Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Age determination and age tie-points of sediment cores from the Timor Sea

The evolution of the Australian monsoon in relation to high-latitude temperature fluctuations over the last termination remains highly enigmatic. Here we integrate high-resolution riverine runoff and dust proxy data from X-ray fluorescence scanner measurements in four well-dated sediment cores, forming a NE-SW transect across the Timor Sea. Our records reveal that the development of the Australian monsoon closely followed the deglacial warming history of Antarctica. A minimum in riverine runoff documents dry conditions throughout the region during the Antarctic Cold Reversal (15-12.9 ka). Massive intensification of the monsoon coincided with Southern Hemisphere warming and intensified greenhouse forcing over Australia during the atmospheric CO2 rise at 12.9-10 ka. We relate the earlier onset of the monsoon in the Timor Strait (13.4 ka) to regional changes in landmass exposure during deglacial sea-level rise. A return to dryer conditions occurred between 8.1 and 7.3 ka following the early Holocene runoff maximum.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

(Table 1) Characteristics of air temperature, sea surface temperature, sea surface salinity, nutrients, and total particulate matter for Admiralty Bay and Potter Cove, King George Island, Antarctica

Since the early 1990s, phytoplankton has been studied and monitored in Potter Cove (PC) and Admiralty Bay (AB), King George/25 de Mayo Island (KGI), South Shetlands. Phytoplankton biomass is typically low compared to other Antarctic shelf environments, with average spring - summer values below 1 mg chlorophyll a (Chl a)/m**3. The physical conditions in the area (reduced irradiance induced by particles originated from the land, intense winds) limit the coastal productivity at KGI, as a result of shallow Sverdrup's critical depths (Zc) and large turbulent mixing depths (Zt). In January 2010 a large phytoplankton bloom with a maximum of around 20 mg Chl a/m**3, and monthly averages of 4 (PC) and 6 (AB) mg Chl a/m**3, was observed in the area, making it by far the largest recorded bloom over the last 20 yr. Dominant phytoplankton species were the typical bloom-forming diatoms that are usually found in the western Antarctic Peninsula area. Anomalously cold air temperature and dominant winds from the eastern sector seem to explain adequate light : mixing environment. Local physical conditions were analyzed by means of the relationship between Zc and Zt, and conditions were found adequate for allowing phytoplankton development. However, a multiyear analysis indicates that these conditions may be necessary but not sufficient to guarantee phytoplankton accumulation. The relation between maximum Chl a values and air temperature suggests that bottom-up control would render such large blooms even less frequent in KGI under the warmer climate expected in the area during the second half of the present century.

Strontium concentrations and isotopic compositions of anhydrites from the TAG active mound

Sr isotope analyses have been conducted on anhydrite samples from the TAG (Trans-Atlantic Geotraverse) active hydrothermal mound (26°08?N, Mid-Atlantic Ridge) that have previously been shown to exhibit two distinct patterns of REE behavior when normalized to TAG end-member hydrothermal fluid. Despite differences in REE patterns, the Sr isotope data indicate that all the anhydrites precipitated from fluids with a similar range of hydrothermal fluid and seawater components, and all but one were seawater-dominated (52%-75%). Speciation calculations using the EQ3/6 software package for geochemical modeling of aqueous systems suggest that the REE complexation behavior in different fluid mixing scenarios can explain the variations in the REE patterns. Anhydrites that exhibit relatively flat REE patterns [(La_bs)/(Yb_bs) = 0.8-2.0; subscript bs indicates normalization to end-member black smoker hydrothermal fluid] and a small or no Eu anomaly [(Eu_bs)/(Eu*_bs) = 0.8-2.0] are inferred to have precipitated from mixes of end-member hydrothermal fluid and cold seawater. REE complexes with hard ligands (e.g., fluoride and chloride) are less stable at low temperatures and trivalent Eu has an ionic radius similar to that of Ca2+ and the other REE, and so they behave coherently. In contrast, anhydrites that exhibit slight LREE-depletion [(La_bs)/(Yb_bs) = 0.4-1.4] and a distinct negative anomaly [(Eu_bs)/(Eu*_bs) = 0.2-0.8] are inferred to have precipitated from mixes of end-member hydrothermal fluid and conductively heated seawater. The LREE depletion results from the presence of very stable LREE chloro-complexes that effectively limit the availability of the LREE for partitioning into anhydrite. Above 250°C, Eu is present only in divalent form as chloride complexes, and discrimination against Eu2+ is likely due to both the mismatch in ionic radii between Eu2+ and Ca2+, and the strong chloro-complexation of divalent Eu which promotes stability in the fluid and inhibits partitioning of Eu2+ into precipitating anhydrite. These variations in REE behavior attest to rapid fluctuations in thermal regime, fluid flow and mixing in the subsurface of the TAG mound that give rise to heterogeneity in the formation conditions of individual anhydrite crystals.

