Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.

Geochemistry of some manganese nodules

The manganese nodules occur in greater or less quantity all over the ocean-bed, and most abundantly in the Pacific. They occur in all sizes, from minute grains to masses of a pound weight, and even greater, and form nodular concretions of concentric shells, round a nucleus, which is very frequently a piece of pumice or a shark's tooth. Their outside has a peculiar and very characteristic mammillated surface, which enables them to be identified at a glance. When freshly brought up they are very soft, being easily scraped to powder with a knife. They gradually get harder on exposure to the air. The powder, heated in a closed tube, gives out water which re-acts alkaline, and has an empyreumatic odour. Heated with strong hydrochloric acid, it liberates abundance of chlorine, and the residue which remains is white, consisting of silica, clay, and sand, the sand being the same as is found in the bottom mud from the same locality. Their composition varies greatly, different nodules containing different quantities of mechanically admixed mud, and the number of different elements found in them is very large. Copper, iron, cobalt, nickel, manganese, alumina, lime, magnesia, silica, and phosphoric acid have been detected in a large number; but I have not as yet been able to make a complete analysis of any of them. I have, however, made a few determinations of the most important component substances. For this purpose the outside and densest layers of the nodules were selected, and portions of them were pulverised and dried for ten or twelve hours at 140° C. The amount of chlorine liberated on treatment with hydrochloric acid was determined by Bunsen's method, and the iron was determined by titration with stannous chloride. The samples analysed were from four different localities.

Granulometry and Bulk Geochemistry of Nearshore Sediments, Herschel Island, Yukon Territory, Canada

This dataset contains the results of granulometric and bulk geochemical analyses of Van Veen surface samples obtained by the Alfred Wegener Institute (AWI) in the course of the 2012 and 2013 summer field seasons. The sampling was performed along transects in depths generally <13 m, to a distance of about <5 km off Herschel Island. In 2012, 75 samples in Pauline Cove and in the vicinity of Simpson Point were obtained. Sample collection was expanded in 2013, on transects established the previous year, with additional locations in Tetris Bay and Workboat Passage. Samples consisted of approximately 100 g of the top 3-6 cm of sediment, and were frozen in the field and freeze dried at the AWI before undergoing analytical procedures. Sample locations were recorded with the onboard global positioning system (GPS) unit. Grain size distributions in our study were obtained using laser diffractometry at the AWI (Beckman Coulter LS200) on the <1 mm fraction of samples oxidized with 30% H2O2 until effervescence ceased to remove organics. Some samples were also sieved using a sieve stack with 1 phi intervals. GRADISTAT (Blott and Pye, 2001) was used to calculate graphical grain size statistics (Folk and Ward, 1957). Grain diameters were logarithmically transformed to phi values, calculated as phi=-log2d, where d is the grain diameter in millimeters (Blott and Pye, 2001; Krumbein, 1934). Freeze dried samples were ground and ground using an Elemetar Vario EL III carbon-nitrogen-sulphur analyzer at the AWI to measure total carbon (TC) and total nitrogen (TN). Tungsten oxide was added to the samples as a catalyst to the pyrolysis. Following this analysis, total organic carbon (TOC) was determined using an Elementar VarioMax. Stable carbon isotope ratios of 13C/12C of 118 samples were determined on a DELTAplusXL mass spectrometer (ThermoFisher Scientific, Bremen) at the German Research Centre for Geosciences (GFZ) in Potsdam, Germany . An additional analysis on 69 samples was carried out at the University of Hamburg with an isotope ratio mass spectrometer (Delta V, Thermo Scientific, Germany) coupled to an elemental analyzer (Flash 2000, Thermo Scientific, Germany). Prior to analysis, soil samples were treated with phosphoric acid (43%) to release inorganic carbon. Values are expressed relative to Vienna Peedee belemnite (VPDB) using external standards (USGS40, -26.4 per mil VPDB and IVA soil 33802153, -27.5 per mil VPDB).

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

Fatty acid composition, and bacteria and meiofauna abundance in sediment cores PS71/013 and PS71/085 during POLARSTERN cruise ANT-XXIV/2

During the RV Polarstern ANT XXIV-2 cruise to the Southern Ocean and the Weddell Sea in 2007/2008, sediment samples were taken during and after a phytoplankton bloom at 52°S 0°E. The station, located at 2960 m water depth, was sampled for the first time at the beginning of December 2007 and revisited at the end of January 2008. Fresh phytodetritus originating from the phytoplankton bloom first observed in the water column had reached the sea floor by the time of the second visit. Absolute abundances of bacteria and most major meiofauna taxa did not change between the two sampling dates. In the copepods, the second most abundant meiofauna taxon after the nematodes, the enhanced input of organic material did not lead to an observable increase of reproductive effort. However, significantly higher relative abundances of meiofauna could be observed at the sediment surface after the remains of the phytoplankton bloom reached the sea floor. Vertical shifts in meiofauna distribution between December and January may be related to changing pore-water oxygen concentration, total sediment fatty acid content, and pigment profiles measured during our study. Higher oxygen consumption after the phytoplankton bloom may have resulted from an enhanced respiratory activity of the living benthic component, as neither meiofauna nor bacteria reacted with an increase in individual numbers to the food input from the water column. Based on our results, we infer that low temperatures and ecological strategies are the underlying factors for the delayed response of benthic deep-sea copepods, in terms of egg and larval production, to the modified environmental situation.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.

