Daniel Birgel

A multiple proxy and model study of Cretaceous upper ocean temperatures and atmospheric CO2 concentrations

foraminiferal d 18 O 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 87 Sr/ 86 Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The d 13 C values of phytane, combined with foraminiferal d 13 C 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 d 18 O 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 d 13 C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.

Molecular fossils reveal fluid composition and flow intensity at a Cretaceous seep

An isolated Hauterivian marine limestone from the Crimean Peninsula containing masses of articulated specimens of the dimerelloid brachiopod Peregrinella has previously been interpreted to represent a hydrocarbon-seep deposit. In order to constrain the intensity of seepage and the composition of fl uids, we investigated the lipid biomarker inventory of this seep limestone. The dominant biomarkers are (13)C-depleted isoprenoids including tail-to-tail linked pentamethylicosane (delta(13)C value: -108 parts per thousand), representing molecular fossils of methanotrophic archaea. This observation reveals that the seepage fl uids contained methane. Because the seep carbonates have been found to be only moderately (13)C-depleted (delta(13)C values as low as -14 parts per thousand), a signifi cant contribution from a less (13)C-depleted carbon source than methane, probably marine carbonate, is apparent. Such a degree of admixture of marine carbonate is typical for seep limestones resulting from low fl ow rates. The observed biomarker pattern with the prominent occurrence of biphytanes, but lacking crocetane, reveals that the methanotrophic archaea at the Hauterivian seep site were similar to archaea of the ANME-1 cluster. Archaea of this cluster are known to be able to cope with lower methane concentrations than ANME-2 archaea; therefore ANME-1 archaea are better adapted to low seepage rates and diffusive fl ow. The Peregrinella limestone contains only a small amount of early diagenetic cement. Based on a comparison with biomarker patterns of other ancient seep deposits, it is apparent that diffusive seepage typically results in limestones with little cement, whereas advective, more intense seepage appears to favor cement precipitation. If applied with caution, this supposed relationship can be used as a fi rst approximation of seepage intensity.

A new constraint on the antiquity of anaerobic oxidation of methane: Late Pennsylvanian seep limestones from southern Namibia

Late Pennsylvanian seep limestones (ca. 300 Ma) enclosed in the Ganigobis shales in southern Namibia formed by microbial activity. The process that induced carbonate precipitation was the anaerobic oxidation of methane. The presence of 13 C-depleted pentamethylicosane (PMI) (−113‰) and a mixture of crocetane and phytane (−112‰) in concert with similarly 13 C-depleted pseudohomologous series of regular isoprenoids reveals that methanotrophic archaea oxidized methane anaerobically at the ancient seep site. Biphytane and a C 39 pseudohomologue are other archaeal molecular fossils with δ 13 C values of −99‰ and −97‰, respectively. The former presence of sulfate-reducing bacteria as the syntrophic partners of methanotrophic archaea in the anaerobic oxidation of methane is indicated by isotopically depleted iso - and anteiso -alkanes. These compounds most probably derive from non-isoprenoidal monoethers and diethers, synthates of sulfate-reducing bacteria. These findings show that anaerobic oxidation of methane is at least 300 m.y. old, extending the record of this process for ~140 m.y. As the molecular fossils of archaea and bacteria are preserved in a product of their own metabolic activity (i.e., methane-derived carbonates with δ 13 C values as low as −51‰), the syngenicity of molecular fossils and enclosing deposits is unambiguous. This reveals that microbially formed rocks can represent excellent archives for studying past biogeochemical processes.

Lipid Biomarker Patterns of Phosphogenic Sediments from Upwelling Regions

Sediments of upwelling regions off Namibia, Peru, and Chile contain dense populations of large nitrate-storing sulfide-oxidizing bacteria, Thiomargarita, Beggiatoa, and Thioploca. Increased contents of monounsaturated C16 and C18 fatty acids have been found at all stations studied, especially when a high density of sulfide oxidizers in the sediments was observed. The distribution of lipid biomarkers attributed to sulfate reducers (10MeC16:0 fatty acid, ai-C15:0 fatty acid, and mono-O-alkyl glycerol ethers) compared to the distribution of sulfide oxidizers indicate a close association between these bacteria. As a consequence, the distributions of sulfate reducers in sediments of Namibia, Peru, and Chile are closely related to differences in the motility of the various sulfide oxidizers at the three study sites. Depth profiles of mono-O-alkyl glycerol ethers have been found to correlate best with the occurrence of large sulfide-oxidizing bacteria. This suggests a particularly close link between mono-O-alkyl glycerol ether-synthesizing sulfate reducers and sulfide oxidizers. The interaction between sulfide-oxidizing bacteria and sulfate-reducing bacteria reveals intense sulfur cycling and degradation of organic matter in different sediment depths.

