Determination of sulfite and manganese in sediments from the K/T boundary

The solid-state-physics technique of electron spin resonance (ESR) has been employed in an exploratory study of marine limestones and impact-related deposits from Cretaceous-Tertiary (KT) boundary sites including Spain (Sopelana and Caravaca), New Jersey (Bass River), the U.S. Atlantic continental margin (Blake Nose, ODP Leg 171B/1049/A), and several locations in Belize and southern Mexico within -600 km of the Chicxulub crater. The ESR spectra of SO3(1-) (a radiation-induced point defect involving a sulfite ion substitutional for CO3(2-) which has trapped a positive charge) and Mn(2+) in calcite were singled out for analysis because they are unambiguously interpretable and relatively easy to record. ESR signal strengths of calcite-related SO3(1-) and Mn(2+) have been studied as functions of stratigraphic position in whole-rock samples across the KT boundary at Sopelana, Caravaca, and Blake Nose. At all three of these sites, anomalies in SO3(1-) and/or Mn(2+) intensities are noted at the KT boundary relative to the corresponding background levels in the rocks above and below. At Caravaca, the SO3(1-) background itself is found to be lower by a factor of 2.7 in the first 30,000 years of the Tertiary relative to its steady-state value in the last 15,000 years of the Cretaceous, indicating either an abrupt and quasi-permanent change in ocean chemistry (or temperature) or extinction of the marine biota primarily responsible for fixing sulfite in the late Cretaceous limestones. An exponential decrease in the Mn(2+) concentration per unit mass calcite, [Mn(2+)], as the KT boundary at Caravaca is approached from below (1/e characteristic length =1.4 cm) is interpreted as a result of post-impact leaching of the seafloor. Absolute ESR quantitative analyses of proximal impact deposits from Belize and southern Mexico group naturally into three distinct fields in a twodimensional [SO3(1-)]-versus-[Mn(2+)] scatter plot. These fields contain (I) limestone ejecta clasts, (II) accretionary lapilli, and (III) a variety of SO3(1-) -depleted/Mn(2+) enriched impact deposits. Data for the investigated non-impact-related Cretaceous and Tertiary marine limestones (Spain and Blake Nose) fall outside of these three fields. With reference to thes enon-impact deposits, fields I, II, and III can be respectively characterized as Mn(2+) -depleted, SO3(1-) -enhanced, and SO3(1-) -depleted. It is proposed that (1) field I represents calcites from the Yucatin Platform, and that the Mn(2+) -depleted signature can be used as an indicator of primary Chicxulub ejecta in deep marine environments and (2) field II represents calcites that include a component formed in the vapor plume, either from condensation in the presence of CO2/SO3(1-) -rich vapors, or reactions between CaO and CO2/SO3 rich vapors, and that this SO3(1-) -enhanced signature can be used as an indicator of impact vapor plume deposits. Given these two propositions, the ESR data for the Blake Nose deposits are ascribed to the presence of basal coarse calcitic Chicxulub ejecta clasts, while the finer components that are increasingly represented toward the top are interpreted to contain high- SO3(1-) calcite from the vapor plume. The apparently-undisturbed Bass River deposit may contain even higher concentrations of vapor-plume calcite. None of the three components included in field III appear to be represented at distal, deep marine KT-boundary sites; this field may include several types of impact-related deposits of diverse origins and diagenetic histories.

Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

(Table 2) Planktonic to benthic foraminifera ratios at DSDP Site 63-468

In recent years there has been considerable discussion concerning the biostratigraphic correlations between planktonic zonations and the classical Neogene California benthic foraminiferal stages. One of the primary objectives of IPOD Leg 63 was to investigate these correlations and to determine the possibility of temporal variation of the benthic stages between California land sections and the outer Continental Borderland. In addition, it was anticipated that analyses of the benthic foraminiferal faunas at Site 468 would provide critical information on the paleoenvironmental history of the outer borderland. The provincial benthic Neogene foraminiferal stages were established by Kleinpell (1938) for the Miocene and Natland (1952) for the Pliocene-Pleistocene; both are well-documented in designated type sections. These stages have been used for interbasinal correlations, although time-transgressive problems have been suggested by several authors (Bandy, 1971; Ingle, 1967, 1973; Crouch and Bukry, 1979). An important biostratigraphic sequence occurs at Site 468, significant because of its relatively shallow depth of approximately 1700 meters. The samples yield well-preserved benthic foraminiferal faunas throughout most of the Neogene sequence and are accompanied by abundant well-preserved calcareous and siliceous planktonic assemblages. It is this co-occurrence of both planktonic and benthic faunas that enables the correlation of outer continental margin sediments with those of the classical land-based sections of southern California.

