Role of the N- and C-lobes of calmodulin in the activation of Ca(2+)/calmodulin-dependent protein kinase II.

Understanding the principles of calmodulin (CaM) activation of target enzymes will help delineate how this seemingly simple molecule can play such a complex role in transducing Ca (2+)-signals to a variety of downstream pathways. In the work reported here, we use biochemical and biophysical tools and a panel of CaM constructs to examine the lobe specific interactions between CaM and CaMKII necessary for the activation and autophosphorylation of the enzyme. Interestingly, the N-terminal lobe of CaM by itself was able to partially activate and allow autophosphorylation of CaMKII while the C-terminal lobe was inactive. When used together, CaMN and CaMC produced maximal CaMKII activation and autophosphorylation. Moreover, CaMNN and CaMCC (chimeras of the two N- or C-terminal lobes) both activated the kinase but with greater K act than for wtCaM. Isothermal titration calorimetry experiments showed the same rank order of affinities of wtCaM > CaMNN > CaMCC as those determined in the activity assay and that the CaM to CaMKII subunit binding ratio was 1:1. Together, our results lead to a proposed sequential mechanism to describe the activation pathway of CaMKII led by binding of the N-lobe followed by the C-lobe. This mechanism contrasts the typical sequential binding mode of CaM with other CaM-dependent enzymes, where the C-lobe of CaM binds first. The consequence of such lobe specific binding mechanisms is discussed in relation to the differential rates of Ca (2+)-binding to each lobe of CaM during intracellular Ca (2+) oscillations.

Vapnikite Ca<SUB>3UO6 – a new double-perovskite mineral from pyrometamorphic larnite rocks of the Jabel Harmun, Palestinian Autonomy, Israel

The new mineral species vapnikite, Ca3UO6, was found in larnite pyrometamorphic rocks of the Hatrurim Formation at Jabel Harmun in the Judean desert, Palestinian Autonomy, Israel. Vapnikite is an analogue of the synthetic ordered double-perovskite β-Ca3UO6 and is isostructural with the natural fluorperovskite – cryolite Na3AlF6. Vapnikite Ca3UO6 (P21/n,Z = 2, a = 5.739(1), b = 5.951(1), c = 8.312(1) Å, β = 90.4(1)°, V = 283.9(1) Å3) forms yellow-brown xenomorphic grains with a strong vitreous lustre. Small grains up to 20 – 30 m m in size are wedged between larnite, brownmillerite and ye'elimite. Vapnikite has irregular fracture, cleavage and parting were not observed. The calculated density is 5.322 g cm–3, the microhardness is VHN25 = 534 kg mm–2 (mean of seven measurements) corresponding to the hardness of ~5 on the Mohs scale. The crystal structure of vapnikite Ca3UO6 differs from that of its synthetic analogue β-Ca3UO6 by having a larger degree of Ca, U disorder. Vapnikite formed at the high-temperature retrograde stage of pyrometamorphism when larnite rocks were altered by fluids/melts of high alkalinity.

Freshening of the Alaska Coastal Current Recorded By Coralline Algal Ba/Ca Ratios

Arctic Ocean freshening can exert a controlling influence on global climate, triggering strong feedbacks on ocean-atmospheric processes and affecting the global cycling of the world's oceans. Glacier-fed ocean currents such as the Alaska Coastal Current are important sources of freshwater for the Bering Sea shelf, and may also influence the Arctic Ocean freshwater budget. Instrumental data indicate a multiyear freshening episode of the Alaska Coastal Current in the early 21st century. It is uncertain whether this freshening is part of natural multidecadal climate variability or a unique feature of anthropogenically induced warming. In order to answer this, a better understanding of past variations in the Alaska Coastal Current is needed. However, continuous long-term high-resolution observations of the Alaska Coastal Current have only been available for the last 2 decades. In this study, specimens of the long-lived crustose coralline alga Clathromorphum nereostratum were collected within the pathway of the Alaska Coastal Current and utilized as archives of past temperature and salinity. Results indicate that coralline algal Mg/Ca ratios provide a 60 year record of sea surface temperatures and track changes of the Pacific Decadal Oscillation, a pattern of decadal-to-multidecadal ocean-atmosphere climate variability centered over the North Pacific. Algal Ba/Ca ratios (used as indicators of coastal freshwater runoff) are inversely correlated to instrumentally measured Alaska Coastal Current salinity and record the period of freshening from 2001 to 2006. Similar multiyear freshening events are not evident in the earlier portion of the 60 year Ba/Ca record. This suggests that the 21st century freshening of the Alaska Coastal Current is a unique feature related to increasing glacial melt and precipitation on mainland Alaska.

