ALBERT

Description: Seasonal (Spring and Summer 2002) concentrations of dissolved (〈0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO3, PO4, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO4 and NO3 (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 102– 8.2 × 103 μmol d−1). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 103 μmol d−1 (inland, freshwater well) vs. 2.1 × 105 μmol d−1(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.

Description: A mass balance for the naturally-occurring radium isotopes (224Ra, 223Ra, 228Ra, and 226Ra) in Jamaica Bay, NY, was conducted by directly estimating the individual Ra contributions of wastewater discharge, diffusion from fine-grained subtidal sediments, water percolation through marshes, desorption from resuspended particles, and water exchange at the inlet. The mass balance revealed a major unknown source term accounting for 19–71% of the total Ra input, which could only be resolved by invoking a source from submarine groundwater. Shallow (〈 2 m depth) groundwater from permeable sediments in Jamaica Bay was brackish and enriched in Ra relative to surface bay waters by over two orders of magnitude. To balance Ra fluxes, a submarine groundwater input of 0.8 × 109–9.0 × 109 L d− 1 was required. This flux was similar for all four isotopes, with individual estimates varying by less than a factor of 2. Our calculated groundwater flux was 6- to 70-fold higher than the fresh groundwater discharge to the bay estimated by hydrological methods, but closely matched direct flow rates measured with seepage meters. This suggests that a substantial portion of the discharge consisted of recirculated seawater. The magnitude of submarine groundwater discharge varied seasonally, in the order: summer 〉 autumn 〉 spring. Chemical analyses suggest that the recirculated seawater component of submarine groundwater delivers as much dissolved nitrogen to the bay as the fresh groundwater flux.

Description: A liquid chromatograph/mass spectrometry (LC/MS) method was developed for the simultaneous quantitation of seven compounds (safflor yellow A, puerarin, daidzein, ginsenosides (Rg(1), Rb(1), Rd), and notoginsenoside R(1)) in rat plasma samples with sufficient sensitivity to facilitate analysis of samples collected after an intravenous injection of Naodesheng. The plasma samples were subjected to protein precipitation with acetone, and analyzed using negative atmospheric pressure chemical ionization mass spectrometry in selected ion monitoring (SIM) mode with baicalin as an internal standard. Good linearity for all the seven compounds was observed. The intra- and inter-day precision of analysis was 〈15.0% for each compound, and the accuracy ranged from 90.0% to 109.0%. This quantitation method was successfully applied to a pharmacokinetic study of following intravenous injection of rats with Naodesheng

Description: Centropages typicus is one of the most common, abundant and best studied calanoid copepods in neritic waters of the Mediterranean Sea, which means it can provide useful information about the long-term dynamics of the Mediterranean epipelagic ecosystem. This paper presents the first comparative overview of the seasonal and long-term variability of C. typicus in different Mediterranean regions. This review is based on quantitative information from the published literature and novel data from five ongoing zooplankton time-series carried out in the Mallorca Island (Balearic Sea), the Bay of Villefranche (Ligurian Sea), the Gulf of Naples (Tyrrhenian Sea), the Gulf of Trieste (North Adriatic Sea), and the Saronikos Gulf (Aegean Sea). In most Mediterranean regions, C. typicus has a perennial occurrence, with peaks of abundance that reflect the succession of different generations. Throughout the Mediterranean, the annual cycle of C. typicus is characterized by minima in winter and major peaks in April–June, which is earlier than those observed in European Atlantic waters, where the peaks are more frequently recorded in summer and fall. In the regions investigated, the annual cycle shows remarkable similarities in terms of timing, but notable differences in the peak height; populations are far more abundant in coastal north-western regions and less abundant in the eastern basin. In the long-term, changes in C. typicus phenology observed in the Bay of Villefranche and in the Gulf of Naples are related to the North Atlantic Oscillation (NAO) index. In these two regions, the species responds to climate forcing similarly in terms of average seasonal patterns (bi-modal patterns in years of positive NAO, unimodal patterns in years of negative NAO) but oppositely in terms of quantity, indicating different influence of the NAO on the two regions. At decadal scales, C. typicus populations show high interannual variability with marked geographical differences. In some areas, the patterns are clearly characterized by alternate phases of higher and lower annual abundances, at higher frequency (mainly 1–2 years) in the Gulf of Naples, and lower frequency in the Saronikos Gulf (mainly 4–5 years) and in the Gulf of Trieste (mainly 5–6 years). Synchronous phases of increasing or decreasing abundance are discernable only for a few sites and short periods, for example from 1998 to 2000 in the Gulf of Naples, Gulf of Trieste and Saronikos Gulf. The regional differences observed in the long-term patterns of C. typicus populations suggest that the temporal dynamics of this species are significantly more affected by local conditions than by any possible common driving force acting at basin scale through teleconnections.

Description: Seven new fungal polyketides possessing linear pentaene structures ending in cyclic moieties were isolated from the mycelium extract of a marine sponge-derived Penicillium rugulosum. Feeding of C-13-labeled acetate and L-methionine was used to verify the polyketide origin of prugosene A1. It could also be shown that prugosenes B1 and C1 were formed from prugosene A1 by hydrolysis and decarboxylation of its oxabicyclo[2.2.1]heptane unit.

Description: Planktic foraminiferal census data, faunal sea surface temperatures (SSTs) and oxygen isotopic and lithic records from a site in the northeast Atlantic were analyzed to study the interglacial dynamics of Marine Isotope Stage (MIS) 11, a period thought to closely resemble the Holocene on the basis of orbital forcing. Interglacial conditions during MIS 11 persisted for approximately 26 ka. After the main deglacial meltwater processes ceased, a 10- to 12-ka-long transitional period marked by significant water mass circulation changes occurred before surface waters finally reached their thermal maximum. This SST peak occurred between 400 and 397 ka, inferred from the abundance of the most thermophilic foraminiferal species and was coincident with lowest sea level according to benthic isotope values. The ensuing stepwise SST decrease characterizes the overall climate deterioration preceding the increase in global ice volume by ∼ 3 ka. This cooling trend was followed by a more pronounced cold event that began at 388 ka, and that terminated in the recurrence of icebergs at the site around 382 ka. Because the water mass configuration of early MIS 11 evolved quite differently from that of the early Holocene, there is little evidence that MIS 11 can serve as an appropriate analogue for a future Holocene climate, despite the similarity in some orbital parameters.

Description: Variably altered dacite from the PACMANUS vent field in the eastern Manus back-arc basin, Papua New Guinea, was studied to determine the textural and mineralogical characteristics of hydrothermal alteration taking place in the immediate subsurface of this modern seafloor hydrothermal system. Detailed textural investigations show that fluid flow through the glassy dacite has been strongly controlled by the primary volcanic textures. Quench fractures and networks of interconnected perlitic cracks linking vesicles provided pathways for hydrothermal fluids flowing up to the seafloor. Hydrothermal alteration along these pathways resulted in the formation of pseudoclastic textures. Textural evidence suggests that alteration of the glassy dacite has not been sustained. The samples have been affected by incipient hydrothermal alteration that is typically not preserved in ancient volcanic-rock-hosted massive sulfide deposits. Interaction of the glassy dacite with hydrothermal fluids primarily resulted in the conversion of volcanic glass to dioctahedral smectite. Only minor amounts of trioctahedral smectite were formed. Destruction of the volcanic glass and the formation of smectite caused pronounced changes in the chemistry of the dacite samples, in particular a decrease in the SiO2 whole-rock content and the Na2O/K2O ratio. The two alkali elements behaved differently during hydrothermal alteration due to preferential incorporation of K into the interlayer position of the newly formed dioctahedral smectite. Smectite formation occurred under rock-dominated conditions although the addition of Mg was required to form trioctahedral smectite from the silicic volcanic glass. Primary plagioclase was resistant to hydrothermal alteration highlighting the fact that the destruction of volcanic glass and feldspar are not necessarily contemporaneous in massive sulfide forming hydrothermal systems. Incipient alteration of the glassy dacite close to the seafloor occurred at temperatures below 150 °C in an environment that allowed the development of steep temperature gradients. Comparison of the new data to the findings of deep drilling during ODP Leg 193 suggests that the smectite-rich alteration in the immediate subsurface of the PACMANUS hydrothermal vent field represents the low-temperature equivalent of illite- and chlorite-rich alteration associations forming in the upflow zones of the hydrothermal fluids in the deeper portion of the volcanic sequence.

Description: New high resolution carbon isotope stratigraphies from two basinal pelagic carbonate successions in northern Germany (Halle and Oerlinghausen, Münsterland Cretaceous Basin) resolve late Cenomanian to early Mid-Turonian carbon cycle variations at timescales of less than 100 kyr. Beside the major carbon isotope excursion of the late Cenomanian oceanic anoxic event (OAE 2), 11 small-scale distinct features are precisely resolved in the δ13C carbonate curve and related to boreal macrofossil zonations. The small-scale carbon isotope events correspond to secular δ13C carbonate variations identified previously in the English Chalk. The boreal high-resolution δ13C carbonate curve shows a detailed coincidence with two Tethyan δ13C curves from Italy, what demonstrates the interregional significance of the δ13C dates and allows their correlation within error limits of ± 40 kyr. Furthermore, the new δ13C curve enables the calibration of boreal and tethyan macro- and microfossil zonations. Accordingly, the Tethyan calcareous nannoplankton boundary NC13/NC14 corresponds to the boreal FO of C. woollgari, the index taxon for the Lower-Middle Turonian boundary. The cyclic appearance and the temporal spacing of the small-scale carbon isotope events suggest that orbital forcing exerted control on surface water productivity and organic matter preservation at the sea floor.

Description: Permeabilities in the subducting slab appear to be too low and dihedral angles between fluid and relevant minerals too high to allow for porous flow, hence fluid channelization is critical for the understanding of subduction zone fluid fluxes. In this review we will outline how fluid channelization controls reaction rates and element redistributions during metamorphism of the subducting plate as well as trace element compositions of subduction-related fluids during flow. Channelized fluid flow predicts that from a rock point of view, most formerly subducted material will show only very limited evidence for fluid flow, consistent with the rarity of observed high fluid fluxes in subduction-related rocks. Aqueous fluid produced by dehydration reactions will not percolate through large rock volumes, but rather will be carried away from the dehydration sites by a veining network. Indeed evidence for significant aqueous-fluid fluxes have been found in high-pressure veins with adjacent selvages. In such selvages, large lithophile elements (LILE's) generally show the highest mobilities, followed by light (L) rare earth elements (REE) and then heavy (H) REE. Compared to high field strength elements (HFSE), even Th shows higher mobilities. From a fluid point of view, equilibrium between aqueous fluid and surrounding rock will only be approached at sites of fluid production and mineral reaction. However, this fluid can be significantly modified while moving upwards through a veining network where the wallrocks are out of equilibrium with the fluid. In a subducting slab, such reactive fluid flow can preferentially dissolve minerals and release their trace elements (e.g. Ba in phengite, Th and La in monazite). The degree of change in aqueous-fluid composition will depend on the amount of fluid–mineral surface interaction. The chemical exchange reactions will not be possible to model by trace element partition coefficients alone, instead future models need to incorporate kinetic parameters such as surface reaction rates.

Description: Controversy over the oxygen isotope composition of seawater began in the 1950's, since which time there has been no agreement over whether the oxygen isotope composition of the oceans has changed over time. Resolving this uncertainty would allow the δ18O values of demonstrably well preserved marine authigenic precipitates to be used to reconstruct surface climate trends back to early Archean times and would help towards a more quantitative description of Earth's global water cycle on geological time scales. Isotopic studies of marine carbonate and silica reveal a trend of increasing δ18O values with decreasing age since the Archean. This trend has been interpreted by some to reflect a progressive increase in seawater δ18O through time; however, it is generally accepted on the basis of ophiolite studies and theoretical considerations that seawater δ18O cannot change significantly because of the buffering effects of ocean crust alteration at mid-ocean ridges. As a result many alternative interpretations have been proposed, including meteoric alteration; warmer paleoclimates; higher seawater pH; salinity stratification and biased sampling. Here we review these interpretations in the light of an updated compilation of marine carbonate δ18O from around the world, covering the Phanerozoic and Precambrian rock records. Recent models of the geological water cycle demonstrate how long-term trends in chemical weathering and hydrothermal circulation can indeed influence the O-isotope composition of the global ocean to the extent necessary to explain the carbonate δ18O trend, with residual variation attributed to climatic fluctuations and post-depositional alteration. We present the further development of an existing model of the geological water cycle. In the model, seawater δ18O increased from about − 13.3‰ to − 0.3‰ over a period of 3.4 Ga, with average surface temperatures fluctuating between 10 °C to 33 °C, which is consistent with known biological constraints. Similar temperature variations are also obtained, although with higher starting seawater δ18O composition, when more conservative approaches are used that take into account the systematic effects of diagenetic alteration on mean calcite δ18O values. In contrast to much published opinion, the average δ18O value of ocean crust in the model remained relatively unchanged throughout all model runs. Invariable ophiolite δ18O values can, therefore, not be used as a definitive argument against changing seawater δ18O. The most likely explanation for the long-term trend in seawater δ18O invokes two stepwise increases in the ratio of high- to low-temperature fluid/rock interactions. An initial increase may have occurred close to the Archean–Proterozoic boundary, but a possibly more significant increase took place near the Proterozoic–Phanerozoic boundary. Possible explanations for extremely low seawater δ18O during the Archean include higher continental weathering rates caused by a combination of higher atmospheric pCO2 (necessarily combined with high CO2 outgassing rates), a greater abundance of relatively easily weathered volcanic rocks in greenstone belts and partial emergence of spreading ridges. The second increase may have been caused by the suppression of low-temperature overprinting of ocean crust alteration by the formation of a thick sediment cover on ridge flanks due to the emergence of shelly plankton at the beginning of the Phanerozoic. Postulated increases in spreading ridge depths since the Archean would also have enhanced the efficiency of vertical heat flux and changed the depth at which hydrothermal fluids boil, both of which would favour high- over low-temperature interactions with time.

Description: The active continental margin off south-central Chile (36° to 40°S) is transitional between the tectonically erosive, empty-trench margin north of Juan Fernandez Ridge and the accretionary, trench-filled margin south of the Chile Triple Junction. The small width of the presently active accretionary wedge (maximum width of 25 to 50 km) argues for past phases of tectonic erosion. At present, this sector shows indications of contemporaneous accretion, subduction, and underplating of sediment, as well as readjustment of the slope by various mass-wasting processes. In this context, this study aims to examine the Neogene sedimentary processes on the continental margin from dredge samples recovered during R/V SONNE cruise SO161-5 within this transitional domain using lithology, sandstone petrology, shale mineralogy, and analysis of sedimentary structures. Our results yield that the principal transport of material occurs in high-energy turbidity currents and debris flows via submarine canyons deeply cutting the continental slope, whereas sediment on the shelf is transported by strong coast-parallel bottom currents and trapped by submarine canyons cutting into the shelf. A wide range of mass-wasting processes including slumping, debris flows, evolving to low-density turbidity currents and mud flows, rework the slope sediments. In contrast, thick undisturbed sequences of mostly hemipelagic sediments accumulate in active slope basins, which are largely protected from mass movements. XRD analyses revealed early diagenetic lithification and overall burial depths of up to ∼ 230 mbsf, suggesting a shallow-subsurface cycle of sedimentation, subsidence, diagenesis, uplift, erosion, and resedimentation. The composition of sandstones is dominated by volcanic rock fragments of Andean provenance. Along-strike modal changes reflect a southward increase in glacially denudation and rainfall, the combination of which caused more intense erosion of volcanic rocks and exposure, weathering and, as a result, increased fluvial transport of metamorphic and plutonic rocks to the sea.

Description: Measurements of bromoform (CHBr3), diiodomethane (CH2I2), chloroiodomethane (CH2ICl) and bromoiodomethane (CH2IBr) were made in the water column (5–100 m depth) of the Southern Ocean within 0–40 km of the Antarctic sea ice during the ANTXX1/2 transect of the German R/V Polarstern, at five locations between 70–72°S and 9–11°W in the Antarctic spring/summer of 2003–2004. Some of the profiles exhibited a very pronounced layer of surface sea-ice meltwater, as evidenced by salinity minima and temperature maxima, along with surface maxima in concentrations of CHBr3, CH2I2, CH2ICl and CH2IBr. These results are consistent with in situ surface halocarbon production by ice algae liberated from the sea ice, although production within the sea ice followed by transport cannot be entirely ruled out. Additional sub-surface maxima in halocarbons occurred between 20 and 80 m. At a station further from shore and not affected by surface sea-ice meltwater, surface concentrations of CH2I2 were decreased whereas CH2ICl concentrations were increased compared to the stations influenced by meltwater, consistent with photochemical conversion of CH2I2 to CH2ICl, perhaps during upward mixing from a layer at ∼ 70 m enhanced in iodocarbons. Mean surface (5–10 m) water concentrations of halocarbons in these coastal Antarctic waters were 57 pmol l− 1 CHBr3 (range 44–78 pmol l− 1), 4.2 pmol l− 1 CH2I2 (range 1.7–8.2 pmol l− 1), 0.8 pmol l− 1 CH2IBr (range 0.2–1.4 pmol l− 1), and 0.7 pmol l− 1 CH2ICl (range 0.2–2.4 pmol l− 1). Concurrent measurements in air suggested a sea-air flux of bromoform near the Antarctic coast of between 1 and 100 (mean 32.3, median 10.4) nmol m− 2 day− 1 and saturation anomalies of 557–1082% (mean 783%, median 733%), similar in magnitude to global shelf values. In surface samples affected by meltwater, CH2I2 fluxes ranged from 0.02 to 6.1 nmol m− 2 day− 1, with mean and median values of 1.9 and 1.1 nmol m− 2 day− 1, respectively.

