(Table 1) Planktonic foraminifera counts and stable oxygen isotope ratios of Pacific Ocean surface sediments

Core-top samples from the eastern tropical Pacific (10°N to 20°S) were used to test whether the ratio between Globorotalia menardii cultrata and Neogloboquadrina dutertrei abundance (Rc/d) and the oxygen isotope composition (?18O) of planktonic foraminifera can be used as proxies for the latitudinal position of the Equatorial Front. Specifically, this study compares the ?18O values of eight species of planktonic foraminifera (Globigerinoides ruber sensu stricto (ss) and sensu lato (sl), Globigerinoides sacculifer, Globigerinoides triloba, Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, Globorotalia menardii menardii, Globorotalia menardii cultrata and Globorotalia tumida) with the seasonal hydrography of the region, and evaluates the application of each species or combination of species for paleoceanographic reconstructions. The results are consistent with sea surface temperature and water column stratification patterns. We found that in samples north of 1°N, the Rc/d values tend to be higher and d18O values of G. ruber, G. sacculifer, G. triloba, P. obliquiloculata, N. dutertrei, and G. menardii cultrata tend to be lower than those from samples located south of 1°N. We suggest that the combined use of Rc/d and the d18O difference between G. ruber and G. tumida or between P. obliquiloculata and G. tumida are the most suitable tools for reconstructing changes in the latitudinal position of the Equatorial Front and changes in the thermal stratification of the upper water column in the eastern tropical Pacific.

Radiocarbon ages and pollen record of a sediment core from Lake Lyadhej-To

An 1180-cm long core recovered from Lake Lyadhej-To (68°15'N, 65°45'E, 150 m a.s.l.) at the NW rim of the Polar Urals Mountains reflects the Holocene environmental history from ca. 11,000 cal. yr BP. Pollen assemblages from the diamicton (ca. 11,000-10,700 cal. yr BP) are dominated by Pre-Quaternary spores and redeposited Pinaceae pollen, pointing to a high terrestrial input. Turbid and nutrient-poor conditions existed in the lake ca. 10,700-10,550 cal. yr BP. The chironomid-inferred reconstructions suggest that mean July temperature increased rapidly from 10.0 to 11.8 °C during this period. Sparse, treeless vegetation dominated on the disturbed and denuded soils in the catchment area. A distinct dominance of planktonic diatoms ca. 10,500-8800 cal. yr BP points to the lowest lake-ice coverage, the longest growing season and the highest bioproductivity during the lake history. Birch forest with some shrub alder grew around the lake reflecting the warmest climate conditions during the Holocene. Mean July temperature was likely 11-13 °C and annual precipitation-400-500 mm. The period ca. 8800-5500 cal. yr BP is characterized by a gradual deterioration of environmental conditions in the lake and lake catchment. The pollen- and chironomid-inferred temperatures reflect a warm period (ca. 6500-6000 cal. BP) with a mean July temperature at least 1-2 °C higher than today. Birch forests disappeared from the lake vicinity after 6000 cal. yr BP. The vegetation in the Lyadhej-To region became similar to the modern one. Shrub (Betula nana, Salix) and herb tundra have dominated the lake catchment since ca. 5500 cal. yr BP. All proxies suggest rather harsh environmental conditions. Diatom assemblages reflect relatively short growing seasons and a longer persistence of lake-ice ca. 5500-2500 cal. yr BP. Pollen-based climate reconstructions suggest significant cooling between ca. 5500 and 3500 cal. yr BP with a mean July temperature 8-10 °C and annual precipitation-300-400 mm. The bioproductivity in the lake remained low after 2500 cal. yr BP, but biogeochemical proxies reflect a higher terrestrial influx. Changes in the diatom content may indicate warmer water temperatures and a reduced ice cover on the lake. However, chironomid-based reconstructions reflect a period with minimal temperatures during the lake history.

Determinants of internal and external R&D offshoring: Evidence from Spanish firms

This paper analyzes the determinants of R&D offshoring of Spanish firms using information from the Panel of Technological Innovation. We find that being an exporter, international technological cooperation, continuous R&D engagement, applying for patents, being a for-eign subsidiary, and firm size are factors that positively affect the decision to offshore R&D. In addition, we find that a lack of financing is an obstacle relatively more important for inde-pendent firms than for firms that belong to business groups. For these latter, we also obtain that the factors that influence the decision to offshore R&D differ depending on whether the firm purchases the R&D services within the group or through the market: a higher degree of importance assigned to internal sources of information for innovation as compared to mar-ket sources increases (decreases) the probability of R&D offshoring only through the group (market).