Ground truthing the Cd/Ca-carbon isotope relationship in foraminifera of the Greenland-Iceland-Norwegian Seas

In order to examine whether the paleoceanographic nutrient proxies, d13C and cadmium/calcium in foraminiferal calcite, are well coupled to nutrients in the region of North Atlantic Deep Water formation, we present da ta from two transects of the Greenland-Iceland-Norwegian Seas. Along Transect A (74.3°N, 18.3°E to 75.0°N, 12.5°W, 15 stations), we measured phosphate and Cd concentrations of modern surface sea water. Along Transect B (64.5°N, 0.7°W to 70.4°N, 18.2°W, 14 stations) we measured Cd/Ca ratios and d13C of the planktonic foraminifera Neogloboquadrina pachyderma sinistral in core top sediments. Our results indicate that Cd and phosphate both vary with surface water mass and are well correlated along Transect A. Our planktonic foraminiferal d13C data indicate similar nutrient variation with water mass along Transect B. Our Cd/Ca data hint at the same type of nutrient variability, but interpretations are hampered by low values close to the detection limit of this technique and therefore relatively large error bars. We also measured Cd and phosphate concentrations in water depth profiles at three sites along Transect A and the d13C of the benthic foraminifera Cibicidoides wuellerstorfi along Transect B. Modern sea water depth profiles along Transect A have nutrient depletions at the surface and then constant values at depths greater than 100 meters. The d13C of planktonic and benthic foraminifera from Transect B plotted versus depth also reflect surface nutrient depletion and deep nutrient enrichment as seen at Transect A, with a small difference between intermediate and deep waters. Overall we see no evidence for decoupling of Cd/Ca ratio and d13C in foraminiferal calcite from water column nutrient concentrations along these transects in a region of North Atlantic Deep Water formation.

Mg/Ca and stable oxygen measurement of the past 27 Ma of ODP Hole 120-747A

We explore the applicability of paired Mg/Ca and 18O/16O measurements on benthic foraminifera from Southern Ocean site 747 to paleoceanographic reconstructions on pre-Pleistocene timescales. We focus on the late Oligocene through Pleistocene (27-0 Ma) history of paleotemperatures and the evolution of the d18O values of seawater (d18Osw) at a temporal resolution of ~100-200 kyr. Absolute paleotemperature estimates depend on assumptions of how Mg/Ca ratios of seawater have changed over the past 27 Myr, but relative changes that occur on geologically brief timescales are robust. Results indicate that at the Oligocene to Miocene boundary (23.8 Ma), temperatures lag the increase in global ice-volume deduced from benthic foraminiferal d18O values, but the smaller-scale Miocene glaciations are accompanied by ocean cooling of -1°C. During the mid-Miocene phase of Antarctic ice sheet growth (~15-13 Ma), water temperatures cool by ~3°C. Unlike the benthic foraminiferal d18O values, which remain relatively constant thereafter, temperatures vary (by 3°C) and reach maxima at ~12 and ~8.5 Ma. The onset of significant Northern Hemisphere glaciation during the late Pliocene is synchronous with an ~4°C cooling at site 747. A comparison of our d18Osw curve to the Haq et al. (1987, doi:10.1126/science.235.4793.1156 ) sea level curve yields excellent agreement between sequence boundaries and times of increasing seawater 18O/16O ratios. At ~12-11 Ma in particular, when benthic foraminiferal d18O values do not support a further increase in ice volume, the d18Osw curve comes to a maximum that corresponds to a major mid-Miocene sea level regression. The agreement between the character of our Mg/Ca-based d18Osw curve and sequence stratigraphy demonstrates that benthic foramaniferal Mg/Ca ratios can be used to trace the d18Osw on pre-Pleistocene timescales despite a number of uncertainties related to poorly constrained temperature calibrations and paleoseawater Mg/Ca ratios. The Mg/Ca record also highlights that deep ocean temperatures can vary independently and unexpectedly from ice volume changes, which can lead to misinterpretations of the d18O record.