Description: Latent heat polynyas are regions generating strong ice formation, convection and extensive water mass formation. Here we report on the effects of these processes on resuspension of sediments and subsequent methane release from the seafloor and on the resulting excess methane concentration in surface water on a polar shelf during winter. The study is based on measurements of concentration and δ13C values of methane, water temperature, salinity, light transmission and sea ice data collected in March 2003 in Storfjorden, southern Svalbard. In winter, strong and persistent northeasterly winds create polynyas in eastern Storfjorden and cause ice formation. The resulting brine-enriched water cascades from the Storfjordbanken into the central depression thereby enhancing the turbulence near the seafloor. A distinct benthic nepheloid layer was observed reflecting the resuspension of sediments by the cascading dense bottom water. High concentrations of 13C-depleted methane suggest submarine discharge of methane with the resuspended sediments. As the source of the submarine methane, we propose recent bacterial methanogenesis near the sediment surface because of extremely high accumulation rates of organic carbon in Storfjorden. Convective mixing transports newly released methane from the bottom to the sea surface. This eventually results in an excess concentration in surface water with respect to the atmospheric equilibrium, and a sea-air flux of methane during periods of open water. When a new ice cover is formed, methane becomes trapped in the water column and subsequently oxidized. Thus, the residual methane is strongly enriched in 13C in relation to the δ13CCH4δ13CCH4 signature of atmospheric methane. Our results show that latent heat polynyas may induce a direct pathway for biogases like methane from sediments to the atmosphere through coupling of biogeochemical and oceanographic processes. Extrapolating these processes to all Arctic ocean polynyas, we estimate a transfer of CH4 between 0.005 and 0.02 Tg yr−1. This is not a large contribution but the fluxes from the polynyas are 20–200 times larger than the ocean average and the methane evasion process in polynyas is certainly one that can be altered under climate change.

Description: The Sibao Orogen in South China is one of the poorest known Grenville-aged orogenic belts through which the Neoproterozoic supercontinent Rodinia assembled. We report here the first UV laser spot 40Ar/39Ar mica and SHRIMP U–Pb zircon ages from a rare Grenville-aged metamorphic complex, the Tianli Schists, in the eastern Sibao Orogen. Our U–Pb zircon provenance ages indicate that the protolith of the Tianli Schists was a clastic sedimentary succession most likely derived from the Yangtze Block. The depositional age of the protolith is younger than 1530 Ma, as constrained by the youngest detrital zircon grains, but is older than 1040 Ma as constrained by the oldest 40Ar/39Ar muscovite ages. The Yangtze Block provenance for the Tianli Schists suggests that the Sibaoan ophiolitic complexes in northeastern Jiangxi, the ca. 970 Ma Xiwan adakitic granite intrusions, and the ca. 900 Ma(?) Xiwan blueschists, all to the northwest of the study region, were likely formed during the closure of a back-arc basin along the margin of the Yangtze Block. Our in situ UV laser 40Ar/39Ar results from S1 and S2 muscovites suggest that the Tianli Schists underwent metamorphism and deformation at 1042 ± 7 Ma to 1015 ± 4 Ma, the oldest known metamorphic event in the eastern Sibao Orogen. Muscovite/biotite cooling ages of ca. 968 ± 4 and 942 ± 8 Ma are recorded by deformed and recrystallised muscovite and biotite, respectively, indicating tectonic reactivation before 900 Ma, during the later stages of the Sibao Orogeny. Together with previous results from the western Sibao Orogen, our work suggests that the closure of the ocean between the Yangtze and Cathaysia Blocks during the assembly of Rodinia was diachronous: ≥1000 Ma at the western Sibao Orogen and ca. 900 Ma at the eastern Sibao Orogen.

Description: Annonaceous acetogenins are a large class of naturally occurring polyketides exhibiting potent anticancer activities. Based on our previous discovery of AA005, a multi-ether mimic of natural acetogenins having potent antitumor activities and significant selectivity between normal cells and cancer cells, a new series of mimics containing a terminal lactam were designed, synthesized and evaluated. Bioactivity study against cancer cells shows that the N-methylated lactam-containing compounds 3, 4, and 5 exhibit comparable potencies to that of AA005, as well as the similar selectivity to cancer cells. Hydrocarbon-length effects of N-alkyl were further explored through synthesizing derivatives 24–26, and application of this derivation protocol to the fluorescent labeling was also investigated.

Description: A wide variety of environmental records is necessary for analysing and understanding the complex Late Quaternary dynamics of permafrost-dominated Arctic landscapes. A NE Siberian periglacial key region was studied in detail using sediment records, remote sensing data, and terrain modelling, all incorporated in a geographical information system (GIS). The study area consists of the Bykovsky Peninsula and the adjacent Khorogor Valley in the Kharaulakh Ridge situated a few kilometres southeast of the Lena Delta. In this study a comprehensive cryolithological database containing information from 176 sites was compiled. The information from these sites is based on the review of previously published borehole data, outcrop profiles, surface samples, and our own field data. These archives cover depositional records of three periods: from Pliocene to Early Pleistocene, the Late Pleistocene and the Holocene. The main sediment sequences on the Bykovsky Peninsula consist of up to 50 m thick ice-rich permafrost deposits (Ice Complex) that were accumulated during the Late Pleistocene. They were formed as a result of nival processes around extensive snowfields in the Kharaulakh Ridge, slope processes in these mountains (such as in the Khorogor Valley), and alluvial/proluvial sedimentation in a flat accumulation plain dominated by polygonal tundra in the mountain foreland (Bykovsky Peninsula). During the early to middle Holocene warming, a general landscape transformation occurred from an extensive Late Pleistocene accumulation plain to a strongly thermokarst-dominated relief dissected by numerous depressions. Thermokarst subsidence had an enormous influence on the periglacial hydrological patterns, the sediment deposition, and on the composition and distribution of habitats. Climate deterioration, lake drainage, and talik refreezing occurred during the middle to late Holocene. The investigated region was reached by the post-glacial sea level rise during the middle Holocene, triggering thermo-abrasion of ice-rich coasts and the marine inundation of thermokarst depressions.

Description: Historic data from the Russian-American Hydrochemical Atlas of Arctic Ocean together with data from the TRANSDRIFT II 1994 and TUNDRA 1994 cruises have been used to assess the spatial and inter-annual variability of carbon and nutrient fluxes, as well as air–sea CO2 exchange in the Laptev and western East Siberian Seas during the summer season. Budget computations using summer data of dissolved inorganic phosphate (DIP), dissolved inorganic nitrogen (DIN) and dissolved inorganic carbon (DIC) gives that the Laptev Sea shelf is a net sink of DIP and DIN of 2.5×106, 23.2×106 mol d−1, respectively, while it is a net source of DIC (excluding air–sea exchange) of 1249×106 mol d−1. In the East Siberian Seas the budget computations give 0.5×106, −11.4×106 and −173×106 mol d−1 (minus being a sink) for DIP, DIN, and DIC, respectively. In summers, the Laptev Sea Shelf is net autotrophic while the East-Siberian Sea Shelf is net heterotrophic, and both systems are weak net denitrifying. The Laptev Sea Shelf takes up 2.1 mmol CO2 m−2 d−1 from atmosphere, whereas the western part of the East-Siberian Sea Shelf loose 0.3 mmol CO2 m−2 d−1 to the atmosphere. The variability of DIP, DIN and DIC fluxes during summer in the different regions of the Laptev and East Siberian Seas depends on bottom topography, river runoff, exchange with surrounding seas and wind field.

Description: Particulate matter in aquatic systems is an important vehicle for the transport of particulate organic carbon (POC). Its accurate measurement is of central importance for the understanding of marine carbon cycling. Previous work has shown that GF/F-filter-based bottle-sample-derived concentration estimates of POC are generally close to or higher than large-volume in-situ-pump-derived values (and in some rare cases in subzero waters are up to two orders of magnitude higher). To further investigate this phenomenon, water samples from the surface and mid-water Northeast Atlantic and the Baltic Sea were analyzed. Our data support a bias of POC concentration estimates caused by adsorption of nitrogen-rich dissolved organic material onto GF/F filters. For surface-ocean samples the mass per unit area of exposed filter and composition of adsorbed material depended on the filtered volume. Amounts of adsorbed OC were enhanced in the surface ocean (typically 0.5 μmol cm− 2 of exposed filter) as compared to the deep ocean (typically 0.2 μmol cm− 2 of exposed filter). These dependencies should be taken into account for future POC methodologies. Bottle/pump differences of samples that were not corrected for adsorption were higher in the deep ocean than in the surface ocean. This discrepancy increased in summer. It is shown that POC concentration estimates that were not corrected for adsorption depend not only on the filtered volume, true POC concentration and mass of adsorbed OC, but also on the filter area. However, in all cases we studied, correction for adsorption was important, but not sufficient, to explain bottle/pump differences. Artificial formation of filterable particles and/or processes leading to filterable material being lost from and/or missed by sample-processing procedures must be considered. It can be deduced that the maximum amounts of POC and particulate organic nitrogen (PON) that can be artificially formed per liter of filtered ocean water are ∼ 3–4 μM OC (5–10% of dissolved OC) and ∼ 0.2–0.5 μM ON (2–10% of dissolved ON), respectively. The relative sensitivities of bottle and pump procedures, and of surface- and deep-ocean material, to artificial particle formation and the missing/losing of material are evaluated. As present procedures do not exist to correct for all possible biasing effects due to artificial particle formation and/or miss/loss of filterable material, uncertainties of filtration-based estimates of POC concentrations need further testing. The challenge now is to further constrain the magnitude of the biasing effects that add to the adsorption effect to reduce the uncertainties of estimates of POC concentrations, inventories and fluxes in the ocean.

Description: A 1.5 km long, 1 km wide and 70–80 m high carbonate mound was identified on the mid-slope region of the subduction accretionary sedimentary prism offshore Vancouver Island ∼ 3.5 km west of Ocean Drilling Program (ODP) Site 889 and Integrated Ocean Drilling Program (IODP) Site U1327. Seabed-video images show the presence of seafloor carbonate as well as chemosynthetic communities. A high-resolution single channel seismic survey with close line spacing, recording coherent reflectivity down to about 400 m beneath the seafloor, provided acoustic images of this mound and of the gas hydrate bottom-simulating reflector (BSR) beneath it. The mound is interpreted to have developed as a structural topographic high in the hanging wall of a large reverse fault formed at the base of the current seaward slope. The fault zone provides pathways for fluids including gas to migrate to the seafloor where diagenetic carbonate forms and cements the near-surface sediments. To examine the thermal effect of possible upward fluid flow beneath the mound, heat flow at the mound and in the neighbouring region was calculated from the depth of the BSR below the seafloor. These data were combined with heat flow calculated over a broader region from previous multi-channel seismic data. Heat flow within the flattest portion of the surrounding 4 km by 8 km region averages ∼ 74 mW/m2. Taking this value to represent the regional or background heat flow, a simple 2D analytical method was used to calculate theoretical heat flow variations due to topography. Across the mound, most of the variability is explained by topographic effects, including a local 6 mW/m2 negative anomaly over the central mound and a large 20 mW/m2 positive anomaly over the mound steep side slope. However, just south of the mound, there is a 6–7 mW/m2 positive anomaly in a 2-km-long band that has predominantly flat seafloor. Most of this anomaly is probably unrelated to topographic effects, but rather likely due to warm upward fluid flow along faults or fracture zones.

Description: Numerous marine demosponges serve as habitats to phylogenetically complex microbial communities, with population densities exceeding those of seawater by several orders of magnitude. 16S rRNA gene-based studies have enabled a detailed phylogenetic description of the microorganisms associated with sponges, whereas environmental genomics analyses are beginning to reveal insights into their metabolic and physiological properties. Additionally, metagenomic approaches provide access to functional genes and gene clusters, thereby paving the way for the heterologous expression of novel bioactive substances from microbial symbionts of marine invertebrates.

Description: A method for the quantification of heme b in marine phyto- and bacterioplankton is described. Heme b was extracted from filtered cells using a solution of 2.5% octyl (3-glucopyranoside in 0.02 M ammonium hydroxide. The extract was analysed by high performance liquid chromatography diode array spectrophotometry. Maximum absorbance for heme b was at 400 nm. Heme b was separated from other pigments using a polystyrene divinyl benzene stationary phase and a gradient elution programme with 0.1% (v:v) nonafluoropentanoic acid in water and 50:50 (v:v) isopropanol:acetonitrile as the mobile phases. Heme b was quantified using Fe (III) protoporphyrin IX chloride (hemin) standards. The detection limit, calculated from 3 X s.d. of the lowest standard was 0.08 pmol or 1.57 nM with a 50 mu L injection volume. The first data for heme b in marine phyto- and bacterioplankton are reported. Heme b contents are reported for the eukaryotes Thalassiosira weissflogii, Thalassiosira oceanica, Dunaliella tertiolecta and Emiliania huxleyi, and the prokaryotes Synechococcus WH8102, WH7803, RCC307, Erythrobacter litoralis, Roseobacter denitrificans and Vibrio natriegens. For T. weissflogii, T. oceanica, D. tertiolecta and E. huxleyi cellular heme b concentrations varied between 12 and 60 mu mol L-1 and chlorophyll a to heme b ratios varied between 216 and 309

Description: The Earth’s crust has played an important role in all aspects of this planet’s evolution. This chapter presents a review of our current understanding of the physical properties of the crust on a global basis. This understanding comes from extensive seismic measurements using many techniques, as well as nonseismic geophysics, including gravity, magnetic, geoelectric, and heat flow measurements. Seismic measurements include those that employ active (man-made) sources and those that use passive (naturally occurring) sources. Deep seismic reflection profiles provide a seismic image of the crust in twodimensions with a high (50–100 m) resolution. Local earthquake tomography can provide three-dimensional (3-D) seismic images at moderate (500–1000 m) resolution and higher, depending on the number and spacing of seismographs. Nonseismic methods provide estimates of crustal density, magnetic properties, conductivity and geotherms (temperature vs depth). The crust in deep ocean basins is 6–7 km thick and has a relatively uniform seismic velocity structure, but there are numerous oceanic regions with anomalous crustal structure, including mid-ocean ridges, trenches, volcanic islands, and oceanic plateaux. Ocean–continent passive margins are also highly variable in structure, and may be classified as volcanic versus nonvolcanic margins. Continental crust ranges in thickness from 16 to 80 km, and has a highly variable seismic velocity and density structure. The proportions of continental crust, by area, are 69% shield and platform (cratons), 15% old and young orogens, 9% extended (stretched) crust, 6 % magmatic arc, and 1% rifts. The weighted mean continental crustal thickness and average crustal velocity are 41 km (SD 6.2 km) and 6.45 km s−1 (SD 0.21 km s−1), respectively. A global geographic distribution of seismic data has made it possible to create global crustal models with cell sizes as small as 2 ° × 2 °. These models provide a complete description of seismic velocities and density within the crust and uppermost mantle, including, where present, ice, water, and sedimentary layers and the crystalline crust (parameterized in three layers, upper, middle and lower crust), and sub-Moho properties. The crust is the most intensely studied region of the Earth’s interior and consequently is the best understood in terms of its structure, composition, and evolution.

Description: The Mediterranean outflow water (MOW) paleocirculation during the last 50,000 years has been inferred from the grain-size distribution of contourite beds in core MD99-2341 from the Gulf of Cadiz (Southern Iberian Margin–Atlantic Ocean). Three main contourite facies are described. Their vertical succession defines two contourite sequences that reveal past variations of the MOW bottom-current velocity. A comparison of contourite sequences and the planktonic δ18O record of core MD99-2341 with the δ18O record from Greenland Ice Core GISP2 show a close correlation of sea-surface water conditions and deep-sea contouritic sedimentation in the Gulf of Cadiz with Northern Hemisphere climate variability on millennial timescales. A high MOW velocity prevailed during Dansgaard-Oeschger stadials, Heinrich events and the Younger Dryas cold climatic interval. The MOW velocity was comparatively low during the warm Dansgaard-Oeschger interstadials, Bølling-Allerød and the Early Holocene. Rapid sea-level fluctuations on the order of 35 m during Marine Oxygen Isotope Stage 3 are considered to have exerted limiting controls on the MOW volume transport and thus positively modulated the MOW behaviour during the last 50 kyr.

