Pore water isotopic ratios of CO2 and SO4, and sediment CH4 content of ODP Leg 164 sites

A unique set of geochemical pore-water data, characterizing the sulfate reduction and uppermost methanogenic zones, has been collected at the Blake Ridge (offshore southeastern North America) from Ocean Drilling Program (ODP) Leg 164 cores and piston cores. The d13C values of dissolved CO2 (sum CO2) are as 13C-depleted as -37.7 per mil PDB (Site 995) at the sulfate-methane interface, reflecting a substantial contribution of isotopically light carbon from methane. Although the geochemical system is complex and difficult to fully quantify, we use two methods to constrain and illustrate the intensity of anaerobic methane oxidation in Blake Ridge sediments. An estimate using a two-component mixing model suggests that ~24% of the carbon residing in the sum CO2 pool is derived from biogenic methane. Independent diagenetic modeling of a methane concentration profile (Site 995) indicates that peak methane oxidation rates approach 0.005 µmol/cm**3/yr, and that anaerobic methane oxidation is responsible for consuming ~35% of the total sulfate flux into the sediments. Thus, anaerobic methane oxidation is a significant biogeochemical sink for sulfate, and must affect interstitial sulfate concentrations and sulfate gradients. Such high proportions of sulfate depletion because of anaerobic methane oxidation are largely undocumented in continental rise sediments with overlying oxic bottom waters. We infer that the additional amount of sulfate depleted through anaerobic methane oxidation, fueled by methane flux from below, causes steeper sulfate gradients above methane-rich sediments. Similar pore water chemistries should occur at other methane-rich, continental-rise settings associated with gas hydrates.

Main components and isotopic composition of gases from mineral waters of the Taman Peninsula and Caucasus

Helium isotope composition as an indicator of the mantle-derived component was studied in gases from mineral springs, stratal waters, and mud volcanoes developed west of the Teberda River valley (10 objects) and two springs in the central segment of the Greater Caucasus orogen between the active El'brus and Kazbek volcanoes. In the western segment of the orogen ratios of 3He/4He = R_corr vary from 46x10**-8 to 114x10**-8 (from 0.33 to 0.81 R_atm, where R_atm = 1.4x10**-6 is the atmospheric ratio). They are substantially lower relative to ratios in the vicinity of El'brus and Kazbek and close to those in samples from the central segment (from 70x10**-8 to 134x10**-8 (from 0.50 to 0.96 R_atm), as well as to ratios previously recorded in the Caucasian Mineral Waters (CMW) area. Moreover, concentration of 3He in them is notably higher than its crustal radiogenic level characteristic of mud volcanoes in the Taman Peninsula, where 3He/4He varies from 1.4x10**-8 to 2.8x10**-8 (from 0.01 to 0.02 R_atm). Nitrogen-methane gas from northern piedmonts of the western Caucasus also contains nonatmogenic components including radiogenic 40Ar (40Ar/36Ar = 900), excessive nitrogen (~87% of total N2 concentration in sample) and mantle He. These data specify distribution of mantle derivates along the orogen strike and age of intrusive magmatic activity in its different segments.

Results from field observations and in situ 13C feeding experiments in the Nazaré Canyon conducted during RRS James Cook 10 cruise Leg 2

Submarine canyon systems provide a heterogeneous habitat for deep-sea benthos in terms of topography, hydrography, and the quality and quantity of organic matter present. Enhanced meiofauna densities as found in organically enriched canyon sediments suggest that nematodes, as the dominant metazoan meiobenthic taxon, may play an important role in the benthic food web of these sediments. Very little is known about the natural diets and trophic biology of deep-sea nematodes, but enrichment experiments can shed light on nematode feeding selectivity and trophic position. An in-situ pulse-chase experiment (Feedex) was performed in the Nazaré Canyon on the Portuguese margin in summer 2007 to study nematode feeding behaviour. 13C-labelled diatoms and bacteria were added to sediment cores which were then sampled over a 14-day period. There was differential uptake by the nematode community of the food sources provided, indicating selective feeding processes. 13C isotope results revealed that selective feeding was less pronounced at the surface, compared to the sediment subsurface. This was supported by a higher trophic diversity in surface sediments compared to the subsurface, implying that more food items may be used by the nematode community at the sediment surface. Predatory and scavenging nematodes contributed relatively more to biomass than other feeding types and can be seen as key contributors to the nematode food web at the canyon site. Non-selective deposit feeding nematodes were the dominant trophic group in terms of abundance and contributed substantially to total nematode biomass. The high levels of 'fresh' (bioavailable) organic matter input and moderate hydrodynamic disturbance of the canyon environment lead to a more complex trophic structure in canyon nematode communities than that found on the open continental slope, and favours predator/scavengers and non-selective deposit feeders.

Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

Ikaite of sediment cores from the Zaire deep-sea fan

Most concentration profiles of sulfate in continental margin sediments show constant or continuously increasing gradients from the benthic boundary layer down to the deep sulfate reduction zone. However, a very marked change in this gradient has been observed several meters below the surface at many locations, which has been attributed to anoxic sulfide oxidation or to non-local transport mechanisms of pore waters. The subject of this study is to investigate whether this feature could be better explained by non-steady state conditions in the pore-water system. To this end, data are presented from two gravity cores recovered from the Zaire deep-sea fan. The sediments at this location can be subdivided into two sections. The upper layer, about 10 m thick, consists of stratified pelagic deposits representing a period of continuous sedimentation over the last 190 kyr. It is underlain by a turbidite sequence measuring several meters in thickness, which contains large crystals of authigenic calcium carbonate (ikaite: CaCO3·6H2O). Ikaite delta13C values are indicative of a methane carbon contribution to the CO2 pool. Radiocarbon ages of these minerals, as well as of the adjacent bulk sediments, provide strong evidence that the pelagic sediments have overthrust the lower section as a coherent block. Therefore, the emplacement of a relatively undisturbed sediment package is postulated. Pore-water profiles show the depth of the sulfate-methane transition zone within the turbiditic sediments. By the adaptation of a simple transport-reaction model, it is shown that the change in the geochemical environmental conditions, resulting from this slide emplacement, and the development towards a new steady state are fully sufficient to explain all features related to the pore-water profiles, particularly, [SO4]2- and dissolved inorganic carbon (DIC). The model shows that the downslope transport took place about 300 yr ago.

Sable isotope record and sediment composition of Cretaceous samples of Deremara Rise

We estimate tropical Atlantic upper ocean temperatures using oxygen isotope and Mg/Ca ratios in well-preserved planktonic foraminifera extracted from Albian through Santonian black shales recovered during Ocean Drilling Program Leg 207 (North Atlantic Demerara Rise). On the basis of a range of plausible assumptions regarding seawater composition at the time the data support temperatures between 33° and 42°C. In our low-resolution data set spanning ~84-100 Ma a local temperature maximum occurs in the late Turonian, and a possible minimum occurs in the mid to early late Cenomanian. The relation between single species foraminiferal d18O and Mg/Ca suggests that the ratio of magnesium to calcium in the Turonian-Coniacian ocean may have been lower than in the Albian-Cenomanian ocean, perhaps coincident with an ocean 87Sr/86Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The d13C values of phytane, combined with foraminiferal d13C and inferred temperatures, were used to estimate atmospheric carbon dioxide concentrations through this interval. Estimates of atmospheric CO2 concentrations range between 600 and 2400 ppmv. Within the uncertainty in the various proxies, there is only a weak overall correspondence between higher (lower) tropical temperatures and more (less) atmospheric CO2. The GENESIS climate model underpredicts tropical Atlantic temperatures inferred from ODP Leg 207 foraminiferal d18O and Mg/Ca when we specify approximate CO2 concentrations estimated from the biomarker isotopes in the same samples. Possible errors in the temperature and CO2 estimates and possible deficiencies in the model are discussed. The potential for and effects of substantially higher atmospheric methane during Cretaceous anoxic events, perhaps derived from high fluxes from the oxygen minimum zone, are considered in light of recent work that shows a quadratic relation between increased methane flux and atmospheric CH4 concentrations. With 50 ppm CH4, GENESIS sea surface temperatures approximate the minimum upper ocean temperatures inferred from proxy data when CO2 concentrations specified to the model are near those inferred using the phytane d13C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.

