Organic and inorganic geochemistry and archaeal community composition of hypersaline sediments from Orca Basin, RV Atlantis Expedition AT18-02

Among the most extreme habitats on Earth, dark, deep, anoxic brines host unique microbial ecosystems that remain largely unexplored. As the terminal step of anaerobic degradation of organic matter, methanogenesis is a potentially significant but poorly constrained process in deep-sea hypersaline environments. We combined biogeochemical and phylogenetic analyses as well as incubation experiments to unravel the origin of methane in hypersaline sediments of Orca Basin in the northern Gulf of Mexico. Substantial concentrations of methane (up to 3.4 mM) coexisted with high concentrations of sulfate (16-43 mM) in two sediment cores retrieved from the northern and southern parts of Orca Basin. The strong depletion of 13C in methane (-77 to -89 per mill) pointed towards a biological source. While low concentrations of competitive substrates limited the significance of hydrogenotrophic and acetoclastic methanogenesis, the presence of non-competitive methylated substrates (methanol, trimethylamine, dimethyl sulfide, dimethylsulfoniopropionate) supported the potential for methane generation through methylotrophic methanogenesis. Thermodynamic calculations demonstrated that hydrogenotrophic and acetoclastic methanogenesis were unlikely to occur under in situ conditions, while methylotrophic methanogenesis from a variety of substrates was highly favorable. Likewise, carbon isotope relationships between methylated substrates and methane supported methylotrophic methanogenesis as the major source of methane. Stable isotope tracer and radiotracer experiments with 13C bicarbonate, acetate and methanol as well as 14C-labeled methylamine indicated that methylotrophic methanogenesis was the predominant methanogenic pathway. Based on 16S rRNA gene sequences, halophilic methylotrophic methanogens related to the genus Methanohalophilus dominated the benthic archaeal community in the northern basin but also occurred in the southern basin. High abundances of methanogen lipid biomarkers such as intact polar and polyunsaturated hydroxyarchaeols were detected in sediments from the northern basin, with lower abundances in the southern basin. Strong 13C-depletion of saturated and monounsaturated hydroxyarchaeol were consistent with methylotrophic methanogenesis as the major methanogenic pathway. Collectively, the availability of methylated substrates, thermodynamic calculations, experimentally determined methanogenic activity as well as lipid and gene biomarkers strongly suggested methylotrophic methanogenesis as predominant pathway of methane formation in the presence of sulfate in Orca Basin sediments.

Isotopic composition of diet and tissues, and isotope discrimination factors for pink-footed and barnacle geese, Svalbard

Breeding in the high Arctic is time constrained and animals should therefore start with their annual reproduction as early as possible. To allow for such early reproduction in migratory birds, females arrive at the breeding grounds either with body stores or they try to rapidly develop their eggs after arrival using local resources. Svalbard breeding barnacle geese Branta leucopsis have to fly non-stop for about 1100 km from their last continental staging site to the archipelago making the transport of body stores costly. However, environmental conditions at the breeding grounds are highly unpredictable favouring residual body stores allowing for egg production after arrival on the breeding grounds. We estimated the reliance on southern continental resources, i.e. body stores for egg formation, in barnacle geese using stable isotope ratios in the geese's forage along the flyway and in their eggs. Females adopted mixed breeding strategies by using southern resources as well as local resources to varying extents for egg formation. Southern capital in lipid-free yolk averaged 41% (range: 23-65%), early laid eggs containing more southern capital than eggs laid late in the season. Yolk lipids and albumen did not vary over time and averaged a southern capital proportion of 54% (range: 32-73%) and 47% (range: 25-88%), respectively. Our findings indicate that female geese vary the use of southern resources when synthesizing their eggs and this allocation also varies among egg tissues. Their mixed and flexible use of distant and local resources potentially allows for adaptive adjustments to environmental conditions encountered at the archipelago just before breeding.

