Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.

Geochemistry and age determination of zircons in Cretaceous to Quaternary sediments

In central Antarctica, drainage today and earlier back to the Paleozoic radiates from the Gamburtsev Subglacial Mountains (GSM). Proximal to the GSM past the Permian-Triassic fluvial sandstones in the Prince Charles Mountains (PCM) are Cretaceous, Eocene, and Pleistocene sediment in Prydz Bay (ODP741, 1166, and 1167) and pre-Holocene sediment in AM04 beneath the Amery Ice Shelf. We analysed detrital zircons for U-Pb ages, Hf-isotope compositions, and trace elements to determine the age, rock type, source of the host magma, and "crustal" model age (T(C)DM). These samples, together with others downslope from the GSM and the Vostok Subglacial Highlands (VSH), define major clusters of detrital zircons interpreted as coming from (1) 700 to 460 Ma mafic granitoids and alkaline rock, epsilon-Hf 9 to -28, signifying derivation 2.5 to 1.3 Ga from fertile and recycled crust, and (2) 1200-900 Ma mafic granitoids and alkaline rock, epsilon-Hf 11 to -28, signifying derivation 1.8 to 1.3 Ga from fertile and recycled crust. Minor clusters extend to 3350 Ma. Similar detrital zircons in Permian-Triassic, Ordovician, Cambrian, and Neoproterozoic sandstones located along the PaleoPacific margin of East Antarctica and southeast Australia further downslope from central Antarctica reflect the upslope GSM-VSH nucleus of the central Antarctic provenance as a complex of 1200-900 Ma (Grenville) mafic granitoids and alkaline rocks and older rocks embedded in 700-460 Ma (Pan-Gondwanaland) fold belts. The wider central Antarctic provenance (CAP) is tentatively divided into a central sector with negative ?Hf in its 1200-900 Ma rocks bounded on either side by positive epsilon-Hf. The high ground of the GSM-VSH in the Permian and later to the present day is attributed to crustal shortening by far-field stress during the 320 Ma mid-Carboniferous collision of Gondwanaland and Laurussia. Earlier uplifts in the ~500 Ma Cambrian possibly followed the 700-500 Ma assembly of Gondwanaland, and in the Neoproterozoic the 1000-900 Ma collisional events in the Eastern Ghats-Rayner Province at the end of the 1300-1000 Ma assembly of Rodinia.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Geochemistry of lavas and dikes from the upper oceanic crust of Hess Deep Rift, eastern Pacific Ocean

Strontium isotopes are useful tracers of fluid-rock interaction in marine hydrothermal systems and provide a potential way to quantify the amount of seawater that passes through these systems. We have determined the whole-rock Sr-isotopic compositions of a section of upper oceanic crust that formed at the fast-spreading East Pacific Rise, now exposed at Hess Deep. This dataset provides the first detailed comparison for the much-studied Ocean Drilling Program (ODP) drill core from Site 504B. Whole-rock and mineral Sr concentrations indicate that Sr-exchange between hydrothermal fluids and the oceanic crust is complex, being dependent on the mineralogical reactions occurring; in particular, epidote formation takes up Sr from the fluid increasing the 87Sr/86Sr of the bulk-rock. Calculating the fluid-flux required to shift the Sr-isotopic composition of the Hess Deep sheeted-dike complex, using the approach of Bickle and Teagle (1992, doi:10.1016/0012-821X(92)90221-G) gives a fluid-flux similar to that determined for ODP Hole 504B. This suggests that the level of isotopic exchange observed in these two regions is probably typical for modern oceanic crust. Unfortunately, uncertainties in the modeling approach do not allow us to determine a fluid-flux that is directly comparable to fluxes calculated by other methods.