Grain-size analysis and geochemistry of sediment core GeoB13602-1

Grain-size, terrigenous element and rock magnetic remanence data of Quaternary marine sediments retrieved at the NW African continental margin off Gambia (gravity core GeoB 13602-1, 13°32.71' N, 17°50.96'W) were jointly analyzed by end-member (EM) unmixing methods to distinguish and budget past terrigenous fluxes. We compare and cross-validate the identified single-parameter EM systems and develop a numerical strategy to calculate associated multi-parameter EM properties. One aeolian and two fluvial EMs were found. The aeolian EM is much coarser than the fluvial EMs and is associated with a lower goethite/hematite ratio, a higher relative concentration of magnetite and lower Al/Si and Fe/K ratios. Accumulation rates and grain sizes of the fluvial sediment appear to be primarily constrained by shore distance (i.e., sea-level fluctuations) and to a lesser extent by changes in hinterland precipitation. High dust fluxes occurred during the Last Glacial Maximum (LGM) and during Heinrich Stadials (HS) while the fluvial input remained unchanged. Our approach reveals that the LGM dust fluxes were ~7 times higher than today's. However, by far the highest dust accumulation occurred during HS 1 (~300 g m**-2 yr** -1), when dust fluxes were ~80 fold higher than today. Such numbers have not yet been reported for NW Africa, and emphasize strikingly different environmental conditions during HSs. They suggest that deflation rate and areal extent of HSs dust sources were much larger due to retreating vegetation covers. Beyond its regional and temporal scope, this study develops new, in principle, generally applicable strategies for multi-method end-member interpretation, validation and flux budgeting calibration.

Mats of psychrophilic thiotrophic bacteria associated with cold seeps of the Barents Sea

This study focused on the bacterial diversity associated with microbial mats of deep-sea cold seeps at the Norwegian continental margin. Study sites included the Storegga and Nyegga areas as well as the Håkon Mosby mud volcano, where the mats occurred at temperatures permanently close to the freezing point of seawater. Two visually different mat types, i.e. small gray mats and extensive white mats, were studied with the aim to determine the identity of the mat-forming sulfide oxidizers, and to investigate which environmental factors (e.g. sulfate reduction and methane oxidation rates) shown here could explain the observed diversity. Sequence data have been submitted to the EMBL database under accession No. FR847864-FR847887 (giant sulfur bacteria), No. FR827864 (Menez Gwen filament; see Supplementary Material) and No. FR875365-FR877509 (except FR875905; remaining partial sequences).

Temperature reconstruction of sediment core SO9-93KL

The Toba volcanic event, one of the largest eruptions during the Quaternary, is documented in marine sediment cores from the northeastern Arabian Sea. On the crest of the Murray Ridge and along the western Indian continental margin, we detected distinct concentration spikes and ash layers of rhyolithic volcanic shards near the marine isotope stage 5-4 boundary with the chemical composition of the "Youngest Toba Tuff". Time series of the Uk'37-alkenone index, planktic foraminiferal species, magnetic susceptibility, and sediment accumulation rates from this interval show that the Toba event occurred between two warm periods lasting a few millennia. Using Toba as an instantaneous stratigraphic marker for correlation between the marine- and ice-core chronostratigraphies, these two Arabian Sea climatic events correspond to Greenland interstadials 20 and 19, respectively. Our data sets thus depict substantial interstadial/stadial fluctuations in sea-surface temperature and surface-water productivity. We show that variable terrigenous (eolian) sediment supply played a crucial role in transferring and preserving the productivity signal in the sediment record. Within the provided stratigraphic resolution of several decades to centennials, none of these proxies shows a particular impact of the Toba eruption. However, our results are additional support that Toba, despite its exceptional magnitude, had only a minor impact on the evolution of low-latitude monsoonal climate on centennial to millennial time scales.

Osmium isotope record of Late Pleistocene sediments

We report high temporal resolution osmium isotopes records of bulk sediment and sediment leachates from DSDP Site 480 (Gulf of California) over the last 30 ka; from ODP Site 849 (Eastern equatorial Pacific) from the last 200 ka and from ODP Site 1002C (Cariaco Basin) across the 9-17 ka time interval in order to critically evaluate claims of a global 10% shift in the 187Os/188Os of seawater from glacial to interglacial intervals. We use organic-rich continental margin sites and carbonate-rich pelagic sites to isolate the temporal variations of the osmium seawater isotopic composition. Our results reveal that variations in 187Os/188Os fail to correlate with global changes in temperature across glacials/interglacials cycles as previously claimed. Instead, these results indicate differences of a few percent in the measured 187Os/188Os between each oceanic basin. We argue that these differences strongly suggest that seawater is not well homogenized with respect to its Os isotope composition.

