945 resultados para Quantitative structure-property relationship


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Organismal survival in marine habitats is often positively correlated with habitat structural complexity at local (within-patch) spatial scales. Far less is known, however, about how marine habitat structure at the landscape scale influences predation and other ecological processes, and in particular, how these processes are dictated by the interactive effect of habitat structure at local and landscape scales. The relationship between survival and habitat structure can be modeled with the habitat-survival function (HSF), which often takes on linear, hyperbolic, or sigmoid forms. We used tethering experiments to determine how seagrass landscape structure influenced the HSF for juvenile blue crabs Callinectes sapidus Rathbun in Back Sound, North Carolina, USA. Crabs were tethered in artificial seagrass plots of 7 different shoot densities embedded within small (1 – 3 m2) or large (>100 m2) seagrass patches (October 1999), and within 10 × 10 m landscapes containing patchy (<50% cover) or continuous (>90% cover) seagrass (July 2000). Overall, crab survival was higher in small than in large patches, and was higher in patchy than in continuous seagrass. The HSF was hyperbolic in large patches and in continuous seagrass, indicating that at low levels of habitat structure, relatively small increases in structure resulted in substantial increases in juvenile blue crab survival. However, the HSF was linear in small seagrass patches in 1999 and was parabolic in patchy seagrass in 2000. A sigmoid HSF, in which a threshold level of seagrass structure is required for crab survival, was never observed. Patchy seagrass landscapes are valuable refuges for juvenile blue crabs, and the effects of seagrass structural complexity on crab survival can only be fully understood when habitat structure at larger scales is considered.