An investigation by AFM and TEM of the mechanism of anodic formation of nanoporosity in n-InP in KOH

The early stages of nanoporous layer formation, under anodic conditions in the absence of light, were investigated for n-type InP with a carrier concentration of ∼3× 1018 cm-3 in 5 mol dm-3 KOH and a mechanism for the process is proposed. At potentials less than ∼0.35 V, spectroscopic ellipsometry and transmission electron microscopy (TEM) showed a thin oxide film on the surface. Atomic force microscopy (AFM) of electrode surfaces showed no pitting below ∼0.35 V but clearly showed etch pit formation in the range 0.4-0.53 V. The density of surface pits increased with time in both linear potential sweep and constant potential reaching a constant value at a time corresponding approximately to the current peak in linear sweep voltammograms and current-time curves at constant potential. TEM clearly showed individual nanoporous domains separated from the surface by a dense ∼40 nm InP layer. It is concluded that each domain develops as a result of directionally preferential pore propagation from an individual surface pit which forms a channel through this near-surface layer. As they grow larger, domains meet, and the merging of multiple domains eventually leads to a continuous nanoporous sub-surface region.

Anodic formation and characterization of nanoporous InP in aqueous KOH electrolytes

The anodic behavior of highly doped (> 1018 cm-3) n-InP in aqueous KOH was investigated. Electrodes anodized in the absence of light in 2- 5 mol dm-3 KOH at a constant potential of 0.5- 0.75 V (SCE), or subjected to linear potential sweeps to potentials in this range, were shown to exhibit the formation of a nanoporous subsurface region. Both linear sweep voltammograms and current-time curves at constant potential showed a characteristic anodic peak, corresponding to formation of the nanoporous region. No porous region was formed during anodization in 1 mol dm-3 KOH. The nanoporous region was examined using transmission electron microscopy and found to have a thickness of some 1- 3 μm depending on the anodization conditions and to be located beneath a thin (typically ∼40 nm), dense, near-surface layer. The pores varied in width from 25 to 75 nm and both the pore width and porous region thickness were found to decrease with increasing KOH concentration. The porosity was approximately 35%. The porous layer structure is shown to form by the localized penetration of surface pits into the InP, and the dense, near-surface layer is consistent with the effect of electron depletion at the surface of the semiconductor.

Anodic behavior of InP: film growth, porous structures and current oscillations.

We review our recent work on the anodization of InP in KOH electrolytes. The anodic oxidation processes are shown to be remarkably different in different concentrations of KOH. Anodization in 2 - 5 mol dm-3 KOH electrolytes results in the formation of porous InP layers but, under similar conditions in a 1 mol dm-3 KOH, no porous structure is evident. Rather, the InP electrode is covered with a thin, compact surface film at lower potentials and, at higher potentials, a highly porous surface film is formed which cracks on drying. Anodization of electrodes in 2 - 5 mol dm-3 KOH results in the formation of porous InP under both potential sweep and constant potential conditions. The porosity is estimated at ~65%. A thin layer (~ 30 nm) close to the surface appears to be unmodified. It is observed that this dense, near-surface layer is penetrated by a low density of pores which appear to connected it to the electrolyte. Well-defined oscillations are observed when InP is anodized in both the KOH and (NH4)2S. The charge per cycle remains constant at 0.32 C cm-2 in (NH4)2S but increases linearly with potential in KOH. Although the characteristics of the oscillations in the two systems differ, both show reproducible and well-behaved values of charge per cycle.

Formation and characterization of porous InP layers in KOH Solutions

Porous InP layers were formed electrochemically on (100) oriented n-InP substrates in various concentrations of aqueous KOH under dark conditions. In KOH concentrations from 2 mol dm-3 to 5 mol dm-3, a porous layer is obtained underneath a dense near-surface layer. The pores within the porous layer appear to propagate from holes through the near-surface layer. Transmission electron microscopy studies of the porous layers formed under both potentiodynamic and potentiostatic conditions show that both the thickness of the porous layer and the mean pore diameter decrease with increasing KOH concentration. The degree of porosity, estimated to be 65%, was found to remain relatively constant for all the porous layers studied.

Comparison of oscillatory behavior on InP electrodes in KOH solutions

The observation of current oscillations under potential sweep conditions when an n-InP electrode is anodized in a KOH electrolyte is reported and compared to the oscillatory behavior noted during anodization in an (NH4)2S electrolyte. In both cases oscillations are observed above 1.7 V (SCE). The charge per cycle was found to increase linearly with potential for the InP/KOH system but was observed to be independent of potential for the InP/(NH4)2S system. The period of the oscillations in the InP/KOH was found to increase with applied potential. In this case the oscillations are asymmetrical and the rising and falling segments have a different dependence on potential. Although the exact mechanism is not yet know for either system, transmission electron microscopy studies show that in both cases, the electrode is covered by a thick porous film in the oscillatory region.

