La tagatose-1,6-bisphosphate aldolase et la fructose-1,6-bisphosphate aldolase de classe I : mécanisme et stéréospécificité

La tagatose-1,6-biphosphate aldolase de Streptococcus pyogenes est une aldolase qui fait preuve d'un remarquable manque de spécificité vis à vis de ses substrats. En effet, elle catalyse le clivage réversible du tagatose-1,6-bisphosphate (TBP), mais également du fructose-1,6-bisphosphate (FBP), du sorbose-1,6-bisphosphate et du psicose-1,6-bisphosphate, quatre stéréoisomères, en dihydroxyacétone phosphate (DHAP) et en glycéraldéhyde-3-phosphate (G3P). Aldolase de classe I, qui donc catalyse sa réaction en formant un intermédiaire covalent obligatoire, ou base de Schiff, avec son susbtrat, la TBP aldolase de S. pyogenes partage 14 % d’identité avec l’enzyme modèle de cette famille, la FBP aldolase de muscle de mammifère. Bien que le mécanime catalytique de la FBP aldolase des mammifères ait été examiné en détails et qu’il soit approprié d’en tirer des renseignements quant à celui de la TBP aldolase, le manque singulier de stéréospécificité de cette dernière tant dans le sens du clivage que celui de la condensation n’est toujours pas éclairci. Afin de mettre à jour les caractéristiques du mécanisme enzymatique, une étude structurale de la TBP aldolase de S. pyogenes, un pathogène humain extrêmement versatile, a été entreprise. Elle a permis la résolution des structures de l’enzyme native et mutée, en complexe avec des subtrats et des inhibiteurs compétitifs, à des résolutions comprises entre 1.8 Å et 2.5 Å. Le trempage des cristaux de TBP aldolase native et mutante dans une solution saturante de FBP ou TBP a en outre permis de piéger un authentique intermédiaire covalent lié à la Lys205, la lysine catalytique. La determination des profils pH de la TBP aldolase native et mutée, entreprise afin d'évaluer l’influence du pH sur la réaction de clivage du FBP et TBP et ìdentifier le(s) résidu(s) impliqué(s), en conjonction avec les données structurales apportées par la cristallographie, ont permis d’identifier sans équivoque Glu163 comme résidu responsable du clivage. En effet, le mode de liaison sensiblement différent des ligands utilisés selon la stéréochimie en leur C3 et C4 permet à Glu163, équivalent à Glu187 dans la FBP aldolase de classe I, d’abstraire le proton sur l’hydroxyle du C4 et ainsi d’amorcer le clivage du lien C3-C4. L’étude du mécanimse inverse, celui de la condensation, grâce par exemple à la structure de l’enzyme native en complexe avec ses substrats à trois carbones le DHAP et le G3P, a en outre permis d’identifier un isomérisme du substrat G3P comme possible cause de la synthèse des isomères en C4 par cette enzyme. Ce résultat, ainsi que la decouverte d’un possible isomérisme cis-trans autour du lien C2-C3 de la base de Schiff formée avec le DHAP, identifié précedemment, permet de cerner presque complètement les particularités du mécanisme de cette enzyme et d’expliquer comment elle est capable de synthétiser les quatres stéréoisomères 3(S/R), 4(S/R). De plus, la résolution de ces structures a permis de mettre en évidence trois régions très mobiles de la protéine, ce qui pourrait être relié au rôle postulé de son isozyme chez S. pyogenes dans la régulation de l’expression génétique et de la virulence de la bactérie. Enfin, la résolution de la structure du mutant Lys229→Met de la FBP aldolase de muscle en complexe avec la forme cyclique du FBP, de même que des études cristallographiques sur le mutant équivalent Lys205→Met de la TBP aldolase de S. pyogenes et des expériences de calorimétrie ont permis d’identifier deux résidus particuliers, Ala31 et Asp33 chez la FBP aldolase, comme possible cause de la discrimination de cette enzyme contre les substrats 3(R) et 4(S), et ce par encombrement stérique des substrats cycliques. La cristallographie par rayons X et la cinétique enzymatique ont ainsi permis d'avancer dans l'élucidation du mécanisme et des propriétés structurales de cette enzyme aux caractéristiques particulières.