Sedimentation and mineral analysis on sediment cores from the Lena Delta

Core and outcrop analysis from Lena mouth deposits have been used to reconstruct the Late Quaternary sedimentation history of the Lena Delta. Sediment properties (heavy mineral composition, grain size characteristics, organic carbon content) and age determinations (14C AMS and IR-OSL) are applied to discriminate the main sedimentary units of the three major geomorphic terraces, which form the delta. The development of the terraces is controlled by complex interactions among the following four factors: (1) Channel migration. According to the distribution of 14C and IR-OSL age determinations of Lena mouth sediments, the major river runoff direction shifted from the west during marine isotope stages 5-3 (third terrace deposits) towards the northwest during marine isotope stage 2 and transition to stage 1 (second terrace), to the northeast and east during the Holocene (first terrace deposits). (2) Eustasy. Sea level rise from Last Glacial lowstand to the modern sea level position, reached at 6-5 ka BP, resulted in back-filling and flooding of the palaeovalleys. (3) Neotectonics. The extension of the Arctic Mid-Ocean Ridge into the Laptev Sea shelf acted as a halfgraben, showing dilatation movements with different subsidence rates. From the continent side, differential neotectonics with uplift and transpression in the Siberian coast ridges are active. Both likely have influenced river behavior by providing sites for preservation, with uplift, in particular, allowing accumulation of deposits in the second terrace in the western sector. The actual delta setting comprises only the eastern sector of the Lena Delta. (4) Peat formation. Polygenetic formation of ice-rich peaty sand (''Ice Complex'') was most extensive (7-11 m in thickness) in the southern part of the delta area between 43 and 14 ka BP (third terrace deposits). In recent times, alluvial peat (5-6 m in thickness) is accumulated on top of the deltaic sequences in the eastern sector (first terrace).

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Calcium isotope ratios of porewaters of ODP Leg 204 holes

The calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during Ocean Drilling Program (ODP) provides first insight into the different processes that control Ca geochemistry in clastic marine, organic-rich sedimentary environments. In 4 sites drilled during Leg 204 at Hydrate Ridge (Cascadia Margin, offshore Oregon/USA), sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section. These reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate, which is reflected in a pronounced decrease in calcium concentration. Although Ca isotope fractionation is observed during carbonate precipitation, Ca concentration in the pore fluids from ODP Leg 204 is decoupled from Ca isotopy, which seems to be mainly controlled by the release of light Ca isotopes that completely overprint the carbonate formation effect. Different processes, such as the release of organically bound Ca, ion exchange and ion pair formation may be responsible for the released light Ca. Deeper within the sedimentary section, additional processes such as ash alteration influence the Ca isotopic composition of the porewater. Two sites, drilled into the deeper core of the accretionary prism, reveal the nature of fluids which have reacted with the oceanic basement. These deep fluids are characterized by relatively high Ca concentrations and low d44/40Ca ratios.

The Paleocene-Eocene boundary in ODP Leg 208 sites

The Paleocene-Eocene thermal maximum (PETM) has been attributed to the rapid release of ~2000 * 10**9 metric tons of carbon in the form of methane. In theory, oxidation and ocean absorption of this carbon should have lowerd deep-sea pH, thereby triggering a rapid (<10,000-year) shoaling of the calcite compensation depth (CCD), followed by gradual recovery. Here we present geochemical data from five new South Atlantic deep-sea sections that constrain the timing and extent of massive sea-floor carbonate dissolution coincident with the PETM. The sections, from between 2.7 and 4.8 kilometers water depth, are marked by a prominent clay layer, the character of which indicates that the CCD shoaled rapidly (<10,000 years) by more than 2 kilometers and recovered gradually (>100,000 years). These findings indicate that a large mass of carbon (>>2000 * 10**9 metric tons of carbon) dissolved in the ocean at the Paleocene-Eocene boundary and that permanent sequestration of this carbon occurred through silicate weathering feedback.