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Executive Summary: Baseline characterization of resources is an essential part of marine protected area (MPA) management and is critical to inform adaptive management. Gray’s Reef National Marine Sanctuary (GRNMS) currently lacks adequate characterization of several key resources as identified in the 2006 Final Management Plan. The objectives of this characterization were to fulfill this need by characterizing the bottom fish, benthic features, marine debris, and the relationships among them for the different bottom types within the sanctuary: ledges, sparse live bottom, rippled sand, and flat sand. Particular attention was given to characterizing the different ledge types, their fish communities, and the marine debris associated with them given the importance of this bottom type to the sanctuary. The characterization has been divided into four sections. Section 1 provides a brief overview of the project, its relevance to sanctuary needs, methods of site selection, and general field procedures. Section 2 provides the survey methods, results, discussion, and recommendations for monitoring specific to the benthic characterization. Section 3 describes the characterization of marine debris. Section 4 is specific to the characterization of bottom fish. Field surveys were conducted during August 2004, May 2005, and August 2005. A total of 179 surveys were completed over ledge bottom (n=92), sparse live bottom (n=51), flat sand (n=20), and rippled sand (n=16). There were three components to each field survey: fish counting, benthic assessment, and quantification of marine debris. All components occurred within a 25 x 4 m belt transect. Two divers performed the transect at each survey site. One diver was responsible for identification of fish species, size, and abundance using a visual survey. The second diver was responsible for characterization of benthic features using five randomly placed 1 m2 quadrats, measuring ledge height and other benthic structures, and quantifying marine debris within the entire transect. GRNMS is composed of four main bottom types: flat sand, rippled sand, sparsely colonized live bottom, and densely colonized live bottom (ledges). Independent evaluation of the thematic accuracy of the GRNMS benthic map produced by Kendall et al. (2005) revealed high overall accuracy (93%). Most discrepancies between map and diver classification occurred during August 2004 and likely can be attributed to several factors, including actual map or diver errors, and changes in the bottom type due to physical forces. The four bottom types have distinct physical and biological characteristics. Flat and rippled sand bottom types were composed primarily of sand substrate and secondarily shell rubble. Flat sand and rippled sand bottom types were characterized by low percent cover (0-2%) of benthic organisms at all sites. Although the sand bottom types were largely devoid of epifauna, numerous burrows indicate the presence of infaunal organisms. Sparse live bottom and ledges were colonized by macroalgae and numerous invertebrates, including coral, gorgonians, sponges, and “other” benthic species (such as tunicates, anemones, and bryozoans). Ledges and sparse live bottom were similar in terms of diversity (H’) given the level of classification used here. However, percent cover of benthic species, with the exception of gorgonians, was significantly greater on ledge than on sparse live bottom. Percent biotic cover at sparse live bottom ranged from 0.7-26.3%, but was greater than 10% at only 7 out of 51 sites. Colonization on sparse live bottom is likely inhibited by shifting sands, as most sites were covered in a layer of sediment up to several centimeters thick. On ledge bottom type, percent cover ranged from 0.42-100%, with the highest percent cover at ledges in the central and south-central region of GRNMS. Biotic cover on ledges is influenced by local ledge characteristics. Cluster analysis of ledge dimensions (total height, undercut height, undercut width) resulted in three main categories of ledges, which were classified as short, medium, and tall. Median total percent cover was 97.6%, 75.1%, and 17.7% on tall, medium, and short ledges, respectively. Total percent cover and cover of macroalgae, sponges, and other organisms was significantly lower on short ledges compared to medium and tall ledges, but did not vary significantly between medium and tall ledges. Like sparse live bottom, short ledges may be susceptible to burial by sand, however the results indicate that ledge height may only be important to a certain threshold. There are likely other factors not considered here that also influence spatial distribution and community structure (e.g., small scale complexity, ocean currents, differential settlement patterns, and biological interactions). GRNMS is a popular site for recreational fishing and boating, and there has been increased concern about the accumulation of debris in the sanctuary and potential effects on sanctuary resources. Understanding the types, abundance, and distribution of debris is essential to improving debris removal and education efforts. Approximately two-thirds of all observed debris items found during the field surveys were fishing gear, and about half of the fishing related debris was monofilament fishing line. Other fishing related debris included leaders and spear gun parts, and non-gear debris included