Total organic carbon (TOC) on ground bulk and carbonate-free sediment samples of ODP Hole 151-911A

A multiproxy analysis of Hole 911A (Ocean Drilling Program (ODP) Leg 151) drilled on the Yermak Plateau (eastern Arctic Ocean) is used to investigate the behaviour of the Svalbard/Barents Sea ice sheet (SBIS) during late Pliocene and early Pleistocene (~3.0-1.7 Ma) climate changes. Contemporary with the 'Mid-Pliocene (~3 Ma) global warmth' (MPGW), a warmer period lasting ~300 kyr with seasonally ice-free conditions in the marginal eastern Arctic Ocean is assumed to be an important regional moisture source, and possibly one decisive trigger for intensification of the Northern Hemisphere glaciation in the Svalbard/Barents Sea area at ~2.7 Ma. An abrupt pulse of ice-rafted debris (IRD) to the Yermak Plateau at ~2.7 Ma reflects distinct melting of sediment-laden icebergs derived from the SBIS and may indicate the protruding advance of the ice sheet onto the outer shelf. Spectral analysis of the total organic carbon (TOC) record being predominantly of terrigenous/fossil-reworked origin indicates SBIS and possibly Scandinavian Ice Sheet response to incoming solar radiation at obliquity and precession periodicities. The strong variance in frequencies near the 41 kyr obliquity cycle between 2.7 and 1.7 Ma indicates, for the first time in the Arctic Ocean, a close relationship of SBIS growth and decay patterns to the Earth's orbital obliquity amplitudes, which dominated global ice volume variations during late Pliocene/early Pleistocene climate changes.

Petroleum System Analysis: Middle Magdalena Valley Basin, Colombia, South America

The purpose of this study is to create a petroleum system model and to assess whether or not the La Luna Formation has potential for unconventional exploration and production in the Middle Magdalena Valley Basin (MMVB), Colombia. Today, the Magdalena River valley is an intermontane valley located between the Central and Eastern Cordillera of Colombia. The underlying basin, however, represents a major regional sedimentary basin that received deposits from the Triassic through the Cenozoic. In recent years Colombia has been of great exploration interest because of its potentially vast hydrocarbon resources, existing petroleum infrastructure, and skilled workforce. Since the early 1900s when the MMVB began producing, it has led to discoveries of 1.9 billion barrels of oil (BBO) and 2.5 trillion cubic feet (Tcf) of gas (Willatt et al., 2012). Colombia is already the third largest producer of oil in South America, and there is good potential for additional unconventional exploration and production in the Cretaceous source rocks (Willatt et al., 2012). Garcia Gonzalez et al. (2009) estimate the potential remaining hydrocarbons in the La Luna Formation in the MMVB to be between 1.15 and 10.33 billion barrels of oil equivalent (BBOE; P90 and P10 respectively), with 2.02 BBOE cumulative production to date. Throughout the 1900s and early 2000s, Cenozoic continental and transitional clastic reservoirs were the primary exploration interest in the MMVB (Dickey, 1992). The Cretaceous source rocks, such as the La Luna Formation, are now the target for unconventional exploration and production. In the MMVB, the La Luna formation is characterized by relatively high total organic carbon (TOC) values, moderate maturity, and adequate thickness and depth (Veigal and Dzelalijal, 2014). The La Luna Formation is composed of Cenomanian-Santonian aged shales, marls, and limestones (Veigal and Dzelalijal, 2014). In addition to the in-situ hydrocarbons, the fractured limestones in the La Luna formation act as secondary reservoirs for light oil from other formations (Veigal and Dzelalijal, 2014). Thus the system can be considered more of a hybrid play, rather than a pure unconventional play. The Cretaceous source rocks of the MMVB exhibit excellent potential for unconventional exploration and production. Due to the complex structural nature of the MMVB, an understanding of the distribution of rocks and variations in rock qualities is essential for reducing risk in this play.