Description: Determining the movement of marine animals is logistically difficult and is currently primarily based on VHF and satellite-tracking telemetry, GPS, acoustic telemetry, and geolocation, all of which have substantial limitations in accurately locating the fine-scale movements of these animals. A recent development—that of dead-reckoning—is being increasingly used to examine the fine-scale movement of animals underwater. The advantages and drawbacks of this approach are quite different to those incurred by the other methods. This paper considers the advances that deadreckoning can bring to the study of the often cryptic movement and behaviour of marine animals at sea. Methods used in determining position via dead-reckoning are presented and consideration is given to results derived from the use of deadreckoning on cetaceans, pinnipeds, penguins and sea turtles; these are complemented by data on cormorants and albatrosses acquired using GPS systems. Suggestions are made as to how movement data derived from these devices can be analysed using indices that allow interpretation over a large variety of temporal and spatial scales.

Description: Total alkalinity (TA) is one of the few measurable quantities that can be used together with other quantities to calculate concentrations of species of the carbonate system (CO2, HCO3 −, CO32−, H+, OH−). TA and dissolved inorganic carbon (DIC) are conservative quantities with respect to mixing and changes in temperature and pressure and are, therefore, used in oceanic carbon cycle models. Thus it is important to understand the changes of TA due to various biogeochemical processes such as formation and remineralization of organic matter by microalgae, precipitation and dissolution of calcium carbonate. Unfortunately deriving such changes from the common expression for TA in terms of concentrations of on-conservative chemical species (HCO3 −, CO3 2 −, B(OH)4 −, H+, OH−, etc.) is rarely obvious. Here an expression for TA (TAec) in terms of the total concentrations of certain major ions (Na+, Cl−, Ca2+ etc.) and the total concentrations of various acid-base species (total phosphate etc.) is derived from Dickson's original definition of TA under the constraint of electroneutrality. Changes of TA by various biogeochemical processes are easy to derive from this so-called explicit conservative expression for TA because each term in this expression is independent of changes of temperature or pressure within the ranges normally encountered in the ocean and obeys a linear mixing relation. Further, the constrains of electroneutrality for nutrient uptake by microalgae and photoautotrophs are discussed. A so-called nutrient-H+-compensation principle is proposed. This principle in combination with TAec allows one to make predictions for changes in TA due to uptake of nutrients that are consistent with observations. A new prediction based on this principle is the change in TA due to nitrogen fixation followed by remineralization of organic matter and subsequent nitrification of ammonia which implies a significant sink of TA in tropical and subtropical regions where most of the nitrogen fixation takes place.

Description: Extreme hydrological events are often triggered by exceptional co-variations of the relevant hydrometeorological processes and in particular by exceptional co-oscillations at various temporal scales. Wavelet and cross wavelet spectral analysis offers promising time-scale resolved analysis methods to detect and analyze such exceptional co-oscillations. This paper presents the state-of-the-art methods of wavelet spectral analysis, discusses related subtleties, potential pitfalls and recently developed solutions to overcome them and shows how wavelet spectral analysis, if combined to a rigorous significance test, can lead to reliable new insights into hydrometeorological processes for real-world applications. The presented methods are applied to detect potentially flood triggering situations in a high Alpine catchment for which a recent re-estimation of design floods encountered significant problems simulating the observed high flows. For this case study, wavelet spectral analysis of precipitation, temperature and discharge offers a powerful tool to help detecting potentially flood producing meteorological situations and to distinguish between different types of floods with respect to the prevailing critical hydrometeorological conditions. This opens very new perspectives for the analysis of model performances focusing on the occurrence and non-occurrence of different types of high flow events. Based on the obtained results, the paper summarizes important recommendations for future applications of wavelet spectral analysis in hydrology.

Description: The element compositions Si, Ca and Al of up to 2 1.1 ka old sediments in about 10 in long cores from the southern basin of the Shaban and Kebrit deeps in the northern Red Sea allowed a classification of major sediment types in carbonate sands and -muds and siliceous oozes. A FeOOH-enriched sediment horizon and a few samples with high Zn values in the Kebrit core indicate a hydrothermal origin probably near the brine-sea water interface with subsequent transport of hydrothermal compounds into the deep sediments. High organic carbon contents up to 8.4% are positively correlated with the Ba concentrations, which suggests that high bioproductivity, and rapid deposition (C-14 dating suggests a sedimentation rate near 70 cm/ka) led to the formation of sapropelic sediments between 11.8 and 13.6 ka (Younger Dryas). Organic petrological observations showed that the sediment organic material largely consists of 〈20 gm-sized roundish fecal pellets (intimate mixtures of organic matter and inorganic constituents) and bituminite. Terrestrial organic matter (pollens of land plants, fusinite etc.) is very rare in the sediment cores from both deeps. Organic-geochemical investigations of kerogens and organic extracts show that a significant (hydrothermal) hydrocarbon production did not occur in near-surface sediments of the Shaban and Kebrit deeps. Rock Eval pyrolysis of kerogens characterised the organic matter to be of type II quality. The delta C-13 values of the kerogens from the most prominent sapropel in the Shaban deep indicate an enrichment of(C-12-rich) nutrients in the water column during postglacial sapropel formation in the Younger Dryas. The n-alkane spectra are dominated by short chain lengths between n-C-15 and n-C-25 Prevailing n-C-15 to n-C-25 alkanes in low mature sediments are indicative of algal and microbial source. Pristane/phytane ratios are generally low (〈 I to similar to 1) which suggests that anoxic conditions prevailed within the anaerobic brine-filled deeps for the whole time covered by the sediments. This again indicates that sapropel formation was caused by high bioproductivity in the northern Red Sea rather than episodic stagnation with better preservation of the organic matter. Long-chain alkenones and sterols are the dominating compounds of the lipid fraction. Cholesterol contents in the sediment cores reflect phases of eukaryotes production in the water column, whereas the positive correlations of dinosterol with TOC and the amounts of total extract suggests that the major organic carbon source in the northern Red Sea during postglacial high-productivity stages were dinoflagellates. Another important carbon source, however, is indicated by the occurrence of 22,29,30-trisnorhopan-21 -one (TNH). Although the formation of TNH from its precursors is not fully understood, this compound probably results from microbial. degradation of intact bacteriohopanepolyols (BHP), which can be used as indicators for bacterial abundances and phyla. TNH is most likely produced at the brine-sea water interface where sedimenting organic matter accumulates and, if the redoxcline corresponds to the density gradient, the organic matter is subjected to efficient aerobic bacterial degradation processes. However, during high bioproductivity stage (Younger Dryas) the redoxcline was probably higher in the water column and thus, a significant TNH production at the brine-sea water interface did not occur at times of sapropel formation in the northern Red Sea deeps. (C) 2007 Elsevier B.V All rights reserved.

Description: Two biotic indices, ATZI Marine Biotic Index (AMBI) and Benthic Quality Index (BQI) have been recently introduced within the EC Water Framework Directive to assess the quality of marine habitats: both are based on sensitivity/tolerance classification and quantitative information on the composition of soft-bottom macrofauna. Their performance, especially with regard to sampling effort was assessed based on two data sets collected in Southern Baltic and one from the Gulf of Lions Mediterranean. AMBI was not affected by sampling effort but BQI was. Two modifications were proposed for BQI (i.e., BQI) (1) the removal of the scaling term (i.e., BQIW), and (2) the replacement of the scaling term by different scaling term (i.e., BQIES). Both modified BQIs were largely independent of sampling effort. Variability was slightly lower for BQIW than for BQIES. BQI was highly correlated with BQIW and with BQIES both in the Southern Baltic and in the Gulf of Lions. However, the proportions of stations, which were not attributed the same ecological quality status (EcoQ) when using BQI and its two modified forms were always high. Differences in ecological classification were mostly due to the scales used to infer EcoQ. Based on this study we recommend to use BQIES in future studies because it apparently constitutes the best compromise in (1) being independent of sampling effort, (2) limiting the variability in computation in relation with sampling effort, (3) being correlated with BQI and corresponding EcoQ.

Description: Extensive ROV-based sampling and exploration of the seafloor was conducted along an eroded transform-parallel fault scarp on the northeastern side of the Guaymas Basin in the Gulf of California to observe the nature of fluids venting from the seafloor, measure the record left by methane-venting on the carbonates from this area, and determine the association with gas hydrate. One gas vent vigorous enough to generate a water-column gas plume traceable for over 800 m above the seafloor was found to emanate from a ∼10-cm-wide orifice on the eroded scarp face. Sediment temperature measurements and topography on a sub-bottom reflector recorded in a transform-parallel seismic reflection profile identified a subsurface thermal anomaly beneath the gas vent. Active chemosynthetic biological communities (CBCs) and extensive authigenic carbonates that coalesce into distinct chemoherm structures were encountered elsewhere along the eroded transform-parallel scarp. The carbon isotopic composition of methane bubbles flowing vigorously from the gas vent (−53.6±0.8‰ PDB) is comparable to methane found in sediment cores taken within the CBCs distributed along the scarp (−51.9±8.1‰ PDB). However, the δ13C value of the CO2 in the vent gas (+12.4±1.1‰ PDB) is very distinct from those for dissolved inorganic carbon (DIC) (−35.8‰ to −2.9‰ PDB) found elsewhere along the scarp, including underneath CBCs. The δ13C values of the carbonate-rich sediments and rocks exposed on the seafloor today also span an unusually large range (−40.9‰ to +12.9‰ PDB) and suggest two distinct populations of authigenic carbonate materials were sampled. Unconsolidated sediments and some carbonate rocks, which have lithologic evidence for near-seafloor formation, have negative δ13C values, while carbonate rocks that clearly formed in the subsurface have positive δ13C values (up to +23.0‰) close to that measured for CO2 in the vent gas. There appears to be two carbon sources for the authigenic carbonates: (1) deeply-sourced, isotopically heavy CO2 (∼+12‰); and (2) isotopically light DIC derived from local anaerobic oxidation of methane at the sulfate–methane interface in the shallow subsurface. Addition of isotopically light methane-derived carbon at the seafloor may completely mask the isotopically heavy CO2 signature (+12.4‰) in the underlying sediments. Thus, the authigenic carbonates may have formed from the same methane- and carbon dioxide-bearing fluid, but under different migration and alteration conditions, depending on how it migrated through the sediment column.

Description: Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world not, vert, similar 112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate not, vert, similar 25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere–land–ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (not, vert, similar 45,000 yr) period of not, vert, similar 0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns, H.C., 2003. Evidence for rapid climate change in the Mesozoic–Palaeogene greenhouse world. The Royal Society, 361: 1885–1916.] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 × 1018 g methane carbon (δ13C = − 60 ‰), equivalent to about 10% to the total modern gas hydrate inventory, generated the δ13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over not, vert, similar 25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Description: New and published data on the composition of melt inclusions in olivine (Fo73–91) from volcanoes of the Kamchatka and northern Kurile Arc are used 1) to evaluate the combined systematics of volatiles (H2O, S, Cl, F) and incompatible trace elements in their parental magmas and mantle sources, 2) to constrain thermal conditions of mantle melting, and 3) to estimate the composition of slab-derived components. We demonstrate that typical Kamchatkan arc-type magmas originate through 5–14% melting of sources similar or slightly more depleted in HFSE (with up to ∼ 1 wt.% previous melt extraction) compared to MORB-source mantle, but strongly enriched in H2O, B, Be, Li, Cl, F, LILE, LREE, Th and U. Mean H2O in parental melts (1.8–2.6 wt.%) decreases with increasing depth to the subducting slab and correlates negatively with both ‘fluid-immobile’ (e.g. Ti, Na, LREE) and most ‘fluid-mobile’ (e.g. LILE, S, Cl, F) incompatible elements, implying that solubility in hydrous fluids or amount of water does not directly control the abundance of ‘fluid-mobile’ incompatible elements. Strong correlation is observed between H2O/Ce and B/Zr (or B/LREE) ratios. Both, calculated H2O in mantle sources (0.1–0.4%) and degrees of melting (5–14%) decrease with increasing depth to the slab indicating that the ultimate source of water in the sub-arc mantle is the subducting oceanic plate and that water flux (together with mantle temperature) governs the extent of mantle melting beneath Kamchatka. A parameterized hydrous melting model [Katz et al. 2003, G3, 4(9), 1073] is utilized to estimate that mantle melting beneath Kamchatka occurs at or below the dry peridotite solidus (1245–1330 °C at 1.5–2.0 GPa). Relatively high mantle temperatures (yet lower than beneath back-arc basins and ocean ridges) suggest substantial corner flow driven mantle upwelling beneath Kamchatka in agreement with numerical models implying non-isoviscous mantle wedge rheology. Data from Kamchatka, Mexico and Central America indicate that 〈 5% melting would take place beneath continental arcs without water flux from the subducting slab. A broad negative correlation appears to exist between crustal thickness and the temperature of magma generation beneath volcanic arcs with larger amounts of decompression melting occurring beneath thinner arc crust (lithosphere). In agreement with the high mantle temperatures, we observe a systematic change in the composition of slab components with increasing slab depth from solute-poor hydrous fluid beneath the volcanic front to solute-rich hydrous melt or supercritical liquid at deeper depths beneath the rear arc. The solute-rich slab component dominates the budget of LILE, LREE, Th and U in the magmas and originates through wet-melting of subducted sediments and/or altered oceanic crust at ≥ 120 km depth. Melting of the upper parts of subducting plates under water flux from deeper lithosphere (e.g. serpentinites), combined with high temperatures in the mantle wedge, may be a more common process beneath volcanic arcs than has been previously recognized.

Description: Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Description: High-resolution multi-frequency and multi-component seismic data were acquired at northern Hydrate Ridge in the accretionary complex of the Cascadia subduction zone to quantify the amount of hydrate and free gas in the sediment. We present a detailed local analysis of four component (4C) ocean bottom seismometer (OBS) data and show the importance of multi-frequency and shear wave data for determining hydrate reservoir properties. A detailed model of the elastic parameters at the bottom simulating reflector (BSR) is developed by using synthetic seismogram modelling. The main focus in this study is an amplitude-versus-offset (AVO) analysis of shear waves, which originate by PS-conversion at the BSR in 73 m below the seafloor (bsf). The AVO analysis enables the determination of the shear wave velocity above the BSR. A velocity of 400 m/s indicates that the presence of gas hydrate in the pore space significantly increases the shear modulus of the sediment above the BSR. Information about the attenuation and the shape of the BSR transition zone is obtained from the frequency-dependent reflection amplitudes of the BSR. The BSR is shown to be a gradual type transition zone of 1.5–2.5 m thickness. Average Q factors of Qp = 150 for P-waves and of Qs = 35 for S-waves are determined within the gas hydrate stability zone (GHSZ). The low Qs factor points to a pronounced attenuation of S-waves in the uppermost sediments. From rock physics modelling, the hydrate concentration is estimated to vary locally between 3–12% of the pore space. Below the BSR, free gas concentrations of 0.5% and 8% are determined for homogeneous and patchy distributed gas, respectively.

Description: Deposits of coral-bearing, marine shell conglomerate exposed at elevations higher than 20 m above present-day mean sea level (MSL) in Bermuda and the Bahamas have previously been interpreted as relict intertidal deposits formed during marine isotope stage (MIS) 11, ca. 360–420 ka before present. On the strength of this evidence, a sea level highstand more than 20 m higher than present-day MSL was inferred for the MIS 11 interglacial, despite a lack of clear supporting evidence in the oxygen-isotope records of deep-sea sediment cores. We have critically re-examined the elevated marine deposits in Bermuda, and find their geological setting, sedimentary relations, and microfaunal assemblages to be inconsistent with intertidal deposition over an extended period. Rather, these deposits, which comprise a poorly sorted mixture of reef, lagoon and shoreline sediments, appear to have been carried tens of meters inside karst caves, presumably by large waves, at some time earlier than ca. 310–360 ka before present (MIS 9–11). We hypothesize that these deposits are the result of a large tsunami during the mid-Pleistocene, in which Bermuda was impacted by a wave set that carried sediments from the surrounding reef platform and nearshore waters over the eolianite atoll. Likely causes for such a megatsunami are the flank collapse of an Atlantic island volcano, such as the roughly synchronous Julan or Orotava submarine landslides in the Canary Islands, or a giant submarine landslide on the Atlantic continental margin.

