ALBERT

Description: Surface and thermocline conditions of the Western Pacific Warm Pool (WPWP) reflect changes in regional and basin scale ocean and atmosphere circulations and in turn may affect climate globally. Previous studies suggest that a range of factors influences the WPWP on different timescales, however the precise forcings and mechanisms are unclear. Combining surface and thermocline records from sediment cores offshore Papua New Guinea we explore the influence of local and remote processes on the WPWP in response to astronomical forcing and changing glacial-interglacial boundary conditions over the past 110 kyr. We find that thermocline temperatures change with variations in Earth's obliquity with higher temperatures coinciding with high obliquity, which is attributed to variations in subduction and advection of the South Pacific Tropical Water. In contrast, rainfall variations associated with meridional migrations of the Intertropical Convergence Zone are primarily driven by changes in insolation due to precession. Records of bulk sedimentary Ti/Ca and foraminiferal Nd/Ca indicate an additional influence of obliquity, which, however, cannot unambiguously be related to changes in precipitation. Finally, our results suggest a thermocline deepening during the Last Glacial Maximum (LGM). A compilation of available proxy records illustrates a dipole-like pattern of LGM thermocline depth anomalies with a shoaling (deepening) in the northern (southern) WPWP. A comparison of the proxy compilation with an ensemble of Paleoclimate Model Intercomparison Project (PMIP) climate model simulations reveals that the spatial pattern of LGM thermocline depth anomalies is mainly attributable to a contraction of the Pacific Walker circulation on its western side.

Description: Highlights: • Chitosan constitutes a good polymer for iron oxide immobilization. • Sorption properties of iron oxides are not inhibited by chitosan coating. • Hybrid materials present good mechanical properties for water pollution treatment. • Arsenic can be efficiently removed using cost-effective hybrid polymeric materials. Abstract Red mud (RM), a waste product generated in the industrial production of aluminium, was recovered for a second use as As(V) adsorbent. RM adsorption properties were compared to those obtained with a nanostructured in-lab synthesized iron oxide, magnetite. Operational problems associated with powdery consistency of raw materials were solved with the synthesis of new polymeric/inorganic hybrid sorbents by dispersing red mud and magnetite in chitosan. The behaviour of raw red mud and magnetite towards As(V) adsorption has been critically compared with that observed for the hybrid materials. pH dependence studies demonstrated that near neutral environments favour As(V) elimination. The sorption kinetics for the iron oxides showed that equilibrium was reached in less than 3 h for raw materials and up to 15 h for immobilized red mud and magnetite. The amount of arsenic sorbed on the four different sorbents as a function of the equilibrium arsenic concentration has been fitted to a Freundlich isotherm and a multilayer adsorption mechanism is proposed. Finally, continuous flow experiments were developed using chitosan immobilized red mud. Results allowed selecting batch conformation as the most effective for As(V) removal.

Description: Highlights • Information of elemental and metalloprotean homeostasis regarding diabetes and hypothyroidism diseases is scare. • The powerful QQQ-ICP tehcnique was coupled with HPLC to determine a large number of elements. • Classification of serum samples from both groups of study was assessed by means of principal component analysis. • Transition elements (associated to protean fractions) probed to have the most influence in the classification model. Diabetes and hypothyroidism are both metabolic diseases with great incidence worldwide. Metalloproteins and metals play key roles in normal glucose metabolism and thyroid hormone synthesis, which are altered in their respective pathologies. The aim of this work was to establish the corresponding multielemental and metalloprotean profiles in a control group (n = 20) compared with a diabetic (n = 20) or hypothyroidism group (n = 20), by exploring a multivariate principal components model. Classification to discriminate these groups was possible based in the quantification of 23 elements (Mg, Al, K, Ca, V, Cr, Zn, Fe, Se, Rb, Pb, Cu, Mn, Co, Ni, U, Sr, Mo, Sb, Ba, Tl, Cd, Ag), and alternatively on the metalloprotein profiles obtained by SEC-ICPMS. Determinations were assessed by means of QQQ-ICP and SEC-ICPMS for total and metalloprotean content, respectively. Samples were classified using Principal Component Analysis chemometric tool. Results showed that there were statistical differences in transitional elements concentrations, such as Zn, Cu, Co, Mn, V, and Cr. For the metal associated protein study, the expression of the fractions of the same transitional elements also were statistically different when compared between control vs diabetic patients, and control vs hypothyroid patients. Se levels showed no differences in both studies among groups. This screening study demonstrates that mass spectrometry methods and data analysis with chemometrics tools may be valuable in order to find possible biomarkers in serum samples of diabetic and hypothyroid patients. Future proteomics analysis are necessary to complete these findings.