(Table 1) TOC, d13C, concentrations of C37 alkenones, crenarchaeol and GDGTs of turbidites

One of the primary prerequisites for the application of organic proxies is that they should not be substantially affected by diagenesis. However, studies have shown that oxic degradation of biomarker lipids can affect their relative distribution. We tested the diagenetic stability of the UK'37 and TEX86 palaeothermometers upon long term oxygen exposure. For this purpose, we studied the distributions of alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in different sections of turbidites at the Madeira Abyssal Plain (MAP) that experienced different degrees of oxygen exposure. Sediments were deposited anoxically on the shelf and then transported by turbidity currents to the MAP, which has oxic bottom water. This resulted in partial degradation of the turbidite organic matter as a result of long term exposure to oxic bottom water. Concentrations of GDGTs and alkenones were reduced by one to two orders of magnitude in the oxidized parts of the turbidites compared to the unoxidized parts, indicating substantial degradation. High-resolution analysis of the Pleistocene F-turbidite showed that the UK'37 index of long chain alkenones increased only slightly (0.01, corresponding to <0.5 °C) in the oxidized part of the turbidite, suggesting minor preferential degradation of the C37:3 alkenone, in agreement with previous studies. TEX86 values showed a small increase (0.02, corresponding to ~2 °C) in the F-turbidite, like UK'37 , while for other Pliocene/Miocene turbidites it either remained unchanged or decreased substantially (up to 0.06, corresponding to ~6 °C). Previous observations showed that the BIT index, a proxy for the contribution of soil organic matter to total organic carbon, was always substantially higher in the oxidized part in all the turbidites, as a result of preferential degradation of marine-derived GDGTs. This relative increase in soil-derived GDGTs affects TEX86, as the isoprenoid GDGT distribution on the continent can be quite different from that in the marine environment. Our results indicate that the organic proxies are affected by long term oxic degradation to different extents; this should be taken into account when applying these proxies in palaeoceanographic studies of sediments which have been exposed to prolonged oxic degradation.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.

Geochemical analysis of surface sediments from the ocean floor and from sea ice in the northern Atlantic and Arctic Oceans

Barium in marine terrigenous surface sediments of the European Nordic Seas is analysed to evaluate its potential as palaeoproductivity proxy. Biogenic Ba is calculated from Ba and Al data using a conventional approach. For the determination of appropriate detrital Ba/Al ratios a compilation of Ba and Al analyses in rocks and soils of the catchments surrounding the Nordic Seas is presented. The resulting average detrital Ba/Al ratio of 0.0070 is similar to global crustal average values. In the southern Nordic Seas the high input of basaltic material with a low Ba/Al ratio is evident from high values of magnetic susceptibility and low Al/Ti ratios. Most of the Ba in the marine surface sediments is of terrigenous and not of biogenic origin. Variability in the lithogenic composition has been considered by the application of regionally varying Ba/Al ratios. The biogenic Ba values are comparable with those observed in the central Arctic Ocean, they are lower than in other oceanic regions. Biogenic Ba values are correlated with other productivity proxies and with oceanographic data for a validation of the applicability in paleoceanography. In the Iceland Sea and partly in the marginal sea-ice zone of the Greenland Sea elevated values of biogenic Ba indicate seasonal phytoplankton blooms. In both areas paleoproductivities may be reconstructed based on Ba and Al data of sediment cores.