Description: Atmospheric deposition fluxes of soluble nutrients (N, P, Si, Fe, Co, Zn) to the tropical North Atlantic were determined during cruise M55 of the German SOLAS programme. Nutrient fluxes were highest in the east of the section along 10°N, owing to the proximity of source regions in West Africa and Europe, and lowest in the west, for both dry and wet deposition modes. In common with other recent studies, atmospheric P and Si inputs during M55 were strongly depleted relative to the stoichiometry of phytoplankton Fe, N, P and Si requirements. Atmospheric N inputs were equivalent to 0.1–4.7% of observed primary productivity during the cruise. Atmospheric nutrient supply was also compared to observed nitrogen fixation rates during M55. While atmospheric Fe supply may have been sufficient to support N fixation (depending on the relationship between our simple Fe leaching experiment and aerosol Fe dissolution in seawater), atmospheric P supply was well below the required rate. The stable nitrogen isotope composition of nitrate–N in aerosol and rain was also determined. Results of a simple model indicate that atmospheric deposition and nitrogen fixation introduce similar amounts of isotopically light nitrogen into surface waters of the study region. This implies that nitrogen isotope-based methods would overestimate nitrogen fixation here by a factor of 2, if atmospheric inputs were not taken into account.

Description: Mud volcanism in the Gulf of Cadiz occurs over a large area extending from the shelf to more than 3500 m water depth and is triggered by compressional stress along the European–African plate boundary, affecting a deeply faulted sedimentary sequence of locally more than 5 km thickness. The investigation of six active sites shows that mud volcano (MV) fluids, on average, are highly enriched in CH4, Li, B, and Sr and depleted in Mg, K, and Br. The purity of the fluids is largely controlled by the intensity of upward directed flow. Flow rates could be constrained by numerical modelling and vary between 〈0.05 and 15 cm yr−1. Application of δD–δ18O systematics identifies clay mineral dehydration, most likely within Mesozoic and Tertiary shales and marls, as the major source of fluids. Hence, Cl and Na in the pore fluids are mostly depleted below seawater values, following a general trend of dilution. However, deviations from this trend occur and are likely caused by the dissolution of halite in evaporitic deposits. Other secondary processes overprinting the original fluid composition may occur along the flow path, such as dissolution of anhydrite or gypsum and/or the formation of calcite and dolomite. Different sources of fluids are also indicated by variations in 87Sr/86Sr, which range from 0.7086 to 0.7099 at the different sites. Dehydration may be induced primarily by overburden and tectonic compression; however, very high concentrations of Li and B, specifically at Captain Arutyunov MV (CAMV) indicate additional leaching at temperatures above 150 °C, which could be explained by the injection of hot fluids along deep penetrating, major E–W strike–slip fault systems. This hypothesis is supported by the occurrence of generally thermogenic, but significantly CH4-enriched, light volatile hydrocarbon gases at CAMV which cannot be explained by shallow microbial methanogenesis. Li and Li/B ratios from different types of hot and cold vents are used to infer that high temperature signals seem to be preserved at various cold vent locations and indicate a closer coupling of both systems in continental margin environments than outlined in previous studies.

Description: Complete sediment subduction at the Costa Rica subduction zone makes this convergent margin an ideal place to investigate the effects of tectonic deformation in situ. We present a seismic reflection study along a line located 3 km landward of the Middle American Trench and oriented parallel to the strike of the décollement. The Ocean Bottom Hydrophone (OBH) seismic data include large offsets and incidence angles at the reflectors. We derive the P- and S-waves velocity distribution below the décollement using a P-wave analysis of amplitude with reflection angle. The investigation shows that there are unexpected large lateral velocity variations at a scale of only a few 100 m. The shear wave velocity in the uppermost subducted sediment varies between 300 and 700 m/s, while the variation of the compressional wave velocity is in a range of 1700 to 2000 m/s. The variation of the vP–vS ratio between 2.8 and 5.2 can only be explained by variations of the pore fluid pressure. The modelled velocities correspond to a normalised pore fluid pressure ratio λ* in the range between 0.02 and 0.93. The most reasonable explanation for these observations is the localised presence of fluids, which are released during diagenesis by smectite to illite transformation. During this process, which takes place in three discrete steps, the interlayer water of the smectite is added to the pore fluid and the permeability of the sediment is decreased. Both effects lead to the formation of small, overpressured cells.

Description: Global Nd–Hf isotope systematics can be mainly described with two linear arrays, the global silicate Earth array (“the terrestrial array”) and the global ferromanganese crust and nodule array (”the seawater array”). The offset between these two arrays provides evidence for the sources and mechanisms by which these elements are added to ocean water. However, the reason for this offset is under debate, with the two preferred hypotheses being (i) incongruent release of Hf during continental weathering and (ii) hydrothermal contribution of Hf to the seawater budget. Here we present new Nd and Hf isotope data on glacio-marine core-top sediments from around the perimeter of the Antarctic continent. The results range from εHf = − 30.0 to εHf = + 3.9 and εNd = − 21.3 to εNd = + 0.9, reflecting the large range of basement ages and lithologies around the Antarctic continent. In Nd–Hf isotope space, they confirm the systematic correlations found in rocks from other parts around the world and provide valuable insights into the previously underrepresented group of sediments with very old provenance. In this paper we revisit the cause for the offset of the seawater array from the terrestrial array using simple mass balance considerations. We use these calculations to test to what degree the seawater array could be a product of preferential weathering of “non-zircon portions” of the upper continental crust, implying retention of zircons in the solid residue of weathering. Lutetium–Hf and Sm–Nd evolution and mixing calculations show that the global seawater array can be generated with continental sources only. On the other hand, a predominantly hydrothermal origin of Hf in the ocean is not possible because the seawater Hf isotopic composition is significantly less radiogenic than hydrothermal sources, and requires a minimum fraction of 50% continental Hf. While hydrothermal sources may contribute some Hf to seawater, continental contributions are required to balance the budget.

Description: A synthesis of backscatter imagery coupled with a large 3D seismic dataset in the Lower Congo Basin (LCB) reveals a patchy distribution of features interpreted to be associated with fluid seepage from 300 m to 2500 m water depth. With the exception of one region of anomalous backscatter positive-relief mounds, all inferred seep sites occur in negative-relief pockmarks. The extensive 3D seismic dataset in the LCB offers a unique opportunity to study the plumbing system that is feeding surface cold seep systems, and in general, to reconstruct the relationship between tectonics and fluid flow in continental margins. The fluid seeps in the LCB are associated with morphologically, stratigraphically or tectonically controlled focused fluid flow. The integration of the geophysical datasets, backscatter imagery coupled to 3D seismic, clearly indicates that fluid seeps are not randomly distributed, but their seabed organization reflects 1) the location of the underlying structure (reservoir or trap) where the fluids are coming from, 2) the geometry and morphology of the reservoir/trap, and 3) the discontinuities in the sedimentary column along which fluids have migrated. In the LCB seafloor pockmarks are always associated with underlying tectonic structures (fault zones, salt diapirs, polygonal faults) or buried sedimentary bodies (turbiditic channels, erosional surfaces), whereas they never occur above sub-horizontal parallel-stratified fine-grained sediments. Even if triggering processes can not be clearly defined here, we propose a model of seafloor fluid seep organization, which represents a new tool for identifying the geometry of flow pathways and the underlying buried bodies where the fluids are originating from. This qualitative 3D model provides insight into the geohydrologic processes of continental margins.

Description: Glaciated continental shelves are characterised by large amphitheatre-like embayments between prominent cross-shelftroughs. The integration of swath bathymetry and high-resolution seismic data (3D, 2D) collected across the western Svalbard continental margin indicates how such embayments form. Although their bathymetric expression resembles headwall scarps of submarine slopefailures, the shelfembayments are the result of the interplay between sediment dynamics and transport underneath fast-moving ice streams in the cross-shelftroughs and the slower-moving parts of the ice sheets on the adjacent shallower shelf banks during full glacial conditions. This is supported by (1) the absence of major landslide deposits at their toe, (2) continuous prograding shelf deposition and (3) absence of landslide-related faulting. Instead, the seismic data suggest a depositional origin of the shelfembayments that is characterised by continuous sediment input at lower rates off a slow-moving ice mass in the centre of the embayment which is fringed by the lateral ice-stream ridges. These findings put into perspective the importance of submarine slopefailure on glaciated margins.

Description: The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O2 within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values 〉 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer. The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.

Description: Characteristics of precipitation including mean precipitation, rain intensity, rain event probability and an index of extreme events from different global climate model simulations are analyzed. Results of numerical experiments with the ECHAM5/MPI-OM general circulation model (GCM) using anthropogenic greenhouse gas emission scenarios SRES-A2 and SRES-B1 have been used. Simulations with the ECHAM5/MPI-OM are compared to the observational data and ERA-40 reanalysis. The basins of major Eurasian rivers such as Volga, Ob, Yenisei and Lena rivers have been chosen for a detailed analysis. Scenario SRES-B1 and SRES-A2 simulations with the ECHAM5/MPI-OM for the 21st century demonstrate an increase of winter precipitation, its intensity and rain event probability as well as heavy precipitation in the catchments areas of Volga, Ob, Yenisei and Lena rivers. Trends for the summer rain intensity and heavy precipitation in the 21st century are also positive but less significant than for winter trends. This is in contrast to the summer rain event probability, which has a negative trend in all analyzed river basins.

Description: The 230Th content of subsurface Bahamas seawater has been estimated from incrementally deposited aragonite skeletons of sclerosponges using U-series age models which imply syndepositional incorporation of 230Th. First order age models, assuming constant growth rate and zero initial 230Th activity, display an average surface age of 63 ± 18 y despite the fact that the surfaces of the organisms were known to be alive at the time collection in the 1990s. A knowledge of the initial 230Th activity is necessary to incorporate the surface age constraint into an age model. In the Bahamas, this approach estimates an initial 230Th/232Th activity ratio of 4.3 ± 1.1 when applied to several individuals of the Caribbean sclerosponge Ceratoporella nicholsoni. These results differ from the same approach applied to previous work on Jamaican sclerosponges accreting aragonite in an environment closer to crustal sources and with less carbonate substrate. We report new measurements of Jamaican sclerosponge suggesting initial activity ratios of 230Th/232Th of ∼1, albeit with a high amount of uncertainty, indicating a regional difference in initial thorium activities. The estimates of initial 230Th/232Th activity ratios in the Bahamas are similar to the dissolved ratio rather than the particulate ratio and can be explained by mixing of open ocean water and bank-top surface water, however no information regarding temporal changes in the amount of initial 230Th/232Th activity available for incorporation into biogenic aragonite can be constrained using this approach. Growth rates do not change after correction for initial thorium and they display an inverse relationship with depth. Although this paper deals uniquely with sclerosponge aragonite, it is likely that the approach can be used on any incrementally deposited biogenic aragonite, provided information is known a priori about the first order growth model and there is evidence that initial thorium incorporation is representative of ambient environment rather than individual physiology.

Description: The stratigraphic succession of widespread tephra layers in west-central Nicaragua was emplaced by highly explosive eruptions from mainly three volcanoes: the Chiltepe volcanic complex and the Masaya and Apoyo calderas. Stratigraphic correlations are based on distinct compositions of tephras. The total tephras combine to a total on-shore volume of about 37 km3 produced during the last ∼ 60 ka. The total erupted magma mass, including also distal volumes, of 184 Gt (DRE) distributes to 84% into 9 dacitic to rhyolitic eruptions and to 16% into 4 basaltic to basaltic–andesitic eruptions. The widely dispersed tephra sheets have up to five times the mass of their parental volcanic edifices and thus represent a significant albeit less obvious component of the arc volcanism. Eruption magnitudes (M = log10(m) − 7 with m the mass in kg), range from M = 4.1 to M = 6.3. Most of the eruptions were dominantly plinian, with eruption columns reaching variably high into the stratosphere, but minor phreatomagmatic phases were also involved. Two phreatomagmatic eruptions, one dacitic and one basaltic–andesitic, produced mostly pyroclastic surges but also fallout from high eruption columns. Comparison of fallout tephra dispersal patterns with present-day, seasonally changing height-dependant wind directions suggests that 8 eruptions occurred during the rainy season while 5 took place during the dry season. The tephra succession documents two major phases of erosion. The first phase, 〉 17 ka ago, appears to be related to tectonic activity whereas the second phase may have been caused by wet climatic conditions between 2 to 6 ka ago. The Apoyo caldera had two large plinian, caldera-forming eruptions in rapid succession about 24 ka ago and should be considered a silicic volcano with long repose times. Three highly explosive basaltic eruptions were generated at the Masaya Caldera within the last 6 ka. Since then frequent but small eruptions and lava effusion were largely limited to the caldera interior. The dacitic Chiltepe volcanic complex experienced six plinian eruptions during the last 17 ka and seems to be an accelerating system in which eruption magnitude increased while the degree of differentiation of erupted magma decreased at the same time. We speculate that the Chiltepe system might produce the next large-magnitude silicic eruption in west-central Nicaragua.

Description: A model for the release of Li, Be and B from progressively dehydrating altered oceanic crust during subduction is presented. Combining clinopyroxene/fluid partition coefficients determined experimentally in an earlier study Brenan et al. [Brenan, J.M., Ryerson, F.J., Shaw, H.F., 1998. The role of aqueous fluids in the slab-to-mantle transfer of boron, beryllium, and lithium during subduction: Experiments and models. Geochim. Cosmochim. Acta 62, 3337–3347] with apparent mineral/clinopyroxene partition coefficients as observed in natural high-pressure metamorphic rocks Marschall et al. [Marschall, H.R., Altherr, R., Ludwig, T., Kalt, A., Gméling, K., Kasztovszky, Zs., 2006a. Partitioning and budget of Li, Be and B in high-pressure metamorphic rocks. Geochim. Cosmochim. Acta 70, 4750–4769] results in a set of mineral/fluid partition coefficients for high-pressure metamorphic minerals. Mineral modes of altered oceanic crust as a function of pressure and temperature along a given subduction path can be derived from thermodynamic calculations using the program PerpleX. Combination of these modes with mineral/fluid partition coefficients results in whole rock/fluid partition coefficients at any stage of the P–T path including information on the amount of fluid released at any depth. Based on these data, the concentrations of Li, Be and B in subducting rocks and released fluids along a given P–T path can be modelled. The derived information on B concentrations in rocks and fluids are combined with the temperature-dependent fractionation of B isotopes in order to model the B isotopic evolution of subducting rocks and released fluids. Model calculations are performed for two slightly different chemical compositions (hydrous MORB without K and with 0.5 wt.% K2O), in order to demonstrate the impact of phengite on the boron budget. Provided the necessary input data are available, the concept of such a model could be employed to quantify the trace element release from the slab from any lithology along any reasonable P–T path.

Description: Pore fluids from the Green Canyon Block in the northern Gulf of Mexico show distinct differences with respect to element concentrations and oxygen, hydrogen, and strontium isotope signatures. The shallowest of the three investigated sites (GC185 or Bush Hill at 540 m water depth) is interpreted as a seafloor piercing mud mound and the two deeper areas (GC415 East and West at 950 and 1050 m water depth) as gas vent and oil seep sites. All three locations accommodate near-surface gas hydrates and the sediment surface is populated with chemosynthetic communities. They are characterized by a distinct increase in salinity with depth. However, the origin of this increasing salinity is different for the GC415 sites and Bush Hill and the depth source of the fluids is considerably different for all sites. The more saline fluids of the GC415 sites result from the dissolution of halite by formation water from two different sources. The fluids of GC415 East have most likely a deeper origin (early Cenozoic or even Mesozoic) and experienced elevated temperatures leading to mineral/water reactions including mineral transformations (e.g. smectite to illite transformation) and dissolution (e.g. feldspar dissolution). This process is expressed by the heavier oxygen isotope values and distinct Li, Sr, and Ca enrichments. The fluids of GC415 West have a shallower origin which is expressed by a smaller enrichment in Li, Sr, and Ca and lighter oxygen isotopes. The fluids from Bush Hill are less saline and its fluid signature indicates intensive water/mineral interaction. Oxygen and hydrogen isotope values as well as Na/Cl and Br/Cl molar ratios suggest that the salt enrichment was caused by phase separation under sub-critical conditions. A simple heat flow model simulation suggests that sub-critical phase separation may have occurred at a depth of ∼ 1650 m at ∼ 350 °C.

Description: We investigated the effects of temporal variability in a disturbance regime on fouling communities at two study sites in a northern-central Chilean bay. Fouling assemblages grown on artificial settlement substrata were disturbed by mechanical removal of biomass at different time intervals. Using one single disturbance frequency (10 disturbance events over 5 months) we applied 7 different temporal disturbance treatments: a constant disturbance regime (identical intervals between disturbance events), and 6 variable treatments where both variableness and sequences of intervals between disturbance events were manipulated. Two levels of temporal variableness (low and high, i.e. disturbance events were either dispersed or highly clumped in time) in the disturbance regime were applied by modifying the time intervals between subsequent disturbance events. To investigate the temporal coupling between disturbance events and other ecological processes (e.g. larval supply and recruitment intensity), three different sequences of disturbance intervals were nested in each of the two levels of temporal variableness. Species richness, evenness, total abundance, and structure of communities that experienced the various disturbance regimes were compared at the end of the experiment (15 days after the last disturbance event). Disturbance strongly influenced the community structure and led to a decrease in evenness and total abundance but not species richness. In undisturbed reference communities, the dominant competitor Pyura chilensis (Tunicata) occupied most available space while this species was suppressed in all disturbed treatments. Surprisingly, neither temporal variableness in the disturbance regime nor the sequence of intervals between disturbance events had an effect on community structure. Temporal variability in high disturbance regimes may be of minor importance for fouling communities, because they are dominated by opportunistic species that are adapted to rapidly exploit available space.