Stable isotope record of planktonic foraminifera of the Atlantic Ocean

The thermal structure of the upper ocean (0-1000 m) is set by surface heat fluxes, shallow wind-driven circulation, and the deeper thermohaline circulation. Its long-term variability can be reconstructed using deep-dwelling planktonic foraminifera that record subsurface conditions. Here we used six species (Neogloboquadrina dutertrei, Globorotalia tumida, Globorotalia inflata, Globorotalia truncatulinoides, Globorotalia hirsuta, and Globorotalia crassaformis) from 66 core tops along a meridional transect spanning the mid-Atlantic (42°N to 25°S) to develop a method for reconstructing past thermocline conditions. We estimated the calcification depths from d18O measurements and the Mg/Ca-temperature relationships for each species. This systematic strategy over this large latitudinal section reveals distinct populations with different Mg/Ca-temperature relationships for G. inflata, G. truncatulinoides, and G. hirsuta in different areas. The calcification depths do not differ among the different populations, except for G. hirsuta, where the northern population calcifies much shallower than the southern population. N. dutertrei and G. tumida show a remarkably constant calcification depth independent of oceanographic conditions. The deepest dweller, G. crassaformis, apparently calcifies in the oxygen-depleted zone, where it may find refuge from predators and abundant aggregated matter to feed on. We found a good match between its calcification depth and the 3.2 ml/l oxygen level. The results of this multispecies, multiproxy study can now be applied down-core to facilitate the reconstruction of open-ocean thermocline changes in the past.

(Table 1) AMS radiocarbon ages from ODP Sites 169-1033 and 169-1034

This paper explores the paleoseismic record potentially preserved in the upper 40 m of hydraulic piston cores collected in 1996 at two sites in Saanich Inlet, British Columbia, during ocean drilling program (ODP) Leg 169S. The ODP cores are missing 1-2 m of water-rich sediment directly underlying the seafloor, but this sediment is preserved in shorter piston cores collected in 1989 and 1991. The upper part of the ODP cores consists of rhythmically laminated (varved) marine mud with intercalated massive beds, interpreted to be debris flow deposits. Some of the debris flow deposits are linked to past earthquakes, including the 1946 Vancouver Island earthquake (M7.2), a great (M8-9) plate-boundary earthquake at the Cascadia subduction zone in January 1700, and a large crustal or plate-boundary earthquake about 1000 yr ago. Earthquakes may also be responsible for debris flows in about AD 1600, 1500, 1250, 1150, 850, 450, 350, 180, and BC 200, 220, 500, 900, and 1050. If so, the average recurrence interval for moderate to large earthquakes, which trigger debris flows in Saanich Inlet, is about 150 yr. This recurrence interval is broadly consistent with the frequency of moderate to large earthquakes in the region during the historical period. Debris flows, however, can also be triggered by non-seismic processes, making it difficult to assemble a complete earthquake record from the Saanich Inlet cores. We propose that extensive debris flow deposits, emplaced by single large failures or many smaller coincident failures, probably have a seismic origin.

Pollen abundances, and temperature and precipitation reconstruction for the Eocene to Oligocene transition in northern high latitudes