Dinoflagellate cyst assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes, and geochemical parameters of sediment core GeoB9508-5

In order to investigate a possible connection between tropical northeast (NE) Atlantic primary productivity, Atlantic meridional overturning circulation (AMOC), and drought in the Sahel region during Heinrich Stadial 1 (HS1), we used dinoflagellate cyst (dinocyst) assemblages, Mg/Ca based reconstructed temperatures, stable carbon isotopes (d13C) and geochemical parameters of a marine sediment core (GeoB 9508-5) from the continental slope offshore Senegal. Our results show a two-phase productivity pattern within HS1 that progressed from an interval of low marine productivity between ~ 19 and 16 kyr BP to a phase with an abrupt and large productivity increase from ~ 16 to 15 kyr BP. The second phase is characterized by distinct heavy planktonic d13C values and high concentrations of heterotrophic dinocysts in addition to a significant cooling signal based on reconstructions of past sea surface temperatures (SST). We conclude that productivity variations within HS1 can be attributed to a substantial shift of West African atmospheric processes. Taken together our results indicate a significant intensification of the North East (NE) trade winds over West Africa leading to more intense upwelling during the last millennium of HS1 between ~ 16 and 15 kyr BP, thus leaving a strong imprint on the dinocyst assemblages and sea surface conditions. Therefore, the two-phase productivity pattern indicates a complex hydrographic setting suggesting that HS1 cannot be regarded as uniform as previously thought.

Benthic foraminifers, isotopes and varimax factors at DSDP Holes 72-517 and 72-518

Pliocene changes in the vertical water mass structure of the western South Atlantic are inferred from changes in benthic foraminiferal assemblages and stable isotopes from DSDP Holes 516A, 517, and 518. Factor analysis of 34 samples from Site 518 reveals three distinct benthic foraminiferal assemblages that have been associated with specific subsurface water masses in the modern ocean. These include a Nuttalides umbonifera assemblage (Factor 1) associated with Antarctic Bottom Water (AABW), a Globocassidulina subglobosa-Uvigerina peregrina assemblage (Factor 2) associated with Circumpolar Deep Water (CPDW), and an Oridorsalis umbonatus-Epistominella exigua assemblage associated with North Atlantic Deep Water (NADW). Bathymetric gradients in d13C between Holes 516A (1313 m), 517 (2963 m), and 518 (3944 m) are calculated whenever possible to monitor the degree of similarity and/or difference in the apparent oxygen utilization (AOU) of water masses located at these depths during the Pliocene. Changes in bathymetric d13C gradients coupled with benthic foraminiferal assemblages record fundamental changes in the vertical water mass structure of the Vema Channel during the Pliocene from 4.1 to 2.7 Ma. At Site 518, the interval from 4.1 to 3.6 Ma is dominated by the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages. The d13C gradient between Holes 518 (3944 m) and 516A (1313 m) undergoes rapid oscillations during this interval though no permanent increase in the gradient is observed. However, d13C values at Site 518 are clearly lighter during this interval. These conditions may be related to increased bottom water activity associated with the re-establishment of the West Antarctic Ice Sheet in the late Gilbert Chron (-4.2 to 3.6 Ma) (Osborn et al., 1982). The interval from 3.6 to 3.2 Ma is marked by a dominance of the G. subglobosa-U. peregrina (Factor 2) assemblage and lack of a strong d13C gradient between Holes 518 (3944 m) and 516A (1313 m). We suggest that shallow circumpolar waters expanded to depths of a least 3944 m (Site 518) during this time. The most profound faunal and isotopic change occurs at 3.2 Ma, and is marked by dominance of the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages, a 1.1 per mil enrichment in d18O, and a large negative increase in the d13C gradient between Holes 518 and 516A. These changes at Site 518 record the vertical displacement of circumpolar waters by AABW and NADW. This change in vertical water mass structure at 3.2 Ma was probably related to a global cooling event and/or final closure of the Central American seaway. A comparison of the present-day d13C structure of the Vema Channel with a reconstruction between 3.2 and 2.7 Ma indicates that circulation patterns during this late Pliocene interval were similar to those of the modern western South Atlantic.

