Geochemical traces across the Paleocene-Eocene thermal maximum on Walvis Ridge

An understanding of sediment redox conditions across the Paleocene-Eocene thermal maximum (PETM) (?55 Ma) is essential for evaluating changes in processes that control deep-sea oxygenation, as well as identifying the mechanisms responsible for driving the benthic foraminifera extinction. Sites cored on the flanks of Walvis Ridge (Ocean Drilling Program Leg 208, Sites 1262, 1266, and 1263) allow us to examine changes in bottom and pore water redox conditions across a ~2 km depth transect of deep-sea sediments of PETM age recovered from the South Atlantic. Here we present measurements of the concentrations of redox-sensitive trace metals manganese (Mn) and uranium (U) in bulk sediment as proxies for redox chemistry at the sediment-water interface and below. All three Walvis Ridge sites exhibit bulk Mn enrichment factors (EF) ranging between 4 and 12 prior to the warming, values at crustal averages (Mn EF = 1) during the warming interval, and a return to pre-event values during the recovery period. U enrichment factors across the PETM remains at crustal averages (U EF = 1) at Site 1262 (deep) and Site 1266 (intermediate depth). U enrichment factors at Site 1263 (shallow) peaked at 5 immediately prior to the PETM and dropped to values near crustal averages during and after the event. All sites were lower in dissolved oxygen content during the PETM. Before and after the PETM, the deep and intermediate sites were oxygenated, while the shallow site was suboxic. Our geochemical results indicate that oxygen concentrations did indeed drop during the PETM but not sufficiently to cause massive extinction of benthic foraminifera.

Late Cretaceous volcaniclastic rocks at DSDP Holes 74-525A and 74-528

Volcaniclastic rocks of Late Cretaceous age occur in four out of five sites (525, 527, 528, 529) drilled on the crest and the northwest flank of the Walvis Ridge during Leg 74. They are mostly interlayered with and overlie basement in the lowermost 10-100 m of the sedimentary section. Rocks from Holes 525A and 528 were studied megascopically and microscopically, by XRD, and XRF chemical analyses of whole-rock major and trace elements were undertaken. The dominant rock of Hole 528 volcaniclastics is a fine-grained (silt to fine sand), mostly matrix-bearing (partly matrix-rich) vitric "tuff," occurring as 5-110 cm thick, partly graded layers, some of which are distinctly bedded. Volcaniclastics of Hole 525A are generally richer in sanidine crystals. Most rocks contain some nonvolcanic clasts, chiefly foraminifers and lesser amounts of shallow-water fossil debris. Scoria shards, clasts of tachylite, and fine-grained basalts as well as chemical analyses suggest a basaltic to intermediate composition for most rocks of Hole 528, whereas volcaniclastics of Hole 525A are more silicic. The occurrence of tachylite and epiclastic, coarse-grained, basaltic clasts throughout the volcaniclastic sequence at Site 528 indicates shallow-water eruptions and perhaps even ocean island volcanism. The minor occurrence in Hole 528 of trachytic? pumice shards with phenocrysts of K-feldspar and the abundance of such shards in rocks from Hole 525A indicate Plinian eruptions characteristic of more mature stages of ocean island evolution. The sedimentary structures of volcaniclastic layers and their occurrence within deep sea calcareous oozes indicate a mass flow origin. Diagenetic alteration of the volcaniclastic rocks is pronounced, and four major stages of glass shard alteration are distinguished. Despite the effects of alteration and small-scale redistribution of elements and the admixture of nonvolcanic components, there were no drastic changes in the chemical composition of the rocks, except for pronounced increases in K and Rb and decreases in Ca and Fe. The basaltic volcaniclastic rocks very much resemble basement basalts in that they are moderately evolved tholeiites derived from an LIL-enriched mantle source with Zr/Nb ratios (Hole 528) of 5 to 6. This, in conjunction with the interbedding of volcaniclastic rocks and basement lavas, indicates contemporaneous seamount or island and basement volcanic activity involving magmas derived from similar sources.

Biogeochemistry (speciation and isotopes of S and C) in bottom sediments, water and bacterial mats from the White Sea

This publication presents results of microbiological and biogeochemical studies in the White Sea. Material was obtained during a series of expeditions in 1999-2002. The studies were carried out in the open part of the White Sea, in the Onega, Dvina and Kandalaksha Bays, as well as in the intertidal zone of the Kandalaksha Bay. Quantitative characteristics of activity of microbial processes in waters and bottom sediments of the White Sea were obtained. The total number of bacteria was equal to 150000-800000 cells/ml, and intensity of dark CO2 assimilation was equal to 0.9-17 µg C/l/day. Bacterial sulfate reduction was equal to 3-150 mg S/m**2/day, and methane formation and oxidation was equal to 13-6840 and 20-14650 µl CH4/m**2/day, respectively. Extremely high values of intensity of all principal microbial processes were found in intertidal sediments rich in organic matter: under decomposing macrophytes, in local pits at the lower intertidal boundary, and in the mouth of a freshwater brook. Average hydrogen sulfide production in highly productive intertidal sediments was 1950-4300 mg S/m**2/day, methane production was 0.5-8.7 ml CH4/m**2/day, and intensity of methane oxidation was up to 17.5 ml CH4/m**2/day. Calculations performed with account for areas occupied by microlandscapes of increased productivity showed that diurnal production of H2S and CH4 per 1 km**2 of the intertidal zone (August) was estimated as 60.8-202 kg S/km**2/day and 192-300 l CH4/km**2/day, respectively.

