Isotopic ratios of methane, ethane, carbon dioxide, inorganic carbon and organic matter from ODP Leg 164 sites

The isotopic characteristics of CH4 (d13C values range from -101.3 per mil to -61.1 per mil PDB, and dD values range from -256 per mil to -136 per mil SMOW) collected during Ocean Drilling Program (ODP) Leg 164 indicate that the CH4 was produced by microbial CO2 reduction and that there is not a significant contribution of thermogenic CH4 to the sampled sediment gas from the Blake Ridge. The isotopic values of CO2 (d13C range -20.6 per mil to +1.24 per mil PDB) and dissolved inorganic carbon (DIC; d13C range -37.7 per mil to +10.8 per mil PDB) have parallel profiles with depth, but with an offset of 12.5 per mil. Distinct downhole variations in the carbon isotopic composition of CH4 and CO2 cannot be explained by closed-system fractionation where the CO2 is solely derived from the locally available sedimentary organic matter (d13C -2.0 per mil ± 1.4 per mil PDB) and the CH4 is derived from CO2 reduction. The observed isotopic profiles reflect the combined effects of upwards gas migration and decreased microbial activity with depth.

Organic matter, isotopic composition of calcite veins in basement basalt and pore water at DSDP Leg 78A Holes

Sediments of the Barbados Ridge complex, cored on DSDP Leg 78A, contain low concentrations of acid-insoluble carbon (0.05-0.25%) and nitrogen (C/N 1.5-5) and dispersed C1-C6 hydrocarbons (100-800 ppb). The concentrations of organic carbon and 13C in organic carbon decrease with depth, whereas the concentration of dispersed hydrocarbons increases slightly with depth. These trends may reflect the slow oxidation of organic matter, with selective removal of 13C and slow conversion of the residual organic matter to hydrocarbons. Very minor indications of nitrogen gas were observed at about 250 meters sub-bottom at two of the drilling sites. Basement basalts have calcite veins with d13C values in the range of 2.0 to 3.2 per mil and d18O-SMOW values ranging from 28.5 to +30.6 per mil. Interstitial waters have d18O-SMOW of 0.2 to -3.5 per mil and dD-SMOW of -2 to -15 per mil. The oxygen isotopic composition of the calcite veins in the basement basalts gives estimated equilibrium fractionation temperatures in the range of 11 to 24°C, assuming precipitation from water with d18O-SMOW in the range of +0.1 to -1.0 per mil. This suggests that basalt alteration and precipitation of vein calcite occurred in contact either with warmer Campanian seawater or, later, with pore water, after burial to depths of 200- 300 meters. Pore waters from all three sites are depleted in deuterium and 18O, and dissolved sulfate is enriched in 34S at Sites 541 and 542, but not at Site 543.

Organic geochemistry of ODP Leg 135 sediment samples

The average total organic carbon (TOC) content obtained after Rock-Eval/TOC analysis of 156 sediment samples from the eight sites cored during Leg 135 is 0.05%. Hence, the TOC content of Leg 135 sediments is extremely low. The organic matter that is present in these samples is probably mostly reworked and oxidized material. Ten sediment samples were selected for extraction and analysis by gas chromatography and gas chromatography-mass spectrometry. Very low amounts of extractable hydrocarbons were obtained and some aspects of the biomarker distributions suggest that these hydrocarbons are not representative of the organic matter indigenous to the samples. A sample of an oil seep from Pili, Tongatapu was also analyzed. The seep is a biodegraded, mature oil that shows many characteristics in common with previously published analyses of oil seeps from Tongatapu. Biomarker evidence indicates that its source is a mature, marine carbonate of probable Late Cretaceous-Early Tertiary age. The source rock responsible for the Tongatapu oil seeps remains unknown.

