Geochemistry of Walvis Ridge basalts

The proposed origins for the Enriched Mantle I component are many and various and some require an arbitrary addition of an exotic component, be it pure sediment or an enriched melt from the subcontinental lithosphere. With Pitcairn, Walvis Ridge is the 'type-locality' for the Enriched Mantle I (EMI) component. We analyzed basalts from DSDP Site 525A, Site 527 and Site 528 on the Walvis Ridge with the aim to constrain the history of its source. The isotopic compositions we measured for the three sites overlap with the values obtained by Richardson et al. (1982a) and extend towards less radiogenic Sr and more radiogenic Pb and Nd isotopic compositions. We used our new trace element and radiogenic isotope (Hf, Nd, Pb and Sr) characterization in combination with the literature data to produce the simplest possible model that satisfies the trace element and isotopic constraints. Although the elevated 207Pb/204Pb with respect to 206Pb/204Pb predicts an ancient origin for EMI, none of the proposed origins had modeled it as such. The data is consistent with the EMI composition being formed by the addition of a melt to a mantle with bulk Earth-like composition followed by melt extraction of a low degree melt. The timing of these two events is such that the metasomatism has to have taken place prior to 4 Ga and the subsequent melt removal before 3.5 Ga. This confirms the expectation of an ancient character for the EMI component. The Walvis Ridge data shows two distinct two component mixing trends: one formed by the less enriched Site 527 and Site 528 basalts and one formed by the Site 525A basalts. The two trends have the EMI endmember in common. The less depleted end of the Site 527-Site 528 basalts is FOZO-like and can be explained by the addition of a recycled component (basaltic oceanic crust plus sediment). This recycled component was altered during subduction. The sense and magnitude of the chemical fractionation resulting from the subduction alteration are in agreement with dehydration experiments on basalts and sediment. Compared to other EMI like basalts the Walvis Ridge basalts have flatter REE patterns and show less fractionation between large ion lithophile and heavy REE elements. Using the isotopic compositions as constrains for the parent-daughter ratios we were able to model the trace element patterns of the basalts as melting between 5 and 10% for Site 525A and between 10 and 15% for the depleted end of the Site 528-Site 527 array. In all cases a significant portion of melting takes place in the garnet stability field.

Chemical element concentrations in sediments from DSDP Holes 60-458 and 60-459

The development of laser ablation-inductively coupled plasma-mass spectrometry has revolutionized the analysis of tephras by providing (1) an efficient and precise method for determining abundances of a wide variety of trace elements at low concentrations in individual glass shards and (2) assessment of geochemical heterogeneities within individual ash horizons. This development is important for petrogenetic studies of intraoceanic arc systems, where tephras provide the most complete temporal record of magmatism. Results from the Izu-Bonin and Mariana arc systems indicate that despite close geographical proximity and similar tectonic evolution, they contrast strongly in terms of geochemical evolution since 35 Ma. Whereas the Mariana tephras have exceptional compositional diversity, ranging from low-K (Oligocene), to high-K (Miocene), and subsequently medium-K compositions (Pliocene-Quaternary), the Izu-Bonin arc has been dominated by low-K compositions throughout. The Mariana increases in K are paralleled by increases in abundances of incompatible trace elements and by increased values of diagnostic ratios (e.g., Nb/yb and Th/yb) regarded as monitors of potential mantle-source fertility. The relative uniformity of Nb/yb and Nb/Zr ratios in Izu-Bonin tephras indicates that cyclic processes of backarc basin development and mantle depletion do not necessarily induce large-scale temporal geochemical variations in the associated arc. Temporal variability within the Mariana arc, and its divergence from the Izu-Bonin arc ca. 13 Ma, can be traced to a major injection of subducted sediment in the Mariana system at this time.