Spatiotemporal monitoring of water quality in coral reefs of Tayrona National Natural Park, Colombian Caribbean, 2011-2013

Tayrona National Natural Park (TNNP; 11°17' - 11°22' N and 73°53' - 74°12' W) is a hotspot of coral reef biodiversity in the Colombian Caribbean, located between the city of Santa Marta (>455,000 inhabitants) and several smaller river mouths (Rio Piedras, Mendihuaca, Guachaca). The region experiences a strong seasonal variation in physical parameters (temperature, salinity, wind, and water currents) due to alternating dry seasons with coastal upwelling and rainy seasons. Here, a range of water quality parameters relevant for coral reef functioning is provided. Water quality was measured directly above local coral reefs (~10 m water depth) by a monthly monitoring for up to 25 months in the four TNNP bays (Chengue, Gayraca, Neguanje, and Cinto) and at sites with different degree of exposition to winds, waves and water currents (exposed vs. sheltered sites) within each bay. The water quality parameters include: inorganic nutrient (nitrate, nitrite and soluble reactive phosphorus), chlorophyll a, particulate organic carbon and nitrogen concentrations (with a replication of n=3) as well as oxygen availability, biological oxygen demand, seawater pH, and water clarity (with a replication of n=4). This is by far the most comprehensive coral reefs water quality dataset for the region. A detailed description of the methods can be found within the referenced publications.

Dissolved organic carbon measured on water bottle samples at time series station DYFAMED

Dissolved organic carbon (DOC) distribution and dynamics are investigated at the DYFAMED site (central Ligurian Sea, NW Mediterranean) in relation to hydrological and biological contexts, using a 4-year time-series dataset (1991-1994). The DYFAMED site is regarded as a one-dimensional station where simple hydrological mechanisms prevail and where the ecosystem is quite well understood. An average vertical profile of DOC concentration ([DOC]) indicates that maximal concentrations and variability are concentrated in the surface layers. For depths >800 m, the annual variations are on average similar to the analytical standard deviation (~2 µM). The "composite" [DOC] distribution (average distribution over a typical year, integrating about 40 monthly profiles) for surface waters (0-200 m) is closely related to hydrological and phytoplanktonic forcings. It exhibits summer DOC accumulation in surface waters, due to spring-summer stratification and successive phytoplanktonic events such as spring and summer blooms, and winter DOC removal to deeper waters, due to intense vertical mixing. The analysis of vertical [DOC] gradient at 100-m depth as a function of the integrated DOC content in the 0-100-m layer makes it possible to objectively distinguish three specific periods: the winter vertical mixing period, the period of stratification and spring phytoplankton bloom, and the period of stratification re-inforcement and summer-fall phytoplankton bloom. We recalculate the vertical DOC fluxes to deep waters using a larger original dataset, after the first direct calculation (Deep-Sea Res. 40 (10) (1993) 1963, 1972) that was reproduced for other oceanic areas. The seasonal variations of the "composite" [DOC] distribution in surface waters are significantly correlated to the apparent oxygen utilization distribution, but the biogeochemical significance of such a correlation is still under examination. The global significance of our local findings is presented and the role of the oceanic DOC in the global carbon cycle is emphasized, especially with respect to several current issues, such as the oceanic "missing sink" and the equivalence between new production and exported production.

(Table 1) CaCO3, terrigenous matter and Corg calculations from DSDP Hole 75-532B

Samples taken at 10 cm intervals from DSDP Core 532B-17 contain variations in carbonate, opal, organic carbon, and terrigenous components that correlate with light-dark cycles in sediment color. The core site, at 1300 m water depth, is well above the CCD, yet the color variations appear to result largely from cyclical fluctuations in carbonate dissolution, which was greater during glacial periods. Higher concentrations of organic carbon and of terrigenous sediment components correlate with enhanced carbonate dissolution, but opal concentrations inversely correlate and suggest that biological productivity at this site diminished during glacial periods. A complicated glacial-interglacial picture emerges from the data. In interglacial times, upwelling associated with the Benguela Current produced abundant opaline material, organic matter was fairly well preserved, and carbonate was only moderately dissolved. In glacial times, the upwelling core shifted as sea level fell and winds intensified. Productivity in the waters over Site 532 decreased, but lateral supply of oxidizable organic matter enhanced carbonate dissolution, giving rise to light-dark cycles in these sediments.

