Assessment of marine litter in the Western Adriatic Sea and its impact on marine biota

Due to its environmental, safety, health and socio-economic impacts, marine litter has been recognized as a 21st century global challenge, so that it has been included in Descriptor 10 of the EU MSFD. For its morphological features and anthropogenic pressures, the Adriatic Sea is very sensitive to the accumulation of debris, but data are inconsistent and fragmented. This thesis, in the framework of DeFishGear project, intents to assess marine litter on beaches and on seafloor in the Western Adriatic sea, and test if debris ingestion by fish occurs. Three beaches were sampled during two surveys in 2015. Benthic litter monitoring was carried out in the FAO GSA17 during fall 2014, using a rapido trawl. Litter ingestion was investigated through gut contents analysis of 260 fish belonging to 8 commercial species collected in Western Gulf of Venice. Average litter density on beaches was 1.5 items/m2 during spring, and decreased to 0.8 items/m2 in summer. Litter composition was heterogeneous and varied among sites, even if no significant differences were found. Most of debris consisted of plastic sheets, fragments, polystyrene pieces, mussels nets and cottons bud sticks, showing that sources are many and include aquaculture, land-based activities and local users of beaches. Average density of benthic litter was 913 items/Km2 (82 Kg/Km2). Plastic dominated in terms of numbers and weight, and consisted mainly of bags, sheets and mussel nets. The highest density was found close to the coast, and sources driving the major differences in litter distribution were mussel farms and shipping lanes. Litter ingestion occurred in 47% of examined fish, mainly consisting of fibers. Among species, S. pilchardus swallowed almost all debris categories. Findinds may provide a baseline to set the necessary measures to manage and minimize marine litter in the Western Adriatic region and to protect aquatic life from plastic pollution, even accounting the possible implications on human health.

Comparison of iron isotope variations in modern and Ordovician siliceous Fe oxyhydroxide deposits

Formation pathways of ancient siliceous iron formations and related Fe isotopic fractionation are still not completely understood. Investigating these processes, however, is difficult as good modern analogues to ancient iron formations are scarce. Modern siliceous Fe oxyhydroxide deposits are found at marine hydrothermal vent sites, where they precipitate from diffuse, low temperature fluids along faults and fissures on the seafloor. These deposits exhibit textural and chemical features that are similar to some Phanerozoic iron formations, raising the question as to whether the latter could have precipitated from diffuse hydrothermal fluids rather than from hydrothermal plumes. In this study, we present the first data on modern Fe oxyhydroxide deposits from the Jan Mayen hydrothermal vent fields, Norwegian-Greenland Sea. The samples we investigated exhibited very low δ56Fe values between -2.09‰ and -0.66‰. Due to various degrees of partial oxidation, the Fe oxyhydroxides are with one exception either indistinguishable from low-temperature hydrothermal fluids from which they precipitated (-1.84‰ and -1.53‰ in δ56Fe) or are enriched in the heavy Fe isotopes. In addition, we investigated Fe isotope variations in Ordovician jasper beds from the Løkken ophiolite complex, Norway, which have been interpreted to represent diagenetic products of siliceous ferrihydrite precursors that precipitated in a hydrothermal plume, in order to compare different formation pathways of Fe oxyhydroxide deposits. Iron isotopes in the jasper samples have higher δ56Fe values (-0.38‰ to +0.89‰) relative to modern, high-temperature hydrothermal vent fluids (ca. -0.40‰ on average), supporting the fallout model. However, formation of the Ordovician jaspers by diffuse venting cannot be excluded, due to lithological differences of the subsurface of the two investigated vent systems. Our study shows that reliable interpretation of Fe isotope variations in modern and ancient marine Fe oxyhydroxide deposits depends on comprehensive knowledge of the geological context. Furthermore, we demonstrate that very negative δ56Fe values in such samples might not be the result of microbial dissimilatory iron reduction, but could be caused instead by inorganic reactions.