Composition of minerals from peridotides at the Mid-Atlantic Ridge, 13°N

Peridotites (diopside-bearing harzburgites) found at 13°N of the Mid-Atlantic Ridge fall into two compositional groups. Peridotites P1 are plagioclase-free rocks with minerals of uniform composition and Ca-pyroxene strongly depleted in highly incompatible elements. Peridotites P2 bear evidence of interaction with basic melt: mafic veinlets; wide variations in mineral composition; enrichment of minerals in highly incompatible elements (Na, Zr, and LREE); enrichment of minerals in moderately incompatible elements (Ti, Y, and HREE) from P1 level to abundances 4-10 times higher toward the contacts with mafic aggregates; and exotic mineral assemblages Cr-spinel + rutile and Cr-spinel + ilmenite in peridotite and pentlandite + rutile in mafic veinlets. Anomalous incompatible-element enrichment of minerals from peridotites P2 occurred at the spinel-plagioclase facies boundary, which corresponds to pressure of about 0.8-0.9 GPa. Temperature and oxygen fugacity were estimated from spinel-orthopyroxene-olivine equilibria. Peridotites P1 with uniform mineral composition record temperature of the last complete recrystallization at 940-1050°C and FMQ buffer oxygen fugacity within the calculation error. In peridotites P2, local assemblages have different compositions of coexisting minerals, which reflects repeated partial recrystallization during heating to magmatic temperatures (above 1200°C) and subsequent reequilibration at temperatures decreasing to 910°C and oxygen fugacity significantly higher than FMQ buffer (delta log fO2 = 1.3-1.9). Mafic veins are considered to be a crystallization product from basic melt enriched in Mg and Ni via interaction with peridotite. The geochemical type of melt reconstructed by the equilibrium with Ca-pyroxene is defined as T-MORB: (La/Sm)_N~1.6 and (Ce/Yb) )_N~2.3 that is well consistent with compositional variations of modern basaltic lavas in this segment of the Mid-Atlantic Ridge, including new data on quenched basaltic glasses.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during Maria S. Merain cruise MSM18/5

Nitrogen fixation data from the cruise number MSM18/5 with research vessel "Maria S. Merian" from 22.08.-20.09.2011 (from Walvis Bay to Walvis Bay) in front of Angola and northern Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (535 ml) at light intensities that resemble the in situ light intensities of the sampling depth after 15N2 gas was injected to the sample. After the incubation time of 6 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta 15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta 15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

Organic geochemistry of sediment samples from Prydz Bay

High molecular weight aliphatic hydrocarbons were extracted from sediments at two sites (741 and 742) drilled during Ocean Drilling Program Leg 119 in Prydz Bay, a major embayment on the continental shelf of East Antarctica. The distributions of n-alkanes and triterpenoid and steroid hydrocarbons suggest that the n-alkanes and steranes are mainly of terrestrial origin and that the hydrocarbons are immature to slightly mature in the Lower Cretaceous sediments and immature to mature in the Tertiary sediments. At Site 741, the Lower Cretaceous depositional sequence, which is generally characterized by immature hydrocarbons, is interrupted by sediment having more mature components, suggesting a change of source during part of Early Cretaceous time. At Site 742, the mature geochemical parameters of a Pliocene sample correlate with results reported elsewhere for Site 739. In all but one of the other Tertiary samples, the geochemical parameters indicate intermediate maturity. The Lower Cretaceous and Pliocene sediments average about 1.9% organic carbon, a value of interest from the point of view of potential sources of petroleum offshore from Antarctica.

Nitrogen isotopic composition in South China Sea sediments

The d15N of surface and down-core sediments spanning the last 20-200 kyr from the entire South China Sea (SCS) ranges only from ~3.0 to ~6.5 per mil, with no correlation with discernible paleoclimatic/oceanographic changes. Detailed profiles of the uppermost sediment column, including fluff samples, indicate a minor diagenetic overprint of 0.3-1.2 per mil at the sediment-water interface. The absence of any correlation with reconstructed (glacial-interglacial) changes in primary production, terrigenous input, and/or sea level related basin configuration is attributed to a complete consumption of nitrate during primary production in this marginal basin during at least the last 140,000 years. This, in turn, implies that the d15N of the nitrate used during primary production remained approximately constant during the last climatic cycle. The proposed scenario infers an unchanged nitrogen isotopic composition of the western Pacific subsurface nitrate between glacial and interglacial stages as well as during terminations and thus constrains proposed changes in the oceanic N inventory.

