Sulphur and iron species in Dvurechenskii mud volcano sediments

The deep Black Sea is known to be depleted in electron-acceptors for sulphide oxidation. This study on depth distributions of sulphur species (S(II), S(0),S(n)**2-,S2O3**2-,SO3**2-,SO4**2-) in the Dvurechenskii mud volcano, a cold seep situated in the permanently anoxic eastern Black Sea basin (Sorokin Trough, 2060 m water depth), showed remarkable concentrations of sulphide oxidation products. Sulphite concentrations of up to 11 µmol L**1-, thiosulphate concentrations of up to 22 µmol L**1-, zero-valent sulphur concentrations of up to 150 µmol L**1- and up to five polysulphide species were measured in the upper 20 cm of the sediment. Electron-acceptors found to be available in the Dvurechenskii mud volcano (DMV) for the oxidation of hydrogen sulphide to sulphide oxidation intermediates are iron-minerals, and probably also reactive manganese phases. Up to 60 µmol g**1- of reactive iron-minerals and up to 170 µmol L**1- dissolved iron was present in the central summit with the highest fluid upflow and fresh mud outflow. Thus, the source for the oxidative power in the DMV are reactive iron phases extruded with the mud from an ancient source in the deeply buried sediments, leading to the formation of various sulphur intermediates in comparably high concentrations. Another possible source of sulphide oxidation intermediates in DMV sediments could be the formation of zero-valent sulphur by sulphate dependent anaerobic microbial oxidation of methane followed by disproportionation of zero-valent sulphur. Sulphide oxidation intermediates, which are produced by these processes, do not reach thermodynamic equilibrium with rhombic sulphur, especially close to the active center of the DMV due to a short equilibration time. Thus, mud volcano sediments, such as in the DMV, can provide oxidizing niches even in a highly reduced environment like the abyssal part of the Black Sea.

d11B and metal/Ca ratios versus size fractions in the Surface and deep dwelling species, ODP Holes 130-806B and 108-664C

We have assessed the reliability of several foraminifer-hosted proxies of the ocean carbonate system (d11B, B/Ca, and U/Ca) using Holocene samples from the Atlantic and Pacific oceans. We examined chemical variability over a range of test sizes for two surface-dwelling foraminifers (Globigerinoides sacculifer and Globigerinoides ruber). Measurements of d11B in G. ruber show no significant relationship with test size in either Atlantic or Pacific sites and appear to provide a robust proxy of surface seawater pH. Likewise there is no significant variability in the d11B of our Atlantic core top G. sacculifer, but we find that d11B increases with increasing test size for G. sacculifer in the Pacific. These systematic differences in d11B are inferred to be a consequence of isotopically light gametogenic calcite in G. sacculifer and its preferential preservation during postdepositional dissolution. The trace element ratio proxies of ocean carbonate equilibria, U/Ca and B/Ca, show systematic increases in both G. ruber and G. sacculifer with increasing test size, possibly as a result of changing growth rates. This behavior complicates their use in paleoceanographic reconstructions. In keeping with several previous studies we find that Mg/Ca ratios increase with increasing size fraction in our well-preserved Atlantic G. sacculifer but not in G. ruber. In contrast to previous interpretations we suggest that these observations reflect a proportionally larger influence of compositionally distinct gametogenic calcite in small individuals compared to larger ones. As with d11B this influences G. sacculifer but not G. ruber, which has negligible gametogenic calcite.

(Table 1) N-isotope record of planktonc foraminifera of sediment core MD02-2550C2

