Paleomegnetic and geochemistry of sediments from the early Aptian Oceanic Anoxic Event

The early Aptian Oceanic Anoxic Event (OAE1a, 120 Ma) represents a geologically brief time interval in the mid-Cretaceous greenhouse world that is characterized by increased organic carbon accumulation in marine sediments, sudden biotic changes, and abrupt carbon-isotope excursions indicative of significant perturbations to global carbon cycling. The brevity of these drastic environmental changes (< 10**6 year) and the typically 10**6 year temporal resolution of the available chronologies, however, represent a critical gap in our knowledge of OAE1a. We have conducted a high-resolution investigation of three widely distributed sections, including the Cismon APTICORE in Italy, Santa Rosa Canyon in northeastern Mexico, and Deep Sea Drilling Project (DSDP) Site 398 off the Iberian margin in the North Atlantic Ocean, which represent a range of depositional environments where condensed and moderately expanded OAE1a intervals are recorded. The objectives of this study are to establish orbital chronologies for these sections and to construct a common, high-resolution timescale for OAE1a. Spectral analyses of the closely-spaced (corresponding to ~5 to 10 kyr) measurements of calcium carbonate content of the APTICORE, magnetic susceptibility (MS) and anhysteretic remanent magnetization (ARM) of the Santa Rosa samples, and MS, ARM and ARM/IRM, where IRM is isothermal remanent magnetization, of Site 398 samples reveal statistically significant cycles. These cycles exhibit periodicity ratios and modulation patterns similar to those of the mid-Cretaceous orbital cycles, suggesting that orbital variations may have modulated depositional processes. Orbital control allows us to estimate the duration of unique, globally identifiable stages of OAE1a. Although OAE1a had a duration of ~1.0 to 1.3 Myr, the initial perturbation represented by the negative carbon-isotope excursion was rapid, lasting for ~27-44 kyr. This estimate could serve as a basis for constraining triggering mechanisms for OAE1a.

Calcareous nannofossil assemblages of Ocean Anoxic Event 2 in ODP Sites 207-1258 and 207-1260

The calcareous nannofossils of the Cenomanian/Turonian boundary interval of Sites 1258 and 1260 (Ocean Drilling Program Leg 207) have been studied in order to understand the depositional environment during Oceanic Anoxic Event 2 (OAE2) in the equatorial Atlantic. Nannofossil assemblages show a significant change in relative abundances during the positive d13Corg excursion interval. The strong increase of the high productivity indicator Zeugrhabdotus erectus and the simultaneous decrease of the oligotrophic taxa Watznaueria barnesiae and Watznaueria fossacincta are indicative of enhanced fertility. The decrease of Eprolithus floralis may be attributed to the surface-water temperature increase during OAE2, which is, however, not very significant (~2-3 °C), as suggested by published TEX86 data. It seems more likely that the decrease of E. floralis during OAE2 was evoked by the breakdown of water-column stratification, indicating it as a deep-dwelling species, which prefers stratified waters with a deep nutricline. Prediscosphaera spp. and Retecapsa ficula, which show a significant increase in relative abundances during OAE2, seem to prefer eutrophic environments, while Amphizygus brooksii and Zeugrhabdotus noeliae lower surface-water fertility. Gartnerago segmentatum, Broinsonia spp., Watznaueria biporta, and Seribiscutum gaultensis decrease in abundances during OAE2. It is not clear if they preferred an oligotrophic environment, cooler surface-waters, or if they were inhabitants of the lower photic zone. Published geochemical data suggest that enhanced fertility and higher temperatures during OAE2 may have been caused by submarine volcanic activity through the release of biolimiting micronutrients into the ocean and carbon dioxide into the atmosphere. The breakdown of water-column stratification may have increased further nutrient availability.

