Eclogitic diamonds from variable crustal protoliths in the northeastern Siberian craton: trace elements and coupled δ13C – δ18O signatures in diamonds and garnet inclusions

Diamonds of eclogitic assemblages are dominant in the placer diamond deposits of the northeastern Siberian platform. In this study we present new trace elements and stable isotopes (δ13C and δ18O) data for alluvial diamonds and their garnet inclusions from this locality. Cr-rich garnets of peridotitic affinity in the studied diamonds have a narrow range of δ18O values from 5.7‰ to 6.2‰, which is largely overlapping with the accepted mantle range. This narrow range suggests that the garnet inclusions showing different REE patterns and little variations in oxygen isotopes may have formed by different processes involving fluid/melts that, however, were in oxygen isotopic equilibrium with the mantle. The trace element composition of the eclogitic garnet inclusions supports a crustal origin for at least the high-Ca garnets, which show flat HREE patterns and in some cases a positive Eu-anomaly. High-Ca eclogitic garnets generally show heavier oxygen isotope compositions (δ18O 6.5–9.6‰) than what is observed in low-Ca garnets (δ18O 5.7–7.4‰). The variability in oxygen isotopes and trace elements is suggested to be inherited from contrasting crustal protoliths. The relationship between the high δ18O values of inclusions and the low δ13C values of the host diamonds implies that the high-Ca garnet inclusions were derived from intensely hydrated (e.g., δ18O > 7‰) and typically oxidised basaltic rock close to the seawater interface, and that the carbon for diamonds was closely associated with this protolith.

Heavy mineral content of ODP Leg 107 holes

Analyses of rock clasts and of heavy minerals in upper Miocene coarse detrital units drilled along the East Sardinia passive-type continental margin (Sites 654, 653, 652, and 656) reveal that the stretched basement contains quite complex rock suites. Taking also into account previous sampling data, in moving from west to east across the margin, the nature of the basement changes drastically. To the west there are mostly Hercynian basement rocks with their cover, referable to the alpine foreland of the Corsica-Sardinia block. To the east, along the lower margin, where crustal thinning is quite severe, the basement contains rock suites referable to a pre-upper Tortonian orogenized zone with units constituting parts of the Alpine and Apenninic chains (presumably with thickened continental crust prior to stretching). Largest thinning and ocean forming occurred then, in a rather short time, mostly at the expense of unstable crust just thickened by orogenetic/tectogenetic processes.

Strike-slip faults mediate the rise of crustal-derived fluids and mud volcanism in the deep sea

We report on newly discovered mud volcanoes located at about 4500 m water depth 90 km west of the deformation front of the accretionary wedge of the Gulf of Cadiz, and thus outside of their typical geotectonic environment. Seismic data suggest that fluid flow is mediated by a >400-km-long strike-slip fault marking the transcurrent plate boundary between Africa and Eurasia. Geochemical data (Cl, B, Sr, 87Sr/86Sr, Delta18O, DeltaD) reveal that fluids originate in oceanic crust older than 140 Ma. On their rise to the surface, these fluids receive strong geochemical signals from recrystallization of Upper Jurassic carbonates and clay-mineral dehydration in younger terrigeneous units. At present, reports of mud volcanoes in similar deep-sea settings are rare, but given that the large area of transform-type plate boundaries has been barely investigated, such pathways of fluid discharge may provide an important, yet unappreciated link between the deeply buried oceanic crust and the deep ocean.

Crustal uplift rates of 4 GPS stations near Jakobshavn Isbrae (2006-2009)

We analyze 2006-2009 data from four continuous Global Positioning System (GPS) receivers located between 5 and 150 km from the glacier Jakobshavn Isbrae, West Greenland. The GPS stations were established on bedrock to determine the vertical crustal motion due to the unloading of ice from Jakobshavn Isbrae. All stations experienced uplift, but the uplift rate at Kangia North, only 5 km from the glacier front, was about 10 mm/yr larger than the rate at Ilulissat, located only ~45 km further away. This suggests that most of the uplift is due to the unloading of the Earth's surface as Jakobshavn thins and loses mass. Our estimate of Jakobshavn's contribution to uplift rates at Kangia North and Ilulissat are 14.6 ± 1.7 mm/yr and 4.9 ± 1.1 mm/yr, respectively. The observed rates are consistent with a glacier thinning model based on repeat altimeter surveys from NASA's Airborne Topographic Mapper (ATM), which shows that Jakobshavn lost mass at an average rate of 22 ± 2 km**3/yr between 2006 and 2009. At Kangia North and Ilulissat, the predicted uplift rates computed using thinning estimates from the ATM laser altimetry are 12.1 ± 0.9 mm/yr and 3.2 ± 0.3 mm/yr, respectively. The observed rates are slightly larger than the predicted rates. The fact that the GPS uplift rates are much larger closer to Jakobshavn than further away, and are consistent with rates inferred using the ATM-based glacier thinning model, shows that GPS measurements of crustal motion are a potentially useful method for assessing ice-mass change models.