Sedimentological analysis of eight cores from the Amundsen Sea

Recent palaeoglaciological studies on the West Antarctic shelf have mainly focused on the wide embayments of the Ross and Amundsen seas in order to reconstruct the extent and subsequent retreat of the West Antarctic Ice Sheet (WAIS) since the Last Glacial Maximum (LGM). However, the narrower shelf sectors between these two major embayments have remained largely unstudied in previous geological investigations despite them covering extensive areas of the West Antarctic shelf. Here, we present the first systematic marine geological and geophysical survey of a shelf sector offshore from the Hobbs Coast. It is dominated by a large grounding zone wedge (GZW), which fills the base of a palaeo-ice stream trough on the inner shelf and marks a phase of stabilization of the grounding line during general WAIS retreat following the last maximum ice-sheet extent in this particular area (referred to as the Local Last Glacial Maximum, 'LLGM'). Reliable age determination on calcareous microfossils from the infill of a subglacial meltwater channel eroded into the GZW reveals that grounded ice had retreated landward of the GZW before ~20.88 cal. ka BP, with deglaciation of the innermost shelf occurring prior to ~12.97 cal. ka BP. Geophysical sub-bottom information from the inner-, mid- and outer shelf indicates grounded ice extended to the shelf edge prior to the formation of the GZW. Assuming the wedge was deposited during deglaciation, we infer the timing of maximum grounded ice extent occurred before ~20.88 cal. ka BP. This could suggest that the WAIS retreat from the outer shelf was already underway during or even prior to the global LGM (~23-19 cal. ka BP). Our new findings give insights into the regional deglacial behaviour of this understudied part of the West Antarctic shelf and at the same time support early deglaciation ages recently presented for adjacent drainage sectors of the WAIS. If correct, these findings contrast with the hypothesis that initial deglaciation of Antarctic Ice Sheets occurred synchronously at ~19 cal. ka BP.

(Table 2) Contents of U, P2O5, CO2, and TOC in phosphorites from Pacific seamounts

Uranium content of in phosphorites from Pacific seamounts does not exceed 10ppm; it is significantly lower than in phosphorites from submarine continental margins and deposits on land. Phosphate is not the main carrier of uranium, which is inhomogeneously distributed in ferromanganese hydroxide-, phosphate-, silicate- and carbonate materials. Uranium associated with phosphate is not isomorphic admixture. Uranium occurs in rocks in fine particles of unknown composition. Ultramicroscopic inclusions of U(IV) oxides have been also found.

Bulk sediment parameters and coarse-fraction analysis of ODP Leg 178 holes

The area west of the Antarctic Peninsula is a key region for studying and understanding the history of glaciation in the southern high latitudes during the Neogene with respect to variations of the western Antarctic continental ice sheet, variable sea-ice cover, induced eustatic sea level change, as well as consequences for the global climatic system (Barker, Camerlenghi, Acton, et al., 1999). Sites 1095, 1096, and 1101 were drilled on sediment drifts forming the continental rise to examine the nature and composition of sediments deposited under the influence of the Antarctic Peninsula ice sheet, which has repeatedly advanced to the shelf edge and subsequently released glacially eroded material on the continental shelf and slope (Barker et al., 1999). Mass gravity processes on the slope are responsible for downslope sediment transport by turbidity currents within a channel system between the drifts. Furthermore, bottom currents redistribute the sediments, which leads to final build up of drift bodies (Rebesco et al., 1998). The high-resolution sedimentary sequences on the continental rise can be used to document the variability of continental glaciation and, therefore, allow us to assess the main factors that control the sediment transport and the depositional processes during glaciation periods and their relationship to glacio-eustatic sea level changes. Site 1095 lies in 3840 m of water in a distal position on the northwestern lower flank of Drift 7, whereas Site 1096 lies in 3152 m of water in a more proximal position within Drift 7. Site 1101 is located at 3509 m water depth on the northwestern flank of Drift 4. All three sites have high sedimentation rates. The oldest sediments were recovered at Site 1095 (late Miocene; 9.7 Ma), whereas sediments of Pliocene age were recovered at Site 1096 (4.7 Ma) and at Site 1101 (3.5 Ma). The purpose of this work is to provide a data set of bulk sediment parameters such as CaCO3, total organic carbon (TOC), and coarse-fraction mass percentage (>63 µm) measured on the sediments collected from the continental rise of the western Antarctic Peninsula (Holes 1095A, 1095B, 1096A, 1096B, 1096C, and 1101A). This information can be used to understand the complex depositional processes and their implication for variations in the climatic system of the western Pacific Antarctic margin since 9.7 Ma (late Miocene). Coarse-fraction particles (125-500 µm) from the late Pliocene and Pleistocene (4.0 Ma to recent) sediments recovered from Hole 1095A were microscopically analyzed to gather more detailed information about their variability and composition through time. These data can yield information about changes in potential source regions of the glacially eroded material that has been transported during repeated periods of ice-sheet movements on the shelf.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

PM and material decay: analysis of dry depositions on horizontal and vertical surrogate surfaces through a Deposition Box system