Diagenetic dolomite formation in Quaternary anoxic diatomaceous muds at DSDP Leg 64 Holes

During drilling in the Gulf of California, diagenetic carbonate rocks were recovered at 7 out of 8 sites. These are primarily dolomites which record 13C isotopic evidence of the incorporation of carbon derived from the decomposition of organic matter. In Hole 479, drilled to a sub-bottom depth of 440 meters on the Guaymas Slope, under a fertile upwelling belt, we recognized an excellent example of deep sea dolomitization in progress. This Quaternary section of organic-carbon- rich, low-carbonate, hemipelagic diatomaceous oozes contains numerous fine-grained, decimeter-thin, episodic beds of dolomite, which show sedimentologic, geochemical, and isotopic evidence of accretion by precipitation below 40 meters sub-bottom in zones of high alkalinity and low sulfate. The beds preserve original sedimentary structures. Carbon-13 varies from +3 to +14 per mil, indicating biogenic CO2 reservoirs related to active methanogenesis. In single beds, 18O values range outwardly from +5 to -7 per mil, reflecting increasing temperature with progressive accretion of dolomite with depth; the values parallel progressive trends in lithification, texture, mineralogy, and fossil preservation. We estimate slow accretion rates on the order of 0.1-0.7 mm/10**3 yr. with burial. Dolomitization does not proceed merely at the expense of nearby nannofossils. Ca and Mg ions must be derived from interstitial waters. The episodic appearance of beds in the sequence seems partly a reflection of latent climate signals. This process of deep sea dolomitization carries implications for hydrocarbon migration, as well as an interpretation of the presence of dolomite in other modern and ancient pelagic to hemipelagic sediment sequences.

Calcium isotope composition of Oceanic Anoxic Events 1a and 2 sediments

Calcium-isotope ratios (d44/42Ca) were measured in carbonate-rich sedimentary sections deposited during Oceanic Anoxic Events 1a (Early Aptian) and 2 (Cenomanian-Turonian). In sections from Resolution Guyot, Mid-Pacific Mountains; Coppitella, Italy; and the English Chalk at Eastbourne and South Ferriby, UK, a negative excursion in d44/42Ca of ~0.20 per mil and ~0.10 per mil is observed for the two events. These d44/42Ca excursions occur at the same stratigraphic level as the carbon-isotope excursions that define the events, but do not correlate with evidence for carbonate dissolution or lithological changes. Diagenetic and temperature effects on the calcium-isotope ratios can be discounted, leaving changes in global seawater composition as the most probable explanation for d44/42Ca changes in four different carbonate sections. An oceanic box model with coupled strontium- and calcium-isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium-isotope ratios. The model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short-lived to affect the oceanic calcium reservoir measurably. A modelled increase in weathering flux, on the order of three times the modern flux, combined with increased hydrothermal activity due to formation of the Ontong-Java Plateau (OAE1a) and Caribbean Plateau (OAE2), can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections. This study presents the first major-element record of a weathering response to Oceanic Anoxic Events.

Biogeochemical processes in anoxic sediment from Lake Plußsee, Germany

In anoxic environments, volatile methylated sulfides like methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. When studying the effect of temperature on hydrogenotrophic microbial activity, we observed formation of DMS in anoxic sediment of Lake Plußsee at 55 °C. Subsequent experiments strongly suggested that the formation of DMS involves fixation of bicarbonate via a reductive pathway in analogy to methanogenesis and engages methylation of MT. DMS formation was enhanced by addition of bicarbonate and further increased when both bicarbonate and H2 were supplemented. Inhibition of DMS formation by 2-bromoethanesulfonate points to the involvement of methanogens. Compared to the accumulation of DMS, MT showed the opposite trend but there was no apparent 1:1 stoichiometric ratio between both compounds. Both DMS and MT had negative d13C values of -62 per mil and -55 per mil, respectively. Labeling with NaH**13CO3 showed more rapid incorporation of bicarbonate into DMS than into MT. The stable carbon isotopic evidence implies that bicarbonate was fixed via a reductive pathway of methanogenesis, and the generated methyl coenzyme M became the methyl donor for MT methylation. Neither DMS nor MT accumulation were stimulated by addition of the methyl-group donors methanol and syringic acid or by the methyl-group acceptor hydrogen sulphide. The source of MT was further investigated in a H2**35S labeling experiment, which demonstrated a microbially-mediated process of hydrogen sulfide methylation to MT that accounted for only <10% of the accumulation rates of DMS. Therefore, the major source of the 13C-depleted MT was neither bicarbonate nor methoxylated aromatic compounds. Other possibilities for isotopically depleted MT, such as other organic precursors like methionine, are discussed. This DMS-forming pathway may be relevant for anoxic environments such as hydrothermally influenced sediments and fluids and sulfate-methane transition zones in marine sediments.