Clay mineralogy of the Cenozoic Pagodroma Group, East Antarctica

The Cenozoic Pagodroma Group in the northern Prince Charles Mountains, East Antarctica, is a glaciomarine succession of fjordal character, comprising four uplifted formations of different ages. The composition of the <2 µm fraction of sediments of the Pagodroma Group was analysed in order to help identify source areas, past weathering conditions and glacial regimes. Both clay and non-clay minerals have been quantified. The assemblage of the upper Oligocene to lower Miocene Mount Johnston Formation is characterised by the dominance of illite and intermediate concentrations of chlorite. Similar to that assemblage is the clay mineral suite of the middle Miocene Fisher Bench Formation, where illite and chlorite together account for 95% of the clay minerals. The middle to upper Miocene Battye Glacier Formation is the only formation with significant and persistent smectite concentrations, although illite is still dominant. The kaolinite concentration is also high and is even higher than that of chlorite. The clay fraction of the upper Pliocene to lower Pleistocene Bardin Bluffs Formation is characterised by maximum kaolinite concentrations and relatively low illite and chlorite concentrations. The bulk of the clay fraction in each formation can be explained by the physical weathering and erosion of a nearby source under glacial conditions. In the case of Mount Johnston Formation and Fisher Bench Formation this source may be situated in the metavolcanic and gneissic rocks of Fisher Massif. The sediments of the Bardin Bluffs Formation indicate a local source within the Amery Oasis, where Proterozoic granitoid rocks and gneisses, and Permo-Triassic fluvial rocks of the Amery Group are exposed. These results suggest a strong local imprint on the glacial sediments as northwards flowing ice eroded the bedrock in these areas. The origin of the clay fraction of the Battye Glacier Formation is a matter of debate. The smectite and kaolinite content most easily can be explained by erosion of sources largely hidden beneath the ice upstream. Less likely, these clay minerals reflect climatic conditions that were much warmer and wetter than today, facilitating chemical weathering.

Late Quaternary benthic foraminiferal record of the Bounty Trough, east of New Zealand

The Bounty Trough, east of New Zealand, lies along the southeastern edge of the present-day Subtropical Front (STF), and is a major conduit via the Bounty Channel, for terrigenous sediment supply from the uplifted Southern Alps to the abyssal Bounty Fan. Census data on 65 benthic foraminiferal faunas (>63 µm) from upper bathyal (ODP 1119), lower bathyal (DSDP 594) and abyssal (ODP 1122) sequences, test and refine existing models for the paleoceanographic and sedimentary history of the trough through the last 150 ka (marine isotope stages, MIS 6-1). Cluster analysis allows recognition of six species groups, whose distribution patterns coincide with bathymetry, the climate cycles and displaced turbidite beds. Detrended canonical correspondence analysis and comparisons with modern faunal patterns suggest that the groups are most strongly influenced by food supply (organic carbon flux), and to a lesser extent by bottom water oxygen and factors relating to sediment type. Major faunal changes at upper bathyal depths (1119) probably resulted from cycles of counter-intuitive seaward-landward migrations of the Southland Front (SF) (north-south sector of the STF). Benthic foraminiferal changes suggest that lower nutrient, cool Subantarctic Surface Water (SAW) was overhead in warm intervals, and higher nutrient-bearing, warm neritic Subtropical Surface Water (STW) was overhead in cold intervals. At lower bathyal depths (594), foraminiferal changes indicate increased glacial productivity and lowered bottom oxygen, attributed to increased upwelling and inflow of cold, nutrient-rich, Antarctic Intermediate Water (AAIW) and shallowing of the oxygen-minimum zone (upper Circum Polar Deep Water, CPDW). The observed cyclical benthic foraminiferal changes are not a result of associations migrating up and down the slope, as glacial faunas (dominated by Globocassidulina canalisuturata and Eilohedra levicula at upper and lower bathyal depths, respectively) are markedly different from those currently living in the Bounty Trough. On the abyssal Bounty Fan (1122), faunal changes correlate most strongly with grain size, and are attributed to varying amounts of mixing of displaced and in-situ faunas. Most of the displaced foraminifera in turbiditic sand beds are sourced from mid-outer shelf depths at the head of the Bounty Channel. Turbidity currents were more prevalent during, but not restricted to, glacial intervals.