Constraining variations in marine N2-fixation over glacial-interglacial timescales is crucial for determining the role of the marine nitrogen cycle in modifying ocean productivity and climate, yet paleo-records from N2-fixation regions are sparse. Here we present new nitrogen isotope (d15N) records of bulk sediment and foraminifera test-bound (FB) nitrogen extending back to the last ice age from the oligotrophic Gulf of Mexico (GOM). Previous studies indicate a substantial terrestrial input during the last ice age and early deglacial, for which we attempt to correct the bulk sediment d15N using its observed relationship with the C/N ratio. Both corrected bulk and FB-d15N reveal a substantial glacial-to-Holocene decrease of d15N toward Holocene values of around 2.5 per mil, similar to observations from the Caribbean. This d15N change is most likely due to a glacial-to-Holocene increase in regional N2-fixation. A deglacial peak in the FB-d15N of thermocline dwelling foraminifera Orbulina universa probably reflects a whole ocean increase in the d15N of nitrate during deglaciation. The d15N of the surface dwelling foraminifera Globigerinoides ruber and the corrected bulk d15N show little sign of this deglacial peak, both decreasing from last glacial values much earlier than does the d15N of O. universa; this may indicate that G. ruber and bulk N reflect the euphotic zone signal of an early local increase in N2-fixation. Our results add to the evidence that, during the last ice age, the larger iron input from dust did not lead to enhanced N2-fixation in this region. Rather, the glacial-to-Holocene decrease in d15N is best explained by a response of N2-fixation within the Atlantic to the deglacial increase in global ocean denitrification.

Animation of micro-computed tomography of bioerosion trace Entobia megastoma made by East Australian bioeroding sponge Cliona celata

Endolithic bioerosion is difficult to analyse and to describe, and it usually requires damaging of the sample material. Sponge erosion (Entobia) may be one of the most difficult to evaluate as it is simultaneously macroscopically inhomogeneous and microstructurally intricate. We studied the bioerosion traces of the two Australian sponges Cliona celata Grant, 1826 (sensu Schönberg 2000) and Cliona orientalis Thiele, 1900 with a newly available radiographic technology: high resolution X-ray micro-computed tomography (MCT). MCT allows non-destructive visualisation of live and dead structures in three dimensions and was compared to traditional microscopic methods. MCT and microscopy showed that C. celata bioerosion was more intense in the centre and branched out in the periphery. In contrast, C. orientalis produced a dense, even trace meshwork and caused an overall more intense erosion pattern than C. celata. Extended pioneering filaments were not usually found at the margins of the studied sponge erosion, but branches ended abruptly or tapered to points. Results obtained with MCT were similar in quality to observations from transparent optical spar under the dissecting microscope. Microstructures could not be resolved as well as with e.g. scanning electron microscopy (SEM). Even though sponge scars and sponge chips were easily recognisable on maximum magnification MCT images, they lacked the detail that is available from SEM. Other drawbacks of MCT involve high costs and presently limited access. Even though MCT cannot presently replace traditional techniques such as corrosion casts viewed by SEM, we obtained valuable information. Especially for the possibility to measure endolithic pore volumes, we regard MCT as a very promising tool that will continue to be optimised. A combination of different methods will produce the best results in the study of Entobia.

Amino acid in Deep Sea Drilling Project cores

Several amino acid diagenetic reactions, which take place in the deep-sea sedimentary environment, were investigated, using various Deep Sea Drilling Project (DSDP) cores. Initially it was found that essentially all the amino acids in sediments are bound in peptide linkages; but, with increasing age, the peptide bonds undergo slow hydrolysis that results in an increasingly larger fraction of amino acids in the free state. The hydrolysis half-life in calcareous sediments was estimated to be ~1-2 million years, while in non-carbonate sediment the hydrolysis rate may be considerably slower. The amino acid compositions and the extent of racemization of several amino acids were determined in various fractions isolated from the sediments. These analyses demonstrated that the mechanism, kinetics, and rate of amino acid diagenesis are highly dependent upon the physical state (i.e., free, bound, etc.) in which the amino acids exist in the sedimentary environment. In the free state, serine and threonine were found to decompose primarily by a dehydration reaction, while in the bound state (residue or HCl-insoluble fraction) a reversible aldol-cleavage reaction is the main decomposition pathway of these amino acids. The change in amino acid composition of the residue fraction with time was suggested to be due to the hydrolysis of peptide bonds, while in foraminiferal tests the compositional changes over geological time are the result of various decomposition reactions. Reversible first-order racemization kinetics are not observed for free amino acids in sediments. The explanation for these anomalous kinetics involves a complex reaction series which includes the hydrolysis of peptide bonds and the very rapid racemization of free amino acids. The racemization rates of free amino acids in sediments were found to be many orders of magnitude faster than those predicted from elevated temperature experiments using free amino acids in aqueous solution. The racemization rate enhancement of free amino acids in sediments may be due to the catalysis of the reaction by trace metals. Reversible first-order kinetics are followed for amino acids in the residue fraction isolated from sediments; the rate of racemization in this fraction is slower than that predicted for protein-bound amino acids. Various applications of amino acid diagenetic reactions are discussed. Racemization and the decomposition reaction of serine and threonine can both be used, with certain limitations, to make rough age estimates of deep-sea sediments back to several million years. The extent of racemization in foraminiferal tests which have been dated by some other independent technique can be used to estimate geothermal gradients, and thus heat flows, and to evaluate the bottom water temperature history in certain oceanic areas.