cans, bottles, and rope. The spatial distribution of debris was concentrated in the center of the sanctuary and was most frequently associated with ledges rather than at other bottom types. Several factors may contribute to this observation. Ledges are often targeted by fishermen due to the association of recreationally important fish species with this bottom type. In addition, ledges are structurally complex and are often densely colonized by biota, providing numerous places for debris to become stuck or entangled. Analysis of observed boat locations indicated that higher boat activity, which is an indication of fishing, occurs in the center of the sanctuary. On ledges, the presence and abundance of debris was significantly related to observed boat density and physiographic features including ledge height, ledge area, and percent cover. While it is likely that most fishing related debris originates from boats inside the sanctuary, preliminary investigation of ocean current data indicate that currents may influence the distribution and local retention of more mobile items. Fish communities at GRNMS are closely linked to benthic habitats. A list of species encountered, probability of occurrence, abundance, and biomass by habitat is provided. Species richness, diversity, composition, abundance, and biomass of fish all showed striking differences depending on bottom type with ledges showing the highest values of nearly all metrics. Species membership was distinctly separated by bottom type as well, although very short, sparsely colonized ledges often had a similar community composition to that of sparse live bottom. Analysis of fish communities at ledges alone indicated that species richness and total abundance of fish were positively related to total percent cover of sessile invertebrates and ledge height. Either ledge attribute was sufficient to result in high abundance or species richness of fish. Fish diversity (H`) was negatively correlated with undercut height due to schools of fish species that utilize ledge undercuts such as Pareques species. Concurrent analysis of ledge types and fish communities indicated that there are five distinct combinations of ledge type and species assemblage. These include, 1) short ledges with little or no undercut that lacked many of the undercut associated species except Urophycis earlii ; 2) tall, heavily colonized, deeply undercut ledges typically with Archosargus probatocephalus, Mycteroperca sp., and Pareques sp.; 3) tall, heavily colonized but less undercut with high occurrence of Lagodon rhomboides and Balistes capriscus; 4) short, heavily colonized ledges typically with Centropristis ocyurus, Halichoeres caudalis, and Stenotomus sp.; and 5) tall, heavily colonized, less undercut typically with Archosargus probatocephalus, Caranx crysos and Seriola sp.. Higher levels of boating activity and presumably fishing pressure did not appear to influence species composition or abundance at the community level although individual species appeared affected. These results indicate that merely knowing the basic characteristics of a ledge such as total height, undercut width, and percent cover of sessile invertebrates would allow good prediction of not only species richness and abundance of fish but also which particular fish species assemblages are likely to occur there. Comparisons with prior studies indicate some major changes in the fish community at GRNMS over the last two decades although the causes of the changes are unknown. Species of interest to recreational fishermen including Centropristis striata, Mycteroperca microlepis, and Mycteroperca phenax were examined in relation to bottom features, areas of assumed high versus low fishing pressure, and spatial dispersion. Both Mycteroperca species were found more frequently when undercut height of ledges was taller. They often were found together in small mixed species groups at ledges in the north central and southwest central regions of the sanctuary. Both had lower mode size and proportion of fish above the fishery size limit in heavily fished areas of the sanctuary (i.e. high boat density) despite the presence of better habitat in that region. Black sea bass, C. striata, occurred at 98% of the ledges surveyed and appeared to be evenly distributed throughout the sanctuary. Abundance was best explained by a positive relationship with percent cover of sessile biota but was also negatively related to presence of either Mycteroperca species. This may be due to predation by the Mycteroperca species or avoidance of sites where they are present by C. striata. Suggestions for monitoring bottom features, marine debris, and bottom fish at GRNMS are provided at the end of each chapter. The present assessment has established quantitative baseline characteristics of many of the key resources and use issues at GRNMS. The methods can be used as a model for future assessments to track the trajectory of GRNMS resources. Belt transects are ideally suited to providing efficient and quantitative assessment of bottom features, debris, and fish at GRNMS. The limited visibility, sensitivity of sessile biota, and linear nature of ledge habitats greatly diminish the utility of other sampling techniques. Ledges should receive the bulk of future characterization effort due to their importance to the sanctuary and high variability in physical structure, benthic composition, and fish assemblages. (PDF contains 107 pages.)