Seawater carbonate chemistry and resource allocation and extracellular acid-base status in the sea urchin Strongylocentrotus droebachiensis during experiments, 2012

Anthropogenic CO2 emission will lead to an increase in seawater pCO2 of up to 80-100 Pa (800-1000 µatm) within this century and to an acidification of the oceans. Green sea urchins (Strongylocentrotus droebachiensis) occurring in Kattegat experience seasonal hypercapnic and hypoxic conditions already today. Thus, anthropogenic CO2 emissions will add up to existing values and will lead to even higher pCO2 values >200 Pa (>2000 µatm). To estimate the green sea urchins' potential to acclimate to acidified seawater, we calculated an energy budget and determined the extracellular acid base status of adult S. droebachiensis exposed to moderately (102 to 145 Pa, 1007 to 1431 µatm) and highly (284 to 385 Pa, 2800 to 3800 µatm) elevated seawater pCO2 for 10 and 45 days. A 45 - day exposure to elevated pCO2 resulted in a shift in energy budgets, leading to reduced somatic and reproductive growth. Metabolic rates were not significantly affected, but ammonium excretion increased in response to elevated pCO2. This led to decreased O:N ratios. These findings suggest that protein metabolism is possibly enhanced under elevated pCO2 in order to support ion homeostasis by increasing net acid extrusion. The perivisceral coelomic fluid acid-base status revealed that S. droebachiensis is able to fully (intermediate pCO2) or partially (high pCO2) compensate extracellular pH (pHe) changes by accumulation of bicarbonate (maximum increases 2.5 mM), albeit at a slower rate than typically observed in other taxa (10 day duration for full pHe compensation). At intermediate pCO2, sea urchins were able to maintain fully compensated pHe for 45 days. Sea urchins from the higher pCO2 treatment could be divided into two groups following medium-term acclimation: one group of experimental animals (29%) contained remnants of food in their digestive system and maintained partially compensated pHe (+2.3 mM HCO3), while the other group (71%) exhibited an empty digestive system and a severe metabolic acidosis (-0.5 pH units, -2.4 mM HCO3). There was no difference in mortality between the three pCO2 treatments. The results of this study suggest that S. droebachiensis occurring in the Kattegat might be pre-adapted to hypercapnia due to natural variability in pCO2 in its habitat. We show for the first time that some echinoderm species can actively compensate extracellular pH. Seawater pCO2 values of >200 Pa, which will occur in the Kattegat within this century during seasonal hypoxic events, can possibly only be endured for a short time period of a few weeks. Increases in anthropogenic CO2 emissions and leakages from potential sub-seabed CO2 storage (CCS) sites thus impose a threat to the ecologically and economically important species S. droebachiensis.

Diatom abundance and fatty acid composition of ice algae and of Calanus glacialis in samples obtained in 2008 in the eastern Beaufort Sea

The copepod Calanus glacialis plays a key role in the lipid-based energy flux in Arctic shelf seas. By utilizing both ice algae and phytoplankton, this species is able to extend its growth season considerably in these seasonally ice-covered seas. This study investigated the impacts of the variability in timing and extent of the ice algal bloom on the reproduction and population success of C. glacialis. The vertical distribution, reproduction, amount of storage lipids, stable isotopes, fatty acid and fatty alcohol composition of C. glacialis were assessed during the Circumpolar Flaw Lead System Study. Data were collected in the Amundsen Gulf, south-eastern Beaufort Sea, from January to July 2008 with the core-sampling from March to April. The reduction in sea ice thickness and coverage observed in the Amundsen Gulf in 2007 and 2008 affected the life strategy and reproduction of C. glacialis. Developmental stages CIII and CIV dominated the overwintering population, which resulted in the presence of very few CV and females during spring 2008. Spawning began at the peak of the ice algal bloom that preceded the precocious May ice break-up. Although the main recruitment may have occurred later in the season, low abundance of females combined with a potential mismatch between egg production/development to the first feeding stage and phytoplankton bloom resulted in low recruitment of C. glacialis in the early summer of 2008.

(Table II, page 668-669) Distribution of elements between minerals soluble in 1M Hydroxylamine hydrochloride (Reducible); in 1m HCL (Acid-soluble) and in the insoluble residue of manganese nodules

Attempts to classify pelagic sediments have been based either on appearance and composition, or on the ultimate origin of the components. In particular it appears feasible to distinguish minerals which crystallized in sea-water from those which formed in magmas, in hydrothermal solution, or by weathering under acidic conditions. It is the case of iron and manganese oxide mineral aggregates which constitute one of the major types of rock encountered on the ocean floor; according to Menard (unpublished) about 10% of the pelagic area of the Pacific is covered by such nodules. The nodules consist of intimately intergrown crystallites of different minerals among those identified, besides detrital minerals and organic matter, are opal, goethite, rutile, anatase, barite, nontronite, and at least three manganese oxide minerals of major importance. Arrhenius and Korkisch (1959) have attempted to separate from each other the different minerals constituting the nodules, in order to establish the details of their structure and the localization of the heavy metal ions. The results demonstrate (Table II) that copper and nickel are concentrated in the manganese oxide phases concentrated in the reducible fraction. Cobalt, part of the nickel and most of the chromium are distributed between these and the acid-soluble group of the non-manganese minerals, dominated by goethite and disordered FeOOH.