(Table 1) Oxygen and carbon isotope compositions of altered carbonates from DSDP Hole 6-53 from the western Pacific Ocean

In the lower part of DSDP core 53.0, partly recrystallized carbonate sediments and well recrystallized limestone breccias of Oligo-Miocene age are associated with altered volcanic flows, lithified tuffs, and tuff breccias, suggesting that carbonate alteration was the result of thermal metamorphism. However, the oxygen isotope compositions of these carbonates (-3.4 to +0.6 per mil rel. PDB) are not compatible with recrystallization and isotope exchange with sea water at high temperatures. Evaluating the effects of the composition of the water which exchanged with the carbonates and of carbonate-water isotope exchange in closed systems yields the following approximate maximum temperature of recrystallization: limestone breccias, 100°C; calcite veins rimming breccia clasts, 30°C; and unconsolidated sediments overlying the breccias, 20°C. Therefore, the volcanics at site 53.0 must have been emplaced into the primary carbonate sediments at relatively low temperatures. Subsequent carbonate alteration was probably a consequence of chemical changes in ambient pore waters resulting from the submarine weathering of volcanic material.

Distribution of sponge spicule types, Goniothecium odontella and Diploneis cf. bomboides in selected spicule clusters from ODP Leg 112 holes (Table 1)

Clusters of sponge spicules found in Quaternary deep-water sediments at Sites 685 and 688 off Peru represent single individuals of small sponges or fragments of larger sponges. The spicule assemblages constituting these clusters probably represent a few demosponge species of the subclass Tetractinomorpha and order Astrophorida, because triaenes and microscleric euasters, as well as abundant monaxons, are present. As proved by incorporated Neogene diatoms, these spicule clusters are allochthonous. The sponge individuals probably inhabited deeper neritic environments during late Neogene time.

Geochemical data from the USGS #1 Portland core, Canon City, Colorado

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events-the Coniacian to Santonian OAE 3-resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high-resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon-rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in d13C indicate that redox-controlled early diagenesis can also significantly alter d13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, d18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.

Planktonic foraminifera of ODP Hole 107-654A

The late Miocene sediments of the Tyrrhenian ODP Site 654 encompass a deepening sequence which begins with glauconite shallow water sands followed by a rapid transition to deep water sediments and culminates with dolomitic mudstones associated with Messinian evaporites. The sequence compares well with the so-called 'Sahelian cycle' and with post-orogenic cycles recognized in peninsular Italy and Sicily. The studied interval, consisting of 55 m thick nannofossil oozes, belongs to the Globorotalia suterae subzone and lower part of the Globorotalia conomiozea Zone, indicating late Tortonian and early Messinian age, respectively. Biomagnetostratigraphic correlation assigns the Tortonian/ Messinian boundary an age of 6.44-6.45 Ma. In addition, six main events have been recognized, based on the range of keeled globorotaliids and coiling direction changes of keeled and unkeeled globorotaliids, which have been correlated to the geomagnetic time-scale. Comparison with North Atlantic sites and land sections of the Guadalquivir basin and northern Morocco provides good correlations with the events documented in these areas. In particular, Event IV, which predates the FO of Globorotalia conomiozea, may be used to recognize the Tortonian/Messinian boundary in extra-Mediterranean areas where G. conomiozea is missing. Variations in the distribution of different species of Globigerinoides are related to changes in the surficial marine environment. Although no clear trends can be recognized on the oxygen and carbon isotope records of Globigerinoides obliquus, the parallelism between the occurrence of low salinity species (G. sacculifer) and peaks of low 5180 values, as well as that of normal salinity species (G. obliquus) and peaks of high d18O values, suggests strong local changes of environmental conditions. The high amplitude of the fluctuations of d18O values suggests important variations in the salinity of the Tyrrhenian Sea, related to a rapidly changing water budget. The major feature of the carbon isotope record is a large decrease between 7.0 and 6.95 Ma, which therefore predates the 6.2 Ma global 'carbon shift'.

(Table 5) Distribution of benthic foraminifers in the late Cretaceous of DSDP Hole 71-511

The book is devoted to stratigraphy of Cretaceous deposits from high latitudes of the southern hemisphere (subantarctic part of the ocean), as well as to geological and climatic Cretaceous history of the area. Correlation with Cretaceous sediments from warm water regions is carried out. Description and photos of characteristic species of planktonic and benthic foraminifera and calcispherulides are given.

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.

Early Maastrichtian stable isotopes: changing deep water sources in the North Atlantic?

We propose that the observed short-term stable isotope fluctuations reflect changes in high- and low-latitude intermediate to deep water sources, based on a high-resolution stable isotope record of planktic and benthic foraminifera from the Early Maastrichtian (~71.3 to ~ 69.6 Ma) of Blake Nose (DSDP Site 390A, North Atlantic). Sources of these waters may have been the low-latitude eastern Tethys and high-latitude North Atlantic. Changes in intermediate to deep water sources were probably steered by eccentricity-controlled insolation fluctuations. Lower insolation favored the formation of high-latitude deep waters due to positive feedback mechanisms resulting in high-latitude cooling. This led to a displacement of low-latitude deep waters at Blake Nose. Higher insolation reduced intermediate to deep-water formation in high latitudes, yielding a more northern flow of low-latitude deep waters.

Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.