Description: Temperature and ration level can differentially affect growth and life history characteristics of marine organisms. In this experiment we reared juvenile cuttlefish, Sepia elliptica, under two feeding regimes (satiation and half satiation) and two temperature regimes (25 and 30°C). This study examined differences in somatic growth, muscle tissue structure and composition as a function of temperature and food levels. We estimated body mass and the concentration of water, carbohydrate, protein and lipid in the mantle muscle tissue for each individual. Both high water temperature and high feeding rations increased growth rates. Temperature appeared to change the rates of muscle fibre generation and fibre growth similarly. In contrast, the ration level altered the relative rates of fibre production and fibre growth. The muscle tissue of individuals reared at 30°C had higher concentrations of carbohydrate and protein. In contrast, increasing ration levels only increased carbohydrate concentrations in the muscle tissue. The muscle tissue of reared juveniles had lower concentrations of carbohydrate and protein than wild individuals of similar size. In conclusion, water temperature and feeding levels both affect somatic growth, but the nature of the effect at the sub-organismal level differs.

Description: We present new nitrogen isotope data from the water column and surface sediments for paleo–proxy validation collected along the Peruvian and Ecuadorian margins between 1°N and 18°S. Productivity proxies in the bulk sediment (organic carbon, total nitrogen, biogenic opal, C37 alkenone concentrations) and 15N/14N ratios were measured at more than 80 locations within and outside the present-day Peruvian oxygen minimum zone (OMZ). Microbial N-loss to N2 in subsurface waters under O2 deficient conditions leaves a characteristic 15N-enriched signal in underlying sediments. We find that phytoplankton nutrient uptake in surface waters within the high nutrient, low chlorophyll (HNLC) regions of the Peruvian upwelling system influences the sedimentary signal as well. How the δ15Nsed signal is linked to these processes is studied by comparing core-top values to the 15N/14N of nitrate and nitrite (δ15NNOx) in the upper 200 m of the water column. Between 1°N and 10°S, subsurface O2 is still high enough to suppress N-loss keeping δ15NNOx values relatively low in the subsurface waters. However δ15NNOx values increase toward the surface due to partial nitrate utilization in the photic zone in this HNLC portion of the system. δ15Nsed is consistently lower than the isotopic signature of upwelled NO3−, likely due to the corresponding production of 15N depleted organic matter. Between 10°S and 15°S, the current position of perennial upwelling cells, HNLC conditions are relaxed and biological production and near-surface phytoplankton uptake of upwelled NO3− are most intense. In addition, subsurface O2 concentration decreases to levels sufficient for N-loss by denitrification and/or anammox, resulting in elevated subsurface δ15NNOx values in the source waters for coastal upwelling. Increasingly higher production southward is reflected by various productivity proxies in the sediments, while the north–south gradient towards stronger surface NO3− utilization and subsurface N-loss is reflected in the surface sediment 15N/14N ratios. South of 10°S, δ15Nsed is lower than maximum water column δ15NNOx values most likely because only a portion of the upwelled water originates from the depths where highest δ15NNOx values prevail. Though the enrichment of δ15NNOx in the subsurface waters is unambiguously reflected in δ15Nsed values, the magnitude of δ15Nsed enrichment depends on both the depth of upwelled waters and high subsurface δ15NNOx values produce by N-loss. Overall, the degree of N-loss influencing subsurface δ15NNOx values, the depth origin of upwelled waters, and the degree of near-surface nitrate utilization under HNLC conditions should be considered for the interpretation of paleo δ15Nsed records from the Peruvian oxygen minimum zone.

Description: One of the most remarkable natural events on Earth are the large lateral flank collapses of oceanic volcanoes, involving volumes of rock exceeding tens ofkm3• These collapses are relatively frequent in recent geological times as supported by evidence found in the geomorphology of volcanic island edifices and associated debris flows deposited on the proximal ocean floor. The Island of Fogo in the Cape Verde archipelago is one of the most active and prominent oceanic volcanoes on Earth. The island has an average diameter of 25 km and reaches a maximum elevation of 2829 m above sea level (m a.s.l.) at Pico do Fogo, a young stratovolcano located within a summit depression open eastward due to a large lateral flank collapse. The sudden collapse of the eastern flank of Fogo Island produced a megatsunami -73 ky ago. The limits of the flank collapse were deduced as well from geomorphologic markers within the island. The headwall of the collapse scar is interpreted as either being located beneath the post-collapse volcanic infill of the summit depression or located further west, corresponding to the Bordeira wall that partially surrounds it. The magnetotelluric (MT) method provides a depth distribution of the ground resistivity obtained by the simultaneous measurement of the natural variations of the electric and magnetic field of the Earth. Two N-S magnetotelluric profiles were acquired across the collapsed area to determine its geometry and boundaries. The acquired MT data allowed the determination of the limits of the collapsed area more accurately as well as its morphology at depth and thickness of the post-collapse infill. According to the newly obtained MT data and the bathymetry of the eastern submarine flank of Fogo, the volume involved in the flank collapse is estimated in -110 km3 • This volume -the first calculated onshore- stands between the previously published more conservative and excessive calculations -offshore- that were exclusively based in geomorphic evidence. The model for the summit depression proposing two caldera collapses preceding the collapse of the eastern flank of Fogo is supported by the MT data.