Palynology and sea surface temperature reconstruction for the mid-Cretaceous Oceanic Anoxic Event 2 at ODP Hole 210-1276A

The mid-Cretaceous is thought to be a greenhouse world with significantly higher atmospheric pCO2 and sea-surface temperatures as well as a much flatter latitudinal thermal gradient compared to the present. This time interval was punctuated by the Cenomanian/Turonian Oceanic Anoxic Event (OAE-2, ~ 93.5 Myr ago), an episode of global, massive organic carbon burial that likely resulted in a large and abrupt pCO2 decline. However, the climatic consequences of this pCO2 drop are yet poorly constrained. We determined the first, high-resolution sea-surface temperature (SST) record across OAE-2 from a deep-marine sedimentary sequence at Ocean Drilling Program (ODP) Site 1276 in the mid-latitudinal Newfoundland Basin, NW Atlantic. By employing the organic palaeothermometer TEX86, we found that SSTs across the OAE-2 interval were extremely high, but were punctuated by a remarkably large cooling (5-11 °C), which is synchronous with the 2.5-5.5 °C cooling in SST records from equatorial Atlantic sites, and the "Plenus Cold Event". Because this global cooling event is concurrent with increased organic carbon burial, it likely acted in response to the associated pCO2 drop. Our findings imply a substantial increase in the latitudinal SST gradient in the proto-North Atlantic during this period of global cooling and reduced atmospheric pCO2, suggesting a strong coupling between pCO2 and latitudinal thermal gradients under greenhouse climate conditions.

Records of past mid-depth ventilation: Cretaceous ocean anoxic event 2 vs. recent oxygen minimum zones

Present day oceans are well ventilated, with the exception of mid-depth oxygen minimum zones (OMZs) under high surface water productivity, regions of sluggish circulation, and restricted marginal basins. In the Mesozoic, however, entire oceanic basins transiently became dysoxic or anoxic. The Cretaceous ocean anoxic events (OAEs) were characterised by laminated organic-carbon rich shales and low-oxygen indicating trace fossils preserved in the sedimentary record. Yet assessments of the intensity and extent of Cretaceous near-bottom water oxygenation have been hampered by deep or long-term diagenesis and the evolution of marine biota serving as oxygen indicators in today's ocean. Sedimentary features similar to those found in Cretaceous strata were observed in deposits underlying Recent OMZs, where bottom-water oxygen levels, the flux of organic matter, and benthic life have been studied thoroughly. Their implications for constraining past bottom-water oxygenation are addressed in this review. We compared OMZ sediments from the Peruvian upwelling with deposits of the late Cenomanian OAE 2 from the north-west African shelf. Holocene laminated sediments are encountered at bottom-water oxygen levels of < 7 µmol/kg under the Peruvian upwelling and < 5 µmol/kg in California Borderland basins and the Pakistan Margin. Seasonal to decadal changes of sediment input are necessary to create laminae of different composition. However, bottom currents may shape similar textures that are difficult to discern from primary seasonal laminae. The millimetre-sized trace fossil Chondrites was commonly found in Cretaceous strata and Recent oxygen-depleted environments where its diameter increased with oxygen levels from 5 to 45 µmol/kg. Chondrites has not been reported in Peruvian sediments but centimetre-sized crab burrows appeared around 10 µmol/kg, which may indicate a minimum oxygen value for bioturbated Cretaceous strata. Organic carbon accumulation rates ranged from 0.7 and 2.8 g C /cm2 /kyr in laminated OAE 2 sections in Tarfaya Basin, Morocco, matching late Holocene accumulation rates of laminated Peruvian sediments under Recent oxygen levels below 5 µmol/kg. Sediments deposited at > 10 µmol/kg showed an inverse exponential relationship of bottom-water oxygen levels and organic carbon accumulation depicting enhanced bioirrigation and decomposition of organic matter with increased oxygen supply. In the absence of seasonal laminations and under conditions of low burial diagenesis, this relationship may facilitate quantitative estimates of palaeo-oxygenation. Similarities and differences between Cretaceous OAEs and late Quaternary OMZs have to be further explored to improve our understanding of sedimentary systems under hypoxic conditions.