Description: The shift of lava geochemistry between volcanic front to rear-arc volcanoes in active subduction zones is a widespread phenomenon. It is somehow linked to an increase of the slab surface depth of the subducting oceanic lithosphere and increasing thickness of the mantle wedge and new constraints for its causes may improve our understanding of magma generation and element recycling in subduction zones in general. As a case study, this paper focuses on the geochemical composition of lavas from two adjacent volcanic centres from the volcanic front (VF) to rear-arc (RA) transition of the Southern Kamchatkan subduction zone, with the aim to examine whether the shift in lava geochemistry is associated with processes in the mantle wedge or in the subducted oceanic lithosphere or both. The trace element and O–Sr–Nd–Hf–Pb (double-spike)-isotopic composition of the mafic Mutnovsky (VF) and Gorely (RA) lavas in conjunction with geochemical modelling provides constraints for the degree of partial melting in the mantle wedge and the nature of their slab components. Degrees of partial melting are inferred to be significantly higher beneath Mutnovsky (∼18%) than Gorely (∼10%). The Mutnovsky (VF) slab component is dominated by hydrous fluids, derived from subducted sediments and altered oceanic crust, eventually containing minor but variable amounts of sediment melts. The composition of the Gorely slab component strongly points to a hydrous silicate melt, most likely mainly stemming from subducted sediments, although additional fluid-contribution from the underlying altered oceanic crust (AOC) is likely. Moreover, the Hf–Nd-isotope data combined with geochemical modelling suggest progressive break-down of accessory zircon in the melting metasediments. Therefore, the drastic VF to RA shift in basalt chemistry mainly arises from the transition of the nature of the slab component (from hydrous fluid to melt) in conjunction with decreasing degrees of partial melting within ∼15 km across-arc. Finally, systematic variations of key inter-element with high-precision Pb-isotope ratios provide geochemical evidence for a pollution of the Mutnovsky mantle source with Gorely melt components but not vice versa, most likely resulting from trench-ward mantle wedge corner flow. We also present a geodynamic model integrating the location of the Mutnovsky and Gorely volcanic centres and their lava geochemistry with the recently proposed thermal structure of the southern Kamchatkan arc and constraints about phase equilibria in subducted sediments and AOC. Herein, the slab surface hosting the subducted sediments suffers a transition from dehydration to melting above a continuously dehydrating layer of AOC. Wider implications of this study are that an onset of (flush-) sediment melting may ultimately be the main trigger for the VF to RA transition of lava geochemistry in subduction zones.

Description: Small-volume pyroclastic density currents (PDCs) are generated frequently during explosive eruptions with little warning. Assessing their hazard requires a physical understanding of their transport and sedimentation processes which is best achieved by the testing of experimental and numerical models of geophysical mass flows against natural flows and/or deposits. To this end we report on one of the most detailed sedimentological studies ever carried out on a series of pristine small-volume PDC deposits from the 1975 eruption of Ngauruhoe volcano, whose emplacement were also witnessed during eruption. Using high-resolution GPS surveys, a series of lateral excavations across the deposits, and bulk sedimentological analysis we constrained the geomorphology, internal structure and texture of the deposits with respect to laterally varying modes of deposition. Deposition from these PDCs began only on slopes at or around the material's angle of repose (c. 30°). In unconfined settings, the granular PDCs are interpreted to have been quasi-steady, forming sheets and lobes around the angle of repose. Where flows were confined, sheet-like proximal facies made up around 10% of the deposit volume at the angle of repose, but 90% of the material was deposited from apparently unsteady inertial granular PDCs as a distal levée-and-channel facies on slopes well below the repose angle. Hence, confined PDCs were able to travel up to 50% farther than unconfined flows. In the distal facies the deposit width is inversely correlated to the local slope, and the height of the levées (above the deposit centreline) is positively correlated with slope. Internally the deposits comprise three parts, a coarse-grained fines-free sole layer that laterally connects to levées (Zone I), an ashy matrix-supported central body (Zone II) and an overlying coarse plaster of clasts (Zone II). Trends in grain-size data suggests these zones derive from a continuous un-mixing of coarse particles from the initial bulk material by granular segregation that preferentially drives large particles to the upper free surface of the flow where they are concentrated at the front of flow before being deposited and overrun. By comparison to analogue experiments, we suggest a model of flow and deposition where the temporally and spatially varying mode of deposition is determined by the flow velocity, the local slope, the vertical velocity gradient, the velocity gradient at the free surface and the vertical deposition rate. Using this model, estimated vertical deposition rates of c. 5 cm s− 1 from the Ngauruhoe PDCs agree with those determined in laboratory experiments on inertial granular flows.

Description: We investigated the effect of CO2 and primary production on the carbon isotopic fractionation of alkenones and particulate organic matter (POC) during a natural phytoplankton bloom dominated by the coccolithophore Emiliania huxleyi. In nine semi-closed mesocosms (~11 m3 each), three different CO2 partial pressures (pCO2) in triplicate represented glacial (~180 ppmv CO2), present (~380 ppmv CO2), and year 2100 (~710 ppmv CO2) CO2 conditions. The largest shift in alkenone isotopic composition (4–5&) occurred during the exponential growth phase, regardless of the CO2 concentration in the respective treatment. Despite the difference of ~500 ppmv, the influence of pCO2 on isotopic fractionation was marginal (1–2&). During the stationary phase, E. huxleyi continued to produce alkenones, accumulating cellular concentrations almost four times higher than those of exponentially dividing cells. Our isotope data indicate that, while alkenone production was maintained, the interaction of carbon source and cellular uptake dynamics by E. huxleyi reached a steady state. During stationary phase, we further observed a remarkable increase in the difference between d13C of bulk organic matter and of alkenones spanning 7–12&. We suggest that this phenomenon is caused mainly by a combination of extracellular release of 13C-enriched polysaccharides and subsequent particle aggregation induced by the production of transparent exopolymer particles (TEP). 2007 Elsevier Inc. All rights reserved.

Description: Four species of marine calcifying algae, the coccolithophores Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 °C, and one species, C. leptoporus, under varying [CO32−], ranging from 105 to 219 μmol/kg. Calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e.g. Emiliania huxleyi (coccolithophores) and Orbulina universa (planktonic foraminifera) as well as inorganically precipitated CaCO3, but also reveal small species specific differences. In contrast to inorganically precipitated calcite, but similar to E. huxleyi and O. universa, the carbonate ion concentration of the medium has no statistically significant influence on the Ca isotope fractionation of C. leptoporus coccoliths; however, combined data of E. huxleyi and C. leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium. Since coccoliths constitute a significant portion of the global oceanic CaCO3 export production, the Ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the Ca sink of the ocean, one of the key parameters for modelling changes to the marine Ca budget over time. For the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic Ca sink (Δsed) of about − 1.3‰, but the observed inter- and intra-species differences point to possible changes in Δsed through earth history, due to changing physico-chemical conditions of the ocean and shifts in floral and faunal assemblages.

Description: Ocean basins are connected by straits and passages, geometrically limiting important heat and salt exchanges which in turn influence the global thermohaline circulation and climate. Such exchange can be modeled in an idealized way by taking into consideration the density-driven two-layer flow along a strait under the influence of rotation. We use a laboratory model of a lock exchange between two reservoirs of different density through a flat-bottom channel with a horizontal narrows, set up on two different platforms: a 1 m diameter turntable, where density interface position was measured by dye attenuation, and the 14 m diameter turntable at Coriolis/LEGI (Grenoble, France), where correlation imaging velocimetry, a particle imaging technique, allowed us to obtain for the first time detailed measurements of the velocity fields in these flows. The influence of rotation is studied by varying a parameter, BuBu, a type of Burger number given by the ratio of the Rossby radius to the channel width at the narrows. In addition, a two-layer version of the Miami Isopycnic Coordinate Model (MICOM) is used, to study the cases with low Burger number. Results from experiments by Dalziel [1988. Two-layer hydraulics: maximal exchange flows. Ph.D. Thesis, Department of Applied Mathematics and Theoretical Physics, University of Cambridge, see also 〈〈http://www.damtp.cam.ac.uk/lab/people/sd103/papers/1988/Thesis_Dalziel.pdf〉〉] are also included for comparison. Time-mean exchange fluxes for any BuBu are in close agreement with the inviscid zero-potential vorticity theory of Dalziel [1990. Rotating two-layer sill flows. In: Pratt, L.J. (Ed.), The Physical Oceanography of Sea Straits. Kluwer Academic, Dordrecht, pp. 343–371] and Whitehead et al. [1974. Rotating hydraulics of strait and sill flows. Geophysical Fluid Dynamics 6, 101–125], who found that fluxes for Bu〉1Bu〉1 mainly vary with channel width, similar to non-rotating flow, but for Bu〈1Bu〈1 are only limited by the Rossby radius. We also show theoretically that non-zero-potential vorticity results in only a small increase in the predicted exchange flux around Bu∼1Bu∼1. The flow characteristics are found to be very different for small and large Burger numbers: for Bu〉1Bu〉1 a steady, two-layer flow was observed that persisted across the channel at the narrows with only some across-channel variation. The distribution of the Froude number is found to give some evidence for hydraulic control in a manner similar to that of non-rotating flows under the influence of bottom drag. Flow for Bu〈0.5Bu〈0.5 does not appear to reach a steady state but instead is characterized by an unsteady, meandering current and several eddies in the strait. Similar instabilities also occur in wide oceanic straits, where several mechanisms, such as barotropic and baroclinic instability, have been proposed and could also be one cause of time variability in our experiments. Both the laboratory experiments and the MICOM results suggest that in the presence of bottom drag or side wall friction some features of the flow, such as the location of the channel crossing, become sensitive to the initial conditions. These effects differ in flows with Bu〉1Bu〉1 and Bu〈1Bu〈1.

Description: Geochemical estimates of N2 fixation in the North Atlantic often serve as a foundation for estimating global marine diazotrophy. Yet despite being well-studied, estimations of nitrogen fixation rates in this basin vary widely. Here we investigate the variability in published estimates of excess nitrogen accumulation rates in the main thermocline of the subtropical North Atlantic, testing the assumptions and choices made in the analyses. Employing one of these previously described methods, modified here with improved estimates of excess N spatial gradients and ventilation rates of the main thermocline, we determine a total excess N accumulation rate of 7.8 ± 1.7 × 1011 mol N yr− 1. Contributions to excess N development include atmospheric deposition of high N:P nutrients (adding excess N at a rate of 3.0 ± 0.9 × 1011 mol N yr− 1 for ∼ 38% of the total), high N:P dissolved organic matter advected into and mineralized in the main thermocline (adding excess N at 2.2 ± 1.1 × 1011 mol N yr− 1 for ∼ 28% of the total), and, calculated by mass balance of the excess N field, N2 fixation (adding excess N at 2.6 ± 2.2 × 1011 mol N yr− 1 for ∼ 33% of the total). Assuming an N:P of 40 and this rate of excess N accumulation due to the process, N2 fixation in the North Atlantic subtropical gyre is estimated at ∼ 4 × 1011 mol N yr− 1. This relatively low rate of N2 fixation suggests that i) the rate of N2 fixation in the North Atlantic is greatly overestimated in some previous analyses, ii) the main thermocline is not the primary repository of N fixed by diazotrophs, and/or iii) the N:P ratio of exported diazotrophic organic matter is much lower than generally assumed. It is this last possibility, and our uncertainty in the N:P ratios of exported material supporting excess N development, that greatly lessens our confidence in geochemical measures of N2 fixation.

Description: We describe the deep structure of the south Colombian–northern Ecuador convergent margin using travel time inversion of wide-angle seismic data recently collected offshore. The margin appears segmented into three contrasting zones. In the North Zone, affected by four great subduction earthquakes during the 20th century, normal oceanic crust subducts beneath the oceanic Cretaceous substratum of the margin underlined by seismic velocities as high as 6.0–6.5 km/s. In the Central Zone the subducting oceanic crust is over-thickened beneath the Carnegie Ridge. A steeper slope and a well-developed, high velocity, Cretaceous oceanic basement characterizes the margin wedge. This area coincides with a gap in significant subduction earthquake activity. In the South Zone, the subducting oceanic crust is normal. The fore-arc is characterized by large sedimentary basins suggesting significant subsidence. Velocities in the margin wedge are significantly lower and denote a different nature or a higher degree of fracturing. Even if the distance between the three profiles exceeds 150 km, the structural segmentation obtained along the Ecuadorian margin correlates well with the distribution of seismic activity and the neotectonic zonation.

Description: Recent ostracod assemblages were investigated from coretop sediment samples collected in the eastern Kara Sea from water depths down to 300 m. A total of 45 species were identified, 27 of them were reported for the Kara Sea for the first time. The Kara Sea data were compared with our results on the distribution of ostracods in the eastern Laptev Sea. The spatial distribution of recent taxa and the ecological groupings demonstrate a clear relation to dominant environmental factors which range from estuarine to full-marine conditions. Four assemblages related to average summer bottom water salinities were established: (1) a freshwater assemblage from the inner estuaries of the Ob' and Yenisei rivers with salinities less than 2 and from thermokarst lagoons of the southern Laptev Sea coast with strong salinization in winter; (2) a brackishwater assemblage of the outer estuaries of the Ob' and Yenisei rivers with salinities up to 26; (3) a mixed euryhaline–marine assemblage dominated by euryhaline species Paracyprideis pseudopunctillata and Heterocyprideis sorbyana from the inner shelf river-affected zone of the Kara and Laptev seas, where salinities range between 26 and 32; (4) a taxonomically diverse marine assemblage dominated by shallow-water marine taxa from the northern parts of the Kara and Laptev shelves and upper continental slope with stable bottom environments and a salinity higher than 32. Abundant euryhaline species found at greater water depths are identified as part of an ice-rafted assemblage. They are possibly entrained into the newly formed fast ice during autumn storms and freeze-up period and then transported to the distal open-sea areas during summer.

Description: The southern Chilean convergent margin, between 50° and 57° S, is shaped by the interaction of the three main plates: Antarctic, South America and Scotia. North of 53° S, the convergence between Antarctic and South America plates is close to orthogonal to the continental margin strike. Here, the deformational style of the accretionary prism is mainly characterized by seaward-verging thrusts and locally by normal faults and fractures, a very limited lateral extension of prism, a very shallow dip (∼ 6°) décollement, and subduction of a thick and relatively undeformed trench sedimentary sequence. South of 53° S, convergence is oblique to the margin, locally, the trench sediments are proto-deformed by double vergence thrusting and the front of the prism grows through landward-verging thrusting. The décollement is sub-horizontal and deep, involving most of the sediment over the oceanic crust in the accretionary process, building a comparatively wide and thicker prism. A Bottom Simulating Reflector is present across the whole prism to the abyssal plan, suggesting the presence of gas in the sediments. The analysis of P- and S-wave velocity reflectivity sections, derived by amplitude versus offset technique (AVO), detailed velocity information and the velocity-derived sediment porosity have been integrated with the structural analysis of the accretionary prism of two selected pre-stack depth migrated seismic lines, aiming to explain the relation between fluid circulation and tectonics. Accretion along double vergence thrust faults may be associated with the presence of overpressured fluid, which decreases the effective shear stress coefficient along the main décollement and within the sediments, and modify the rheolgical properties of rocks. The presence of an adequate drainage network, represented by interconnected faults and fractures affecting the entire sedimentary sequence, can favour the escape of pore fluid toward the sea bottom, while, less permeable and not faulted sediments can favour fluid accumulations. Gravitational and tectonic dewatering, and stratigraphy could control the consolidation and the pore overpressure of sediments involved in subduction along the trench. The results of our analysis suggest the existence of a feedback between tectonic style and fluid circulation.