Seawater carbonate chemistry, calcification and photosynthesis during experiments with corals, 2005

An investigation was conducted to determine the effects of elevated pCO2 on the net production and calcification of an assemblage of corals maintained under near-natural conditions of temperature, light, nutrient, and flow. Experiments were performed in summer and winter to explore possible interactions between seasonal change in temperature and irradiance and the effect of elevated pCO2. Particular attention was paid to interactions between net production and calcification because these two processes are thought to compete for the same internal supply of dissolved inorganic carbon (DIC). A nutrient enrichment experiment was performed because it has been shown to induce a competitive interaction between photosynthesis and calcification that may serve as an analog to the effect of elevated pCO2. Net carbon production, NPC, increased with increased pCO2 at the rate of 3 ± 2% (?mol CO2aq kg?1)?1. Seasonal change of the slope NPC-[CO2aq] relationship was not significant. Calcification (G) was strongly related to the aragonite saturation state ? a . Seasonal change of the G-? a relationship was not significant. The first-order saturation state model gave a good fit to the pooled summer and winter data: G = (8 ± 1 mmol CaCO3 m?2 h?1)(? a ? 1), r 2 = 0.87, P = 0.0001. Both nutrient and CO2 enrichment resulted in an increase in NPC and a decrease in G, giving support to the hypothesis that the cellular mechanism underlying the decrease in calcification in response to increased pCO2 could be competition between photosynthesis and calcification for a limited supply of DIC.

Abundance, Electron transport System (ETS) activity and respiration rates of pelagic decapods from the Benguela upwelling system during AFR258, D356 and MSM17/3

Decapods were sampled with a 1 m**2 MOCNESS (mainly upper 1000 m) in the northern Benguela Current during three cruises in December 2009, September/October 2010 and February 2011. Although pelagic decapods are abundant members of the micronekton community, information about their ecophysiology is very limited. Species-specific regional distribution limits were detected for various decapod species (e.g. Plesionika carinata, Sergestes arcticus, Pasiphaea semispinosa). Significant diel vertical migration patterns were determined for three caridean and three penaeiodean species. Biomass was variable and ranged from 23 to 2770 mg dry mass m**-2 with highest values for P. semispinosa. Fatty acid and stable isotope analyses revealed that the examined decapod species are omnivorous tocarnivorous except for the herbivorous to omnivorous species P. carinata. Calanid copepods such as Calanoides carinatus were identified as an important prey item especially for caridean species. Community consumption rates of pelagic decapods derived from respiration rates ranged from 7 mg C m**-2 d**-1 (231S) to 420 mg C m**-2 d**-1 (191S, 171S). A potential active respiratory carbon flux was calculated for migrating pelagic decapods with 4.4 mg C m**- d**-1 for the upper 200 m and with 2.6 mg C m**-2 d**-1 from the base of the euphotic zone to a depth of 600 m. Overall, pelagic decapods apparently play a more prominent role in the northern Benguela Current ecosystem than previously assumed and may exert a substantial predation impact on calanid copepods (up to 13% d**-1 of standing stock).