Mineralogy of sediments from the Exmouth Plateau and Argo Basin

Correlation of mineral associations from sediment recovered on the northwestern Australian continental margin document the juvenile-to-mature evolution of a segment of the Indian Ocean. Lower Cretaceous sediments contain sandy-to-silty radiolarian claystone that consists of highly smectitic mixed-layered illite/smectite (I/S) in addition to minor amounts of diagenetic pyrite, barite, and rhodochrosite. These immature, poorly sorted sediments were derived from nearby continental margin sources. Discrete bentonite layers and abundant smectite are the alteration products of volcanic material deposited during early basin formation. Abundant quartz-replaced radiolarian tests suggest high surface-water productivity, and calcareous fossils indicate water depths were above the calcite compensation depth (CCD) in the juvenile Indian Ocean. The increase in pelagic carbonate from the mid- to Late Cretaceous signals the transition to mature, open-ocean conditions. Similar to other slowly deposited contemporaneous deep-sea sediments, mid- to Upper Cretaceous sediments of the northwestern margin of Australia contain palygorskite. This palygorskite is associated with calcareous sediment across the ooze-to-chalk transition, detrital mixed-layered I/S, and zeolite minerals in places. This palygorskite occurs above the transformation from opal-A to opal-CT. The underlying opal-CT sediment contains abundant smectite and zeolite minerals. Calcareous sediment dominates the Cenozoic, except at abyssal sites that were not inundated by calcareous turbidites. Paleocene and Eocene sediments contain abundant smectite and zeolite minerals derived from the alteration of volcanic material. Palygorskite was found to be associated with sepiolite and dolomite in Miocene sediments from Site 765 in the Argo Basin. Pliocene and Quaternary sediments contain detrital kaolinite and mixed-layered I/S, abundant opal-A radiolarian tests, and minor amounts of pyrite

Carbonate content in lower Cretaceous sediments of ODP Hole 123-765C

Sediments recovered during Ocean Drilling Program (ODP) Leg 123 from the Argo Abyssal Plain (AAP) consist largely of turbidites derived from the adjacent Australian continental margin. The oldest abundant turbidites are Valanginian-Aptian in age and have a mixed (smarl) composition; they contain subequal amounts of calcareous and siliceous biogenic components, as well as clay and lesser quartz. Most are thin-bedded, fine sand- to mud-sized, and best described by Stow and Piper's model (1984) for fine-grained biogenic turbidites. Thicker (to 3 m), coarser-grained (medium-to-coarse sand-sized) turbidites fit Bouma's model (1962) for sandy turbidites; these generally are base-cut-out (BCDE, BDE) sequences, with B-division parallel lamination as the dominant structure. Parallel laminae most commonly concentrate quartz and/or calcispheres vs. lithic clasts or clay, but distinctive millimeter- to centimeter-thick, radiolarian-rich laminae occur in both fine- and coarse-grained Valanginian-Hauterivian turbidites. AAP turbidites were derived from relatively deep parts of the continental margin (outer shelf, slope, or rise) that lay below the photic zone, but above the calcite compensation depth (CCD). Biogenic components are largely pelagic (calcispheres, foraminifers, radiolarians, nannofossils); lesser benthic foraminifers are characteristic of deep-water (abyssal to bathyal) environments. Abundant nonbiogenic components are mostly clay and clay clasts; smectite is the dominant clay species, and indicates a volcanogenic provenance, most likely the Triassic-Jurassic volcanic suite exposed along the northern Exmouth Plateau. Lower Cretaceous smarl turbidites were generated during eustatic lowstands and may have reached the abyssal plain via Swan Canyon, a submarine canyon thought to have formed during the Late Jurassic. In contrast to younger AAP turbidites, however, Lower Cretaceous turbidites are relatively fine-grained and do not contain notably older reworked fossils. Early in its history, the northwest Australian margin provided mainly contemporaneous slope sediment to the AAP; marginal basins adjacent to the continent trapped most terrigenous detritus, and pronounced canyon incisement did not occur until Late Cretaceous and, especially, Cenozoic time.