Organic matter preservation in turbidites on the Madeira Abyssal Plain

Oxidized intervals of five organic-rich Madeira Abyssal Plain (MAP) turbidites deposited during the Miocene, Pliocene, and Pleistocene all displayed comparable major loss of total organic carbon (TOC) (84 ± 3.1%) accompanied by a negative isotopic (d13C) shift ranging from -0.3 to -2.9 per mil. Major but significantly lower loss of total nitrogen (Ntot, 61 ± 7.1%) also occurred, leading to a decrease in TOC relative to Ntot (C/Ntot) and a +1.3 to 2.7 per mil Ntot isotopic (d15N) shift. Compound specific isotopic measurements on plant wax n-alkanes indicate the terrestrial organic component in the unoxidized deposits is 13C-enriched owing to significant C4 contribution. Selective preservation of terrestrial relative to marine organic carbon could account for the d13C behavior of TOC upon oxidation but only if a 13C-depleted component of the bulk terrestrial signal is selectively preserved in the process. Although the C/Ntot decrease and positive d15N shift seems inconsistent with selective terrestrial organic preservation, results from analysis of a Modern eolian dust sample collected in the vicinity indicate these observations are compatible. Regardless of the specific explanation for these isotopic observations, however, our findings provide evidence that paleoreconstruction of properties such as pCO2 using the d13C of TOC is a goal fraught with uncertainty whether or not the marine sedimentary record considered is 'contaminated' with significant terrestrial input. Nonetheless, despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation, intensive organic geochemical proxies such as the alkenone unsaturation index, UK'37, appear resistant to change and thereby retain their paleoceanographic promise.

Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.

(Table 2) Rates of nitrate and ammonium uptake, concentrations of particulate organic nitrogen and carbon, and dissolved nitrate and ammonium in waters of the Black Sea August-September 1990 and November 1991

To study inorganic nitrogen uptake rates by microplankton in the Black Sea the first 15N-experiments were carried out in August-September 1990 and in November 1991. In surface waters nitrate uptake rates varied from 5.7 to 28.5 nM/l/h in summer and from 1.9 to 7.8 nM/l/h in autumn. In both seasons maximal and minimal rates were observed in frontal zones of shelf/slope areas and in open waters, respectively. In summer average nitrate uptake rate per unit of particulate organic nitrogen was 0.0037 1/h for all stations. In autumn it varied from 0.0007 1/h in the central part of the sea to 0.0033 1/h in the slope near the southeastern Crimean coast. In autumn ammonium uptake rate varied from 7.1 to 22.2 nM/l/h and from 0.0025 to 0.00094 1/h. Ammonium uptake correlated linearly with nitrate uptake, with new production being 22-36% of total summary nitrate and ammonium uptake. There was a linear correlation between nitrogen uptake and chlorophyll a concentrations in the Black Sea. In the water column in autumn both nitrate and ammonium uptake decreased as chlorophyll a concentration diminishes with depth.

Characteristics of sediments from Amvrakikos Gulf, Greece

The evolution of environmental changes during the last decades and the impact on the living biomass in the western part of Amvrakikos Gulf was investigated using abundances and species distributions of benthic foraminifera and lipid biomarker concentrations. These proxies indicated that the gulf has markedly changed due to eutrophication. Eutrophication has led to a higher productivity, a higher bacterial biomass, shifts towards opportunistic and tolerant benthic foraminifera species (e.g. Bulimina elongata, Nonionella turgida, Textularia agglutinans, Ammonia tepida) and a lower benthic species density. Close to the Preveza Strait (connection between the gulf and the Ionian Sea), the benthic assemblages were more diversified under more oxygenated conditions. Sea grass meadows largely contributed to the organic matter at this sampling site. The occurrence of isorenieratane, chlorobactane and lycopane supported by oxygen monitoring data indicated that anoxic (and partly euxinic) conditions prevailed seasonally throughout the western part of the gulf with more severe oxygen depletion towards the east. Increased surface water temperatures have led to a higher stratification, which reduced oxygen resupply to bottom waters. Altogether, these developments led to mass mortality events and ecosystem decline in Amvrakikos Gulf.