Oxygen and carbon isotope ratios for six planktonic foraminifer species from different water depth, Ontong-Java Plateau, Pacific (Table 2)

Stable isotope analyses and scanning electron micrographs have been carried out on six planktonic forminifera species, Pulleniatina obliquiloculata, Globorotalia tumida, Sphaeroidinella dehiscens, Globigerinoides ruber, Globigerinoides sacculifer and Globigerinoides quadrilobatus from eleven box-cores taken at increasing depths in the equatorial Ontong-Java Plateau (Pacific). This allows us to describe the way dissolution affects the microstructures of the tests of the different species and to quantify the changes of isotopic composition. We may conclude that: 1) dissolution effects on test morphology and stable isotope compositions are species dependent, species with a similar habitat showing a similar trend; 2) the shallow water, thin-shelled species are the first to disappear: scanning electron microscope (SEM) work shows alteration of outer layers. Deep water, thick-shelled species are present in all samples: SEM work shows breakdown and disparition of inner layers; 3) for all species there is a similar trend towards increasing delta18O values with increasing water depths and increasing dissolution. This effect may be as high as 0.6 ? per thousand meters for Globorotalia tumida; 4) below the lysocline, around 3500 m, it appears that 13C/12C ratios slightly increase towards equilibrium values for thick shelled species: G. tumida, P. obliquiloculata and S. dehiscens. 14C dates and isotope stratigraphy of two box-cores show that all samples are recent in age, and exclude upward mixing of glacial deposits as an important factor.

(Table 1) Heavy-mineral analyses for DSDP Leg 67 Holes from electron microprobe

Heavy and light minerals were examined in 29 samples from Sites 494, 498, 499, 500, and 495 on the Deep Sea Drilling Project Leg 67 Middle America Trench transect; these sites represent lower slope, trench, and oceanic crust environments off Guatemala. All samples are Quaternary except those from Hole 494A (Pliocene) and Hole 498A (Miocene). Heavy-mineral assemblages of the Quaternary sediments are characterized by an immature pyroxene-amphibole suite with small quantities of olivine and epidote. The Miocene sediments yielded an assemblage dominated by epidote and pyroxene but lacking olivine; the absence of olivine is attributed to selective removal of the most unstable components by intrastratal solution. Light-mineral assemblages of all samples are predominantly characterized by volcanic glass and plagioclase feldspar. The feldspar compositions are compatible with andesitic source rocks and frequently exhibit oscillatory zoning. The heavy- and light-mineral associations of these sediments suggest a proximal volcanic source, most probably the Neogene highland volcanic province of Guatemala. Sand-sized components from Site 495 are mainly biogenic skeletons and volcanic glass and, in one instance (Section 495-5-3), euhedral crystals of gypsum.

Age and chemical composition of apatites from five DSDP and ODP Sites in the Pacific, Atlantic and Indian Oceans

Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ~10° and 70°C over geological time scales of ~15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analyzed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30°C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 µm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30°C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ~30°C. For samples which experienced maximum temperatures between ~30 and 70°C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.

Concentrations of PBDE and BDE congeners in adipose tissue of East Greenland polar bears (Ursus maritimus)

Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean SumPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the SumPBDE concentration. The SumPBDE concentration had a highly significant correlation with SumPCB, SumCHL, dieldrin, HCB and SumHCH concentrations. We found a seasonal pattern of median SumPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression.

Electron spin resonance (ESR) and 14C dating in sediments of Bonaire, Leeward Antilles

The coastal deposits of Bonaire, Leeward Antilles, are among the most studied archives for extreme-wave events (EWEs) in the Caribbean. Here we present more than 400 electron spin resonance (ESR) and radiocarbon data on coarse-clast deposits from Bonaire's eastern and western coasts. The chronological data are compared to the occurrence and age of fine-grained extreme-wave deposits detected in lagoons and floodplains. Both approaches are aimed at the identification of EWEs, the differentiation between extraordinary storms and tsunamis, improving reconstructions of the coastal evolution, and establishing a geochronological framework for the events. Although the combination of different methods and archives contributes to a better understanding of the interplay of coastal and archive-related processes, insufficient separation, superimposition or burying of coarse-clast deposits and restricted dating accuracy limit the use of both fine-grained and coarse-clast geoarchives to unravel decadal- to centennial-scale events. At several locations, distinct landforms are attributed to different coastal flooding events interpreted to be of tsunamigenic origin. Coastal landforms on the western coast have significantly been influenced by (sub)-recent hurricanes, indicating that formation of the coarse-clast deposits on the eastern coast is likely to be related to past events of higher energy.

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.