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Mytilus californianus (Mollusca: Bivalvia), the California marine mussel, occurs in intertidal populations so derise that they are referred to as "Mussel beds." The mussel beds range in physical complexity from structurally simple, essentially mono-layered assemblages, to structurally complex, multi-layered assemblages. The internal environment within the bed varies accordingly. The mussel bed provides either directly or indirectly, habitat, food and shelter for a large community of associated invertebrates. This study examines the relationship between physical complexity of the mussel bed habitat and composition of the associated community.

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ENGLISH: 1. Quantitative phytoplankton samples were collected by the Inter-American Tropical Tuna Commission at the surface and ten meters in the Gulf of Panama, as follows: a) 18-21 March, 1958 (31 stations)-during the height of the upwelling season, b) 10-12 July, 1957 (10 stations)-during the transition to the rainy season at a time when mild upwelling winds reappear, c) 7-8 November, 1957 (15 stations)-during the height of the rainy season. 2. Maximum phytoplankton populations occurred during the upwelling season, followed by a considerable decline during July, and a further Subsidence during November. 3. A remarkable regional uniformity in species composition was observed during the surveys despite regional differences in growth conditions. Diatoms overwhelmingly dominated the communities. 4. During all surveys, the innermost regions, generally north of 8°30'N, were the most productive. The least productive areas were in the offing of San Miguel Bay and Parita Bay, suggesting that nutrient accretion via runoff is inadequate to sustain sizeable autotrophic plant populations in those regions. 5. During all surveys, phytoplankton growth appeared to be limited by nutrient availability. 6. During all surveys, phytoplankton growth appeared to be related to depth of the water column. 7. Although below average rainfall contributed to unusually favorable growth conditions (reduced stability, increased transparency and, presumably, nutrient reserves) during the November survey relative to November 1955 and 1956 at 8°45'N, 79°23'W, the anticipated heightened phytoplankton response was not observed. 8. During the November survey, the local diatom responses and their regional fluctuations could be satisfactorily related to the accompanying surface salinity conditions. However, this correspondence is undoubtedly attributable to factors associated with the observed salinity levels, probably nutrients, rather than salinity directly. 9. Unusually warm conditions occurred during the March survey, attributable to considerably weaker upwelling winds than normally occurring then, which contributed to a considerably lower standing crop and a retardation in succession of three to five weeks relative to that observed during 1955-1957 at 8°45'N, 79°23'W in the Gulf of Panama. 10. During the March survey, a well defined inverse relationship existed between mean temperature and mean diatom abundance in the upper ten meters, and between transparency and mean diatom abundance. A direct relationship occurred between surface salinity and mean diatom abundance in the upper ten meters. These relationships are interpreted to indicate that diatom abundance primarily reflected the nutrient concentrations associated with a given upwelling intensity, rather than describing casual relationships. 11. The survey results indicate that the phytoplankton dynamics observed at 8°45'N, 79°23'W from November, 1954 through May, 1957 are generally representative of the Gulf of Panama. 12. The following new forms, to be described in a later publication, were observed during the surveys: Actinoptychus undulatus f. catenata n.f., Asterionella japonica f. tropicum n.f., Leptocylindrus maximus n. sp., Skeletonema costatum f. tropicum n.f. SPANISH: 1. La Comisión Interamericana del Atun Tropical recolectó en el Golfo de Panama muestras cuantitativas de fitoplancton en la superficie y a los diez metros, como sigue: a) Del 18 al 21 de marzo de 1958 (31 estaciones)-durante el maximum de la estación de afloramiento. b) Del 10 al 12 de julio de 1957 (10 estaciones)-durante la epóca de transición a la estación lluviosa cuando reaparecen los vientos ligeros que causan el afloramiento. c) Del 7 al 8 de noviembre de 1957 (15 estaciones)-durante el maximum de la estación lluviosa. 2. Las poblaciones maximas de fitoplancton aparecieron durante la estación de afloramiento, seguido por una considerable disminución durante el mes de julio y una calma durante noviembre. 3. Durante la investigación se observó una remarcable uniformidad regional en la composición de las especies a pesar de las diferencias regionales en las condiciones de crecimiento. Las diatomeas predominaban en gran numero en las comunidades. 4. Durante todas las investigaciones, las regiones mas cerca de la costa, generalmente al norte de los 8°30'N, eran las mas productivas. Las areas menos productivas fueron las mar afuera de las Bahias de San Miguel y Parita, lo que sugiere que el aumento en las sales nutritivas causado por las escorrentias es inadecuado para sostener poblaciones grandes de plantas autotróficas en estas regiones. 5. Durante todas las investigaciones, el crecimiento del fitoplancton parecio estar limitado por la disponibilidad de las. sales nutritivas. 6. Durante todas las investigaciones el crecimiento del fitoplancton parecio estar relacionado con la profundidad de la columna de agua. 7. Aunque las precipitacion por debajo del promedio normal contribuyo a condiciones desusadamente favorables de crecimiento (estabilidad reducida, aumento de la transparencia y, presumiblemente, de la reserva de sales nutritivas) durante la investigación de noviembre en relación a noviembre de 1955 y de 1956 en los 8°45'N, 79°23'W, no se observo-la alta reacción de fitoplancton que se esperaba. 8. Durante la investigación de noviembre, las reacciones locales de las diatomeas y sus fluctuaciones regionales pudieron relacionarse en forma satisfactoria con condiciones asociadas con la salinidad de la superficie. Sin embargo, esta correspondencia puede atribuirse sin duda a factores asociados con los niveles observados de salinidad, probablemente con las sales nutritivas, en lugar de directamente con la salinidad. 9. Condiciones calurosas no comunes ocurrieron durante la investigación de marzo, las que pueden atribuirse a que los vientos que ocasionan el afloramiento fueran mas debiles que los normales, lo que contribuyó a que la cosecha estable fuera considerablemente mas baja y a la demora de tres a cinco semanas en la sucecion relativa a la que se observó durante 1955-1957 en los 8°45'N, 8°23'W, en el Golfo de Panama. 10. Durante la investigación de marzo, existió una relación inversa bien definida entre la temperatura y la abundancia media de las diatomeas en los diez metros superiores, y entre la transparencia y la abundancia media de las diatomeas. Una relación directa ocurrio entre la salinidad de superficie y la abundancia media de las diatomeas en los diez metros superiores. Estas relaciones se interpretan como indicadoras de que la abundancia de diatomeas refleja primeramente las concentraciones de las sales nutritivas asociadas con una intensidad de afloramiento dada, en lugar de describir relaciones causales. 11. Los resultados de la investigacion indican que la dinamica del fitoplancton observada en los 8°45'N, 79°23'W, desde noviembre de 1954 a mayo de 1957, es generalmente representativa del Golfo de Panama. 12. Durante las investigaciones se observaron las siguientes formas nuevas, las que seran descritas en una publicación posterior: Actinoptychus undulatus f. catenata n.f., Asterionella japonica f. tropicum n.f., Leptocylindrus maximus n. sp., Skeletonema costatum f. tropicum n.f.