Description: Throughout the last similar to 900 kyr, the Late Pleistocene, Earth has experienced periods of cold glacial climate, punctuated by seven abrupt transitions to warm interglacials, the so-called terminations. Although most of glacial ice is located in the Northern Hemisphere (NH), the Southern Hemisphere (SH) seems to play a crucial role in deglaciation. Variation in the seasonal distribution of solar insolation is one candidate for the cause of these climatic shifts. But so far, no simple mechanism has been identified. Here we present a mathematical analysis of variations in midsummer insolation in both hemispheres at 65 degrees latitude. Applying this analysis to the entire Pleistocene, the last 2 Myr, we find that prior to each termination the insolation in both hemispheres increases in concert, with a SH lead. Introducing time and energy thresholds to these overlaps, calculated times for the onsets of the seven terminations by this insolation canon (exceptional overlaps meeting the two threshold prerequisites) are similar to 23, 139, 253, 345, 419, 546 and 632 kyr BP, perfectly matching the geologic record. The timing originates from the interplay between the two orbital parameters obliquity and precession, explaining why terminations occur at integer multiple of the precessional cycle. There is no such constellation between I and 2 Myr BP, the Early Pleistocene, in agreement with Earth's climate at that time. This change in orbital forcing coincides with the Mid Pleistocene Revolution, separating the Late from the Early Pleistocene. Therefore, we hypothesize that the insolation canon is the trigger for glacial terminations. (c) 2006 Elsevier B.V. All rights reserved.

Description: The Nankai accretionary prism is divided into three segments: outer and inner wedges and their transition zone. These wedges reflect different aspects of wedge taper, internal deformation, and basal plate boundary fault. The outer wedge is characterized by narrow critical taper, internal deformation by in-sequence-fold-and-thrust and aseismic décollement. The inner wedge represents a stable narrow taper, weakly deformed internal structure and seismogenic plate boundary fault along its base. The transition zone between the two wedges shows large critical taper with steep surface slope, internal structure of out-of-sequence thrust, and step-down of décollement onto the sediment–oceanic basement interface. The trench slope break and oceanward margin of forearc basin is located around the landward edge of this transition zone. These common aspects might be related to the lithification of both accreted and underthrust sediments and the resultant switch of the plate boundary fault. Deformation and lithification process recorded in exhumed on-land mélange of accretionary complexes suggest that the step-down of the plate boundary décollement occurs around the up-dip limit of seismogenic subduction zone.

Description: A liquid chromatographic–mass spectrometric (LC–MS) method was developed and validated for the simultaneous determination of homoeriodictyol-7-O-β-d-glycoside (HEDT-Glc) and its active metabolite homoeriodictyol (HEDT) in rat tissues and urine. The analytes and internal standard (dihydromyricetin, IS) were detected by using negative atmospheric pressure chemical ionization mass spectrometry in selected ion monitoring (SIM) mode at m/z 464, 301 and 319 for HEDT-Glc, HEDT and IS, respectively. These compounds were eluted on a Luna reverse phase column. The mobile phase was a methanol–water mixture (70:30, v/v) containing 0.1% of formic acid at a flow rate of 0.8 ml/min. The limit of quantification (LOQ) for both HEDT-Glc and HEDT was 10 ng/ml and their limit of detection (LOD) was 1 ng/ml. Calibration curves were linear (r 〉 0.995) over a wide range of the analytes in tissues and urine. The mean extraction recoveries were ≥75.6% for HEDT-Glc and ≥82.4% for HEDT from biological matrixes. Accuracy, expressed as the relative error, ranged from −4.0% to 3.8% for HEDT-Glc and from −2.8% to 4.7% for HEDT. The method was successfully applied to the estimation of HEDT-Glc and its metabolite HEDT in rat tissues and urine.

Description: The type II fatty acid pathway (FAS-II) is a validated target for antimicrobial drug discovery. An activity-guided isolation procedure based on Plasmodium falciparum enoyl-ACP reductase (Pf FabI) enzyme inhibition assay on the n -hexane-, the CHCl3-CHCl3- and the aq MeOH extracts of the Turkish marine sponge Agelas oroides yielded six pure metabolites [24-ethyl-cholest-5α-7-en-3-β-ol (1), 4,5-dibromopyrrole-2-carboxylic acid methyl ester (2), 4,5-dibromopyrrole-2-carboxylic acid (3), (E)-oroidin (4), 3-amino-1-(2-aminoimidazoyl)-prop-1-ene (5), taurine (6)] and some minor, complex fatty acid mixtures (FAMA–FAMG). FAMA, consisting of a 1:2 mixture of (5Z,9Z)-5,9-tricosadienoic (7) and (5Z,9Z)-5,9-tetracosadienoic (8) acids, and FAMB composed of 8, (5Z,9Z)-5,9-pentacosadienoic (9) and (5Z,9Z)-5,9-hexacosadienoic (10) acids in ≈3:3:2 ratio were the most active PfFabI inhibitory principles of the hexane extract (IC50 values 0.35 μg/ml). (E)-Oroidin isolated as free base (4a) was identified as the active component of the CHCl3 extract. Compound 4a was a more potent PfFabI inhibitor (IC50 0.30 μg/ml = 0.77 μM) than the (E)-oroidin TFA salt (4b), the active and major component of the aq MeOH extract (IC50 5.0 μg/ml). Enzyme kinetic studies showed 4a to be an uncompetitive PfFabI inhibitor (Ki: 0.4 ± 0.2 and 0.8 ± 0.2 μM with respect to substrate and cofactor). In addition, FAMA and FAMD (mainly consisting of methyl-branched fatty acids) inhibited FabI of Mycobacterium tuberculosis (MtFabI, IC50s 9.4 and 8.2 μg/ml, respectively) and Escherichia coli (EcFabI, IC50s 0.5 and 0.07 μg/ml, respectively). The majority of the compounds exhibited in vitro antiplasmodial, as well as trypanocidal and leishmanicidal activities without cytotoxicity towards mammalian cells. This study represents the first marine metabolites that inhibit FabI, a clinically relevant enzyme target from the FAS-II pathway of several pathogenic microorganisms.

Description: The Southern California Continental Borderland (SCCB) is part of the broad San Andreas transform-fault plate boundary that consists of a series of fault-bounded, petroleum-generating basins. The SCCB has high heat flow and geothermal gradients produced by thinned continental crust and Neogene volcanism. Barite deposits in the SCCB occur along faults. Barite samples from two sea-cliff sites and four offshore sites in the SCCB were analyzed for mineralogy, chemical (54 elements) and isotopic (S, Sr) compositions, and petrography. Barite from Palos Verdes (PV) Peninsula sea-cliff outcrops is hosted by the Miocene Monterey Formation and underlying basalt; carbonate rocks from those outcrops were analyzed for C, O, and Sr isotopes and the basalt for S isotopes. Cold-seep barite from Monterey Bay, California was analyzed for comparison. SCCB offshore samples occur at water depths from about 500 to 1800 m. Those barites vary significantly in texture and occurrence, from friable, highly porous actively growing seafloor mounds to dense, brecciated, vein barite. This latter type of barite contrasts with cold-seep barite in being much more coarse grained, forms thick veins in places, and completely replaced rock clasts in breccia. The barite samples range from 94 to 99 wt% BaSO4, with low trace-element contents, except for high Sr, Zr, Br, U, and Hg concentrations compared to their crustal abundances. δ34S for SCCB offshore barites range from 21.6‰ to 67.4‰, and for PV barite from 62‰ to 70‰. Pyrite from PV sea-cliff basalt and sedimentary rocks that host the barites averages 7.8‰ and 2.2‰, respectively. Two offshore barite samples have δ34S values (21.6‰, 22.1‰) close to that of modern seawater sulfate, whereas all other samples are enriched to strongly enriched in 34S. 87Sr/86Sr ratios for the barites vary over a narrow range of 0.70830–0.70856 and are much lower than that of modern seawater and also lower than the middle Miocene seawater ratio, the time of deposition of the host rocks for the PV samples. This indicates that the mineralizing fluids were not unaltered seawater. We develop a model in which the barites precipitated both below the sediment–water interface and at the seafloor from low-temperature fluids that circulated along faults. The isotopic, chemical, and textural data indicate that the barites formed by several processes. Mesozoic and Cenozoic basement rocks (crystalline and overlying sedimentary rocks), Quaternary basin fill, turbidite fans, and seawater provided various elements for the barites in different environments. The fluids had a deep-seated source and were hydrothermal in the deeper parts of the system for all the barite types, including the seafloor cold-seep deposit, based on Sr isotopes and regional geothermal gradients. These deep-seated fluids mixed with other fluids as they ascended, including seawater at and near the seafloor. The high δ34S values may have resulted from extreme Rayleigh fractionation during bacterially mediated (semi)closed-system sulfate reduction, probably driven by the flux of methane- and hydrocarbon-bearing fluids through basement rocks and basin sediments. Early diagenetic dolomite and pyrite in the host Monterey Formation in the PV Headland also formed in a zone of sulfate reduction, but within sediment buried only centimeters to a few meters and with a predominantly seawater source for the sulfur. Dolomite occurring with vein barite in the PV Headland formed at temperatures in the range of 40–90 °C. The cold-seep barites have δ34S values near that of modern seawater, although still somewhat fractionated. The barites that precipitated below the sediment–water interface have higher δ34S values, suggesting that the fluids were relatively reduced with molar dissolved barium in excess of dissolved sulfate. Those samples were exposed at the seafloor by uplift along faults and are composed predominantly of massive, brecciated, and vein barite.

Description: A multidisciplinary study in the Gulf of Cadiz is revisited, using additional diagnostic modelling tools. The dissolved trace metal (Cu, Ni, Zn, Co) distributions in the Gulf of Cadiz are analysed using modelled tracer evolutions, field observations and the concept of tracer ages. This study shows that a significant part of the observed metal distributions can be explained by the metal inputs of three river systems (Guadiana, Rio Tinto and Odiel, Guadalquivir) discharging into the Gulf of Cadiz, while the remainder of the signal is most likely associated with the benthic metal remobilisation along the shelf of this coastal region.

Description: There is a paucity of data on dissolved silver in the world's oceans and almost no data for European marine waters. The available data indicate that silver co-varies with silicate in oceanic environments, suggesting a link to biological processes. Nevertheless, silver is a highly toxic element. The main sources of silver for the marine environment derive from anthropogenic inputs, so silver can be used as a tracer for inputs of domestic and industrial pollution. Typical concentrations in seawater samples are very low (pmol/L). These low concentrations, combined with the complexity of the seawater-sample matrix, make the determination of silver in these samples extremely challenging. Developments in sensitive sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) instruments, combined with effective approaches for removal of the seawater matrix, have resulted in powerful analytical methods that can be used to overcome these challenges and help to improve our knowledge on the distribution, effect and fate of silver in the marine environment. This article briefly reviews the analytical techniques used for silver determination in seawater, and describes new trends in analyzing dissolved silver in seawater. © 2007 Elsevier Ltd. All rights reserved.

Description: Aerosol (soluble and total) iron and water-column dissolved (DFe, 〈 0.2 μm) and total dissolvable (TDFe, unfiltered) iron concentrations were determined in the Canary Basin and along a transect towards the Strait of Gibraltar, in order to sample across the Saharan dust plume. Cumulative dust deposition fluxes estimated from direct aerosol sampling during our one-month cruise are representative of the estimated deposition fluxes based on near surface water dissolved aluminium concentrations measured on board. Iron inventories in near surface waters combined with flux estimates confirmed the relatively short residence time of DFe in waters influenced by the Saharan dust plume (6-14 months). Enhanced near surface water concentrations of DFe (5.90-6.99 nM) were observed at the Strait of Gibraltar mainly due to inputs from metal-rich rivers. In the Canary Basin and the transect towards Gibraltar, DFe concentrations (0.07-0.76 nM) were typical of concentrations observed in the surface North Atlantic Waters, with the highest concentrations associated with higher atmospheric inputs in the Canary Basin. Depth profiles showed that DFe and TDFe were influenced by atmospheric inputs in this area with an accumulation of aeolian Fe in the surface waters. The sub-surface minimum of both DFe and TDFe suggests that a simple partitioning between dissolved and particulate Fe is not obvious there and that export may occur for both phases. At depths of around 1000-1300 m, both regeneration and Meddies may explain the observed maximum. Our data suggest that, in deep waters, higher particle concentrations likely due to dust storms may increase the scavenging flux and thus decrease DFe concentrations in deep waters. © 2007 Elsevier B.V. All rights reserved.

Description: The seismic trace is a complex aggregate of reflected and scattered signals from subsurface formation interfaces and heterogeneities. Although many varieties of random noise may also be present in the trace, we know from reacquiring the same seismic survey that seismic data are highly repeatable, indicating that significant information about the subsurface is contained in the trace but not yet used by our standard analysis methods. Seismic scattering is a type of signal contained in the data that is generally not utilized.

Description: Many stress–strain models have been developed for fibre-reinforced polymer (FRP)–confined concrete. These models fall into two categories: (a) design-oriented models in simple closed-form expressions for direct use in design; and (b) analysis-oriented models in which the stress–strain curve is generated via an incremental process. This paper is concerned with analysis-oriented models, and in particular, those models based on the commonly accepted approach in which a model for actively-confined concrete is used as the base model. The paper first provides a critical review and assessment of existing analysis-oriented models for FRP–confined concrete. For this assessment, a database of 48 recent tests conducted by the authors’ group is presented; this database includes 23 new tests which have not previously been published. This assessment clarifies how each of the key elements forming such a model affects its accuracy and identifies a recent model proposed by the authors’ group as being the most accurate. The paper then presents a refined version of this model, which provides more accurate predictions of the stress–strain behaviour, particularly for weakly-confined concrete.

Description: The precipitation of calcium carbonate as a binding salt for the consolidation of loose sand formations is a promising approach. The heterogeneous nucleation and growth of calcite were investigated in supersaturated solutions. The ionic activities in the solutions tested were selected so that they included both supersaturations in which crystal growth took place only following the introduction of seed particles and supersaturations in which precipitation occurred spontaneously past the lapse of induction times. In the latter case the supersaturation conditions were sufficiently low to allow the measurement of induction times preceding the onset of precipitation. The stability domain of the calcium carbonate system was established at pH 8.50, 25 °C, measuring the induction times in the range between 30 min and 2 h. The rates of precipitation following the destabilization of the solutions were measured from the pH and/or concentration–time profiles. The induction times were inversely proportional and rates proportional to the solution supersaturation as expected. The high-order dependence of the rates of precipitation on the solution supersaturation suggested a polynuclear growth mechanism. Fitting of the induction time–supersaturation data according to this model yielded a value of 64 mJ/m2 for the surface energy of the calcite nucleus. In the concentration domain corresponding to stable supersaturated solutions, seeded growth experiments at constant supersaturation showed a second-order dependence on the rates of crystal growth of calcite seed crystals. Inoculation of the stable supersaturated solutions with quartz seed crystals failed to induce nucleation. Raising supersaturation to reach the unstable domain showed interesting features: calcite seed crystals yielded crystal growth kinetics compatible with the polynuclear growth model, without any induction time. The presence of quartz seed crystals reduced the induction times and resulted in nucleation in the bulk solution. The kinetic data in the latter case were consistent with the polynuclear growth model and the surface energy for the newly forming embryo was calculated equal to 31.1 mJ/m2, because of the dominantly heterogeneous nature of the process.

Description: Determination of when and where animals feed and how much they consume is fundamental to understand their ecology and role in ecosystems. However, the lack of reliable data on feeding habits of wild animals, and particularly in marine endotherms, attests to the difficulty in doing this. A promising recent development proposes using a Hall sensor-magnet system, the inter-mandibular angle sensor (IMASEN) attached to animals’ jaws to elucidate feeding events. We conducted trials on captive pinnipeds by feeding IMASEN-equipped animals with prey to examine the utility of this system. Most feeding events were clearly distinguishable from other jaw movements; only small prey items might not be resolved adequately. Based on the results of this study we examined feeding events from free-ranging pinnipeds fitted with IMASENs and dead-reckoners and present data on prey capture and ingestion in relation to the three-dimensional movement patterns of the seals.

Description: Zoning patterns of An content and Fe, Mg and Sr concentrations in plagioclase phenocrysts in andesites from Parinacota Volcano (N. Chile) reflect alternating recharge events with two chemically distinct mafic magmas. These magmas are characterized by low and high Sr contents, similar to two recent mafic flank eruptions. One end-member basaltic andesite shows large Sr enrichment and Heavy Rare Earth depletions and thus equilibrated with lower-crustal rocks at depth where plagioclase (high Sr) is unstable, and garnet (high HREE, Y) is stable. A second end-member magma is lower in Sr, Ba contents and has REE patterns typical for parent magmas elsewhere in the Central Andes. The number of recorded recharge events increases after a catastrophic sector collapse and during the subsequent rebuilding of the stratocone. Variations of An, Fe and Mg contents and morphology of zones suggest also changes in water pressure, including decompression under water under-saturated and water-saturated conditions. Evidence for decompression is more present in post-collapse samples, suggesting that the change in the volcano dynamics involves changes in magma chamber location. This shows the importance of the cone collapse event in the volcano's magmatic evolution. We propose that both end-members are only seen at the surface of Parinacota Volcano because of the particular dynamics of this volcanic system and that similar processes might occur in other volcanic centres of the Central Volcanic Zone.