Anodic oxidation of InP in KOH electrolytes

The anodic behavior of InP in 1 mol dm-3 KOH was investigated and compared with its behavior at higher concentrations of KOH. At concentrations of 2 mol dm-3 KOH or greater, selective etching of InP occurs leading to thick porous InP layers near the surface of the sustrate. In contrast, in 1 mol dm-3 KOH, no such porous layers are formed but a thin surface film is formed at potentials in the range 0.6 V to 1.3 V. The thickness of this film was determined by spectroscopic ellipsometry as a function of the upper potential and the measured film thickness corresponds to the charge passed up to a potential of 1.0 V. Anodization to potentials above 1.5 V in 1 mol dm- 3 KOH results in the growth of thick, porous oxide films (~ 1.2 µm). These films are observed to crack, ex-situ, due to shrinkage after drying in ambient air. Comparisons between the charge density and film thickness measurements indicate a porosity of approximately 77% for such films.

Growth and characterization of anodic Films on InP in KOH and (NH4)2S

The current-voltage characteristics of InP were investigated in (NH4)2S and KOH electrolytes. In both solutions, the observation of current peaks in the cyclic voltammetric curves was attributed to the growth of passivating films. The relationship between the peak currents and the scan rates suggests that the film formation process is diffusion controlled in both cases. The film thickness required to inhibit current flow was found to be much lower on samples anodized in the sulphide solution. Focused ion beam (FIB) secondary electron images of the surface films show that film cracking of the type reported previously for films grown in (NH4)2S is also observed for films grown in KOH. X-ray and electron diffraction measurements indicate the presence of In2O3 and InPO4 in films grown in KOH and In2S3 in films grown in (NH4)2S.

Alkenone unsaturation index and alkenones in ODP Hole 161-977A

A number of essential elements closely related to each other are involved in the Earth's climatic system. The temporal and spatial distribution of insolation determines wind patterns and the ocean's thermohaline pump. In turn, these last two are directly linked to the extension and retreat of marine and continental ice and to the chemistry of the atmosphere and the ocean. The variability of these elements may trigger, amplify, sustain or globalize rapid climatic changes. Paleoclimatic oscillations have been identified in this thesis by using fossil organic compounds synthesized by marine and terrestrial flora. High sedimentation rate deposits at the Barents and the Iberian peninsula continental margins were chosen in order to estimate the climatic changes on centennial time resolution. At the Barents margin, the sediment recovered was up to 15,000 years old (unit ''a'', from latin ''annos'') (M23258; west of the Bjørnøya island). At the Iberian margin, the sediment cores studied covered a wide range of time spans: up to 115,000 a (MD99-2343; north of the Minorca island), up to 250,000 a (ODP-977A; Alboran basin) and up to 420,000 a (MD01-2442, MD01-2443, MD01-2444, MD01-2445; close to the Tagus abyssal plain). At the northern site, inputs containing marine, continental and ancient reworked organic matter provided a detailed reconstruction of climate history at the time of the final retreat of the Barents ice sheet. At the western Barents continental slope, warm climatic conditions were observed during the early Holocene (~from 8,650 a to 5,240 a ago); in contrast, an apparent long-term cooling trend occurred in the late Holocene (~from 5,240 a to 760 a ago), in consistence with other paleoarchives from northern and southern European latitudes. The Iberian margin sites, which were never covered with large ice sheets, preserved exceptionally complete sequences of rapid events during ice ages hitherto not studied in such great detail: during the last glacial (~from 70,900 a to 11,800 a ago), the second glacial (~from 189,300 a to 127,500 a ago), the third ice age (~from 278,600 a to 244,800 a ago) and the fourth (~from 376,300 a to 337,500 a ago). In this thesis, crucial research questions were brought up concerning the severity of different glacial periods, the intensity and rates of the recorded oscillations and the long distance connections related to rapid climate change. The data obtained provide a sound basis to further research on the mechanisms involved in this rapid climate variability. An essential point of the research was the evidence that, over the past 420,000 a, at the whole Iberian margin, warm and stable long periods similar to the Holocene always ended abruptly in few centuries after a gradual deterioration of climate conditions. The detailed estimate of past climate variability provides clues to the natural end of the present warm period. Returning to an ice age in European lands would be exacerbated by a number of factors: a lack of differential solar heating between northern and southern north Atlantic latitudes, enhanced evaporation at low latitudes, and an increase in snowfall or iceberg discharges at northern regions. It must be emphasized that all climatic oscillations observed in this thesis were caused by forces of nature, i.e. the last two centuries were not taken into consideration.