Benthic foraminifera abundance data of sediment core GeoB7926-2

We present a high resolution, multiproxy study of the relationship between pelagic and benthic environments of a coastal upwelling system in the subtropical NE Atlantic Ocean. Marine sediments corresponding to late MIS3 to the Holocene in the radiocarbon dated core GeoB7926, retrieved off Mauritania (21°N) were analysed to reconstruct productivity in surface waters and its linkage to deep waters during the last 35 ka BP. High latitude cold events and changes in atmospheric and oceanographic dynamics influenced upwelling intensity over this time period. Subsequently, this caused changes in primary productivity off this low-latitude coastal upwelling locality. The benthic foraminiferal fauna displays four main community shifts corresponding to fundamental climatic events, first of all during late MIS3 (35-28 ka BP), secondly from 28 to 19 ka BP (including Heinrich event 2 and the LGM), thirdly within Heinrich event 1, the Bølling Allerød and the Younger Dryas (18-11.5 ka BP) and finally during the Holocene (11.5-0 ka BP). In particular, strong pelagic-benthic coupling is apparent in MIS 3, as demonstrated by increased primary productivity, indicated by moderate DAR and the dominance of benthic foraminiferal species which prefer fresh phytodetritus. A decline in upwelling intensity and nutrient availability follows, which resulted in a proportionately larger amount of older, degraded matter, provoking a shift in the benthic foraminifera fauna composition. This rapid response of the benthic environment continues with a progressive increase in upwelling intensity due to sea level and oceanographic changes and according high surface production during the LGM. During Heinrich event 1 and the Younger Dryas, extreme levels of primary production actually hindered benthic environment through the development of low oxygen conditions. After this period, a final change in benthic foraminiferal community composition occurs which indicates a return to more oxygenated conditions during the Holocene.

Distribution of calcareous nannofossils in upper Cretaceous and Cenozoic sediments of the Kerguelen Plateau