Isotopic and chemical compositions of DSDP site 18-174 sediments

The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

Diurnal and seasonal measurements of seawater chemistry, temperature and PAR in Hurricane Hole, U.S. Virgin Islands - 2010-2012

Risk analyses indicate that more than 90% of the world's reefs will be threatened by climate change and local anthropogenic impacts by the year 2030 under "business-as-usual" climate scenarios. Increasing temperatures and solar radiation cause coral bleaching that has resulted in extensive coral mortality. Increasing carbon dioxide reduces seawater pH, slows coral growth, and may cause loss of reef structure. Management strategies include establishment of marine protected areas with environmental conditions that promote reef resiliency. However, few resilient reefs have been identified, and resiliency factors are poorly defined. Here we characterize the first natural, non-reef coral refuge from thermal stress and ocean acidification and identify resiliency factors for mangrove-coral habitats. We measured diurnal and seasonal variations in temperature, salinity, photosynthetically active radiation (PAR), and seawater chemistry; characterized substrate parameters; and examined water circulation patterns in mangrove communities where scleractinian corals are growing attached to and under mangrove prop roots in Hurricane Hole, St. John, US Virgin Islands. Additionally, we inventoried the coral species and quantified incidences of coral bleaching, mortality, and recovery for two major reef-building corals, Colpophyllia natans and Diploria labyrinthiformis, growing in mangrove-shaded and exposed (unshaded) areas. Over 30 species of scleractinian corals were growing in association with mangroves. Corals were thriving in low-light (more than 70% attenuation of incident PAR) from mangrove shading and at higher temperatures than nearby reef tract corals. A higher percentage of C. natans colonies were living shaded by mangroves, and no shaded colonies were bleached. Fewer D. labyrinthiformis colonies were shaded by mangroves, however more unshaded colonies were bleached. A combination of substrate and habitat heterogeneity, proximity of different habitat types, hydrographic conditions, and biological influences on seawater chemistry generate chemical conditions that buffer against ocean acidification. This previously undocumented refuge for corals provides evidence for adaptation of coastal organisms and ecosystem transition due to recent climate change. Identifying and protecting other natural, non-reef coral refuges is critical for sustaining corals and other reef species into the future.

Late Quaternary carbonate and isotope stratigraphy of DSDP Site 90-594 east of South Island, New Zealand

The late Quaternary sequence off eastern South Island, New Zealand, consists of ~100 m of alternating bluish gray pelagic oozes and greenish gray hemipelagic oozes that extend uninterruptedly back to the Brunhes/Matuyama boundary (0.73 m.y.). A very high resolution (~2400 yr.) record of sediment texture, calcium carbonate content, and planktonic and benthic foraminiferal oxygen and carbon isotope composition demonstrates an in-phase cyclical fluctuation between the sedimentary parameters that closely correspond to the pelagic-hemipelagic sedimentation cycles and the isotope composition. Pelagic oozes, formed during interglacial periods of high eustatic sea level, are characterized by calcareous microfossils, relative enrichment in sand and clay sizes, high carbonate contents, reduced delta18O values, and increased delta13C values. Hemipelagic oozes, associated with glacial episodes and lowered eustatic sea level, include common terrigenous material and siliceous microfossils, are enriched in silt sizes, have low carbonate contents, high delta18O values, and low delta13C values. The history of alpine glaciations and associated erosion of the South Island of New Zealand, as expressed by the appearance of hemipelagic oozes, can be correlated directly with the major fluctuations of Northern Hemisphere ice sheets as expressed by the influence of eustatic sea-level changes on the oxygen isotope composition of both planktonic and benthic foraminifers. This high-accumulation-rate record contains conspicuous intervals of highfrequency, high-amplitude isotope variability including the presence of multiple glacial/interglacial intervals within single isotope stages, and offers one of the best sections cored to date for detailed study of the evolution and history of climate change over the last 0.75 m.y.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

(Table 1) Chemical composition of Fe-rich layered silicates from the East Korean Rise, Japan Sea

Mineral and chemical compositions of highly ferruginous layered silicates (HLS) of glauconite sands occurred on the East Korean Rise outside volcanic structures and on an unnamed volcano and the Chentsov Volcano have been studied. The use of cluster and discriminant analyses has resulted to more objectively distinguished groups among HLS, and the use of factor analysis - to illustrate correlations between chemical elements in different groups. It has been found that green mineral assemblages of the East Korean Rise are heterogeneous in terms of morphology, composition and origin, and their formation is a complex multistage process including both neoformation and degradation.