Projected pH reductions by 2100 might put deep North Atlantic biodiversity at risk

This study aims to evaluate the potential for impacts of ocean acidification on North Atlantic deep-sea ecosystems in response to IPCC AR5 Representative Concentration Pathways (RCPs). Deep-sea biota is likely highly vulnerable to changes in seawater chemistry and sensitive to moderate excursions in pH. Here we show, from seven fully coupled Earth system models, that for three out of four RCPs over 17% of the seafloor area below 500 m depth in the North Atlantic sector will experience pH reductions exceeding −0.2 units by 2100. Increased stratification in response to climate change partially alleviates the impact of ocean acidification on deep benthic environments. We report on major pH reductions over the deep North Atlantic seafloor (depth >500 m) and at important deep-sea features, such as seamounts and canyons. By 2100, and under the high CO2 scenario RCP8.5, pH reductions exceeding −0.2 (−0.3) units are projected in close to 23% (~15%) of North Atlantic deep-sea canyons and ~8% (3%) of seamounts – including seamounts proposed as sites of marine protected areas. The spatial pattern of impacts reflects the depth of the pH perturbation and does not scale linearly with atmospheric CO2 concentration. Impacts may cause negative changes of the same magnitude or exceeding the current target of 10% of preservation of marine biomes set by the convention on biological diversity, implying that ocean acidification may offset benefits from conservation/management strategies relying on the regulation of resource exploitation.

Fluid-related inclusions in Alpine high-pressure peridotite reveal trace element recycling during subduction-zone dehydration of serpentinized mantle (Cima di Gagnone, Swiss Alps).

Serpentinites release at sub-arc depths volatiles and several fluid-mobile trace elements found in arc magmas. Constraining element uptake in these rocks and defining the trace element composition of fluids released upon serpentinite dehydration can improve our understanding of mass transfer across subduction zones and to volcanic arcs. The eclogite-facies garnet metaperidotite and chlorite harzburgite bodies embedded in paragneiss of the subduction melange from Cima di Gagnone derive from serpentinized peridotite protoliths and are unique examples of ultramafic rocks that experienced subduction metasomatism and devolatilization. In these rocks, metamorphic olivine and garnet trap polyphase inclusions representing the fluid released during high-pressure breakdown of antigorite and chlorite. Combining major element mapping and laser-ablation ICP-MS bulk inclusion analysis, we characterize the mineral content of polyphase inclusions and quantify the fluid composition. Silicates, Cl-bearing phases, sulphides, carbonates, and oxides document post-entrapment mineral growth in the inclusions starting immediately after fluid entrapment. Compositional data reveal the presence of two different fluid types. The first (type A) records a fluid prominently enriched in fluid-mobile elements, with Cl, Cs, Pb, As, Sb concentrations up to 10(3) PM (primitive mantle), similar to 10(2) PM Tit Ba, while Rb, B, Sr, Li, U concentrations are of the order of 10(1) PM, and alkalis are similar to 2 PM. The second fluid (type B) has considerably lower fluid-mobile element enrichments, but its enrichment patterns are comparable to type A fluid. Our data reveal multistage fluid uptake in these peridotite bodies, including selective element enrichment during seafloor alteration, followed by fluid-rock interaction along with subduction metamorphism in the plate interface melange. Here, infiltration of sediment-equilibrated fluid produced significant enrichment of the serpentinites in As, Sb, B, Pb, an enriched trace element pattern that was then transferred to the fluid released at greater depth upon serpentine dehydration (type A fluid). The type B fluid hosted by garnet may record the composition of the chlorite breakdown fluid released at even greater depth. The Gagnone study-case demonstrates that serpentinized peridotites acquire water and fluid-mobile elements during ocean floor hydration and through exchange with sediment-equilibrated fluids in the early subduction stages. Subsequent antigorite devolatilization at subarc depths delivers aqueous fluids to the mantle wedge that can be prominently enriched in sediment-derived components, potentially triggering arc magmatism without the need of concomitant dehydration/melting of metasediments or altered oceanic crust.

UHP Metamorphism Documented in Ti-chondrodite- and Ti-clinohumite-bearing Serpentinized Ultramafic Rocks from Chinese Southwestern Tianshan