ODP Leg 119 drilled 11 sites on the Kerguelen Plateau (southern Indian Ocean) and Prydz Bay (East Antarctica). Upper Pliocene through Quaternary sediments were recovered at Site 736 on the northern Kerguelen Plateau; calcareous nannofossils occurred in only a few samples. Over 700 m of middle Eocene through Quaternary sediments was cored at Site 737 on the northern Kerguelen Plateau, and calcareous nannofossils are abundant in the middle Eocene through the middle Miocene sediments. Nearly 500 m of sediments ranging from the lower Turanian to the Quaternary was recovered at Site 738 on the southern Kerguelen Plateau; calcareous nannofossils are abundant from the Miocene downward. Calcareous nannofossils are also abundant in the upper Eocene through Miocene section from Site 744 on the southern Kerguelen Plateau. Except for Core 119-746A-13H, the Neogene sequences drilled at deep-water Sites 745 and 746 off the southern Kerguelen Plateau are devoid of calcareous nannofossils. Occurrences of calcareous nannofossils were generally rare and sporadic at Sites 739 and 742 in Prydz Bay and suggest that the diamictite sequences recovered is as old as middle Eocene-early Oligocene age. Other sites drilled in Prydz Bay (Sites 740, 741, and 743) did not yield calcareous nannofossils. Species diversity of calcareous nannofossils was low (about a dozen) in the southern Indian Ocean in the Late Cretaceous. High-latitude nanno floral characteristics are apparent after the Cretaceous/Tertiary boundary extinctions. Cold climatic conditions limited Oligocene calcareous nannofossil assemblages to fewer than a dozen species, and extinctions of species generally were not compensated by originations of new species. Only a few species of calcareous nannofossils were found in the Miocene sequences, in which Coccolithuspelagicus and one or two species of Reticulofenestra exhibit extreme (0%-100%) fluctuations in assemblage dominance, and these fluctuations may reflect rapid fluctuations in the surface-water temperatures. Further deterioration of climate in the late Neogene essentially excluded calcareous nannoplankton from the Southern Ocean. Significantly warmer water conditions during part of the early-middle Pleistocene were inferred by a few lower-middle Pleistocene calcareous nannofossil species found on the Kerguelen Plateau. The calcareous nannofossil zonation of Roth (1978 doi:10.2973/dsdp.proc.44.134.1978) can be applied to the Upper Cretaceous section recovered at Site 738, and the zonation of Okada and Bukry (1980 doi:10.1016/0377-8398(80)90016-X) can be applied without much difficulty to the Paleocene to middle Eocene sequences from the Kerguelen Plateau. However, some conventional upper Paleogene markers are not useful for southern high latitudes, whereas a few nonconventional species events are useful for subdividing the upper Paleogene sequences. The latter species events include the first occurrence (FO) of Reticulofenestra reticulata, the FO and last occurrence (LO) of Reticulofenestra oamaruensis, the LO of Isthmolithus recurvus, and the LO of Chiasmolithus altus. As the Neogene sequences from the southern Indian Ocean contain only a few long-ranging, cold-water species, or are devoid of coccoliths, calcareous nannofossil zonations remain virtually unworkable for the Neogene in the high-latitude southern Indian Ocean as in other sectors of the Southern Ocean.

Geochemical provenance analysis of fine-grained sediment of sediment core AND1-1

Bulk chemical fine-grained sediment compositions from southern Victoria Land glacimarine sediments provide significant constraints on the reconstruction of sediment provenance models in the McMurdo Sound during Late Cenozoic time. High-resolution (~ 1 ka) geochemical data were obtained with a non-destructive AVAATECH XRF Core Scanner (XRF-CS) on the 1285 m long ANDRILL McMurdo Ice Shelf Project (MIS) sediment core AND-1B. This data set is complemented by high-precision chemical analyses (XRF and ICP-OES) on discrete samples. Statistical analyses reveal three geochemical facies which are interpreted to represent the following sources for the sediments recovered in the AND-1B core: 1) local McMurdo Volcanic Group (MVG) rocks, 2) Transantarctic Mountain rocks west of Ross Island (W TAM), and 3) Transantarctic Mountain rocks from more southerly areas (S TAM). Data indicate in combination with other sediment facies analyses (McKay et al., 2009, doi:10.1130/B26540.1) and provenance scenarios (Talarico and Sandroni, 2009, doi:10.1016/j.gloplacha.2009.04.007) that diamictites at the drill site are largely dominated by local sources (MVG) and are interpreted to indicate cold polar conditions with dry-based ice. MVG is interpreted to indicate cold polar condition with dry-based ice. A mixture of MVG and W TAM is interpreted to represent polar conditions and the S TAM facies is interpreted to represent open-marine conditions. Down-core variations in geochemical facies in the AND-1B core are interpreted to represent five major paleoclimate phases over the past 14 Ma. Cold polar conditions with major MVG influence occur below 1045 mbsf and above 120 mbsf. A section of warmer climate conditions with extensive peaks of S TAM influence characterizes the rest of the core, which is interrupted by a section from 525 to 855 mbsf of alternating influences of MVG and W TAM.

