ALBERT

Description: Structure-based inhibitor design has led to the discovery of a number of potent inhibitors of glycogen phosphorylase b (GPb), N-acyl derivatives of β-d-glucopyranosylamine, that bind at the catalytic site of the enzyme. The first good inhibitor in this class of compounds, N-acetyl-β-d-glucopyranosylamine (NAG) (Ki = 32 μM), has been previously characterized by biochemical, biological and crystallographic experiments at 2.3 Å resolution. Bioisosteric replacement of the acetyl group by trifluoroacetyl group resulted in an inhibitor, N-trifluoroacetyl-β-d-glucopyranosylamine (NFAG), with a Ki = 75 μM. To elucidate the structural basis of its reduced potency, we determined the ligand structure in complex with GPb at 1.8 Å resolution. To compare the binding mode of N-trifluoroacetyl derivative with that of the lead molecule, we also determined the structure of GPb–NAG complex at a higher resolution (1.9 Å). NFAG can be accommodated in the catalytic site of T-state GPb at approximately the same position as that of NAG and stabilize the T-state conformation of the 280s loop by making several favourable contacts to Asn284 of this loop. The difference observed in the Ki values of the two analogues can be interpreted in terms of subtle conformational changes of protein residues and shifts of water molecules in the vicinity of the catalytic site, variations in van der Waals interaction, and desolvation effects.

Description: Diffuse intraplate volcanism spanning the Cenozoic on the North, South, Chatham, Auckland, Campbell and Antipodes Islands of New Zealand has produced quartz tholeiitic to basanitic/nephelinitic (including their differentiates) monogenetic volcanic fields and large shield volcanoes. New 40Ar/39Ar ages, combined with published age data, show no correlations among age, location or composition of the volcanoes. Continuous volcanism in restricted areas over long time periods, and a lack of volcanic age progressions in the direction and at the rate of plate motion, are inconsistent with a plume origin for the intraplate volcanism. Although localized extension took place during some episodes of volcanic activity, the degree of extension does not correlate with erupted volumes or compositions. Major and trace element data suggest that the silica-poor volcanic rocks (primarily basanites) were derived through low degrees of partial melting at deeper depths than the more silica-rich volcanic rocks (alkali basalts and tholeiites) and that all melts were produced from ocean island basalt (OIB)-type sources, containing garnet pyroxenite or eclogite. The Sr–Nd–Pb isotope data indicate that the silica-poor rocks were derived from high time-integrated U/Pb (HIMU)-type sources and the silica-rich rocks from more enriched mantle (EM)-type sources, reflecting greater interaction with lithosphere modified by subduction beneath Gondwana. The first-order cause of melting is inferred to be decompression melting in the garnet stability field of upwelling asthenosphere, triggered by removal (detachment) of different parts of the subcontinental lithospheric keel throughout the Cenozoic. In some cases, large thicknesses of keel were removed and magmatism extended over many millions of years. Decompression melting beneath a thick craton generates melts that are likely to be similar to those from the base of the mid-ocean-ridge melting column. At mid-ocean ridges, however, these melts never reach the surface in their pure form due to the swamping effect of larger-degree melts formed at shallower depths. Different volcanic styles in part reflect the mode of removal, and size and shape of detached parts of the lithospheric keel. Removal of continental lithospheric mantle could be an important process for explaining the origin of diffuse igneous provinces on continental lithosphere.

Description: Numerous methane-emitting bottom features, such as seeps, methane clathrate hydrates (clathrates), and mud volcanoes, have been identified recently in the Black Sea. The fluxes of methane from these sources averaged over large spatial scales are unknown. Here we take advantage of the fact that the Black Sea is a semi-enclosed basin with restricted deep water circulation to establish first-order estimates of basin-wide fluxes of methane from these sources to the water column and atmosphere. First, we measured the natural radiocarbon content of methane (14C–CH4) dissolved in the water column and emitted from seeps. The 14C–CH4 results showed that the dominant source of methane to the water column is emitted from seeps and a smaller source is diagenetically produced in relatively modern sediments. The 14C–CH4 results were then used to partition a basin-wide total methane budget; this analysis estimated the basin-wide flux of methane from seeps and clathrates to the water column to be 3.60 to 4.28 Tg yr− 1. Second, a geochemical box model was used to calculate possible distributions of methane inputs from seeps and clathrates as well as provide additional estimates of the basin-wide flux of methane from seeps and clathrates to the water column (4.95 to 5.65 Tg yr− 1).