A profound global climate shift took place at the Eocene-Oligocene transition (~33.5 million years ago) when Cretaceous/early Palaeogene greenhouse conditions gave way to icehouse conditions (Zachos et al., 2001, doi:10.1126/science.1059412; Coxall et al., 2005, doi:10.1038/nature03135; Lear et al., 2008, doi:10.1130/G24584A.1). During this interval, changes in the Earth's orbit and a long-term drop in atmospheric carbon dioxide concentrations (Pagani et al., 2005, doi:10.1126/science.1110063; Pearson and Palmer, 2000, doi:10.1038/35021000; DeConto and Pollard, 2003, doi:10.1038/nature01290) resulted in both the growth of Antarctic ice sheets to approximately their modern size (Coxall et al., 2005, doi:10.1038/nature03135; Lear et al., 2008, doi:10.1130/G24584A.1) and the appearance of Northern Hemisphere glacial ice (Eldrett et al., 2007, doi:10.1038/nature05591; Moran et al., 2006, doi:10.1038/nature04800). However, palaeoclimatic studies of this interval are contradictory: although some analyses indicate no major climatic changes (Kohn et al., 2004, doi:10.1130/G20442.1; Grimes et al., 2005, doi:10.1130/G21019.1), others imply cooler temperatures (Zanazzi et al., 2007, doi:10.1038/nature05551), increased seasonality (Ivany et al., 2000, doi:10.1038/35038044; Terry, 2001, doi:10.1016/S0031-0182(00)00248-0) and/or aridity (Ivany et al., 2000, doi:10.1038/35038044; Terry, 2001, doi:10.1016/S0031-0182(00)00248-0; Sheldon et al., 2002, doi:10.1086/342865; Dupont-Nivet et al., 2007, doi:10.1038/nature05516). Climatic conditions in high northern latitudes over this interval are particularly poorly known. Here we present northern high-latitude terrestrial climate estimates for the Eocene to Oligocene interval, based on bioclimatic analysis of terrestrially derived spore and pollen assemblages preserved in marine sediments from the Norwegian-Greenland Sea. Our data indicate a cooling of ~5 °C in cold-month (winter) mean temperatures to 0-2 °C, and a concomitant increased seasonality before the Oi-1 glaciation event. These data indicate that a cooling component is indeed incorporated in the d18O isotope shift across the Eocene-Oligocene transition. However, the relatively warm summer temperatures at that time mean that continental ice on East Greenland was probably restricted to alpine outlet glaciers.

Radiocarbon dates, grain size measurements and selected foraminifera analysis from sediment cores AvH248260-2 and AvH248260-1, Ameralik Fjord, SW Greenland

Sedimentological and geochemical (XRF) data together with information from diatom and benthic foraminiferal records of a 3.5 m long gravity core from Ameralik Fjord, southern West Greenland, is used for reconstructing late-Holocene environmental changes in this area. The changes are linked to large-scale North Atlantic ocean and climate variability. AMS 14C-dating of benthic foraminifera indicates that the sediment core records the last 4400 years and covers the termination of the Holocene Thermal Maximum (HTM). The late HTM (4.4 3.2 ka BP) is characterized by high accumulation rates of fine (silty) sediments related to strong meltwater discharge from the Inland Ice. The HTM benthic foraminiferal fauna demonstrates the presence of well-ventilated, saline bottom water originating from inflow of subsurface West Greenland Current water of Atlantic (Irminger Sea) origin. The hydrographic conditions were further characterized by limited sea ice probably related to a mild and relatively windy winter climate. After 3.2 ka BP lower fine-grained sedimentation rates, but a larger input from sea-ice rafted or aeolian coarse material prevailed. This can be related to colder atmospheric conditions with a decreased meltwater discharge and more widespread sea-ice cover in the fjord.

Sea surface temperature reconstruction based on alkenones of sediment core M35003-4

Evidence for abrupt climate changes on millennial and shorter timescales is widespread in marine and terrestrial climate records (Dansgard et al., 1993, doi:10.1038/364218a0; Bond et al., 1993, doi:10.1038/365143a0; Charles et al., 1996, doi:10.1016/0012-821X(96)00083-0, Bard et al., 1997, doi:10.1038/385707a0). Rapid reorganization of ocean circulation is considered to exert some control over these changes (Broecker et al., 1985, doi:10.1038/315021a0), as are shifts in the concentrations of atmospheric greenhouse gases (Broecker, 1994, doi:10.1038/372421a0). The response of the climate system to these two influences is fundamentally different: slowing of thermohaline overturn in the North Atlantic Ocean is expected to decrease northward heat transport by the ocean and to induce warming of the tropical Atlantic (Crowley, 1992, doi:10.1029/92PA01058; Manabe and Stouffer, 1997, doi:10.1029/96PA03932), whereas atmospheric greenhouse forcing should cause roughly synchronous global temperature changes (Manabe et al., 1991, doi:10.1175/1520-0442(1991)004<0785:TROACO>2.0.CO;2). So these two mechanisms of climate change should be distinguishable by the timing of surface-water temperature variations relative to changes in deep-water circulation. Here we present a high-temporal-resolution record of sea surface temperatures from the western tropical North Atlantic Ocean which spans the past 29,000 years, derived from measurements of temperature-sensitive alkenone unsaturation in sedimentary organic matter. We find significant warming is documented for Heinrich event H1 (16,900-15,400 calendar years bp) and the Younger Dryas event (12,900-11,600 cal. yr bp), which were periods of intense cooling in the northern North Atlantic. Temperature changes in the tropical and high-latitude North Atlantic are out of phase, suggesting that the thermohaline circulation was the important trigger for these rapid climate changes.