Description: The manganese nodule belt within the Clarion and Clipperton Fracture Zones (CCZ) in the abyssal NE Pacific Ocean is characterized by numerous seamounts, low organic matter (OM) depositional fluxes and meter-scale oxygen penetration depths (OPD) into the sediment. The region hosts contract areas for the exploration of polymetallic nodules and Areas of Particular Environmental Interest (APEI) as protected areas. In order to assess the impact of potential mining on these deep-sea sediments and ecosystems, a thorough determination of the natural spatial variability of depositional and geochemical conditions as well as biogeochemical processes and element fluxes in the different exploration areas is required. Here, we present a comparative study on (1) sedimentation rates and bioturbation depths, (2) redox zonation of the sediments and element fluxes as well as (3) rates and pathways of biogeochemical reactions at six sites in the eastern CCZ. The sites are located in four European contract areas and in the APEI3. Our results demonstrate that the natural spatial variability of depositional and (bio)geochemical conditions in this deep-sea sedimentary environment is much larger than previously thought. We found that the OPD varies between 1 and 4.5 m, while the sediments at two sites are oxic throughout the sampled interval (7.5 m depth). Below the OPD, manganese and nitrate reduction occur concurrently in the suboxic zone with pore-water Mn2+ concentrations of up to 25 µM. The thickness of the suboxic zone extends over depth intervals of less than 3 m to more than 8 m. Our data and the applied transport-reaction model suggest that the extension of the oxic and suboxic zones is ultimately determined by the (1) low flux of particulate organic carbon (POC) of 1–2 mg Corg m−2 d−1 to the seafloor, (2) low sedimentation rates between 0.2 and 1.15 cm kyr−1 and (3) oxidation of pore-water Mn2+ at depth. The diagenetic model reveals that aerobic respiration is the main biogeochemical process driving OM degradation. Due to very low POC fluxes of 1 mg Corg m−2 d−1 to the seafloor at the site investigated in the protected APEI3 area, respiration rates are twofold lower than at the other study sites. Thus, the APEI3 site does not represent the (bio)geochemical conditions that prevail in the other investigated sites located in the European contract areas. Lateral variations in surface water productivity are generally reflected in the POC fluxes to the seafloor across the various areas but deviate from this trend at two of the study sites. We suggest that the observed spatial variations in depositional and (bio)geochemical conditions result from differences in the degree of degradation of OM in the water column and heterogeneous sedimentation patterns caused by the interaction of bottom water currents with seafloor topography.

Description: Mud Volcanism and fluid seepage are widespread phenomena in the Gulf of Cadiz (SW Iberian Margin). In this seismically active region located at the boundary between the African and Eurasian plates, fluid flow is typically focused on deeply rooted active strike-slip faults. The geochemical signature of emanating fluids from various mud volcanoes (MVs) has been interpreted as being largely affected by clay mineral dehydration and recrystallization of Upper Jurassic carbonates. Here we present the results of a novel, fully-coupled 1D basin-scale reactive-transport model capable of simulating major fluid forming processes and related geochemical signatures by considering the growth of the sediment column over time, compaction of sediments, diffusion and advection of fluids, as well as convective and conductive heat flow. The outcome of the model is a realistic approximation to the development of the sediment pore water system over geological time scales in the Gulf of Cadiz. Combined with a geochemical reaction transport model for clay mineral dehydration and calcium carbonate recrystallization, we were able to reproduce measured concentrations of Cl, strontium and 87Sr/86Sr of emanating mud volcano fluids. These results support previously made qualitative interpretations and add further constraints on fluid forming processes, reaction rates and source depths. The geochemical signature at Porto MV posed a specific problem, because of insufficient constraints on non-radiogenic 87Sr/86Sr sources at this location. We favour a scenario of basement-derived fluid injection into basal Upper Jurassic carbonate deposits (Hensen et al., 2015). Although the mechanism behind such basement-derived flow, e.g. along permeable faults, remains speculative at this stage, it provides an additional source of low 87Sr/86Sr fluids and offers an idea on how formation water from the deepest sedimentary strata above the basement can be mobilized and eventually initiate the advection of fluids feeding MVs at the seafloor. The dynamic reactive-transport model presented in this study provides a new tool addressing the combined simulation of complex physical-geochemical processes in sedimentary systems. The model can easily be extended and applied to similar geological settings, and thus help us to provide a fundamental understanding of fluid dynamics and element recycling in sedimentary basins.