Particulate organic matter (POM) of samples from the Lena River delta

Particulate organic matter (POM) derived from permafrost soils and transported by the Lena River represents a quantitatively important terrestrial carbon pool exported to Laptev Sea sediments (next to POM derived from coastal erosion). Its fate in a future warming Arctic, i.e., its remobilization and remineralization after permafrost thawing as well as its transport pathways to and sequestration in marine sediments, is currently under debate. We present one of the first radiocarbon (14C) data sets for surface water POM within the Lena Delta sampled in the summers of 2009 - 2010 and spring 2011 (n = 30 samples). The bulk D14C values varied from -55 to -391 per mil translating into 14C ages of 395 to 3920 years BP. We further estimated the fraction of soil-derived POM to our samples based on (1) particulate organic carbon to particulate nitrogen ratios (POC : PN) and (2) on the stable carbon isotope (d13C) composition of our samples. Assuming that this phytoplankton POM has a modern 14C concentration, we inferred the 14C concentrations of the soil-derived POM fractions. The results ranged from -322 to -884 per mil (i.e., 3060 to 17 250 14C years BP) for the POC : PN-based scenario and from -261 to -944 per mil (i.e., 2370 to 23 100 14C years BP) for the d13C-based scenario. Despite the limitations of our approach, the estimated D14C values of the soil-derived POM fractions seem to reflect the heterogeneous 14C concentrations of the Lena River catchment soils covering a range from Holocene to Pleistocene ages better than the bulk POM D14C values. We further used a dual-carbon-isotope three-end-member mixing model to distinguish between POM contributions from Holocene soils and Pleistocene Ice Complex (IC) deposits to our soil-derived POM fraction. IC contributions are comparatively low (mean of 0.14) compared to Holocene soils (mean of 0.32) and riverine phytoplankton (mean of 0.55), which could be explained with the restricted spatial distribution of IC deposits within the Lena catchment. Based on our newly calculated soil-derived POM D14C values, we propose an isotopic range for the riverine soil-derived POM end member with D14C of -495 ± 153 per mil deduced from our d13C-based binary mixing model and d13C of -26.6 ± 1 per mil deduced from our data of Lena Delta soils and literature values. These estimates can help to improve the dual-carbon-isotope simulations used to quantify contributions from riverine soil POM, Pleistocene IC POM from coastal erosion, and marine POM in Siberian shelf sediments.

Geochemistry of secondary carbonates in ODP Leg 115 basalts

This report presents the results of a study of the stable isotopic and chemical composition of secondary carbonate minerals precipitated within basalts at Ocean Drilling Program Sites 707 and 715. At Site 715, the secondary carbonates are all composed of calcite and display a narrow range of carbon and oxygen stable isotope ratios, with values ranging from -2.75 per mil to 1.95 per mil PDB and -0.27 per mil to 2.86 per mil PDB, respectively. Strontium, iron, and manganese values of the samples are generally low. The geochemistry of Site 715 samples indicates that they precipitated from seawater-domi- nated fluids, at low temperatures, as is typical of secondary carbonates from most Deep Sea Drilling Project sites. In contrast, at Site 707, aragonite, siderite, and manganese-rich calcite occur as secondary carbonates in addition to calcite. The carbon isotopes of the Site 707 carbonates of all rock types are depleted in 13C. Values range from -2.79 per mil to -16.43 per mil PDB. Oxygen isotope values do not show a wide variation, ranging from -1.78 per mil to 1.17 per mil. The strontium contents of the samples range from 5200 to 8100 ppm for aragonites, and from 145 to 862 ppm for calcites. Iron and manganese contents are high in calcites and siderites and low in aragonites. Site 707 carbonates precipitated at low temperatures in a fairly closed system, in which basalt-seawater interaction has greatly influenced the chemistry of the pore fluids. The reactions occurring within the system before and in conjunction with secondary carbonate precipita- tion include oxidation of isotopically light methane, derived from fluids circulating within the basalts, and reduction of substantial amounts of iron and manganese oxides from the basalts.

Stable carbon and oxygen isotopes from samples of the Anaximander seamounts in the eastern Mediterranean Sea

Porous seep-carbonates are exposed at mud volcanoes in the eastern Mediterranean Sea. The 13C-depleted aragonitic carbonates formed as a consequence of the anaerobic oxidation of methane in a shallow sub-surface environment. Besides the macroscopically visible cavernous fabric, extensive carbonate corrosion was revealed by detailed analysis. After erosion of the background sediments, the carbonates became exposed to oxygenated bottom waters that are periodically influenced by the release of methane and upward diffusion of hydrogen sulphide. We suggest that carbonate corrosion resulted from acidity locally produced by aerobic oxidation of methane and hydrogen sulphide in the otherwise, with respect to aragonite, oversaturated bottom waters. Although it remains to be tested whether the mechanisms of carbonate dissolution suggested herein are valid, this study reveals that a better estimate of the significance of corrosion is required to assess the amount of methane-derived carbon that is permanently fixed in seep-carbonates.