The southwestern Tianshan (China) metamorphic belt records high-pressure (HP) to ultrahigh-pressure (UHP) conditions corresponding to a cold oceanic subduction-zone setting. Serpentinites enclosing retrogressed eclogite and rodingite occur as lenses within metapelites in the UHP unit, which also hosts coesite-bearing eclogites. Based on the petrology and petrography of these serpentinites, five events are recognized: (1) formation of a wehrlite–harzburgite–dunite association in the mantle; (2) retrograde metamorphism and partial hydration during exhumation of the mantle rocks close to the seafloor; (3) oceanic metamorphism leading to the first serpentinization and rodingitization; (4) UHP metamorphism during subduction; (5) retrograde metamorphism during exhumation together with a second serpentinization. The peak metamorphic mineral assemblage of the serpentinized wehrlite comprises Ti-chondrodite + olivine + antigorite + chlorite + magnetite + brucite. A computed pseudosection for this serpentinized wehrlite shows that the Al content in antigorite is mostly sensititive to temperature but can also be used to constrain pressure. The average XAl = 0·204 ± 0·026 of antigorite (XAl = Al (a.p.f.u.)/8, where Al is in atoms per formula unit for a structural formula M48T34O85(OH)62, and M and T are octahedral and tetrahedral sites, respectively) included in Ti-chondrodite and average XAl = 0·203 ± 0·019 of antigorite in the matrix result in a well-constrained peak metamorphic temperature of 510–530°C. Peak pressures are less precisely constrained at 37 ± 7 kbar. The Tianshan serpentinites thus record UHP metamorphic conditions and represent the deepest subducted serpentinites discovered so far. The retrograde evolution occurs within the stability field of brucite + antigorite + olivine + chlorite and formation of Ti-clinohumite at the expense of Ti-chondrodite has been observed, suggesting isothermal decompression. The resulting P–T path is in excellent agreement with the metamorphic evolution of country rocks, indicating that the UHP unit in Tianshan was subducted and exhumed as a coherent block. To refine the metamorphic path of the ultramafic rocks, we have investigated the stability fields of Ti-chondrodite and Ti-clinohumite using piston-cylinder experiments. A total of 11 experiments were conducted at 25–55 kbar and 600–750°C in a F-free natural system. Combined with previous experiments and information from natural rocks we constructed a petrogenetic grid for the stability of Ti-chondrodite and Ti-clinohumite in F-free peridotite compositions. The formation of Ti-chondrodite in serpentinites requires a minimum pressure of about 26 kbar, whereas in Ti-rich systems it can form at considerably lower pressures. A key finding is that at UHP conditions, F-free Ti-chondrodite or Ti-clinohumite breaks down in the presence of orthopyroxene between 700 and 750°C, at temperatures that are significantly lower than those of the terminal breakdown reactions of these humite minerals. These breakdown reactions are an additional source of fluid during prograde subduction of serpentinites.

Dating prograde fluid pulses during subduction by in situ U–Pb and oxygen isotope analysis

Keywords High-pressure fluids · Whiteschists · U–Pb dating · Oxygen isotopes · Ion microprobe · Metasomatism Introduction The subduction of crustal material to mantle depths and its chemical modification during burial and exhumation contribute to element recycling in the mantle and the formation of new crust through arc magmatism. Crustal rocks that Abstract The Dora-Maira whiteschists derive from metasomatically altered granites that experienced ultrahighpressure metamorphism at ~750 °C and 40 kbar during the Alpine orogeny. In order to investigate the P–T–time– fluid evolution of the whiteschists, we obtained U–Pb ages from zircon and monazite and combined those with trace element composition and oxygen isotopes of the accessory minerals and coexisting garnet. Zircon cores are the only remnants of the granitic protolith and still preserve a Permian age, magmatic trace element compositions and δ18O of ~10 ‰. Thermodynamic modelling of Si-rich and Si-poor whiteschist compositions shows that there are two main fluid pulses during prograde subduction between 20 and 40 kbar. In Si-poor samples, the breakdown of chlorite to garnet + fluid occurs at ~22 kbar. A first zircon rim directly overgrowing the cores has inclusions of prograde phlogopite and HREE-enriched patterns indicating zircon growth at the onset of garnet formation. A second main fluid pulse is documented close to peak metamorphic conditions in both Si-rich and Si-poor whiteschist when talc + kyanite react to garnet + coesite + fluid. A second metamorphic overgrowth on zircon with HREE depletion was observed in the Si-poor whiteschists, whereas a single metamorphic overgrowth capturing phengite and talc inclusions was observed in the Si-rich whiteschists. Garnet rims, zircon rims and monazite are in chemical and isotopic equilibrium for oxygen, demonstrating that they all formed at peak metamorphism at 35 Ma as constrained by the age of monazite (34.7 ± 0.4 Ma) and zircon rims (35.1 ± 0.8 Ma). The prograde zircon rim in Si-poor whiteschists has an age that is within error indistinguishable from the age of peak metamorphic conditions, consistent with a minimum rate of subduction of 2 cm/year for the Dora-Maira unit. Oxygen isotope values for zircon rims, monazite and garnet are equal within error at 6.4 ± 0.4 ‰, which is in line with closed-system equilibrium fractionation during prograde to peak temperatures. The resulting equilibrium Δ18Ozircon-monazite at 700 ± 20 °C is 0.1 ± 0.7 ‰. The in situ oxygen isotope data argue against an externally derived input of fluids into the whiteschists. Instead, fluidassisted zircon and monazite recrystallisation can be linked to internal dehydration reactions during prograde subduction. We propose that the major metasomatic event affecting the granite protolith was related to hydrothermal seafloor alteration post-dating Jurassic rifting, well before the onset of Alpine subduction.