Mg/Ca and stable isotope record of benthic foraminifera of the Paleocene-Eocene Thermal Maximum

A rapid increase in greenhouse gas levels is thought to have fueled global warming at the Paleocene-Eocene Thermal Maximum (PETM). Foraminiferal magnesium/calcium ratios indicate that bottom waters warmed by 4° to 5°C, similar to tropical and subtropical surface ocean waters, implying no amplification of warming in high-latitude regions of deep-water formation under ice-free conditions. Intermediate waters warmed before the carbon isotope excursion, in association with downwelling in the North Pacific and reduced Southern Ocean convection, supporting changing circulation as the trigger for methane hydrate release. A switch to deep convection in the North Pacific at the PETM onset could have amplified and sustained warming.

Geochemistry of oceanic crust of the North Atlantic

87Sr/a6Sr ratios, Sr, K, Rb and Cs contents and the petrology of basalts and secondary phases recovered from deep basement drilling at DSDP Sites 332B, 417A, 417D and 418A show that the oceanic crust alters in four distinct stages characterized by formation of palagonite, smectite and calcite (Stages I, II and III, respectively). Stage IV represents the final compaction of the crust, including a dehydration of the crust without major chemical changes. Isotopic age determinations by Hart and Staudigel (1978, doi:10.1029/GL005i012p01009) and Richardson et al. (doi:10.1029/JB085iB12p07195), show that, at least for Atlantic-type crustal regimes, Stage I and II last for a maximum of 3 m.y., and Stage III lasts beyond Stage I and II, but is probably completed in significantly less than 10 m.y. Stage IV is long-lived and may still be active at 100 m.y. Stages I and II, the phase of halmyrolysis, include geochemically significant interactions between seawater and basalt for the upper 500 m of layer II and involve volumes of seawater containing a large basaltic component. Stage III solutions show evidence of less seawater-basalt interaction, at least to depths of 500 m; calcites deposited from these solutions have Sr isotopic ratios close to seawater values; but also have very low Sr/Ca ratios indicating a large basalt Ca component in the solutions. Smectite formation is the result of the interaction of seawater and basalt. The initial 87Sr/a6Sr ratios of smectites represent the Sr isotopic composition of the solution when the smectite is being formed. Thereafter, alkalies may be continuously added to interlayer positions in the smectite in order of decreasing hydration energy (Cs is more enriched than Rb, Rb more than K). The later-formed carbonates have very low alkali concentrations, and 87Sr/86Sr ratios identical to contemporaneous seawater. Therefore, since the alkali concentrations in a whole rock sample are affected by different alteration processes, the alkali concentrations alone are not reliable indicators of the degree of alteration.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Radiocarbon dataing, stable oxygen isotopes, and Mg/Ca ratios in surface sediment samples of the tropical eastern Indian Ocean

Shell chemistry of planktic foraminifera and the alkenone unsaturation index in 69 surface sediment samples in the tropical eastern Indian Ocean off West and South Indonesia were studied. Results were compared to modern hydrographic data in order to assess how modern environmental conditions are preserved in sedimentary record, and to determine the best possible proxies to reconstruct seasonality, thermal gradient and upper water column characteristics in this part of the world ocean. Our results imply that alkenone-derived temperatures record annual mean temperatures in the study area. However, this finding might be an artifact due to the temperature limitation of this proxy above 28°C. Combined study of shell stable oxygen isotope and Mg/Ca ratio of planktic foraminifera suggests that Globigerinoides ruber sensu stricto (s.s.), G. ruber sensu lato (s.l.), and G. sacculifer calcify within the mixed-layer between 20 m and 50 m, whereas Globigerina bulloides records mixed-layer conditions at ~50 m depth during boreal summer. Mean calcifications of Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, and Globorotalia tumida occur at the top of the thermocline during boreal summer, at ~75 m, 75-100 m, and 100 m, respectively. Shell Mg/Ca ratios of all species show a significant correlation with temperature at their apparent calcification depths and validate the application of previously published temperature calibrations, except for G. tumida that requires a regional Mg/Ca-temperature calibration (Mg/Ca = 0.41 exp (0.068*T)). We show that the difference in Mg/Ca-temperatures of the mixed-layer species and the thermocline species, particularly between G. ruber s.s. (or s.l.) and P. obliquiloculata, can be applied to track changes in the upper water column stratification. Our results provide critical tools for reconstructing past changes in the hydrography of the study area and their relation to monsoon, El Niño-Southern Oscillation, and the Indian Ocean Dipole Mode.