Physical properties and elastic constants of ODP Holes 137-504B and 140-504B upper crustal rocks

Seismic velocities have been measured at confining pressures of 100 MPa and 600 MPa for sheeted dike samples recovered during Ocean Drilling Program Legs 137 and 140. The compressional- and shear-wave velocities show an increase with depth at Hole 504B, which is in sharp contrast to the atmospheric pressure velocity measurements performed as part of the shipboard analyses. Rocks exposed to different types of alteration and fracture patterns show distinct changes in their physical properties. The seismic reflectors observed on the vertical seismic profile (VSP) experiment performed during Leg 111 may have been caused by low velocity zones resulting from alteration. The amount of fracturing and hydrothermal alteration in several zones also may have contributed to the acoustic impedance contrast necessary to produce the E5 reflector. Poisson's ratios calculated from laboratory velocity measurements show several low values at depths ranging from 1600 mbsf to 2000 mbsf, which tends to follow similar trends obtained from previous oceanic refraction experiments. A comparison of physical properties between samples recovered from Hole 504B and ophiolite studies in the Bay of Islands and Oman shows a good correlation with the Bay of Islands but significant differences from the measurements performed in the Oman complex.

Lead, sulphate, and aluminium concentrations and lead crustal enrichment factors in Mt. Logan ice core during pre-anthropogenic to modern periods

A high-resolution, 8000 year-long ice core record from the Mt. Logan summit plateau (5300 m asl) reveals the initiation of trans-Pacific lead (Pb) pollution by ca. 1730, and a >10-fold increase in Pb concentration (1981-1998 mean = 68.9 ng/l) above natural background (5.6 ng/l) attributed to rising anthropogenic Pb emissions from Asia. The largest rise in North Pacific Pb pollution from 1970-1998 (end of record) is contemporaneous with a decrease in Eurasian and North American Pb pollution as documented in ice core records from Greenland, Devon Island, and the European Alps. The distinct Pb pollution history in the North Pacific is interpreted to result from the later industrialization and less stringent abatement measures in Asia compared to North America and Eurasia. The Mt. Logan record shows evidence for both a rising Pb emissions signal from Asia and a trans-Pacific transport efficiency signal related to the strength of the Aleutian Low.

Gravity mapping in the southern Weddell Sea region, Antarctica (Scale 1:2 000 000)

New maps of free-air and the Bouguer gravity anomalies on the Weddell Sea sector (70-81° S, 6-75° W) of Antarctica are presented. These maps are based on the first computer compilation of available gravity data collected by ''Sevmorgeologia'' in 1976-89 in the southern Weddell Sea and adjacent coasts of western Dronning Maud Land (WDML) and Coats Land. The accomplished gravity studies comprise airborne observations with a line spacing of about 20 km and conventional measurements at over-the-ice points, which were spaced at 10-30 km and supplemented by seismic soundings. Hence, anomalies on the maps represent mainly large-scale and deep crustal features. The dominant feature in free-air gravity map is a large dipolar gravity anomaly stretching along the continental margin. Following the major grain of seabed morphology this shelf-edge/slope anomaly (SESA) is clearly divided into three segments characterized by diverse anomaly amplitudes, wavelengths and trends. They are associated with continental margins of different geotectonic provinces of Antarctica surrounding the Weddell Sea. Apparent distinctions in the SESA signatures are interpreted as the gravity expression of tectonic, deep crustal structure segmentation of the continental margin. The prominent gravity highs (100-140 mGal) of the shelf edge anomaly mapped along WDML are assumed to represent high-density mantle injections intruded into the middle/lower crust during initial rifting of continental breakup. Enlarged wavelengths and diminished amplitudes of the gravity anomaly westwards, along the Weddell Sea embayment (WSE) margin, reflect a widening of the continental slope and a significant increase in thickness of underlying sediment strata. Low amplitude, negative free-air anomalies in the Filchner-Ronne Ice Shelves (FRIS) contrast sharply with the dominating positive anomalies offshore. This indicates a greater sedimentary thickness of the basin in this area. Crustal response to the enlarged sediment load is impressed in mostly positive features of the Bouguer gravity field observed here. Two pronounced positive Bouguer anomalies of 50-70 mGal and an average widths of 200 km dominate the Weddell Sea embayment margins towards the Antarctic Peninsula and the East Antarctic craton. They correlate well with very deep seabed troughs (> 1000 m below sea level). The gravity highs are most likely caused by a shallow upper mantle underneath graben-rift structures evolved at the margins of the WSE basin. A regional zone (> 100 km in width) of the prominent Bouguer and free-air negative anomalies (-40 to -60 mGal) adjacent Coats Land to the north of the ice shelf edge may indicate the presence of the thick old cratonic crust far offshore beneath the Weddell Sea Embayment.