Middle Eocene to Pleistocene calcareous nannofossils of ODP Leg 113 holes

Long sequences of Upper Cretaceous through Quaternary sediments rich in calcareous and siliceous microfossils were recovered at Ocean Drilling Program Sites 689 and 690 on Maud Rise off East Antarctica. These sites have become the southernmost anchor in the Atlantic Basin for bio-, magneto-, chemostratigraphic, and paleobiogeographic studies. ODP Sites 692 and 693 on the Weddell Sea margin of East Antarctica and Site 696 on the South Orkney microcontinent of West Antarctica yielded calcareous nannofossils within some stratigraphic intervals. Sites 691, 692, 694, 695, and 697 did not recover Cenozoic calcareous nannofossils. Calcareous nannofossil biostratigraphy suggests a major hiatus across the Paleogene/Neogene boundary at Sites 689 and 690, and two additional hiatuses in the middle Eocene-lower Oligocene section at Site 690. Correlation with magnetostratigraphy reveals: the last occurrence (LO) of Reticulofenestra umbilica at Maud Rise is over 1 m.y. younger than that at the middle-latitude sites; the LO of Isthmolithus recurvus is synchronous in the middle-latitude and high-latitude areas (about 34.8 Ma); Reticulofenestra oamaruensis ranges from 38.0 to 36.0 Ma at Maud Rise; Reticulofenestra reticulata has a shorter range at Maud Rise (42.1 to 38.9 Ma) than at the middle-latitude DSDP Site 516; the range of Chiasmolithus oamaruensis is diachronous over different latitudes; and the LO of Chiasmolithus solitus is a good datum at 41.3 Ma from 30°S to 65°S in the South Atlantic Ocean. Comparison of calcareous nannofossil abundances in a latitudinal transect shows: Reticulofenestra bisecta is a temperate-water species and its LO, which crosses below that of Chiasmolithus altus at Maud Rise, is not applicable for the Paleogene/Neogene boundary in high southern latitude areas; Clausicoccus fenestratus is rare or absent at Maud Rise and can not be used as a marker; Coccolithus formosus is a warm-water species which disappeared earlier toward higher latitudes. Calcareous nannofossil assemblages indicate that by at least the middle Eocene, surface water temperatures became considerably lower in the high southern latitudes than in the middle-latitude areas and that there have been more extreme cold events in the high latitudes during the Neogene. Bicolumnus ovatus n. gen., n. sp. is proposed in this paper.

Planktonic foraminifera in late Eocene to Pleistocene sediments of ODP Hole 120-747A and 120-749B

Late Eocene to Pleistocene planktonic foraminifers from Leg 120 Holes 747A and 749B on the Kerguelen Plateau were quantitatively analyzed. Microperforate tenuitellid forms dominate the Oligocene to middle Miocene, and 17 species (including the new species Tenuitella jamesi and Tenuitellinata selleyi) are recorded. A lineage zonation of tenuitellid foraminifers is proposed as an alternative scheme for refinement of the Oligocene-Miocene biostratigraphy in high latitudes. Progressive or abrupt alterations in morphological characters within this lineage, producing different morphotypes or species, coincided with prolonged or sudden changes in paleoclimate. These microperforate planktonic foraminifers thus appear to have potential as indicators of cold-water masses and temperature fluctuations in post-Eocene oceans.

Geochemistry at DSDP Site 60-456

Basalts in two holes spaced 200 meters apart at DSDP Site 456 in the Mariana Trough both show a downward sequence of nonoxidative and oxidative zones of alteration, each 10 to 15 meters thick, overlying fresh basalts. Basalts in the nonoxidative zone have been extensively chloritized and have vein and vesicle fillings of quartz, opal, chlorite, calcite, and pyrite. Minor sulfides are chalcopyrite and digenite. Basalts in the oxidative zone have abundant smectites and iron hydroxides and are variably enriched in K, Rb, and Ba, unlike the nonoxidative basalts above them. We propose that the oxidative zone was a zone of mixing between high-temperature, reduced hydrothermal fluids moving horizontally beneath impermeable sediments at the top of the pillowed basement lavas and cold, oxygenated seawater in interpillow voids deeper in the basement. Recrystallized vitric tuffs immediately above the basalts containing authigenic quartz and wairakite, as well as occurrence of chlorite, epidote, and chalcopyrite in the basalts, suggest temperatures of alteration in excess of 200°C.