Anaerobic and Aerobic Oxidation of Methane at Late Cretaceous Seeps in the Western Interior Seaway, USA

The Late Cretaceous (Campanian) Tepee Buttes represent a series of conical, fossiliferous limestone deposits embedded in marine shales that deposited in the Western Interior Seaway. The previously suggested origin of the Tepee Buttes at methane-seeps was confirmed by this study. δ13C values as low as −50‰ of early diagenetic carbonate phases of two Tepee Buttes near Pueblo (Colorado) reveal that methane was the major carbon source. Molecular fossils released from a methane-seep limestone contain abundant 13C-depleted archaeal lipids (PMI, biphytane; δ 13C: −118 and −102‰), derived from anaerobic methanotrophs. A suite of 13C-depleted bacterial biomarkers (branched fatty acids; −73 to −51‰) reflects the former presence of sulfate-reducing bacteria, corroborating that a syntrophic consortium of archaea and bacteria mediating anaerobic oxidation of methane already existed in Cretaceous times. Molecular fossils also suggest that methane was not exclusively oxidized in an anaerobic process. A series of unusual C34/C35-8,14-secohexahydrobenzohopanes with low δ13C values (−110 and −107‰) points to the presence of aerobic methanotrophic bacteria at the ancient seep site.

FORMATION OF DEGLACIAL MICROBIALITES IN CORAL REEFS OFF TAHITI (IODP 310) INVOLVING SULFATE-REDUCING BACTERIA

Abstract During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene–Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up ≤80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

The Paleoecology, Habitats, and Stratigraphic Range of the Enigmatic Cretaceous Brachiopod Peregrinella

Modern and Cenozoic deep-sea hydrothermal-vent and methane-seep communities are dominated by large tubeworms, bivalves and gastropods. In contrast, many Early Cretaceous seep communities were dominated by the largest Mesozoic rhynchonellid brachiopod, the dimerelloid Peregrinella, the paleoecologic and evolutionary traits of which are still poorly understood. We investigated the nature of Peregrinella based on 11 occurrences world wide and a literature survey. All in situ occurrences of Peregrinella were confirmed as methane-seep deposits, supporting the view that Peregrinella lived exclusively at methane seeps. Strontium isotope stratigraphy indicates that Peregrinella originated in the late Berriasian and disappeared after the early Hauterivian, giving it a geologic range of ca. 9.0 (+1.45/–0.85) million years. This range is similar to that of rhynchonellid brachiopod genera in general, and in this respect Peregrinella differs from seep-inhabiting mollusks, which have, on average, longer geologic ranges than marine mollusks in general. Furthermore, we found that (1) Peregrinella grew to larger sizes at passive continental margins than at active margins; (2) it grew to larger sizes at sites with diffusive seepage than at sites with advective fluid flow; (3) despite its commonly huge numerical abundance, its presence had no discernible impact on the diversity of other taxa at seep sites, including infaunal chemosymbiotic bivalves; and (4) neither its appearance nor its extinction coincides with those of other seep-restricted taxa or with global extinction events during the late Mesozoic. A preference of Peregrinella for diffusive seepage is inferred from the larger average sizes of Peregrinella at sites with more microcrystalline carbonate (micrite) and less seep cements. Because other seep-inhabiting brachiopods occur at sites where such cements are very abundant, we speculate that the various vent- and seep-inhabiting dimerelloid brachiopods since Devonian time may have adapted to these environments in more than one way.

Are the large filamentous microfossils preserved in Messinian gypsum colorless sulfide-oxidizing bacteria?