Airborne Particulate Matter (PM), can get removed from the atmosphere through wet and dry mechanisms, and physically/chemically interact with materials and induce premature decay. The effect of dry depositions is a complex issue, especially for outdoor materials, because of the difficulties to collect atmospheric deposits repeatable in terms of mass and homogeneously distributed on the entire investigated substrate. In this work, to overcome these problems by eliminating the variability induced by outdoor removal mechanisms (e.g. winds and rainfalls), a new sampling system called ‘Deposition Box’, was used for PM sampling. Four surrogate materials (Cellulose Acetate, Regenerated Cellulose, Cellulose Nitrate and Aluminum) with different surfaces features were exposed in the urban-marine site of Rimini (Italy), in vertical and horizontal orientations. Homogeneous and reproducible PM deposits were obtained and different analytical techniques (IC, AAS, TOC, VP-SEM-EDX, Vis-Spectrophotometry) were employed to characterize their mass, dimension and composition. Results allowed to discriminate the mechanisms responsible of the dry deposition of atmospheric particles on surfaces with different nature and orientation and to determine which chemical species, and in which amount, tend to preferentially deposit on them. This work demonstrated that “Deposition Box” can represent an affordable tool to study dry deposition fluxes on materials and results obtained will be fundamental in order to extend this kind of exposure to actual building and heritage materials, to investigate the PM contribution in their decay.

Analysis Of The Dna Fourier Transform-infrared Microspectroscopic Signature Using An All-reflecting Objective.

The Fourier transform-infrared (FT-IR) signature of dry samples of DNA and DNA-polypeptide complexes, as studied by IR microspectroscopy using a diamond attenuated total reflection (ATR) objective, has revealed important discriminatory characteristics relative to the PO2(-) vibrational stretchings. However, DNA IR marks that provide information on the sample's richness in hydrogen bonds have not been resolved in the spectral profiles obtained with this objective. Here we investigated the performance of an all reflecting objective (ARO) for analysis of the FT-IR signal of hydrogen bonds in DNA samples differing in base richness types (salmon testis vs calf thymus). The results obtained using the ARO indicate prominent band peaks at the spectral region representative of the vibration of nitrogenous base hydrogen bonds and of NH and NH2 groups. The band areas at this spectral region differ in agreement with the DNA base richness type when using the ARO. A peak assigned to adenine was more evident in the AT-rich salmon DNA using either the ARO or the ATR objective. It is concluded that, for the discrimination of DNA IR hydrogen bond vibrations associated with varying base type proportions, the use of an ARO is recommended.

Effect Of Platform Connection And Abutment Material On Stress Distribution In Single Anterior Implant-supported Restorations: A Nonlinear 3-dimensional Finite Element Analysis.

Although various abutment connections and materials have recently been introduced, insufficient data exist regarding the effect of stress distribution on their mechanical performance. The purpose of this study was to investigate the effect of different abutment materials and platform connections on stress distribution in single anterior implant-supported restorations with the finite element method. Nine experimental groups were modeled from the combination of 3 platform connections (external hexagon, internal hexagon, and Morse tapered) and 3 abutment materials (titanium, zirconia, and hybrid) as follows: external hexagon-titanium, external hexagon-zirconia, external hexagon-hybrid, internal hexagon-titanium, internal hexagon-zirconia, internal hexagon-hybrid, Morse tapered-titanium, Morse tapered-zirconia, and Morse tapered-hybrid. Finite element models consisted of a 4×13-mm implant, anatomic abutment, and lithium disilicate central incisor crown cemented over the abutment. The 49 N occlusal loading was applied in 6 steps to simulate the incisal guidance. Equivalent von Mises stress (σvM) was used for both the qualitative and quantitative evaluation of the implant and abutment in all the groups and the maximum (σmax) and minimum (σmin) principal stresses for the numerical comparison of the zirconia parts. The highest abutment σvM occurred in the Morse-tapered groups and the lowest in the external hexagon-hybrid, internal hexagon-titanium, and internal hexagon-hybrid groups. The σmax and σmin values were lower in the hybrid groups than in the zirconia groups. The stress distribution concentrated in the abutment-implant interface in all the groups, regardless of the platform connection or abutment material. The platform connection influenced the stress on abutments more than the abutment material. The stress values for implants were similar among different platform connections, but greater stress concentrations were observed in internal connections.