Composition of bottom sediments from the anoxic Mogil'noe Lake, Kil'din Island (Barents Sea)

In summer 2006 integrated geological, geochemical, hydrological, and hydrochemical studies were carried out in the relict anoxic Mogil'noe Lake (down to 16 m depths) located in the Kil'din Island in the Barents Sea. Chemical and grain size compositions of bottom sediments from the lake (permanently anoxic basin) and from the Baltic Sea deeps (periodically anoxic basins) were compared. Vertical location of the hydrogen sulfide layer boundary in the lake (9-11 m depths) was practically the same from 1974 up to now. Concentrations of suspended matter in the lake in June and July 2006 appeared to be close to its summer concentrations in seawater of the open Baltic Sea. Muds from the Mogil'noe Lake compared to those of the Baltic Sea deeps are characterized by fluid and flake consistency and by pronounced admixtures of sandy and silty fractions (probably of eolic origin). Lacustrine mud contains much plant remains; iron sulfides and vivianite were also found. Concentrations of 22 elements determined in lacustrine bottom sediments were of the same levels as those found here 33 years ago. Concentrations also appeared to be close to those in corresponding grain size types of bottom sediments in the Baltic Sea. Low C_org/N values (aver. 5.0) in muds of the Mogil'noe Lake compared to ones for muds of the Baltic Sea deeps (aver. 10) evidence considerable planktogenic component in organic matter composition of the lacustrine muds. No indications were reveled for anthropogenic contaminations of the lacustrine bottom sediments with toxic metals.

Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

Calcareous dinoflagellate cycst in the mid-Cenomanian Boreal realm

A transect from the bathyal to proximal shelf facies of the Boreal Realm was investigated to compare spatial and temporal distribution changes of calcareous dinoflagellate cysts (c-dinocysts) throughout the mid-Cenomanian in order to gain information on the ecology of these organisms. Pithonelloideae dominated the cyst assemblages to more than 95% on the shelf, a prevalence that can be observed throughout most of the Upper Cretaceous. The affinity of this group with the dinoflagellates, which is still controversially discussed, can be confirmed, based on evidence from morphological features and distribution patterns. The consistent prevalence of Pithonella sphaerica and P. ovalis in c-dinocyst assemblages throughout the Upper Cretaceous indicates that they were produced more frequently than cysts of the other species and might, therefore, represent a vegetative dinoflagellate life stage. P. sphaerica and P. ovalis are interpreted as eutrophic species. P. sphaerica is the main species in a marginal-shelf upwelling area, offshore Fennoscandia. Here, sedimentary cyclicity appears to have been reduced to the strongest light/dark changes, while in the outer shelf sediments, light/dark cycles are well-developed and show pronounced temporal assemblage changes. Cyclic fluctuations in the P. sphaerica / P. ovalis ratio reflect shifts of the preferred facies zones and indicate changes in surface mixing patterns. During periods of enhanced surface mixing most parts of the shelf were well-ventilated, and nutrient-enriched surface waters led to high productivity and dominance of the Pithonelloideae. These conditions on the shelf contrasted with those in the open ocean, where more oligotrophic and probably stratified waters prevailed, and an assemblage with very few Pithonelloideae and dominance of Cubodinellum renei and Orthopithonella ? gustafsonii was characteristic. While orbitally-forced light/dark sedimentary cyclicity of the shelf sections was mainly related to surface-water carbonate productivity changes, no cyclic modulation of productivity was observed in the oceanic profile. Therefore, dark layer formation in the open ocean was predominantly controlled by the cyclic establishment of anoxic bottom water conditions. Orbitally-forced interruptions in mixing on the shelf resulted in cyclic periods of stratification and oligotrophy in the surface waters, an expansion of oceanic species to the outer shelf, and a shelfward shift of pithonelloid-facies zones, which were probably related to shelfward directed oceanic ingressions.