(Appendix 1) Crustal helium-4 abundance and flux data for ODP Hole 130-806B

The mass accumulation rates (MARs) of aeolian dust in the ocean basins provide an important record of climate in the continental source regions of atmospheric dust and of the prevailing wind patterns responsible for dust transport in the geologic past. The incorporation of other terrigenous components such as volcanic ashes in seafloor sediments, however, often obscures the aeolian dust record. We describe a new approach which uses the delivery rate of crustal 4He to seafloor sediments as a proxy for the mass accumulation rate of old continental dust which is unaffected by the addition of other terrigenous components. We have determined the flux of crustal 4He delivered to the seafloor of the Ontong Java Plateau (OJP) in the western equatorial Pacific over the last 1.9 Myrs. Crustal 4He fluxes vary between 7.7 and 30 ncc/cm**2/kyr and show excellent correlation with global climate as recorded by oxygen isotopes, with high crustal 4He fluxes associated with glacial periods over the entire interval studied. Furthermore, the onset of strong 100 kyr glacial-interglacial climate cycling is clearly seen in the 4He flux record about 700 kyrs ago. These data record variations in the supply of Asian dust in response to climate driven changes in the aridity of the Asian dust sources, consistent with earlier work on Asian dust flux to the northern Pacific Ocean. However, in contrast to previous studies of sites in the central and eastern equatorial Pacific Ocean, there is no evidence that the Inter Tropical Convergence Zone (an effective rainfall barrier to the southward transport of northern hemisphere dust across the equator in the central and eastern Pacific) has influenced the delivery of Asian dust to the OJP. The most likely carrier phase for crustal helium in these sediments is zircon, which can reasonably account for all the 4He observed in the samples. As a first order estimate, these results suggest that the mass accumulation rate of Asian dust on the OJP over the last 1.9 Myrs varied from about 4 to 15 mg/ cm**2/kyr. In contrast, previous studies show that over the same interval the total MAR of terrigenous dust (i.e. Asian dust plus local volcanics) on OJP varied between about 34 and 90 mg/ cm**2/kyr.

Métodos diferenciales e interferométricos para la evaluación de deformaciones de la corteza terrestre mediante técnicas GNSS e InSAR = Differential and interferometric methods for evaluation of crustal deformation using GNSS and InSAR techniques