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A new method is described and evaluated for visually sampling reef fish community structure in environments with highly diverse and abundant reef fish populations. The method is based on censuses of reef fishes taken within a cylinder of 7.5 m radius by a diver at randomly selected, stationary points. The method provides quantitative data on frequency of occnrrence, fish length, abundance, and community composition, and is simple, fast, objective, and repeatable. Species are accumulated rapidly for listing purposes, and large numbers of samples are easily obtained for statistical treatment. The method provides an alternative to traditional visual sampling methods. Observations showed that there were no significant differences in total numbers of species or individuals censused when visibility ranged between 8 and 30 m. The reefs and habitats sampled were significant sources of variation in number of species and individuals censused, but the diver was not a significant influence. Community similarity indices were influenced significantly by the specific sampling site and the reef sampled, but were not significantly affected by the habitat or diver (PDF file contains 21 pages.)

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Background: Over many years, it has been assumed that enzymes work either in an isolated way, or organized in small catalytic groups. Several studies performed using "metabolic networks models'' are helping to understand the degree of functional complexity that characterizes enzymatic dynamic systems. In a previous work, we used "dissipative metabolic networks'' (DMNs) to show that enzymes can present a self-organized global functional structure, in which several sets of enzymes are always in an active state, whereas the rest of molecular catalytic sets exhibit dynamics of on-off changing states. We suggested that this kind of global metabolic dynamics might be a genuine and universal functional configuration of the cellular metabolic structure, common to all living cells. Later, a different group has shown experimentally that this kind of functional structure does, indeed, exist in several microorganisms. Methodology/Principal Findings: Here we have analyzed around 2.500.000 different DMNs in order to investigate the underlying mechanism of this dynamic global configuration. The numerical analyses that we have performed show that this global configuration is an emergent property inherent to the cellular metabolic dynamics. Concretely, we have found that the existence of a high number of enzymatic subsystems belonging to the DMNs is the fundamental element for the spontaneous emergence of a functional reactive structure characterized by a metabolic core formed by several sets of enzymes always in an active state. Conclusions/Significance: This self-organized dynamic structure seems to be an intrinsic characteristic of metabolism, common to all living cellular organisms. To better understand cellular functionality, it will be crucial to structurally characterize these enzymatic self-organized global structures.

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Abstract: In order to investigate the effects of the grain size distribution and the micro-structure of soils on the mechani- cal characteristics, some static triaxial compression tests were carried out, and then the relationship of stress-strain and the strength behavior of silty sand were compared among undisturbed samples with different grain size distribution, undis- turbed and remolded samples with the same grain size distribution, and reconstituted samples (or called mixed samples) with different grain size distribution. The effects of grain size distribution and structure on the mechanic behavior of silty sands were mainly analyzed. It is shown that the obvious differences of the mechanical characteristics between undis- turbed soils and remolded soils are caused by the differences of soil structures. Although the grain size distribution are different between two soil samples, their mechanical characteristics may be close to each other, or may have obvious differences because of the effects of micro-structure.

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DNA recognition is an essential biological process responsible for the regulation of cellular functions including protein synthesis and cell division and is implicated in the mechanism of action of some anticancer drugs. Studies directed towards defining the elements responsible for sequence specific DNA recognition through the study of the interactions of synthetic organic ligands with DNA are described.

DNA recognition by poly-N-methylpyrrolecarboxamides was studied by the synthesis and characterization of a series of molecules where the number of contiguous N-methylpyrrolecarboxamide units was increased from 2 to 9. The effect of this incremental change in structure on DNA recognition has been investigated at base pair resolution using affinity cleaving and MPE•Fe(II) footprinting techniques. These studies led to a quantitative relationship between the number of amides in the molecule and the DNA binding site size. This relationship is called the n + 1 rule and it states that a poly-N methylpyrrolecarboxamide molecule with n amides will bind n + 1 base pairs of DNA. This rule is consistent with a model where the carboxamides of these compounds form three center bridging hydrogen bonds between adjacent base pairs on opposite strands of the helix. The poly-N methylpyrrolecarboxamide recognition element was found to preferentially bind poly dA•poly dT stretches; however, both binding site selection and orientation were found to be affected by flanking sequences. Cleavage of large DNA is also described.

One approach towards the design of molecules that bind large sequences of double helical DNA sequence specifically is to couple DNA binding subunits of similar or diverse base pair specificity. Bis-EDTA-distamycin-fumaramide (BEDF) is an octaamide dimer of two tri-N methylpyrrolecarboxamide subunits linked by fumaramide. DNA recognition by BEDF was compared to P7E, an octaamide molecule containing seven consecutive pyrroles. These two compounds were found to recognize the same sites on pBR322 with approximately the same affinities demonstrating that fumaramide is an effective linking element for Nmethylpyrrolecarboxamide recognition subunits. Further studies involved the synthesis and characterization of a trimer of tetra-N-methylpyrrolecarboxamide subunits linked by β-alanine ((P4)_(3)E). This trimerization produced a molecule which is capable of recognizing 16 base pairs of A•T DNA, more than a turn and a half of the DNA helix.

DNA footprinting is a powerful direct method for determining the binding sites of proteins and small molecules on heterogeneous DNA. It was found that attachment of EDTA•Fe(II) to spermine creates a molecule, SE•Fe(II), which binds and cleaves DNA sequence neutrally. This lack of specificity provides evidence that at the nucleotide level polyamines recognize heterogeneous DNA independent of sequence and allows SE•Fe(II) to be used as a footprinting reagent. SE•Fe(II) was compared with two other small molecule footprinting reagents, EDTA•Fe(II) and MPE•Fe(II).

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Large quantities of teleseismic short-period seismograms recorded at SCARLET provide travel time, apparent velocity and waveform data for study of upper mantle compressional velocity structure. Relative array analysis of arrival times from distant (30° < Δ < 95°) earthquakes at all azimuths constrains lateral velocity variations beneath southern California. We compare dT/dΔ back azimuth and averaged arrival time estimates from the entire network for 154 events to the same parameters derived from small subsets of SCARLET. Patterns of mislocation vectors for over 100 overlapping subarrays delimit the spatial extent of an east-west striking, high-velocity anomaly beneath the Transverse Ranges. Thin lens analysis of the averaged arrival time differences, called 'net delay' data, requires the mean depth of the corresponding lens to be more than 100 km. Our results are consistent with the PKP-delay times of Hadley and Kanamori (1977), who first proposed the high-velocity feature, but we place the anomalous material at substantially greater depths than their 40-100 km estimate.