Geochemistry of Cretaceous sills and lava flows of ODP Holes 129-800A and 129-802A

On the basis of their respective eruptive environments and chemical characteristics, alkalic dolerite sills from the northern Pigafetta Basin (Site 800) and tholeiitic pillow lavas from the Mariana Basin (Site 802) sampled during Ocean Drilling Program Leg 129 are considered to represent examples of the widespread mid-Cretaceous volcanic event in the western Pacific. Both groups of basic rocks feature mild, low-grade, anoxic smectite-celadonite-carbonate-pyrite alteration; late-stage oxidation is very limited in extent, with the exception of the uppermost sill unit at Site 800. The aphyric and nonvesicular Site 800 alkalic dolerite sills are all well-evolved mineralogically and chemically, being mainly of hawaiite composition, and are similar to ocean island basalts. They are characterized by high contents of incompatible elements (for example, 300-400 ppm Zr), well-fractionated rare earth element patterns ([La/Yb]N 18-21) and HIMU isotopic characters. They probably represent deep-sea, lateral, intrusive off-shoots from nearby seamounts of similar age. The olivine-plagioclase +/- clinopyroxene phyric tholeiitic pillow lavas and thin flows of Site 802 are nonvesicular and quench-textured throughout. Relative to normal-type mid-ocean ridge basalt, they are enriched in large-ion-lithophile elements, exhibit flat (unfractionated) rare earth element patterns and have distinctive (lower) Zr/Nb, Zr/Ta, La/Ta, and Hf/Th ratios. Overall they are compositionally and isotopically similar to the mid-Cretaceous tholeiites of the Nauru basin and the Ontong-Java and Manihiki plateaus. The Site 802 tholeiites differ from the thickened crustal segments of the oceanic plateaus, however, in apparently representing only a thin veneer over the local basement in an off-axis environment.

The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

Geochemistry of Cenozoic sediments from the central Artic Ocean

Integrated Ocean Drilling Program (IODP) Expedition 302 (Arctic Coring Expedition, ACEX) recovered a unique sediment record from the central Arctic Ocean, revealing that this region underwent major environmental fluctuations since the Late Cretaceous. Major and trace element composition of 1,300 samples were determined using X-ray fluorescence (XRF). The results show significant compositional variability of the sediments with depth that can be attributed to changes in (a) provenance and pathways of detrital material, (b) paleoenvironmental conditions and depositional processes, and (c) diagenetic overprint of the primary record. In addition to existing lithological units, we introduce new geochemical units for a more process-related approach interpreting the ACEX record. In detail, via the geochemical signature of Siberian flood basalts we are able to reconstruct the discontinuous rifting and deepening of the central Lomonosov Ridge during the Paleogene, accompanied by changing current regimes and the onset of sea ice. Eocene biosiliceous sedimentation took place in a relatively shallow setting under predominantly anoxic bottom water conditions, causing a positive anoxia-productivity feedback, although water column stratification was repeatedly interrupted by ventilation events. Anoxic to sulfidic conditions were even more extreme after biosilica production ceased, and significant amounts of pyrite were deposited on the Lomonosov Ridge. Especially in organic matter-rich Paleogene deposits, diagenetic processes obscured the paleoenvironmental signals. Fundamental environmental changes occurred in the Middle Eocene, but geochemical and micropaleontological proxies point not to the identical sediment depth. After approximately 26 Ma of non-deposition or erosion, the Middle Miocene record shows the transition to dominantly oxic bottom water conditions, although suboxic diagenesis seemingly affected these deposits.