Palynological counts (dinoflagellate cysts) and foraminiferal geochemistry (d18O, d18C, Mg/Ca) of the Pliocene-Pleistocene transition in the North Atlantic

The position of the North Atlantic Current (NAC) during the intensification of Northern Hemisphere glaciation (iNHG) has been evaluated using dinoflagellate cyst assemblages and foraminiferal geochemistry from a ~260 kyr interval straddling the base of the Quaternary System from two sites: eastern North Atlantic Deep Sea Drilling Project Site 610 in the path of the present NAC and central North Atlantic Integrated Ocean Drilling Program Site U1313 in the subtropical gyre. Stable isotope and foraminiferal Mg/Ca analyses confirm cooling near the marine isotope stage (MIS) G7-G6 transition (2.74 Ma). However, a continued dominance of the dinoflagellate cyst Operculodinium centrocarpum sensu Wall and Dale (1966) indicates an active NAC in the eastern North Atlantic for a further 140 kyr. At MIS 104 (~2.60 Ma), a profound dinoflagellate cyst assemblage turnover indicates NAC shutdown in the eastern North Atlantic, implying elevated atmospheric pressure over the Arctic and a resulting shift in the westerlies that would have driven the NAC. These findings challenge recent suggestions that there was no significant southward shift of the NAC or the Arctic Front during iNHG, and reveal a fundamental climatic reorganization near the base of the Quaternary.

(Table 1) Sulfur contents and isotope composition in rocks and minerals from DSDP/ODP Hole 504B

DSDP Hole 504B is the only hole in oceanic crust to penetrate through the volcanic section and into hydrothermally altered sheeted dikes. We have carried out petrologic and sulfur isotopic analyses of sulfide and sulfate minerals and whole rocks from the core in order to place constraints on the geochemistry of sulfur during hydrothermal alteration of ocean crust. The nearly 600 m-thick pillow section has lost sulfur to seawater and has net d34S = -1.8 per mil due to degassing of SO2 during crystallization and subsequent low temperature interaction with seawater. Hydrothermally altered rocks in the 200 m-thick transition zone are enriched in S and 34S (4300 ppm and +3.0 +/-1.2 per mil, respectively), whereas the more than 500 m of sheeted dikes contain 720 ppm S with d34S = +0.6 +/-1.4 per mil. These data are consistent with the presence of predominantly basaltic sulfur in hydrothermal fluids deep in the crust: following precipitation of anhydrite during seawater recharge, small amounts of seawater sulfate were reduced at temperatures >250°C through conversion of igneous pyrrhotite to secondary pyrite and minor oxidation of ferrous iron in the crust. The S- and 34S-enrichments of the transition zone are the results of seawater sulfate reduction and sulfide deposition during subsurface mixing between upwelling hot (up to 350°C) hydrothermal fluids and seawater. Seawater sulfate was probably reduced through oxidation of ferrous iron in hydrothermal fluids and in the transition zone rocks. Alteration of the upper crust resulted in loss of basaltic sulfur to seawater, fixation of minor seawater sulfur in the crust and redistribution of magmatic sulfur within the crust. This caused net increases in sulfur content and d34S of the upper 1.8 km of the oceanic crust.

Petrography, microprobe analyses and isotope composition of ultramafic rock from the northern Haskard Highlands, Shackleton Range, East Antarctica

In the Shackleton Range of East Antarctica, garnet-bearing ultramafic rocks occur as lenses in supracrustal high-grade gneisses. In the presence of olivine, garnet is an unmistakable indicator of eclogite facies metamorphic conditions. The eclogite facies assemblages are only present in ultramafic rocks, particularly in pyroxenites, whereas other lithologies - including metabasites - lack such assemblages. We conclude that under high-temperature conditions, pyroxenites preserve high-pressure assemblages better than isofacial metabasites, provided the pressure is high enough to stabilize garnet-olivine assemblages (i.e. >=18-20 kbar). The Shackleton Range ultramafic rocks experienced a clockwise P-T path and peak conditions of 800-850 °C and 23-25 kbar. These conditions correspond to ~70 km depth of burial and a metamorphic gradient of 11-12 °C/km that is typical of a convergent plate-margin setting. The age of metamorphism is defined by two garnet-whole-rock Sm-Nd isochrons that give ages of 525 ± 5 and 520 ± 14 Ma corresponding to the time of the Pan-African orogeny. These results are evidence of a Pan-African suture zone within the northern Shackleton Range. This suture marks the site of a palaeo-subduction zone that likely continues to the Herbert Mountains, where ophiolitic rocks of Neoproterozoic age testify to an ocean basin that was closed during Pan-African collision. The garnet-bearing ultramafic rocks in the Shackleton Range are the first known example of eclogite facies metamorphism in Antarctica that is related to the collision of East and West Gondwana and the first example of Pan-African eclogite facies ultramafic rocks worldwide. Eclogites in the Lanterman Range of the Transantarctic Mountains formed during subduction of the palaeo-Pacific beneath the East Antarctic craton.

Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.

Fatty acid composition, element concentration and isotope ratios of sea ice algae sampled in Rijpfjorden, Svalbard

The accelerating decrease of Arctic sea ice substantially changes the growth conditions for primary producers, particularly with respect to light. This affects the biochemical composition of sea ice algae, which are an essential high-quality food source for herbivores early in the season. Their high nutritional value is related to their content of polyunsaturated fatty acids (PUFAs), which play an important role for successful maturation, egg production, hatching and nauplii development in grazers. We followed the fatty acid composition of an assemblage of sea ice algae in a high Arctic fjord during spring from the early bloom stage to post bloom. Light conditions proved to be decisive in determining the nutritional quality of sea ice algae, and irradiance was negatively correlated with the relative amount of PUFAs. Algal PUFA content decreased on average by 40 % from April to June, while algal biomass (measured as particulate carbon, C) did not differ. This decrease was even more pronounced when algae were exposed to higher irradiances due to reduced snow cover. The ratio of chlorophyll a (chl a) to C, as well as the level of photoprotective pigments, confirmed a physiological adaptation to higher light levels in algae of poorer nutritional quality. We conclude that high irradiances are detrimental to sea ice algal food quality, and that the biochemical composition of sea ice algae is strongly dependent on growth conditions.

Concentration and isotope composition of sulphur in sediments and pore water at DSDP Leg 70 Holes

Data obtained while investigating the mounds area near the Galapagos Spreading Center demonstrate the direct influence of solutions derived from the interaction of seawater and young oceanic crust on the sedimentary cover. Investigation of metalliferous sediments from the mid-oceanic ridges, the Galapagos mounds, and the FAMOUS-area zone formations have shown that this influence and the resulting products are dependent on composition, temperature, and conditions of solution input. The study of sulfur in upwardly migrating solutions and the interaction of these solutions with sediments is of great interest. Investigations of different types of hydrothermally derived formations (Edmond, et al., 1979; Spiess et al., 1980; Styrt et al., 1981; Rosanova 1976; Grinenko et al., 1978) have shown the significant role of sulfur-bearing minerals in deposits formed from hightemperature solutions. In contrast, the addition of hydrothermal sulfur is negligible in those metalliferous sediments that precipitated as a result of the interaction between the solutions and open seawater (Bonatti et al., 1972, 1976; Gordeev et al., 1979; Migdisov, Bogdanov, et al., 1979). For example, sulfides are absent in clearly oxidized metalliferous sediments from the East Pacific Rise (EPR). Barite sulfur from these sediments is identical with seawater sulfate sulfur in isotope composition (Grinenko et al., 1978). Gurvich and Bogdanov (1977) have suggested that barium from EPR metalliferous sediments results completely from biological activity and from the components of ocean waters. Edmond et al. (1979) report that low-temperature springs from the Galapagos Rift axis contain two types of solutions: those with and those without H2S.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Benthic foraminiferal fauna and isotope record in Holocene sediments of the northwest Indian Ocean

Historically, the Holocene has been considered an interval of relatively stable climate. However, recent studies from the northern Arabian Sea (Netherlands Indian Ocean Program 905) suggested high-amplitude climate shifts in the early and middle Holocene based on faunal and benthic isotopic proxy records. We examined benthic foraminiferal faunal and stable isotopic data from Ocean Drilling Program (ODP) Site 723 and total organic carbon data from ODP Site 724, Oman Margin (808 and 593 m water depths, respectively). At Site 723 the mid-Holocene shift in d18O values of infaunal benthic species Uvigerina peregrina (1.4 per mil) is 3 times larger than that of epifaunal benthic species Cibicides kullenbergi recorded at Site NIOP 905 off Somalia. However, none of the five other benthic species we measured at Hole 723A exhibits such a shift in d18O. We speculate that the late Holocene d18O decrease in U. peregrina represents species-specific changes in ecological habitat or food preference in response to changes in surface and deep ocean circulation. While the stable isotopic data do not appear to indicate a middle Holocene climatic shift, our total organic carbon and benthic faunal assemblage data do indicate that the early Holocene deep Arabian Sea was influenced by increased ventilation perhaps by North Atlantic Deep Water and/or Circumpolar Deep Water incursions into the Indian Ocean, leading to remineralization of organic matter and a relatively weak early Holocene oxygen minimum zone in the northwest Arabian Sea in spite of strong summer monsoon circulation.