Is Thyroid Stunning Clinically Relevant? A Retrospective Analysis Of 208 Patients.

Current guidelines have advised against the performance of (131)I-iodide diagnostic whole body scintigraphy (dxWBS) to minimize the occurrence of stunning, and to guarantee the efficiency of radioiodine therapy (RIT). The aim of the study was to evaluate the impact of stunning on the efficacy of RIT and disease outcome. This retrospective analysis included 208 patients with differentiated thyroid cancer managed according to a same protocol and followed up for 12-159 months (mean 30 ± 69 months). Patients received RIT in doses ranging from 3,700 to 11,100 MBq (100 mCi to 300 mCi). Post-RIT-whole body scintigraphy images were performed 10 days after RIT in all patients. In addition, images were also performed 24-48 hours after therapy in 22 patients. Outcome was classified as no evidence of disease (NED), stable disease (SD) and progressive disease (PD). Thyroid stunning occurred in 40 patients (19.2%), including 26 patients with NED and 14 patients with SD. A multivariate analysis showed no association between disease outcome and the occurrence of stunning (p = 0.3476). The efficacy of RIT and disease outcome do not seem to be related to thyroid stunning.

Combined Analysis Of νμ Disappearance And νμ→νe Appearance In Minos Using Accelerator And Atmospheric Neutrinos.

We report on a new analysis of neutrino oscillations in MINOS using the complete set of accelerator and atmospheric data. The analysis combines the ν(μ) disappearance and ν(e) appearance data using the three-flavor formalism. We measure |Δm(32)(2)| = [2.28-2.46] × 10(-3) eV(2) (68% C.L.) and sin(2)θ(23) = 0.35-0.65 (90% C.L.) in the normal hierarchy, and |Δm(32)(2)| = [2.32-2.53] × 10(-3) eV(2) (68% C.L.) and sin(2)θ(23) = 0.34-0.67 (90% C.L.) in the inverted hierarchy. The data also constrain δ(CP), the θ(23} octant degeneracy and the mass hierarchy; we disfavor 36% (11%) of this three-parameter space at 68% (90%) C.L.

Phylogenetic Analysis Of The Microbial Community In Hypersaline Petroleum Produced Water From The Campos Basin.

In this work the archaea and eubacteria community of a hypersaline produced water from the Campos Basin that had been transported and discharged to an onshore storage facility was evaluated by 16S recombinant RNA (rRNA) gene sequence analysis. The produced water had a hypersaline salt content of 10 (w/v), had a carbon oxygen demand (COD) of 4,300 mg/l and contains phenol and other aromatic compounds. The high salt and COD content and the presence of toxic phenolic compounds present a problem for conventional discharge to open seawater. In previous studies, we demonstrated that the COD and phenolic content could be largely removed under aerobic conditions, without dilution, by either addition of phenol degrading Haloarchaea or the addition of nutrients alone. In this study our goal was to characterize the microbial community to gain further insight into the persistence of reservoir community members in the produced water and the potential for bioremediation of COD and toxic contaminants. Members of the archaea community were consistent with previously identified communities from mesothermic reservoirs. All identified archaea were located within the phylum Euryarchaeota, with 98 % being identified as methanogens while 2 % could not be affiliated with any known genus. Of the identified archaea, 37 % were identified as members of the strictly carbon-dioxide-reducing genus Methanoplanus and 59 % as members of the acetoclastic genus Methanosaeta. No Haloarchaea were detected, consistent with the need to add these organisms for COD and aromatic removal. Marinobacter and Halomonas dominated the eubacterial community. The presence of these genera is consistent with the ability to stimulate COD and aromatic removal with nutrient addition. In addition, anaerobic members of the phyla Thermotogae, Firmicutes, and unclassified eubacteria were identified and may represent reservoir organisms associated with the conversion hydrocarbons to methane.