Bulk sediment element analysis of sediment cores GeoB10065-9 and GeoB10065-7, offshore northwest Sumba Island, Indonesia

The Australian-Indonesian monsoon has a governing influence on the agricultural practices and livelihood in the highly populated islands of Indonesia. However, little is known about the factors that have influenced past monsoon activity in southern Indonesia. Here, we present a ~6000 years high-resolution record of Australian-Indonesian summer monsoon (AISM) rainfall variations based on bulk sediment element analysis in a sediment archive retrieved offshore northwest Sumba Island (Indonesia). The record suggests lower riverine detrital supply and hence weaker AISM rainfall between 6000 yr BP and ~3000 yr BP compared to the Late Holocene. We find a distinct shift in terrigenous sediment supply at around 2800 yr BP indicating a reorganization of the AISM from a drier Mid Holocene to a wetter Late Holocene in southern Indonesia. The abrupt increase in rainfall at around 2800 yr BP coincides with a grand solar minimum. An increase in southern Indonesian rainfall in response to a solar minimum is consistent with climate model simulations that provide a possible explanation of the underlying mechanism responsible for the monsoonal shift. We conclude that variations in solar activity play a significant role in monsoonal rainfall variability at multi-decadal and longer timescales. The combined effect of orbital and solar forcing explains important details in the temporal evolution of AISM rainfall during the last 6000 years. By contrast, we find neither evidence for volcanic forcing of AISM variability nor for a control by long-term variations in the El Niño-Southern Oscillation (ENSO).

Holocene flood frequency across the Central Alps

The frequency of large-scale heavy precipitation events in the European Alps is expected to undergo substantial changes with current climate change. Hence, knowledge about the past natural variability of floods caused by heavy precipitation constitutes important input for climate projections. We present a comprehensive Holocene (10,000 years) reconstruction of the flood frequency in the Central European Alps combining 15 lacustrine sediment records. These records provide an extensive catalog of flood deposits, which were generated by flood-induced underflows delivering terrestrial material to the lake floors. The multi-archive approach allows suppressing local weather patterns, such as thunderstorms, from the obtained climate signal. We reconstructed mainly late spring to fall events since ice cover and precipitation in form of snow in winter at high-altitude study sites do inhibit the generation of flood layers. We found that flood frequency was higher during cool periods, coinciding with lows in solar activity. In addition, flood occurrence shows periodicities that are also observed in reconstructions of solar activity from 14C and 10Be records (2500-3000, 900-1200, as well as of about 710, 500, 350, 208 (Suess cycle), 150, 104 and 87 (Gleissberg cycle) years). As atmospheric mechanism, we propose an expansion/shrinking of the Hadley cell with increasing/decreasing air temperature, causing dry/wet conditions in Central Europe during phases of high/low solar activity. Furthermore, differences between the flood patterns from the Northern Alps and the Southern Alps indicate changes in North Atlantic circulation. Enhanced flood occurrence in the South compared to the North suggests a pronounced southward position of the Westerlies and/or blocking over the northern North Atlantic, hence resembling a negative NAO state (most distinct from 4.2 to 2.4 kyr BP and during the Little Ice Age). South-Alpine flood activity therefore provides a qualitative record of variations in a paleo-NAO pattern during the Holocene. Additionally, increased South Alpine flood activity contrasts to low precipitation in tropical Central America (Cariaco Basin) on the Holocene and centennial time scale. This observation is consistent with a Holocene southward migration of the Atlantic circulation system, and hence of the ITCZ, driven by decreasing summer insolation in the Northern hemisphere, as well as with shorter-term fluctuations probably driven by solar activity.