Description: Hydrographic surveys in three consecutive seasons in the Irminger Sea in 2001/2002 have revealed six physical regimes (zones) in which different surface mixing and spring re-stratification processes dominate. They are the South Irminger Current, the North Irminger Current, the Central Irminger Sea, the Polar-origin East Greenland Current, the Atlantic-origin East Greenland Current and the Reykjanes Ridge. The variations in restratification processes in particular have significant implications for the timing of shallow spring mixed layer development and therefore the timing and strength of the spring bloom. The relative roles of heat and freshwater in controlling re-stratification are examined for each hydrographic zone, and it is shown that the simplest concept of solar warming generating spring stratification is appropriate for the Irminger Current and the central Irminger Sea. However in the East Greenland Current and the Reykjanes Ridge zones, the springtime arrival of fresh or saline water at the surface dominates re-stratification and generates the earliest and strongest spring blooms of the region. In the cool fresh centre of the Irminger Sea the relatively low chlorophyll-a throughout the year cannot be wholly explained by stratification or nutrient concentrations. Details of the annual cycle in temperature, salinity, chlorophyll-a and nutrients are presented for each hydrographic zone

Description: Exploring the potentials of new methods in palaeothermometry is essential to improve our understanding of past climate change. Here, we present a refinement of the published δ44/40Ca-temperature calibration investigating modern specimens of planktonic foraminifera Globigerinoides sacculifer and apply this to sea surface temperature (SST) reconstructions over the last two glacial–interglacial cycles. Reproduced measurements of modern G. sacculifer collected from surface waters describe a linear relationship for the investigated temperature range (19.0–28.5 °C): δ44/40Ca [‰] = 0.22 (±0.05)∗SST [°C] −4.88. Thus a change of δ44/40Ca[‰] of 0.22 (±0.05) corresponds to a relative change of 1 °C. The refined δ44/40Camodern-calibration allows the determination of both relative temperature changes and absolute temperatures in the past. This δ44/40Camodern-calibration for G. sacculifer has been applied to the tropical East Atlantic sediment core GeoB1112 for which other SST proxy data are available. Comparison of the different data sets gives no indication for significant secondary overprinting of the δ44/40Ca signal. Long-term trends in reconstructed SST correlate strongly with temperature records derived from oxygen isotopes and Mg/Ca ratios supporting the methods validity. The observed change of SST of approximately 3 °C at the Holocene-last glacial maximum transition reveals additional evidence for the important role of the tropical Atlantic in triggering global climate change, based on a new independent palaeothermometer.

Description: 10.1016/j.epsl.2005.10.027

Description: A mud volcano area in the deep waters (〉 2000 m) of the Black Sea was studied by hydroacoustic measurements during several cruises between January 2002 and June 2004. Gas bubbles in the water column give strong backscatter signals and thus can be detected even in great water depths by echosounders as the 38 kHz EK500 scientific split-beam system that was used during the surveys. Because of their shape in echograms and to differentiate against geochemical plumes and real upwelling bubble-water plumes, we call these hydroacoustic manifestations of bubbles in the water column ‘flares’. Digital recording and processing of the data allows a 3D visualization and data comparison over the entire observation period, without artefacts caused by changing system settings. During our surveys, we discovered bubble release from three separate mud volcanoes, Dvurechenskiy (DMV), Vodianitskiy (VMV) and the Nameless Seep Site (NSS), in about 2080 m water depth simultaneously. Bubble release was observed between 9 June 2003 and 5 June 2004. The most frequently surveyed, DMV, was found to be inactive during very intensive studies in January 2002. The first activity was observed on 27 June 2002, which finally ceased between 5 and 15 June 2004 after a period of continuously decreasing activity. This observed 2-yr bubble-release period at a mud volcano may give an indication for the duration of active periods. The absence of short-term variations (within days or hours) may indicate that the bubble release from the observed mud volcanoes does not undergo rapid changes. The recorded echograms show that bubbles rise about 1300 m high through the water column, to a final water depth of about 770 m, which is ∼75 m below the phase boundary of pure methane hydrate in the Black Sea. With a release depth from 2068 m and a detected rise height of 1300 m, the flare at VMV is among the deepest and highest reported so far, and gives evidence of highly extended bubble life times (up to 108 min) in deep marine environments. To better understand how a methane bubble (gas analyses of the pore water and gas hydrate gave 99.4% methane) can rise so high without dissolving, we applied a recently developed bubble dissolution model that takes into account a decreased mass transfer due to an immediately formed gas-hydrate rim. Using the hydroacoustically determined bubble rising speeds (19–22 cm/s at the bottom; 12–14 cm/s at the flare top) and the relation between the rising speed of ‘dirty’/gas hydrate rimmed bubbles and the bubble size, we could validate that a gas-hydrate-rimmed bubble with a diameter of 9 mm could survive the 1300-m-rise through the water column, before it is finally dissolved. A diameter of about 9 mm is reasonable for bubbles released at seep sites and the coincidence between the observed bubble rising speed and the model approach of a 9-mm bubble supports the assumption of gas-hydrate-rimmed bubbles