Description: Extensive explorations have been performed in the northern part of the island of Dugi Otok in the Adriatic Sea (Croatia) with the purpose of extraction of fresh and/or brackish water. The island is predominantly composed of karstified carbonate rocks of the Cretaceous age. The explorations included geological and hydrogeological mapping of the area, geophysical surveys (by means of the geoelectric tomography method, electrical resistivity sounding, and surface seismic refraction), exploratory core drilling, hydrochemical in situ and laboratory explorations, and the pumping test with the calculation of rock mass parameters. Based on the obtained results, it was concluded that it is possible to exploit the groundwater with a pumping quantity of 5 l/s without intrusion of salt water into the fresh-water lens. Choosing a pumping regime based on the parameters of the aquifer (rock mass hydraulic conductivity order of magnitude 10−4–10−6 m/s), and knowing the parameters of the well, as well as the tidal efficiency, should reduce the possibility of intrusion to the minimum. Because of the systematic quality of the performed explorations and obtained results, the island of Dugi Otok can serve as a typical example for such kinds of exploration works on other karstic islands. Hydrogeological composition behaves partly according to Ghyben–Herzberg‘s law, but because of the nature of the karstic hydrogeological system, such a statement needs to be accepted approximately because of the highly complicated relationships.

Description: Due to the high mortality rates and poor growth generally observed in Octopus vulgaris paralarval rearing experiments, it was decided to organize a working group in order to formulate recommendations to tackle this problem. Over a dozen scientists representing the most active current research groups related to this subject attended the meeting in Vigo, Spain, in November 2005. The aim of this working group was to determine the bottlenecks that prevent success in paralarval rearing, define the most appropriate rearing conditions, and identify required future research. This paper describes rearing techniques for the O. vulgaris paralarvae used by the different research participant teams, with regard to tank systems, feeding environment, and diets (Artemia, crustacean zoeae, sandeel flakes, copepods, etc.). Additionally, it includes other related themes such as the culture of Artemia and copepods, organisms that are commonly used in paralarval rearing. When embarking on O. vulgaris rearing it is advised to use prey rich in DHA (docosaenoic acid, 22:6n-3) and EPA (eicosapentaenoic acid, 20:5n-3), and with high DHA/EPA ratio. Such prey could be enriched Artemia, accompanied or not by crustacean zoeae or any microdiet. It is also recommended that, in future studies, values of growth and survival rates are recorded at the beginning of the benthic phase, in order to compare them to successful previous studies. Dry weight and DHA/EPA ratio of paralarvae may also be good criteria to define paralarval viability and evaluate success of the rearing system. It is further concluded that the nutritional aspect is the most important factor influencing larval mortality. Certain lipids (phospholipids, cholesterol, and polyunsaturated fatty acids), amino acids (lysine, leucine and arginine), and essential elements (e.g. copper) play a relevant role in the larval nutrition. It is believed that the PUFA content, especially DHA and EPA, constitutes one of the basic nutritional requirements. Regarding new research lines, no standardized system for paralarval rearing exists, and it is essential to make progress on this issue. Research on nutritional requirements is considered an area of highest priority, especially the development of a specific enrichment for Artemia, the search for alternative live preys, and the development of suitable formulated diets.

Description: Dissolved organic carbon (DOC) in the oceans is one of the largest dynamic carbon reservoirs on earth. The composition and fate of this carbon reservoir is of great interest to earth scientists, atmospheric scientists, and biologists who study global biogeochemical cycles and global warming. Current techniques for the extraction and purification of dissolved organic matter (DOM) from seawater for research purposes recover at best only 30 wt% of DOC. A new technique for the recovery of DOM from seawater has been developed by combining electrodialysis and reverse osmosis. Here we present shipboard results and laboratory work to show the feasibility of our technique. DOC recoveries exceeding 60% and even exceeding 90% for one seawater sample have been found. Analysis of samples recovered using this technique will yield new insights into the cycling of DOC in the oceans.

Description: We measured the presence, viability and potential toxicity of cyanobacteria in ships’ ballast tanks during three domestic voyages through the North American Great Lakes. Using molecular methods, the toxin-producing forms of Microcystis and Anabaena were monitored in ballast water after ships’ ballast tanks were filled at their first port of call, and at subsequent ports as ships transited the Great Lakes. Microcystis was detected in ballast water at intermediate and final ports of call in all three experiments, but the presence of Anabaena was more variable, suggesting low abundance or patchy distribution in ballast tanks. Both species were detected in ballast water up to 11 days old. Detection of the microcystin synthetase gene, mcyE, in ballast tanks indicated entrained cells were capable of producing microcystin, and further analyses of RNA indicated the toxin was being expressed by Microcystis, even after 11 days in dark transit. These data demonstrate within-basin transport and delivery of planktonic harmful algal bloom (HAB) species to distant ports in the world's largest freshwater reservoir, with potential implications for drinking water quality. These implications are discussed with respect to management of microbial invasions and the fate of introduced phytoplankton in their receiving environment.

Description: Ballast water was sampled on 12 occasions before and after an exchange process carried out in regional seas in order to assess the efficiency of this type of ballast water management at reducing the abundance and diversity of phytoplankton. Although there was an overall reduction in the average abundance and number of taxa after exchange this was not consistent between tanks and voyages. On some occasions there were changes in species composition after exchange and, in some cases, there were increases in potentially harmful species after the exchange process. Factors such as the depth of the water during the exchange process, the season and the method of exchange influenced the efficacy of the exchange process. The variability in the results after exchange mean that this is unlikely to be a ballast water management method that would give consistent results and careful consideration would have to be given to the suitability of using this method in regional seas as a means of reducing the risk of introducing non-native species.

Description: The current paper summarizes catch and effort data for Swedish fisheries in the Baltic Sea prior to the standardized recording of fish catches, evaluates spatial and temporal variations and gives interpretations of selected findings. Long-term datasets (1868–1913) of species having different environmental preferences (and of different origin) – marine, migratory and freshwater – are presented for several Swedish counties extending from the Bothnian Bay to the Bornholm Basin. Herring (Clupea harengus membras) was the most important commercial fish-based on landings and also on the amount of historical records available. In addition, herring landings have undoubtedly fluctuated the most. Other commercially important fish were cod (Gadus morhua), salmon and trout (Salmo spp.), flounder (Platichthys flesus), eel (Anguilla anguilla) and whitefish (Coregonus lavaretus). Different species exhibited different patterns of catch dynamics. In general, the 1880s and the 1890s can be characterized as ‘good fishing years’ for the Swedish Baltic fisheries: catches of herring and cod were high while fishing effort indices were relatively stable. Sprat was not represented in the catch data and may have been recorded as herring. For several species, regions and time periods, catch–effort relationship exhibited clear coupling. However, in several cases, insufficient or lack of effort-related information hampered data interpretations. In summary, the Swedish fisheries during the late 19th century generally exploited the same species as presently (including a dominance by clupeids), but the relative contributions of individual species have changed.

Description: Pb isotope systematics have already been used successfully to demonstrate that the lavas of the arc-basin terrains of the SW Pacific are derived from two mantle domains, one of Pacific-like character and the other of Indian-like character. However, the mobility of Pb during subduction and alteration has mainly restricted the fingerprinting of domains to fresh lavas of MORB composition. We demonstrate that the less alteration-sensitive Hf–Nd isotope projection also discriminates successfully between ‘Pacific’ and ‘Indian’ domains, and thus enables us to extend mantle domain fingerprinting to the back-arc basin basalts and boninites of the Lau and North Fiji Basins and the volcanic arc lavas of the Kermadec, Tonga and Vanuatu arcs. Fingerprinting is facilitated by the observation that the Hf isotope ratio is independent of subduction-input parameters, indicating that Hf has been essentially conservative during the subduction process. Subducted Nd has been added to the mantle source, but subtracting this numerically using the magnitude of negative Hf anomalies filters out the subduction effect. The data show that the ‘Indian’ domain provides the source for magmas erupted at ridges, and arcs near these ridges, that have propagated southwards following the 12 Ma collision of the Ontong-Java Plateau with the Vitiaz Trench. This indicates that the ‘Indian’ domain is actually derived from SOPITA mantle (South Pacific Isotopic and Thermal Anomaly) — mantle modified by the Samoa and other plumes outboard of the trench which only entered the SW Pacific arc-basin system after the Ontong-Java Plateau collision removed the slab barrier at 〈 12 Ma. In the west, mantle flows beneath the network of south-propagating ridges in the North Fiji and NW Lau Basins, undergoing progressive depletion until the final loss of plume components produces an N-MORB mantle (Indian MORB Mantle) composition in the south North Fiji Basin and Central Lau Spreading Centre. In the east, newly-depleted Samoan plume mantle provides the source for the boninites and depleted arc tholeiites of the northern Tonga arc.

Description: Filtration of ballast water was investigated as a means of minimizing the introduction of nonindigenous zooplankton and phytoplankton by ships visiting the North American Great Lakes-St. Lawrence Seaway system (GLSLSS). An automatic backwash screen filtration (ABSF) system with nominal filtration options of 25, 50 or 100 μm was mounted on the deck of an operating Seaway-sized dry bulk carrier, the MV Algonorth. Water was pumped through the ABSF with a deck mounted pump at 341 m3 hr−1 during routine ship operations in the GLSLSS, and effectiveness of the various screen pore sizes at removing taxonomic categories of zooplankton and phytoplankton was measured using matched treatment and control ballast tanks. The smallest pore sizes (25 and 50 μm) performed better than the 100 μm pore size at removing biological material. There was no difference in the filtration efficiency of the 25 and 50 μm screens relative to macro- or microzooplankton in these tests, but this result was probably due to low densities of macrozooplankton, and soft-bodied (aloricate) characteristics of the microzooplankton present. The 25 and 50 μm pore sizes were subjected to more controlled tests on board a stationary barge platform equipped with triplicate 700 L catchment bins moored in Duluth Harbor of Lake Superior. In these tests, filter pore size, organism size and rigidity influenced zooplankton removal efficiency by the ABSF. The 25 μm screen reduced both macrozooplankton and microzooplankton significantly more than the 50 μm screen. Zooplankton width was more determinative of filtration performance than length, and both filters removed loricate species of rotifers significantly more efficiently than aloricate species of the same length and width size classes. The 25 and 50 μm ABSF also significantly reduced algal densities, with the exception of colonial and filamentous green algae (50 μm only). Filter efficiency relative to algal particles was influenced by filter pore size, organism morphology and structure, and intake density, while algal particle size was not determinative. This research provides compelling evidence that 25 or 50 μm filtration is a potentially powerful means of reducing densities of organisms discharged by ships operating in the Great Lakes but an additional treatment step would be necessary to effectively minimize risk and meet the International Maritime Organization's discharge standards associated with organisms of all sizes in the water column.

Description: In this study, we examine the simulation results from the paleoclimate version of the National Center of Atmospheric Research coupled Climate System Model (CSM 1.4) for the Last Glacial Maximum (LGM) in order to understand changes in the South Atlantic (SA) circulation relative to the Present Day (PD). The LGM simulation is validated with the available proxy data in the region. The results show good agreement, except in the eastern equatorial and eastern SA region, where the model is not able to reproduce the correct cloud cover and the associated air–sea interactions. Ocean transport in the PD simulation is in good agreement with observational estimates. Results show that at subsurface levels there are two distinct patterns: (i) strengthening of the transport for the LGM in the southern SA (35°S to 25°S); and (ii) weakening of the mass transport in the northern SA (25°S to the Equator). In intermediate layers, there is an intensification of the subtropical gyre and a northward shift of the South Equatorial Current (SEC) bifurcation for the LGM. This leads to the intensification of the southward transport by the Brazil Current (BC) and the associated BC recirculation cell in the southern basin for the LGM. This shift in the position of the SEC bifurcation leads to a weakening in the northward transport and the western recirculation of the central SEC in the northern basin. This northward shift of the SEC (upper limit of the subtropical gyre) is consistent with the northward shift observed in the subtropical convergence zone and suggests a displacement of the sub-tropical gyre 3°–5° towards the Equator. In deeper layers, a shallower and weaker North Atlantic Deep Water (NADW) circulation in the LGM contributes to the reduction of the southward transport in the northern part of the basin and is associated with a greater northward intrusion of Antarctic Bottom Water. This intrusion plus the increase of the Indian Water inflow is responsible for the northward transport intensification in the southern basin.

Description: Seismic attribute analysis and interpretation of high-resolution 3D- and 2D-seismic data reveal focussed fluid flow processes through the gas hydrate stability zone (GHSZ) at the northern flank of the giant Storegga Slide. Diffusive fluid migration predominantly starts from a widespread polygonal fault system in fine-grained sediments of the Miocene Kai Formation. The overlying 600–700 m thick Plio–Pleistocene Naust Formation shows spatially related soft-sediment deformation and overlying fluid conduits. A low relief antiform structure connects to an overlying 250 m high, 300 m wide and 3 km elongated columnar zone, where seismic signatures suggest self-enhanced permeability, i.e. natural hydraulic fracturing. “Push-down” effects create an elongated depression caused by increased gas accumulations where a cluster of vertical cylindrical acoustic pipe structures originates. These pipe clusters pierce the GHSZ and indicate focussed fluid flow pathways originating from potentially overpressured sediments. High seismic reflection amplitudes at the seafloor above the pipe structures may indicate pockmarks with authigenic carbonates and/or gas hydrates. The observed objects and seismic features presented are not stand-alone indicators for fluid flow, but a joint perspective illustrates that they are vertically tied together providing new insights to the effects of focussed fluid flow.

Description: Porewater data from vent sites of the northeastern shelf off Sakhalin Island, Sea of Okhotsk, exhibit bottom-water concentrations down to a sediment depth of up to 300 cm. Below this depth, solute concentrations rapidly change due to methanogenesis and anaerobic methane oxidation (AMO). The profile shapes suggest an irrigation-like process that mixes on a meter scale. At these sites active gas emanation into the overlying water column and near-surface gas hydrates are commonly observed. We propose that methane gas bubbles rise through the soft surface sediments and cause mixing of the porewater. Mathematically, the bubble-induced irrigation can be described by eddy diffusion enhancing the diffusive transport of solutes by several orders of magnitude. A 3-D numerical transport-reaction model was developed to investigate the parameters defining the mixing process, such as bubble rise velocity, tube size, tube distribution in the sediment, and ebullition frequency. Model consistency with the field data requires eddy diffusivities ⩾1 × 105 cm2/a, tube densities of 〉4 tubes/m2 (equivalent to a tube spacing of 〈40 cm), active gas seepage for more than a few weeks or months, and moderate to low diagenetic reaction rates of solutes. The corresponding methane gas fluxes that are predicted from the results of the model realizations range from 1 × 103–5 × 105 L/(m2 a). Due to bubble mixing, solute fluxes in these sediments are increased by a factor of 3 and the maximum AMO rate by a factor of 7.

Description: The possible sources of pre-anthropogenic Pb contributed to the world's oceans have been the focus of considerable study. The role of eolian dust versus riverine inputs has been of particular interest. With better calibration of isotopic records from central Pacific ferromanganese crusts using Os isotope stratigraphy it now appears that deep water Pb isotopic compositions were effectively homogeneous over a distance of 5000 km for the past 80 Myr. The composition shifted slightly from high 206Pb/204Pb ratios in the range of 18.87 ± 0.02 before 65 Ma to lower values of 18.62 ± 0.02 by 45 Ma and then gradually increased again very slightly to the present day ratio of 18.67 ± 0.02. The regional homogeneity provides evidence of a dominant well-mixed atmospheric source the most likely candidate for which is volcanic aerosols contributed either directly or as soluble condensates on eolian dust. The slight shift in Pb isotope composition of deep waters in the central Pacific between 65 and 45 Ma may be the result of a regional- or perhaps global-scale change in the sources of volcanic exhalations and volcanic activity caused by an increase in the importance of melting and assimilation of older continental crustal components over the Cenozoic

Description: A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ44/40CaSW) over the Phanerozoic. The compiled δ44/40CaSW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations. A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ44/40CaSW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine 87Sr/86Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO2, discharge and erosion rates to estimate continental weathering fluxes. The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ44/40CaSW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite–aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ44/40CaSW. As to the causes of the short-term oscillations recorded in the secular δ44/40CaSW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.