Sedimentological and geophysical investigation of sediment cores from the Amundsen Sea

Ice loss from the marine-based, potentially unstable West Antarctic Ice Sheet (WAIS) contributes to current sea-level rise and may raise sea level by up to 3.3 to 5 meters in the future. Over the past few decades, glaciers draining the WAIS into the Amundsen Sea Embayment (ASE) have shown accelerated ice flow, rapid thinning and grounding-line retreat. However, the long-term context of this ice-sheet retreat is poorly constrained, limiting our ability to accurately predict future WAIS behaviour. Here we present a new chronology for WAIS retreat from the inner continental shelf of the eastern ASE based on radiocarbon dates from three marine sediment cores. The ages document a retreat of the grounding line to within ~93 km of its modern position before 11.7±0.7 kyr BP (thousand years before present). This early deglaciation is consistent with ages for grounding-line retreat from the western ASE. Our new data demonstrate that, other than in the Ross Sea, WAIS retreat in the ASE has not continued progressively since the Last Glacial Maximum. Furthermore, our results suggest that the grounding-line position in the ASE was predominantly stable throughout the Holocene, and that any episodes of fast retreat similar to that observed today must have been short-lived. Alternatively, today's rapid retreat was unprecedented during the Holocene. Therefore, the current ice loss must originate in recent changes in regional climate, ocean circulation or ice-sheet dynamics. Incorporation of these results into models is essential to produce robust predictions of future ice-sheet change and its contribution to sea-level rise.

Radiocarbon ages, dose rates, water isotopic composition and hydrochemistry of samples from Komakuk Beach and Herschel Island

Terrestrial permafrost archives along the Yukon Coastal Plain (northwest Canada) have recorded landscape development and environmental change since the Late Wisconsinan at the interface of unglaciated Beringia (i.e. Komakuk Beach) and the northwestern limit of the Laurentide Ice Sheet (i.e. Herschel Island). The objective of this paper is to compare the late glacial and Holocene landscape development on both sides of the former ice margin based on permafrost sequences and ground ice. Analyses at these sites involved a multi-proxy approach including: sedimentology, cryostratigraphy, palaeoecology of ostracods, stable water isotopes in ground ice, hydrochemistry, and AMS radiocarbon and infrared stimulated luminescence (IRSL) dating. AMS and IRSL age determinations yielded full glacial ages at Komakuk Beach that is the northeastern limit of ice-free Beringia. Herschel Island to the east marks the Late Wisconsinan limit of the northwest Laurentide Ice Sheet and is composed of ice-thrust sediments containing plant detritus as young as 16.2 cal ka BP that might provide a maximum age on ice arrival. Late Wisconsinan ice wedges with sediment-rich fillings on Herschel Island are depleted in heavy oxygen isotopes (mean d18O of -29.1 per mil); this, together with low d-excess values, indicates colder-than-modern winter temperatures and probably reduced snow depths. Grain-size distribution and fossil ostracod assemblages indicate that deglaciation of the Herschel Island ice-thrust moraine was accompanied by alluvial, proluvial, and eolian sedimentation on the adjacent unglaciated Yukon Coastal Plain until ~11 cal ka BP during a period of low glacio-eustatic sea level. The late glacial-Holocene transition was marked by higher-than-modern summer temperatures leading to permafrost degradation that began no later than 11.2 cal ka BP and caused a regional thaw unconformity. Cryostructures and ice wedges were truncated while organic matter was incorporated and soluble ions were leached in the thaw zone. Thermokarst activity led to the formation of ice-wedge casts and deposition of thermokarst lake sediments. These were subsequently covered by rapidly accumulating peat during the early Holocene Thermal Maximum. A rising permafrost table, reduced peat accumulation, and extensive ice-wedge growth resulted from climate cooling starting in the middle Holocene until the late 20th century. The reconstruction of palaeolandscape dynamics on the Yukon Coastal Plain and the eastern Beringian edge contributes to unraveling the linkages between ice sheet, ocean, and permafrost that have existed since the Late Wisconsinan.