La actividad volcánica interviene en multitud de facetas de la propia actividad humana, no siempre negativas. Sin embargo, son más los motivos de peligrosidad y riesgo que incitan al estudio de la actividad volcánica. Existen razones de seguridad que inciden en el mantenimiento del seguimiento y monitorización de la actividad volcánica para garantizar la vida y la seguridad de los asentamientos antrópicos en las proximidades de los edificios volcánicos. En esta tesis se define e implementa un sistema de monitorización de movimientos de la corteza en las islas de Tenerife y La Palma, donde el impacto social que representa un aumento o variación de la actividad volcánica en las islas es muy severo. Aparte de la alta densidad demográfica del Archipiélago, esta población aumenta significativamente, en diferentes periodos a lo largo del año, debido a la actividad turística que representa la mayor fuente de ingresos de las islas. La población y los centros turísticos se diseminan predominantemente a lo largo de las costas y también a lo largo de los flancos de los edificios volcánicos. Quizá el mantenimiento de estas estructuras sociales y socio-económicas son los motivos más importantes que justifican una monitorización de la actividad volcánica en las Islas Canarias. Recientemente se ha venido trabajando cada vez más en el intento de predecir la actividad volcánica utilizando los nuevos sistemas de monitorización geodésica, puesto que la actividad volcánica se manifiesta anteriormente por deformación de la corteza terrestre y cambios en la fuerza de la gravedad en la zona donde más tarde se registran eventos volcánicos. Los nuevos dispositivos y sensores que se han desarrollado en los últimos años en materias como la geodesia, la observación de la Tierra desde el espacio y el posicionamiento por satélite, han permitido observar y medir tanto la deformación producida en el terreno como los cambios de la fuerza de la gravedad antes, durante y posteriormente a los eventos volcánicos que se producen. Estos nuevos dispositivos y sensores han cambiado las técnicas o metodologías geodésicas que se venían utilizando hasta la aparición de los mismos, renovando métodos clásicos y desarrollando otros nuevos que ya se están afianzando como metodologías probadas y reconocidas para ser usadas en la monitorización volcánica. Desde finales de la década de los noventa del siglo pasado se han venido desarrollando en las Islas Canarias varios proyectos que han tenido como objetivos principales el desarrollo de nuevas técnicas de observación y monitorización por un lado y el diseño de una metodología de monitorización volcánica adecuada, por otro. Se presenta aquí el estudio y desarrollo de técnicas GNSS para la monitorización de deformaciones corticales y su campo de velocidades para las islas de Tenerife y La Palma. En su implementación, se ha tenido en cuenta el uso de la infraestructura geodésica y de monitorización existente en el archipiélago a fin de optimizar costes, además de complementarla con nuevas estaciones para dar una cobertura total a las dos islas. Los resultados obtenidos en los proyectos, que se describen en esta memoria, han dado nuevas perspectivas en la monitorización geodésica de la actividad volcánica y nuevas zonas de interés que anteriormente no se conocían en el entorno de las Islas Canarias. Se ha tenido especial cuidado en el tratamiento y propagación de los errores durante todo el proceso de observación, medida y proceso de los datos registrados, todo ello en aras de cuantificar el grado de fiabilidad de los resultados obtenidos. También en este sentido, los resultados obtenidos han sido verificados con otros procedentes de sistemas de observación radar de satélite, incorporando además a este estudio las implicaciones que el uso conjunto de tecnologías radar y GNSS tendrán en un futuro en la monitorización de deformaciones de la corteza terrestre. ABSTRACT Volcanic activity occurs in many aspects of human activity, and not always in a negative manner. Nonetheless, research into volcanic activity is more likely to be motivated by its danger and risk. There are security reasons that influence the monitoring of volcanic activity in order to guarantee the life and safety of human settlements near volcanic edifices. This thesis defines and implements a monitoring system of movements in the Earth’s crust in the islands of Tenerife and La Palma, where the social impact of an increase (or variation) of volcanic activity is very severe. Aside from the high demographic density of the archipelago, the population increases significantly in different periods throughout the year due to tourism, which represents a major source of revenue for the islands. The population and the tourist centres are mainly spread along the coasts and also along the flanks of the volcanic edifices. Perhaps the preservation of these social and socio-economic structures is the most important reason that justifies monitoring volcanic activity in the Canary Islands. Recently more and more work has been done with the intention of predicting volcanic activity, using new geodesic monitoring systems, since volcanic activity is evident prior to eruption because of a deformation of the Earth’s crust and changes in the force of gravity in the zone where volcanic events will later be recorded. The new devices and sensors that have been developed in recent years in areas such as geodesy, the observation of the Earth from space, and satellite positioning have allowed us to observe and measure the deformation produced in the Earth as well as the changes in the force of gravity before, during, and after the volcanic events occur. The new devices and sensors have changed the geodetic techniques and methodologies that were used previously. The classic methods have been renovated and other newer ones developed that are now vouched for as proven recognised methodologies to be used for volcanic monitoring. Since the end of the 1990s, in the Canary Islands various projects have been developed whose principal aim has been the development of new observation and monitoring techniques on the one hand, and the design of an appropriate volcanic monitoring methodology on the other. The study and development of GNSS techniques for the monitoring of crustal deformations and their velocity field is presented here. To carry out the study, the use of geodetic infrastructure and existing monitoring in the archipelago have been taken into account in order to optimise costs, besides complementing it with new stations for total coverage on both islands. The results obtained in the projects, which are described below, have produced new perspectives in the geodetic monitoring of volcanic activity and new zones of interest which previously were unknown in the environment of the Canary Islands. Special care has been taken with the treatment and propagation of errors during the entire process of observing, measuring, and processing the recorded data. All of this was done in order to quantify the degree of trustworthiness of the results obtained. Also in this sense, the results obtained have been verified with others from satellite radar observation systems, incorporating as well in this study the implications that the joint use of radar technologies and GNSS will have for the future of monitoring deformations in the Earth’s crust.