Description: The warmest millennia of at least the past 250,000 years occurred during the Last Interglaciation, when global ice volumes were similar to or smaller than today and systematic variations in Earth's orbital parameters aligned to produce a strong positive summer insolation anomaly throughout the Northern Hemisphere. The average insolation during the key summer months (M, J, J) was ca 11% above present across the Northern Hemisphere between 130,000 and 127,000 years ago, with a slightly greater anomaly, 13%, over the Arctic. Greater summer insolation, early penultimate deglaciation, and intensification of the North Atlantic Drift, combined to reduce Arctic Ocean sea ice, allow expansion of boreal forest to the Arctic Ocean shore across vast regions, reduce permafrost, and melt almost all glaciers in the Northern Hemisphere. Insolation, amplified by key boundary condition feedbacks, collectively produced Last Interglacial summer temperature anomalies 4–5 °C above present over most Arctic lands, significantly above the average Northern Hemisphere anomaly. The Last Interglaciation demonstrates the strength of positive feedbacks on Arctic warming and provides a potentially conservative analogue for anticipated future greenhouse warming.

Description: Using high quality 3D seismic data within the Lower Congo Basin (LCB), we have identified pockmarks that are aligned above the sinuous belt of a buried turbiditic palaeo-channel, 1000 m beneath the seafloor. Geochemical analyses on cores (GC traces), taken in the centre of four of these pockmarks along this channel, show no clear evidence for migrated oil. But, some features of the GC traces, including elevated baselines (UCM〉34 μg/g) and a broad molecular weight range of n-alkanes with little odd–even preference, may be interpreted as indicating the presence of thermogenic hydrocarbons in the cores. Seismic profiles show that these pockmarks developed above two main features representative of pore fluid escape during early compaction: (1) closely spaced normal faults affecting the upper 0–800 ms TWT of the sedimentary column. This highly faulted interval (HFI) appears as a hexagonal network in plane view, which is characteristic of a volumetrical contraction of sediments in response to pore fluid escape. (2) Buried palaeo-pockmarks and their underlying chimneys seem to be rooted at the channel–levee interface. The chimneys developed during early stages of burial and are now connected to the HFI. This study shows that the buried turbiditic channel now concentrates thermogenic fluids that can migrate through early chimneys and polygonal faults to reach the seafloor within some pockmarks. Using a multidisciplinary approach within the Lower Congo Basin, combining 3D seismic data and geochemical analyses on cores, we trace the fluid history from early compaction expelling pore fluids to later migration of thermogenic hydrocarbons.

Description: Based on high-resolution 3D seismic data sets, we document the subsurface reservoir architecture and organization of a portion of the Oligocene–Miocene stratigraphy within the Congo Basin, offshore southwestern Africa. Within the 3D seismic volume, we have identified four levels of turbiditic palaeochannels, which are separated by low-amplitude continuous reflectors interpreted as hemipelagic sediments. Geochemical analyses on sediment samples taken within overlying seafloor pockmarks reveal the presence of thermogenic gases and oils, suggesting that deep-seated fluids have migrated through both the channel deposits and the impermeable layers between them, forming a conduit to the surface. Deep thermogenic fluids produced within Cretaceous source rocks are preferentially entrapped within coarse-grained turbiditic Oligocene–Miocene palaeochannels. We show in this study that the vertical stacking pattern of turbiditic palaeochannels allows the best pathway for fluids migration. Once the fluids migrate to the upper layer (i.e., Upper Miocene) of palaeochannels, they can reach the seafloor via migration along a highly faulted interval composed of polygonal faults. They are temporarily inhibited below an interpreted 300-m-thick gas hydrate layer marked by a strong BSR on seismic profiles. Fluids accumulate under the hydrate stability zone to form a thick layer of free gas. The generation of excess pore fluid pressure in the free gas accumulation leads to the release of fluids along faults of the highly faulted interval forming pockmarks on the seafloor. Ultimately, we show in this study that fluids are progressively concentrated in the sedimentary column and aligned pockmarks on the seafloor may represent a focused fluid flow from stacked turbiditic palaeochannels.