Detailed analysis of travel time, ray parameter and waveform data from 29 events occurring in the distance range 9° to 40° reveals the upper mantle structure beneath an oceanic ridge to depths of over 900 km. More than 1400 digital seismograms from earthquakes in Mexico and Central America yield 1753 travel times and 58 dT/dΔ measurements as well as high-quality, stable waveforms for investigation of the deep structure of the Gulf of California. The result of a travel time inversion with the tau method (Bessonova et al., 1976) is adjusted to fit the p(Δ) data, then further refined by incorporation of relative amplitude information through synthetic seismogram modeling. The application of a modified wave field continuation method (Clayton and McMechan, 1981) to the data with the final model confirms that GCA is consistent with the entire data set and also provides an estimate of the data resolution in velocity-depth space. We discover that the upper mantle under this spreading center has anomalously slow velocities to depths of 350 km, and place new constraints on the shape of the 660 km discontinuity.

Seismograms from 22 earthquakes along the northeast Pacific rim recorded in southern California form the data set for a comparative investigation of the upper mantle beneath the Cascade Ranges-Juan de Fuca region, an ocean-continent transit ion. These data consist of 853 seismograms (6° < Δ < 42°) which produce 1068 travel times and 40 ray parameter estimates. We use the spreading center model initially in synthetic seismogram modeling, and perturb GCA until the Cascade Ranges data are matched. Wave field continuation of both data sets with a common reference model confirms that real differences exist between the two suites of seismograms, implying lateral variation in the upper mantle. The ocean-continent transition model, CJF, features velocities from 200 and 350 km that are intermediate between GCA and T7 (Burdick and Helmberger, 1978), a model for the inland western United States. Models of continental shield regions (e.g., King and Calcagnile, 1976) have higher velocities in this depth range, but all four model types are similar below 400 km. This variation in rate of velocity increase with tectonic regime suggests an inverse relationship between velocity gradient and lithospheric age above 400 km depth.

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Ternary alloys of nickel-palladium-phosphorus and iron-palladium- phosphorus containing 20 atomic % phosphorus were rapidly quenched from the liquid state. The structure of the quenched alloys was investigated by X-ray diffraction. Broad maxima in the diffraction patterns, indicative of a glass-like structure, were obtained for 13 to 73 atomic % nickel and 13 to 44 atomic % iron, with palladium adding up to 80%.

Radial distribution functions were computed from the diffraction data and yielded average interatomic distances and coordination numbers. The structure of the amorphous alloys could be explained in terms of structural units analogous to those existing in the crystalline Pd3P, Ni3P and Fe3P phases, with iron or nickel substituting for palladium. A linear relationship between interatomic distances and composition, similar to Vegard's law, was shown for these metallic glasses.

Electrical resistivity measurements showed that the quenched alloys were metallic. Measurements were performed from liquid helium temperatures (4.2°K) up to the vicinity of the melting points (900°K- 1000°K). The temperature coefficient in the glassy state was very low, of the order of 10-4/°K. A resistivity minimum was found at low temperature, varying between 9°K and 14°K for Nix-Pd80-x -P20 and between 17°K and 96°K for Fex-Pd80-x -P20, indicating the presence of a Kondo effect. Resistivity measurements, with a constant heating rate of about 1.5°C/min,showed progressive crystallization above approximately 600°K.

The magnetic moments of the amorphous Fe-Pd-P alloys were measured as a function of magnetic field and temperature. True ferromagnetism was found for the alloys Fe32-Pd48-P20 and Fe44-Pd36-P20 with Curie points at 165° K and 380° K respectively. Extrapolated values of the saturation magnetic moments to 0° K were 1.70 µB and 2.10 µB respectively. The amorphous alloy Fe23-Pd57-P20 was assumed to be superparamagnetic. The experimental data indicate that phosphorus contributes to the decrease of moments by electron transfer, whereas palladium atoms probably have a small magnetic moment. A preliminary investigation of the Ni-Pd-P amorphous alloys showed that these alloys are weakly paramagnetic.