Stretching lattice models of protein folding

A new class of experiments that probe folding of individual protein domains uses mechanical stretching to cause the transition. We show how stretching forces can be incorporated in lattice models of folding. For fast folding proteins, the analysis suggests a complex relation between the force dependence and the reaction coordinate for folding.

Stretching single-domain proteins: Phase diagram and kinetics of force-induced unfolding

Single-molecule force spectroscopy reveals unfolding of domains in titin on stretching. We provide a theoretical framework for these experiments by computing the phase diagrams for force-induced unfolding of single-domain proteins using lattice models. The results show that two-state folders (at zero force) unravel cooperatively, whereas stretching of non-two-state folders occurs through intermediates. The stretching rates of individual molecules show great variations reflecting the heterogeneity of force-induced unfolding pathways. The approach to the stretched state occurs in a stepwise “quantized” manner. Unfolding dynamics and forces required to stretch proteins depend sensitively on topology. The unfolding rates increase exponentially with force f till an optimum value, which is determined by the barrier to unfolding when f = 0. A mapping of these results to proteins shows qualitative agreement with force-induced unfolding of Ig-like domains in titin. We show that single-molecule force spectroscopy can be used to map the folding free energy landscape of proteins in the absence of denaturants.

Mechanism for nucleic acid chaperone activity of HIV-1 nucleocapsid protein revealed by single molecule stretching

The nucleocapsid protein (NC) of HIV type 1 is a nucleic acid chaperone that facilitates the rearrangement of nucleic acids into conformations containing the maximum number of complementary base pairs. We use an optical tweezers instrument to stretch single DNA molecules from the helix to coil state at room temperature in the presence of NC and a mutant form (SSHS NC) that lacks the two zinc finger structures present in NC. Although both NC and SSHS NC facilitate annealing of complementary strands through electrostatic attraction, only NC destabilizes the helical form of DNA and reduces the cooperativity of the helix-coil transition. In particular, we find that the helix-coil transition free energy at room temperature is significantly reduced in the presence of NC. Thus, upon NC binding, it is likely that thermodynamic fluctuations cause continuous melting and reannealing of base pairs so that DNA strands are able to rapidly sample configurations to find the lowest energy state. The reduced cooperativity allows these fluctuations to occur in the middle of complex double-stranded structures. The reduced stability and cooperativity, coupled with the electrostatic attraction generated by the high charge density of NC, is responsible for the nucleic acid chaperone activity of this protein.

Identification of the overtone of the Fe-CO stretching mode in heme proteins: a probe of the heme active site.

Two CO-isotope sensitive lines have been detected in the overtone region of the resonance Raman spectra of CO-bound hemeproteins. One line is assigned as the overtone of the Fe-CO stretching mode and is located in the 1000- to 1070-cm-1 region. The other line is found in the 1180- to 1210-cm-1 region and is assigned as a combination between a porphyrin mode, nu 7, and the Fe-CO stretching mode. The high intensities of these lines, which in the terminal oxidase class of proteins are of the same order as those of the fundamental stretching mode, indicate that the mechanism of enhancement for modes involving the Fe-CO moiety is different from that for the modes of the porphyrin macrocycle and call for reexamination of Raman theory of porphyrins as applied to axial ligands. The anharmonicity of the electronic potential function was evaluated, revealing that in the terminal oxidases the anharmonicity is greater than in the other heme proteins that were examined, suggesting a distinctive interaction of the bound CO with its distal environment in this family. Furthermore, the anharmonicity correlates with the frequency of the C-O stretching mode, demonstrating that both of these parameters are sensitive to the Fe-CO bond energy. The overtone and combination lines involving the bound CO promise to be additional probes of heme protein structural properties.