Cold-Water Coral Distributions in the Drake Passage Area from Towed Camera Observations - Initial Interpretations

Seamounts are unique deep-sea features that create habitats thought to have high levels of endemic fauna, productive fisheries and benthic communities vulnerable to anthropogenic impacts. Many seamounts are isolated features, occurring in the high seas, where access is limited and thus biological data scarce. There are numerous seamounts within the Drake Passage (Southern Ocean), yet high winds, frequent storms and strong currents make seafloor sampling particularly difficult. As a result, few attempts to collect biological data have been made, leading to a paucity of information on benthic habitats or fauna in this area, particularly those on primarily hard-bottom seamounts and ridges. During a research cruise in 2008 six locations were examined (two on the Antarctic margin, one on the Shackleton Fracture Zone, and three on seamounts within the Drake Passage), using a towed camera with onboard instruments to measure conductivity, temperature, depth and turbidity. Dominant fauna and bottom type were categorized from 200 randomized photos from each location. Cold-water corals were present in high numbers in habitats both on the Antarctic margin and on the current swept seamounts of the Drake Passage, though the diversity of orders varied. Though the Scleractinia (hard corals) were abundant on the sedimented margin, they were poorly represented in the primarily hard-bottom areas of the central Drake Passage. The two seamount sites and the Shackleton Fracture Zone showed high numbers of stylasterid (lace) and alcyonacean (soft) corals, as well as large numbers of sponges. Though data are preliminary, the geological and environmental variability (particularly in temperature) between sample sites may be influencing cold-water coral biogeography in this region. Each area observed also showed little similarity in faunal diversity with other sites examined for this study within all phyla counted. This manuscript highlights how little is understood of these isolated features, particularly in Polar regions.

Noble metal abundances in ODP Leg 115 basalts (Table 1)

A comparison of 50 basalts recovered at Sites 706, 707, 713, and 715 along the Reunion hotspot trace during Ocean Drilling Program Leg 115 in the Indian Ocean shows that seafloor alteration had little effect on noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir), determined by inductively coupled plasma-mass spectrometry (ICP-MS), which generally tend to decrease with magma evolution. Their compatible-element behavior may be related to the precipitation of Ir-Os-based alloys, chromite, sulfides, and/or olivine and clinopyroxene in some combination. The simplest explanation indicates silicate control of concentrations during differentiation. Basalts from the different sites show varying degrees of alkalinity. Noble metal abundances tend to increase with decreasing basalt alkalinity (i.e., with increasing percentages of mantle melting), indicating that the metals behave as compatible elements during mantle melting. The retention of low-melting-point Au, Pd, and Rh in mantle sulfides, which mostly dissolve before significant proportions of Ir-Os-based alloys melt, explains increasing Pd/Ir ratios with decreasing alkalinity (increasing melting percentages) in oceanic basalts. High noble metal concentrations in Indian Ocean basalts (weighted averages of Au, Pd, Rh, Pt, Ru, and Ir in Leg 115 basalts are 3.2, 8.1, 0.31, 7.3, 0.22, and 0.11 ppb, respectively), compared with basalts from some other ocean basins, may reflect fundamental primary variations in upper- mantle noble metal abundances