The thick gypsum deposits formed in the Mediterranean Basin during the Messinian salinity crisis incorporate dense mazes of filamentous fossils, which were interpreted as algae or cyanobacteria, thus pointing to a shallow-marine subtidal or intertidal environment. The data presented here reveal that these filaments represent remains of colorless, vacuolated sulfide-oxidizing bacteria. This interpretation is supported by the presence of small crystal aggregates of iron sulfide (pyrite) and associated polysulfide within the filamentous fossils. Pyrite and polysulfide are considered to result from early diagenetic transformation of original zero-valent sulfur globules stored within the cells, which is a clade-diagnostic feature of living and degraded sulfur bacteria. In addition to filamentous fossils, the studied gypsum crystals contain remains of euryhaline and stenohaline diatoms and clay-rich aggregates interpreted as alteration products of marine snow floccules. This peculiar fossil assemblage reflects conditions of increased productivity in the water column, triggered by high fluxes of nutrients into the basin during phases of enhanced riverine runoff and freshwater discharge. This study confirms that gypsum evaporites have great potential to preserve the early stages of the taphonomic alteration of bacterial cells, shedding light on the paleoecology of ancient hypersaline environments.

Seep deposits from northern Istria, Croatia: a first glimpse into the Eocene seep fauna of the Tethys region

Three isolated limestone deposits and their fauna are described from a middle Eocene Flysch succession in northwestern Istria, Croatia. The limestones are identified as ancient methane-seep deposits based on fabrics and characteristic mineral phases, δ 13 C carbonate values as low as −42.2 ‰ and 13 C-depleted lipid biomarkers indicative of methane-oxidizing archaea. The faint bedding of the largest seep deposit, the great dominance of authigenic micrite over early diagenetic fibrous cement, as well as biomarker patterns indicate that seepage was diffusive rather than advective. Apart from methanotrophic archaea, aerobic methanotrophic bacteria were present at the Eocene seeps as revealed by 13 C-depleted lanostanes and hopanoids. The observed corrosion surfaces in the limestones probably reflect carbonate dissolution caused by aerobic methanotrophy. The macrofauna consists mainly of chemosymbiotic bivalves such as solemyids ( Acharax ), thyasirids ( Thyasira ) and lucinids ( Amanocina ). The middle Eocene marks the rise of the modern seep fauna, but so far the fossil record of seeps of this age is restricted to the North Pacific region. The taxa found at Buje originated during the Cretaceous Period, whereas taxa typical of the modern seep fauna such as bathymodiolin mussels and vesicomyid clams are absent. Although this is only a first palaeontological glimpse into the biogeography during the rise of the modern seep fauna, it agrees with biogeographic investigations based on the modern vent fauna indicating that the dominant taxa of the modern seep fauna first appeared in the Pacific Ocean.

Methane seepage in a Cretaceous greenhouse world recorded by an unusual carbonate deposit from the Tarfaya Basin, Morocco

During the Cretaceous major episodes of oceanic anoxic conditions triggered large scale deposition of marine black shales rich in organic carbon. Several oceanic anoxic events (OAEs) have been documented including the Cenomanian to Turonian OAE 2, which is among the best studied examples to date. This study reports on a large limestone body that occurs within a black shale succession exposed in a coastal section of the Tarfaya Basin, Morocco. The black shales were deposited in the aftermath of OAE 2 in a shallow continental sea. To decipher the mode and causes of carbonate formation in black shales, a combination of element geochemistry, palaeontology, thin section petrography, carbon and oxygen stable isotope geochemistry and lipid biomarkers are used. The 13C‐depleted biphytanic diacids reveal that the carbonate deposit resulted, at least in part, from microbially mediated anaerobic oxidation of methane in the shallow subseafloor at a hydrocarbon seep. The lowest obtained δ13Ccarbonate values of −23·5‰ are not low enough to exclude other carbon sources than methane apart from admixed marine carbonate, indicating a potential contribution from in situ remineralization of organic matter contained in the black shales. Nannofossil and trace metal inventories of the black shales and the macrofaunal assemblage of the carbonate body reveal that environmental conditions became less reducing during the deposition of the background shales that enclose the carbonate body, but the palaeoenvironment was overall mostly characterized by high productivity and episodically euxinic bottom waters. This study reconstructs the evolution of a hydrocarbon seep that was situated within a shallow continental sea in the aftermath of OAE 2, and sheds light on how these environmental factors influenced carbonate formation and the ecology at the seep site.