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The fine-scale seismic structure of the central Mexico, southern Peru, and southwest Japan subduction zones is studied using intraslab earthquakes recorded by temporary and permanent regional seismic arrays. The morphology of the transition from flat to normal subduction is explored in central Mexico and southern Peru, while in southwest Japan the spatial coincidence of a thin ultra-slow velocity layer (USL) atop the flat slab with locations of slow slip events (SSEs) is explored. This USL is also observed in central Mexico and southern Peru, where its lateral extent is used as one constraint on the nature of the flat-to-normal transitions.

In western central Mexico, I find an edge to this USL which is coincident with the western boundary of the projected Orozco Fracture Zone (OFZ) region. Forward modeling of the 2D structure of the subducted Cocos plate using a finite-difference algorithm provides constraints on the velocity and geometry of the slab’s seismic structure in this region and confirms the location of the USL edge. I propose that the Cocos slab is currently fragmenting into a North Cocos plate and a South Cocos plate along the projection of the OFZ, by a process analogous to that which occurred when the Rivera plate separated from the proto-Cocos plate 10 Ma.

In eastern central Mexico, observations of a sharp transition in slab dip near the abrupt end of the Trans Mexican Volcanic Belt (TMVB) suggest a possible slab tear located within the subducted South Cocos plate. The eastern lateral extent of the USL is found to be coincident with these features and with the western boundary of a zone of decreased seismicity, indicating a change in structure which I interpret as evidence of a possible tear. Analysis of intraslab seismicity patterns and focal mechanism orientations and faulting types provides further support for a possible tear in the South Cocos slab. This potential tear, together with the tear along the projection of the OFZ to the northwest, indicates a slab rollback mechanism in which separate slab segments move independently, allowing for mantle flow between the segments.

In southern Peru, observations of a gradual increase in slab dip coupled with a lack of any gaps or vertical offsets in the intraslab seismicity suggest a smooth contortion of the slab. Concentrations of focal mechanisms at orientations which are indicative of slab bending are also observed along the change in slab geometry. The lateral extent of the USL atop the horizontal Nazca slab is found to be coincident with the margin of the projected linear continuation of the subducting Nazca Ridge, implying a causal relationship, but not a slab tear. Waveform modeling of the 2D structure in southern Peru provides constraints on the velocity and geometry of the slab’s seismic structure and confirms the absence of any tears in the slab.

In southwest Japan, I estimate the location of a possible USL along the Philippine Sea slab surface and find this region of low velocity to be coincident with locations of SSEs that have occurred in this region. I interpret the source of the possible USL in this region as fluids dehydrated from the subducting plate, forming a high pore-fluid pressure layer, which would be expected to decrease the coupling on the plate interface and promote SSEs.

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The influence of composition on the structure and on the electric and magnetic properties of amorphous Pd-Mn-P and Pd-Co-P prepared by rapid quenching techniques were investigated in terms of (1) the 3d band filling of the first transition metal group, (2) the phosphorus concentration effect which acts as an electron donor and (3) the transition metal concentration.

The structure is essentially characterized by a set of polyhedra subunits essentially inverse to the packing of hard spheres in real space. Examination of computer generated distribution functions using Monte Carlo random statistical distribution of these polyhedra entities demonstrated tile reproducibility of the experimentally calculated atomic distribution function. As a result, several possible "structural parameters" are proposed such as: the number of nearest neighbors, the metal-to-metal distance, the degree of short-range order and the affinity between metal-metal and metal-metalloid. It is shown that the degree of disorder increases from Ni to Mn. Similar behavior is observed with increase in the phosphorus concentration.

The magnetic properties of Pd-Co-P alloys show that they are ferromagnetic with a Curie temperature between 272 and 399°K as the cobalt concentration increases from 15 to 50 at.%. Below 20 at.% Co the short-range exchange interactions which produce the ferromagnetism are unable to establish a long-range magnetic order and a peak in the magnetization shows up at the lowest temperature range . The electric resistivity measurements were performed from liquid helium temperatures up to the vicinity of the melting point (900°K). The thermomagnetic analysis was carried out under an applied field of 6.0 kOe. The electrical resistivity of Pd-Co-P shows the coexistence of a Kondo-like minimum with ferromagnetism. The minimum becomes less important as the transition metal concentration increases and the coefficients of ℓn T and T^2 become smaller and strongly temperature dependent. The negative magnetoresistivity is a strong indication of the existence of localized moment.

The temperature coefficient of resistivity which is positive for Pd- Fe-P, Pd-Ni-P, and Pd-Co-P becomes negative for Pd-Mn-P. It is possible to account for the negative temperature dependence by the localized spin fluctuation model and the high density of states at the Fermi energy which becomes maximum between Mn and Cr. The magnetization curves for Pd-Mn-P are typical of those resulting from the interplay of different exchange forces. The established relationship between susceptibility and resistivity confirms the localized spin fluctuation model. The magnetoresistivity of Pd-Mn-P could be interpreted in tenns of a short-range magnetic ordering that could arise from the Rudennan-Kittel type interactions.