Petrology and geochemistry at DSDP Site 89-462

The 16 samples of Deep Sea Drilling Project (DSDP) Leg 89 basalts that we analyzed for whole rock major and trace elements and for mineralogic compositions are identical to some of the basalts recovered during Leg 61. Leg 89 samples are mostly olivine-plagioclase-clinopyroxene sparsely phyric basalts and exhibit a wide variety of textures. These basalts have lower TiO2 at a given Mg/(Mg+Fe2+)*100 than MORB (midocean ridge basalt). We recognize three major chemical types of basalts in the Nauru Basin. We believe that different degrees of partial melting, modified by fractional crystallization and possibly by magma mixing at shallow depths, can explain the chemical differences among the three groups. This petrogenetic model is consistent with the observed downhole chemical-chronostratigraphic relations of the samples. New 87Sr/86Sr and U3Nd/144Nd analyses of basalt samples from DSDP Site 462 indicate that the Nauru Basin igneous complex is within the Sr-Nd isotopic range of ocean island basalt. Thus the Nauru Basin igneous complex resembles MORB in many aspects of its chemistry, morphology, and secondary alteration patterns (Larson, Schlanger, et al., 1981), but not in its isotopic characteristics. If it were not for the unambiguous evidence that the Nauru Basin complex was erupted off-ridge, the complex could easily be interpreted as normal oceanic layer 2. For this reason, we speculate that the Nauru Basin igneous complex was produced in an oceanic riftlike environment when multiple, fast-propagating rifts were formed during the fast seafloor spreading episode in the Cretaceous.

Organic geochemistry of sediments from North Alex Mud Vulcano

Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF) where seepage into the bottom water has been observed at several mud volcanoes (MVs) including North Alex MV (NAMV). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of d13C ~-46.6 per mil VPDB and dD ~-228 per mil VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate-methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of d13C-CH4 ~-60 per mil VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas.

Petrophysical investigation on sediment core CRP-3 from the Ross Sea, Antarctica

A suite of petrophysical properties - velocity, resistivity, bulk density, porosity, and matrix density - was measured on 88 core plugs from the CRP-3 drillhole. Core-plug bulk densities were used to recalibrate both whole-core and downhole bulk density logs. Core-plug measurements of matrix density permit conversion of the whole-core and downhole bulk density logs to porosity. Both velocity and formation factor (a normalized measure of resistivity) are strongly correlated with porosity. The velocity/porosity pattern is similar to that for the lower part of CRP-2A and is consistent with the empirical relationship for sandstones. Core-plug and whole-core measurements of P-wave velocity at atmospheric pressure exhibit excellent agreement. Measurements of velocity as a function of pressure indicate a significantly higher velocity sensitivity to pressure than has been observed at CRP-1 and CRP-2A; rebound or presence of microcracks at CRP-3 may be responsible. The percentage difference between velocities at in situ pressures and atmospheric pressures increases downhole from 0% at the seafloor to 9% at the bottom. This pattern can be used to correct whole-core velocity data, measured at atmospheric pressure, to in situ velocities for depth-to-time conversion and associated comparison to the seismic profile across the drillsite

Geophysical logging on sediment core and hole CRP-3 from the Ross Sea, Antarctica

Cape Roberts drillhole CRP-3 in the northern part of McMurdo Sound (Ross Sea, Antarctica) targeted the western margin of the Victoria Land basin to investigate Neogene to Palaeogene climatic and tectonic history by obtaining continuous core and downhole logs (Cape Roberts Science Team, 2000). The CRP-3 drillhole extended to 939.42 mbsf (meters below seafloor) at a water depth of 297 m. The first downhole measurements after drilling were the temperature and salinity logs. Both were measured at the beginning and at the end of each of the three logging phases. Although an equilibrium temperature state may not have been fully reached after drilling, the temperature and salinity profiles seem to be scarcely disturbed. The average overall temperature gradient calculated from all temperature measurements is 28.5 K/km; remarkably lower than the temperature gradients found in other boreholes in the western Ross See and the Transantarctic Mountains. Anomalies in the salinity profiles at the beginning of each logging phase were no longer present at the end of the corresponding logging phase. This pattern indicates that drilling mud invaded the formation during drilling operations and flowed back into the borehole after drilling ceased. Thus, zones of temperature and salinity anomalies identify permeable zones in the formation and may be pathways for fluid flow. Radiogenic heat production, calculated from the radionuclide contents, is relatively low, with average values between 0.5 and 1.0 pW/m3. The highest values (up to 2 µW/m3) were obtained for the lower part of the Beacon Sandstone below 855 mbsf. The heat flow component due to radiogenic heat production integrated over the entire borehole is 0.7 mW/m2. Thermal conductivities range from 1.3 to 3 W/mK with an average value of 2.1 W/mK over the Tertiary section. Together with the average temperature gradient of 28.5 K/km this yields an average heat flow value of 60 mW/m2.