Geochemistry of North Atlantic Igneous Province basalts

New Sr-Nd-Pb-Hf data require the existence of at least four mantle components in the genesis of basalts from the the North Atlantic Igneous Province (NAIP): (1) one (or more likely a small range of) enriched component(s) within the Iceland plume, (2) a depleted component within the Iceland plume (distinct from the shallow N-MORB source), (3) a depleted sheath surrounding the plume and (4) shallow N-MORB source mantle. These components have been available since the major phase of igneous activity associated with plume head impact during Paleogene times. In Hf-Nd isotope space, samples from Iceland, DSDP Leg 49 (Sites 407, 408 and 409), ODP Legs 152 and 163 (southeast Greenland margin), the Reykjanes Ridge, Kolbeinsey Ridge and DSDP Leg 38 (Site 348) define fields that are oblique to the main ocean island basalt array and extend toward a component with higher 176Hf/177Hf than the N-MORB source available prior to arrival of the plume, as indicated by the compositions of Cretaceous basalts from Goban Spur (~95 Ma). Aside from Goban Spur, only basalts from Hatton Bank on the oceanward side of the Rockall Plateau (DSDP Leg 81) lie consistently within the field of N-MORB, which indicates that the compositional influence of the plume did not reach this far south and east ~55 Ma ago. Thus, Hf-Nd isotope systematics are consistent with previous studies which indicate that shallow MORB-source mantle does not represent the depleted component within the Iceland plume (Thirlwall, J. Geol. Soc. London 152 (1995) 991-996; Hards et al., J. Geol. Soc. London 152 (1995) 1003-1009; Fitton et al., 1997 doi:10.1016/S0012-821X(97)00170-2). They also indicate that the depleted component is a long-lived and intrinsic feature of the Iceland plume, generated during an ancient melting event in which a mineral (such as garnet) with a high Lu/Hf was a residual phase. Collectively, these data suggest a model for the Iceland plume in which a heterogeneous core, derived from the lower mantle, consists of 'enriched' streaks or blobs dispersed in a more depleted matrix. A distinguishing feature of both the enriched and depleted components is high Nb/Y for a given Zr/Y (i.e. positive DeltaNb), but the enriched component has higher Sr and Pb isotope ratios, combined with lower epsilon-Nd and epsilon-Hf. This heterogeneous core is surrounded by a sheath of depleted material, similar to the depleted component of the Iceland plume in its epsilon-Nd and epsilon-Hf, but with lower 87Sr/86Sr, 208Pb/204Pb and negative DeltaNb; this material was probably entrained from near the 670 km discontinuity when the plume stalled at the boundary between the upper and lower mantle. The plume sheath displaced more normal MORB asthenosphere (distinguished by its lower epsilon-Hf for a given epsilon-Nd or Zr/Nb ratio), which existed in the North Atlantic prior to plume impact. Preliminary data on MORBs from near the Azores plume suggest that much of the North Atlantic may be 'polluted' not only by enriched plume material but also by depleted material similar to the Iceland plume sheath. If this hypothesis is correct, it may provide a general explanation for some of the compositional diversity and variations in inferred depth of melting (Klein and Langmuir, 1987 doi:10.1029/JB092iB08p08089) along the MAR in the North Atlantic.

Chemistry of sulfide deposits from ODP Site 106-649

In Snake Pit massive sulfide fragments and friable, unconsolidated material recovered during ODP Leg 106, isocubanite and pyrite are generally the predominant phases, followed by marcasite, chalcopyrite, sphalerite, and pyrrhotite. Detailed analyses of paragenetic relations of minerals indicate that isocubanite first precipitated together with pyrrhotite. With decreasing temperature, chalcopyrite and sphalerite precipitated, and at the latest stage colloform sphalerite-pyrite (or colloform marcasite) formed. Isocubanite usually has exsolution lamellae of chalcopyrite and less commonly of pyrrhotite. The average bulk chemical composition of the friable, unconsolidated material indicates that it is rich in copper, reflecting the dominance of isocubanite in the specimens, and is characterized by high Co, low Pb, and Ag contents. Sulfur isotope ratios are very uniform, ranging in d34S from +1.2 to +2.8 per mil. The obtained values are apparently low, compared to those for the eastern Pacific sulfide samples, reflecting a smaller contribution of seawater sulfate in the Snake Pit sulfide deposit.