Mg/Ca and stable oxygen isotope ratios of Uvigerina spp. from the Southern Ocean

The sensitivity to temperature of Mg/Ca ratios in the shallow-infaunal benthic foraminifera Uvigerina spp. has been assessed. Core-top calibrations over ~1-20 °C show a range in sensitivity of 0.065-0.084 mmol/mol/°C but few data are available spanning the temperature range anticipated in deep-sea records over glacial-interglacial cycles. In contrast to epibenthic foraminiferal species, carbonate ion saturation appears not to affect Mg/Ca significantly. A method based on estimating the ratio of the temperature sensitivity of foraminiferal Mg/Ca to that of d18Ocalcite shows that sensitivity for Mg/Ca at the high end of the observed core-top range (~0.1 mmol/mol/°C) is required for consistency with LGM-Holocene differences in each property as constrained by independent proxy data. This is supported by a Mg/Ca record for Uvigerina spp. generated for the Southern Ocean over the past 440,000 years from Ocean Drilling Program Site 1123 (Chatham Rise, New Zealand). The record shows variability that correlates with climate oscillations. The LGM deep ocean temperature derived from the Mg/Ca record is -1.1 ± 0.3 °C. Transformation to temperature allows estimates to be made of changes in bottom water temperature and seawater d18O and comparison made with literature records. Analysis reveals a ~2.5-kyr lead in the record of temperature over calcite d18O and a longer lead over seawater d18O. This is a reflection of larger phase offsets at eccentricity periods; phase offsets at tilt and precession are within error zero.

Enigmas monetarios en el derecho local. Los mencales y maravedís en los fueros castellanos

La historia de la moneda en la Castilla medieval ha estado siempre mediatizada por la convivencia no siempre armónica entre dos sistemas monetarios muy diferentes. Uno basado en la plata, de origen europeo, otro centrado en el oro, de raíces árabes. La necesidad de conectar y de establecer unas equivalencias entre ellos se convirtió pronto en una necesidad, máxime cuando las monedas de oro incrementaron sus variantes. En esta compleja situación aparecen mencales y maravedís citados conjuntamente en muchos fueros: Zorita, Uclés, Cuenca,... sin que su naturaleza quede del todo clara. Este artículo compara estas referencias y analiza las equivalencias que los unen. Como colofón al trabajo podemos afirmar que los maravedís citados en cada texto corresponden a monedas áureas de distinto peso y valor mientras el mencal es identificado con un ponderal de oro que los relaciona.

Molecular mechanism of activation-triggered subunit exchange in Ca(2+)/calmodulin-dependent protein kinase II.

Activation triggers the exchange of subunits in Ca(2+)/calmodulin-dependent protein kinase II (CaMKII), an oligomeric enzyme that is critical for learning, memory, and cardiac function. The mechanism by which subunit exchange occurs remains elusive. We show that the human CaMKII holoenzyme exists in dodecameric and tetradecameric forms, and that the calmodulin (CaM)-binding element of CaMKII can bind to the hub of the holoenzyme and destabilize it to release dimers. The structures of CaMKII from two distantly diverged organisms suggest that the CaM-binding element of activated CaMKII acts as a wedge by docking at intersubunit interfaces in the hub. This converts the hub into a spiral form that can release or gain CaMKII dimers. Our data reveal a three-way competition for the CaM-binding element, whereby phosphorylation biases it towards the hub interface, away from the kinase domain and calmodulin, thus unlocking the ability of activated CaMKII holoenzymes to exchange dimers with unactivated ones.

Molecular mechanism of activation-triggered subunit exchange in Ca(2+)/calmodulin-dependent protein kinase II.

Activation triggers the exchange of subunits in Ca(2+)/calmodulin-dependent protein kinase II (CaMKII), an oligomeric enzyme that is critical for learning, memory, and cardiac function. The mechanism by which subunit exchange occurs remains elusive. We show that the human CaMKII holoenzyme exists in dodecameric and tetradecameric forms, and that the calmodulin (CaM)-binding element of CaMKII can bind to the hub of the holoenzyme and destabilize it to release dimers. The structures of CaMKII from two distantly diverged organisms suggest that the CaM-binding element of activated CaMKII acts as a wedge by docking at intersubunit interfaces in the hub. This converts the hub into a spiral form that can release or gain CaMKII dimers. Our data reveal a three-way competition for the CaM-binding element, whereby phosphorylation biases it towards the hub interface, away from the kinase domain and calmodulin, thus unlocking the ability of activated CaMKII holoenzymes to exchange dimers with unactivated ones.