonic foraminifer faunal record of rapid climatic changes of sediment core GIK17938-2

A high-resolution planktonic foraminifer record from a core recovered from the South China Sea (SCS) (Sonne 17938-2: 19°47.2'N, 117° 32.3E; 2840 m; Delta t c. 250-1000 years) shows rapid millennial-scale changes in the western Pacific marginal sea climate during the last 30,000 years. The SCS is the largest western Pacific marginal sea off the southeast Asian continent, the area today dominated by seasonal monsoon changes. Quantitative analyses of planktonic foraminifer faunal abundance data frorn the core indicate large downcore variations in the relative abundances of the dominant taxa since about 30,000 years ago in the isotope stage 3. Further analyses indicate that the abundance of G. inflata, a good indicator species for cold SST (~13°-19°C) and deep MLD (~100-125 m) waters shows abrupt shifts. During stages 2 and 3, the abundance record of G. infiata tends to be punctuated by quasi-periodie short intervals (~2000-3000 yrs) where its abundance reaches 15% or greater, superimposed on generally low (5-10%) background values. This pattern suggests an instability of surface ocean conditions of the SCS during the past 30,000 years. The abrupt abundance changes of G. infiata correlate well with similar climatic changes observed from a GISP2 ice core 8180, and North Atlantic core DSDP 609 N. pachyderma (s.) and lithic grain abundances during 'Heinrich evcnts'. These results suggest that the millennial-scale variability of climate is not peculiar to the Atlantic region. Apparently, the rapid SCS climatic changes during Heinrich events are driven by effective mechanisms, of particularly the effects of shifts in the latitudinal position of the Siberia High Pressure System.

Sea-surface reconstruction of the east-equatorial South Atlantic

In order to reconstruct Late Quatemary variations of surface oceanography in the eastequatorial South Atlantic, time series of sea-surface temperatures (SST) and paleoproductivity were established from cores recovered in the Guinea and Angola Basins, and at the Walvis Ridge. These records, based on sedimentary alkenone and organic carbon concentrations, reveal that during the last 350,000 years surface circulation and productivity changes in the east-equatorial South Atlantic were highiy sensitive to climate forcing at 23- and 100-kyr periodicities. Covarying SST and paleoproductivity changes at the equator and at the Walvis Ridge appear to be driven by variations in zonal trade-wind intensity, which forces intensification or reduction of coastal and equatorial upwelling, as well as enhanced Benguela cold water advection from the South. Phase relationships of precessional variations in the paleoproductivity and SST records from the distinct sites were evaluated with respect to boreal summer insolation over Africa, movements of southem ocean thermal fronts, and changes in global ice volume. The 23-kyr phasing implies a sensitivity of eastem South Atlantic surface water advection and upwelling to West African monsoon intensity and to changes in the position ofthe subtropical high pressure cell over the South Atlantic, both phenomena which modulate zonal strength of southeasterly trades. SST and productivity changes north of 20°S lack significant variance at the 41-kyr periodicity; and at the Walvis Ridge and the equator lead changes in ice volume. This may indicate that obliquity-driven clirnate change, characteristic for northem high latitudes, e.g fluctuations in continental ice masses, did not substantially influence subtropical and tropical surface circulation in the South Atlantic. At the 23-kyr cycle SST and productivity changes in the eastern Angola Basin lag those in the equatorial Atlantic and at the Walvis Ridge by about 3500 years. This lag is explained by variations in cross-equatorial surface water transport and west-east countercurrent retum flow modifying precessional variations of SST and productivity in the eastem Angola Basin relative to those in the mid South Atlantic area under the central field of zonal trade winds. Sea level-related shifts of upwelling cells in phase with global clirnate change may be also recorded in SST and productivity variability along the continental margin off Southwest Africa. They may account for the delay of the paleoceanogreaphic signal from continental margin sites with respect to that from the pelagic sites at the equator and the Walvis Ridge.