(Table 1) Summary of sampling points described and main petrographic, morphological and geochemical characteristics

Targeted sampling on the Dolgovskoy Mound (northern Shatsky Ridge) revealed the presence of spectacular laterally extensive and differently shaped authigenic carbonates. The sampling stations were selected based on sidescan sonar and profiler images that show patchy backscatter and irregular and discontinuous reflections in the near subsurface. The interpretation of acoustic data from the top part of the mound supports the seafloor observations and the sampling that revealed the presence of a complex subsurface plumbing system characterized by carbonates and gas. The crusts sampled consist of carbonate cemented layered hemipelagic sedimentary Unit 1 associated with several centimetres thick microbial mats. Three different carbonate morphologies were observed: (a) tabular slabs, (b) subsurface cavernous carbonates consisting of void chambers up to 20 cm**3 in size and (c) chimney and tubular conduits vertically oriented or forming a subhorizontal network in the subsurface. The methanogenic origin of the carbonates is established based on visual observations of fluids seepage structures, 13C depletion of the carbonates (d13C varying between -36.7 per mil and -27.4 per mil), and by thin carbonate layers present within the thick microbial mats. Laboratory experiments with a Hele-Shaw cell were conducted in order to simulate the gas seepage through contrasting grain size media present on the seafloor. Combined petrography, visual observations and sandbox simulations allowed a characterization of the dynamics and the structures of the plumbing system in the near subsurface. Based on sample observations and the experiments, three observed morphologies of authigenic carbonates are interpreted, respectively, as (a) Darcian porous flow through the finely laminated clayey/coccolith-rich layers, (b) gas accumulation chambers at sites where significant fluid escape was impeded by thicker clayey layers forming the laminated Unit1 and (c) focussed vertical fluid venting and subhorizontal migration of overpressured fluids released from (b). The Hele-Shaw cell experiments represent a promising tool for investigating shallow fluid flow pathways in marine systems.

Stable carbon isotope composition of benthic foraminifera from sediments of the Skagerrak, North Sea

The sediment cores 225514 and 225510 were recovered from 420 and 285 m water depth, respectively. They were investigated for their benthic foraminiferal delta13C during the last 500 years. Both cores were recovered from the southern flank of the Skagerrak. The delta13C values of Uvigerina mediterranea and other shallow infaunal species in both cores indicate that organic matter rain rates to the seafloor varied around a mean value until approximately AD 1950 after which they increased. This increase might result from changes in the North Atlantic Current System and a co-occurring persistently high North Atlantic Oscillation index state in the 1980s to 1990s, rather than from anthropogenic eutrophication. Using delta13C mean values of multiple species, we reconstruct delta13C gradients of dissolved inorganic carbon (DIC) within pore waters for the time periods AD 1500 to 1950 and AD 1950 to 2000. The calculated delta13CDIC ranges, interpreted as indicating total organic matter remineralization due to respiration, are generally bigger in Core 225514 than in Core 225510. Since mean delta13C values of U. mediterranea suggest that organic matter rain rates were similar at both locations, differences in total organic matter remineralization are attributed to differing oxygen availability. However, oxygen concentrations in the overlying bottom water masses are not likely to have differed significantly. Thus, we suggest that organic matter remineralization was controlled by oxygen availability within the sediments, reflecting strong differences in sedimentation rates at the two investigated core sites. Based on the assumptions that tests of benthic foraminiferal species inhabiting the same microhabitat depth should show equal delta13C values unless they are affected by vital effects and that Globobulimina turgida records pore water delta13CDIC, we estimate microhabitat-corrected vital effects for several species with respect to G. turgida: >0.7 per mil for Cassidulina laevigata, >1.3 per mil for Hyalinea balthica, and >0.7 per mil for Melonis barleeanus. Melonis zaandami seems to closely record pore water delta13CDIC.

Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.