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Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.

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O Centro Cirúrgico é um serviço especializado com estrutura física e organizacional complexa, normas e rotinas rigorosas, intensa atividade técnica, aparato tecnológico que requer profissionais treinados. A pesquisa teve como objeto de estudo os fatores de riscos ocupacionais e os problemas de saúde decorrentes do trabalho, identificados pelos profissionais de enfermagem de um Centro Cirúrgico de um Hospital Universitário da cidade do Rio de Janeiro. Os objetivos foram: analisar os fatores de riscos ocupacionais que possibilitam o aparecimento de problemas de saúde nos profissionais de enfermagem do Centro Cirúrgico segundo esses trabalhadores; descrever as características sociodemográficas dos profissionais lotados no Centro Cirúrgico; levantar os fatores de risco do ambiente cirúrgico identificados pelos trabalhadores de enfermagem do Centro Cirúrgico de um Hospital Universitário; e, discutir a relação entre os riscos do ambiente de trabalho e os problemas de saúde autoreferidos por trabalhadores de enfermagem do Centro Cirúrgico. A metodologia usada foi uma pesquisa não-experimental, de natureza descritiva, com abordagem quantitativa, desenvolvida em um centro cirúrgico de um hospital universitário federal da cidade do Rio de Janeiro. A população escolhida foi composta de trabalhadores da equipe de enfermagem, lotados no mínimo há seis meses neste serviço e que aceitassem participar da pesquisa. O questionário de coleta de dados utilizado foi adaptado por Mauro dos Guias e Avaliação de riscos em indústrias de Boix e Vogel. O estudo foi submetido e aprovado pelo Comitê de Ética em Pesquisa (CEP) do Hospital Universitário em estudo, através Parecer Consubstanciado no. 287/10, protocolo no. 217/09. Os dados foram analisados através do Programa Statistical Package for the Social Sciences (SPSS), versão 13.0. Os riscos biológicos foram os mais apontados pelos trabalhadores de enfermagem, seguidos dos riscos químicos, ergonômicos e de acidentes ou mecânicos. As doenças provocadas pelo trabalho mais referidas foram o estresse, a lombalgia, as varizes, a fadiga muscular e os problemas de articulação. As doenças agravadas pelo trabalho mais citadas foram as varizes, a lombalgia, os problemas de articulação, o estresse, as lesões de coluna vertebral, os problemas digestivos e os transtornos do sono. Conclui-se que o Serviço estudado possui riscos inerentes às atividades desenvolvidas que caracterizam os problemas relacionados pelos trabalhadores, e que são passíveis de controle através da intensificação de um Programa de Prevenção de Riscos Ambientais voltado para o Centro Cirúrgico. A partir da NR 17 e a 32, pode-se consultar as diretrizes para prevenção dos riscos encontrados. Uma estratégia de reposição digna de pessoal de enfermagem é imprescindível, assim como estudo e implantação de um Programa de Prevenção de Riscos laborais aos trabalhadores do Centro Cirúrgico, e utilização do questionário aos demais membros da equipe multiprofissional.

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This thesis is divided into three chapters. In the first chapter we study the smooth sets with respect to a Borel equivalence realtion E on a Polish space X. The collection of smooth sets forms σ-ideal. We think of smooth sets as analogs of countable sets and we show that an analog of the perfect set theorem for Σ11 sets holds in the context of smooth sets. We also show that the collection of Σ11 smooth sets is ∏11 on the codes. The analogs of thin sets are called sparse sets. We prove that there is a largest ∏11 sparse set and we give a characterization of it. We show that in L there is a ∏11 sparse set which is not smooth. These results are analogs of the results known for the ideal of countable sets, but it remains open to determine if large cardinal axioms imply that ∏11 sparse sets are smooth. Some more specific results are proved for the case of a countable Borel equivalence relation. We also study I(E), the σ-ideal of closed E-smooth sets. Among other things we prove that E is smooth iff I(E) is Borel.

In chapter 2 we study σ-ideals of compact sets. We are interested in the relationship between some descriptive set theoretic properties like thinness, strong calibration and the covering property. We also study products of σ-ideals from the same point of view. In chapter 3 we show that if a σ-ideal I has the covering property (which is an abstract version of the perfect set theorem for Σ11 sets), then there is a largest ∏11 set in Iint (i.e., every closed subset of it is in I). For σ-ideals on 2ω we present a characterization of this set in a similar way as for C1, the largest thin ∏11 set. As a corollary we get that if there are only countable many reals in L, then the covering property holds for Σ12 sets.