Description: Boron and Pb isotopic compositions together with B–U–Th–Pb concentrations were determined for Pacific and Indian mantle-type mid-ocean ridge basalts (MORB) obtained from shallow drill holes near the Australian Antarctic Discordance (AAD). Boron contents in the altered samples range from 29.7 to 69.6 ppm and are extremely enriched relative to fresh MORB glass with 0.4–0.6 ppm B. Similarly the δ11B values range from 5.5‰ to 15.9‰ in the altered basalts and require interaction with a δ11B enriched fluid similar to seawater ∼ 39.5‰ and/or boron isotope fractionation during the formation of secondary clays. Positive correlations between B concentrations and other chemical indices of alteration such as H2O CO2, K2O, P2O5, U and 87Sr/86Sr indicate that B is progressively enriched in the basalts as they become more altered. Interestingly, δ11B shows the largest isotopic shift to + 16‰ in the least altered basalts, followed by a continual decrease to + 5–6‰ in the most altered basalts. These observations may indicate a change from an early seawater dominated fluid towards a sediment-dominated fluid as a result of an increase in sediment cover with increasing age of the seafloor. The progression from heavy δ11B towards lighter values with increasing degrees of alteration may also reflect increased formation of clay minerals (e.g., saponite). A comparison of 238U/204Pb and 206Pb/204Pb in fresh glass and variably altered basalt from Site 1160B shows extreme variations that are caused by secondary U enrichment during low temperature alteration. Modeling of the U–Pb isotope system confirms that some alteration events occurred early in the 21.5 m.y. history of these rocks, even though a significant second pulse of alteration happened at ∼ 12 Ma after formation of the crust. The U–Pb systematics of co-genetic basaltic glass and variably low temperature altered basaltic whole rocks are thus a potential tool to place age constraints on the timing of alteration and fluid flow in the ocean crust.

Description: Cosmopolitan nature of the marine bryozoan Electra pilosa was studied to clarify geographic structure and to outline evolution and phylogeography of the species. Several local populations from the Northeast Atlantic (North Sea and Baltic Sea), Arctic (Barents Sea and White Sea) and Indo-West Pacific (New Zealand) were compared. In addition, we examined the closely related species E. posidoniae from the Mediterranean Sea. Phylogenetic analysis based on both 16S and 18S rDNA indicate that the Indo-West Pacific E. pilosa is a sister species to the Atlantic–Mediterranean clade, with the latter including the species E. posidoniae and the Atlantic population of E. pilosa. The topology of the phylogenetic tree leads us to conclude that E. pilosa is a paraphyletic species group relative to E. posidoniae, and a molecular dating of its divergence is consistent to geologic events associated with the closure of the Tethys Sea.

Description: Bathymetric and conventional multichannel seismic surveys offshore Nicaragua and Costa Rica have revealed numerous mud mounds beneath which the generally widespread BSR is not well imaged. However, many of the mounds are partially capped by patches of authigenic carbonate crusts, so it was not clear if the semitransparent seismic facies and the apparent gaps in the BSR beneath the mounds are real or due to poor normal-incidence seismic penetration through the cap rocks. To address these problems, a high-resolution seismic survey was carried out over the continental slope of the Nicaraguan Pacific margin using a deep towed multichannel seismic streamer (DTMCS) along with a sidescan sonar system (DTS) to image submarine mud mounds and the associated BSR. The proximity of the very short (39 m active length) but high-resolution 17 channel streamer to the seafloor of the deep towed system allows greatly improved lateral resolution whereas the relatively large source-receiver offset allows the undershooting of the cap rocks. For the first time our data show that the BSR in many cases continues but rises beneath the mounds. This is consistent with the advection of deep warm fluids and thus increased heat flow through the mounds. The occurrence of mud mounds seems to be controlled by the locations of faults.

Description: Suboxic sapropel S1 sediments of the eastern Mediterranean carry an untypically light δ98/95Mo signal, being even lighter than oxic Mn-enriched sediments and Mn-crusts/nodules, which were previously thought to carry the lightest Mo isotope values. The evaluation and comparison of oxic S1, diagenetically overprinted oxic S1, and suboxic S1 sediments indicates that this light isotope signal is primarily an oxic signal that has been overprinted by secondary diagenetic processes occurring after sediment burial. Such secondary processes bear the potential of additional Mo isotope fractionation in particular in non-steady state diagenetic environments that involve the discontinuous re-location of the redox boundary.

Description: Elevated concentrations of dioxins in ancient ball clay from the Mississippi Embayment suggest natural formation of dioxins in the environment. Evidence for such natural formation in ball clay derives from unique congener profiles in undisturbed ancient clay deposits and from the lack of other anthropogenic contaminants. Here we present novel evidence of natural formation of dioxins based on congener-specific carbon isotopic analysis of octachlorodibenzo-p-dioxin (OCDD) in ball clays from the USA and Japan. The analyses were performed using a combination of double-column high performance liquid chromatography clean-up and two-dimensional gas chromatography–isotope ratio mass spectrometry. Elevated concentrations of OCDD found in ball clays from the USA and Japan were isotopically distinguished from the anthropogenic source materials (fly ash and pentachlorophenol) and environmental samples (sediment and soil). The isotopic signatures and the occurrence of OCDD in ancient ball clays deposited in the Tertiary Era provide evidence for the in situ formation of dioxins.

Description: High precision measurements of 226Ra–230Th–238U disequilibria and Ba concentrations are reported for samples from two chemically zoned trachyte deposits from Fogo volcano, São Miguel, Azores. High-precision U-series disequilibria measurements by plasma ionization multicollector mass spectrometry were performed on pumice lapilli and volcanic glass separates from Fogo 1563 A.D. (∼ 0.14 km3) and the ∼ 4.7 ka Fogo A (∼ 0.7 km3) deposits in order to quantify the time scales of magmatic processes. Observed (226Ra)/Ba–(230Th)/Ba relationships in Fogo 1563 are compatible with a conventional instantaneous fractional crystallization model and a pre-eruptive magma residence time of ∼ 50 y. However, the Fogo A data cannot be explained by instantaneous fractional crystallization, and require a prolonged crystallization history. Continuous differentiation models better explain the observed 226Ra–230Th variations within the Fogo deposits and may be more realistic in general. Such models suggest magma residence times prior to eruption of ∼ 50–80 years for Fogo 1563, and ∼ 4.7 ka for the larger volume Fogo A eruption. These time scales represent liquid residence ages rather than the crystallization ages documented in most previous magmatic time scale studies, and allow constraints to be placed on the time scales necessary for the development of chemical zonation within the Fogo magma chamber. Our results indicate that calculated time scales are relatively insensitive to the precise nature of the continuous differentiation models, and further indicate that meaningful magma differentiation time scales can be obtained despite open system behavior, because the Ra–Th disequilibria are overwhelmingly controlled by feldspar fractionation. Calculated time scales are, however, extremely sensitive to DRa/DBa ratios. We therefore emphasize the crucial importance to better constrain the relative partitioning of Ra and Ba when employing Ra–Th disequilibrium data to constrain the rates and time scales of igneous processes.

Description: We estimate the effective elastic thickness (Te) along the Deccan–Reunion hotspot track using admittance analysis of seafloor topography and the free-air gravity field, both corrected for the thermal effects of a cooling lithosphere. Our results reveal that the volcanic edifices (Saya de Malha Bank, Chagos–Maldives–Laccadives Ridge) formed in the first 30 Myr after the Deccan volcanism [not, vert, similar 65 Myr], on lithosphere with Te values of 4 ± 2 km, while the younger volcanic edifices on the African plate (Reunion, Mauritius, Nazareth Bank) were emplaced on lithosphere with Te values of 17 ± 9 km. These estimates suggest that the hotspot volcanism occurred on juvenile lithosphere in the first 30 Myr, implying that the mid-ocean ridge remained near the hotspot for not, vert, similar 30 Myr. In contrast, in the last 30 Myr volcanism occurred on aged lithosphere in an intraplate setting, which might indicate that the mid-ocean ridge migrated rapidly to the north after the African plate moved over the hotspot. This conclusion of a rapid shift from plume-influenced mid-ocean ridge (MOR) volcanism to intraplate plume volcanism is supported by geochemical (major and trace element) interpretations of data from Ocean Drilling Program (ODP) Leg 115. An estimate of the melt-production rate shows a striking increase in the small Te region relative to the large Te region of the hotspot track, which suggest a strong interrelation between Te and melt production. However, there is also variation of melt emplacement rates within the region of low Te that may be due to unknown changes in the rates of plate motions or somewhat episodic melt production.

Description: Water transported within the subducting oceanic lithosphere into the Earth's interior affects a wealth of subduction zone processes, including intraslab earthquakes and arc magmatism. In recent years growing evidence suggests that much of the hydration of oceanic plates occurs at the trench–ocean slope right before subduction. Here, normal faults are created while the rigid lithosphere bends into the trench. Offshore of Middle America, multi-channel seismic reflection imaging suggests that bending-related faults cut into the uppermost mantle, providing a mechanism for hydration and transformation of mantle peridotites into serpentinites. Seismic wide-angle reflection and refraction data were collected coincident with one of the seismic profiles where the faults have been imaged. Travel time inversion provides evidence that both crustal and uppermost mantle velocities are reduced with respect to the velocity structure found in mature oceanic crust away from deep-sea trenches. If mantle velocity reduction is solely produced by hydration, velocities indicate 10–15% of serpentinization in the uppermost 3 km of the mantle, where seismic data provide enough resolution. A small network of ocean bottom hydrophones, deployed for about a month, detected ∼ 3 local micro earthquakes per day. Earthquake epicentres align with fault scarps at the seafloor and continuous earthquake activity might be an important process to facilitate the percolation of seawater into the upper mantle.

Description: TOPO-EUROPE addresses the 4-D topographic evolution of the orogens and intra-plate regions of Europe through a multidisciplinary approach linking geology, geophysics, geodesy and geotechnology. TOPO-EUROPE integrates monitoring, imaging, reconstruction and modelling of the interplay between processes controlling continental topography and related natural hazards. Until now, research on neotectonics and related topography development of orogens and intra-plate regions has received little attention. TOPO-EUROPE initiates a number of novel studies on the quantification of rates of vertical motions, related tectonically controlled river evolution and land subsidence in carefully selected natural laboratories in Europe. From orogen through platform to continental margin, these natural laboratories include the Alps/Carpathians–Pannonian Basin System, the West and Central European Platform, the Apennines–Aegean–Anatolian region, the Iberian Peninsula, the Scandinavian Continental Margin, the East-European Platform, and the Caucasus–Levant area. TOPO-EUROPE integrates European research facilities and know-how essential to advance the understanding of the role of topography in Environmental Earth System Dynamics. The principal objective of the network is twofold. Namely, to integrate national research programs into a common European network and, furthermore, to integrate activities among TOPO-EUROPE institutes and participants. Key objectives are to provide an interdisciplinary forum to share knowledge and information in the field of the neotectonic and topographic evolution of Europe, to promote and encourage multidisciplinary research on a truly European scale, to increase mobility of scientists and to train young scientists. This paper provides an overview of the state-of-the-art of continental topography research, and of the challenges to TOPO-EUROPE researchers in the targeted natural laboratories

Description: Late Glacial to Holocene ice retreat was investigated along a 120 km long fjord system, reaching from Gran Campo Nevado (GCN) to Seno Skyring in the southernmost Andes (53°S). The aim was to improve the knowledge on regional and global control on glacier recession with special emphasis on latitudinal shifting of the westerlies. The timing of ice retreat was derived from peat and sediment cores, using mineralogical and chemical characteristics, and pollen as proxies. Stratigraphy was based on 14C-AMS ages and tephrochronology. The ice retreat of the Seno Skyring Glacier lobe is marked by an ice rafted debris layer which was formed around 18,300 to 17,500 cal. yr B.P. Subsequently, fast glacier retreat occurred until around 15,000 to 14,000 cal. yr B.P. during which around 84% of Skyring Glacier were lost. This fast recession was probably also triggered by an increase of the Equilibrium Line Altitude (ELA) from 200 to 300 m. Subsequently, the ice surface was lowered below the ELA in an area that previously made up more than 50% of the accumulation area. Much slower retreat and glacier fluctuations of limited extent in the fjord channel system northeast of GCN occurred between around 14,000 to 11,000 cal. yr B.P. during both the Antarctic Cold Reversal and the Younger Dryas. This slow down of retreat indicates a decline in the general warming trend and/or increased precipitation, due to a southward migration of the westerlies. After around 11,000 cal. yr B.P. pollen distribution shows evolved Magellanic Rainforest and similar climate as at present, which lasted throughout most of the Holocene. Only Late Neoglacial moraine systems were formed in the period 1220–1460 AD, and subsequently in the 1620s AD, and between 1870 and 1910 AD. The results indicate that the Gran Campo Nevado ice cap has reacted more sensitive and partly distinct to climate change, compared to the Patagonian Ice Field.

Description: The extraction of a deepwater radiogenic isotope signal from marine sediments is a powerful, though under-exploited, tool for the characterisation of past climates and modes of ocean circulation. The radiogenic and radioactive isotope compositions (Nd, Pb, Th) of ambient deepwater are stored in authigenic Fe–Mn oxyhydroxide coatings in marine sediments, but the unambiguous separation of the isotopic signal in this phase from other sedimentary components is difficult and measures are needed to ensure its seawater origin. Here the extracted Fe–Mn oxyhydroxide phase is investigated geochemically and isotopically in order to constrain the potential and the limitations of the reconstruction of deepwater radiogenic isotope compositions from marine sediments. Our results show that the isotope compositions of elements such as Sr and Os obtained from the Fe–Mn oxyhydroxide fraction are easily disturbed by detrital contributions originating from the extraction process, whereas the seawater isotope compositions of Nd, Pb and Th can be reliably extracted from marine sediments in the North Atlantic. The main reason is that the Nd, Pb and Th concentrations in the detrital phase of pelagic sediments are much lower than in the Fe–Mn oxyhydroxide fractions. This is reflected in Al/Nd, Al/Pb and Al/Th ratios of the Fe–Mn oxyhydroxide fractions, which are as low as or even lower than those of hydrogenetic ferromanganese crusts. Mass balance calculations illustrate that the use of the 87Sr/86Sr isotope composition to confirm the seawater origin of the extracted Nd, Pb and Th isotope signals is misleading. Even though the 87Sr/86Sr in the Fe–Mn oxyhydroxide fractions is often higher than the seawater Sr isotope composition, the corresponding detrital contribution does not translate into altered seawater Nd, Pb and Th isotope compositions due to mass balance constraints. Overall the rare earth element patterns, elemental ratios, as well as the mass balance calculations presented here highlight the potential of using authigenic Fe–Mn oxyhydroxide coatings as paleoceanographic archives for the analysis of past seawater Nd, Pb and Th isotope compositions.

Description: Iron is limiting phytoplankton productivity in large parts of today's oceans, the so-called HNLC (high nutrient low chlorophyll) areas. It is a key component in photosynthesis during which inorganic carbon fixation in most phytoplankton species is sustained by so-called carbon concentrating mechanisms (CCMs). Here we investigate CCM regulation in the coccolithophore Emiliania huxleyi in response to varying degrees of iron limitation by means of membrane-inlet mass spectrometry. Compared to iron replete conditions rates of both active CO2 and HCO-3 uptake were markedly reduced under iron limitation leading to significantly diminished growth rates. Moreover, there was a concomitant decrease in CCM efficiency, reflected in an increased CO2 loss from the cell in relation to carbon fixation. Under such conditions higher values for carbon isotope fractionation (∈P) would be expected. However, direct measurements of ∈P showed that carbon isotope fractionation was insensitive to changes in growth rates and CCM activity. This can be explained by concomitant changes in internal DIC fluxes in and out of the chloroplast as demonstrated with a simple cell model comprising two compartments. Thus, carbon isotope fractionation reflects the ability of phytoplankton to actively control their inorganic carbon acquisition depending on environmental conditions. The insensitivity of carbon isotope fractionation to changes in the availability of iron could be of interest for paleoreconstructions in the HNLC areas of today's oceans.

Description: The effect of phytoplankton cell size on the variation of nutrient uptake and exudation rates is examined: we first present an overview of the relationship between the variation of the growth and loss parameters and cell size. We then investigate the effect of cell-size-dependent parameters on the development of an entire phytoplankton community by means of a numerical, vertically resolved nutrient phytoplankton model. The model represents phytoplankton size distributions in three different ways, namely one configuration with explicit representation of 14 size classes, one configuration with constant-slope power-law spectral representation, and one configuration with variable-slope power-law spectral representation. The size-dependent configurations are further compared to a size-independent configuration. Consistent with theory, the explicit and variable-slope spectral model simulations predict increased importance of larger cells, or "flat" size distribution under conditions of low light and high nutrients, while smaller cells ("steep" size distributions) may dominate in oligotrophic, well-lit regimes. In some situations the variable-slope spectral model seems to be sufficient to reflect the phytoplankton size distribution; however, especially in the deep phytoplankton maximum a unimodal rather than power-law spectral description might be more appropriate to reproduce results of the explicit 14-size-class model. The assumption of a fixed spectral slope, according to which larger size classes gain importance especially during bloom periods, is not consistent with the underlying theory, and does not agree with the results of the size-discrete model. The comparison of model predictions with variations of phytoplankton size distribution observed in the field is hampered by the sparsity of data, especially for the winter season. A half-saturation constant that represents the nutrient uptake of the entire phytoplankton community (K*) compares well to published values. (C) 2007 Elsevier Ltd. All rights reserved.