Teleseismic array analysis of upper mantle compressional velocity structure

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.

Influence of composition on the structure and properties of Fe-Pd-P and Ni-Pd-P amorphous alloys

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 Ni_x-Pd_80-x -P₂₀ and between 17°K and 96°K for Fe_x-Pd_80-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 µ_B and 2.10 µ_B 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.

Seismic structure along transitions from flat to normal subduction: central Mexico, southern Peru, and southwest Japan

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.

Influence of composition on the structure, electric and magnetic properties of Pd-Mn-P and Pd-Co-P amorphous alloys

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.

Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

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.

Smooth sets for borel equivalence relations and the covering property for σ-ideals of compact sets

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 I^int (i.e., every closed subset of it is in I). For σ-ideals on 2^ω 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.

Studies on the role of histones in the structure and function of chromatin

Studies on the dissociation of histones from chromatin by increasing concentrations of sodium deoxycholate (DOC) have shown that histrone II is removed at lowest concentrations of DOC, while slightly higher concentrations remove histones III and IV. Still higher concentrations remove histone I.

The complete separation of chromatin and ¹⁴C-DOC by sucrose sedimentation indicated that the binding of DOC to chromatin is readily and completely reversible.

The dissociation of histones from chromatin by increasing concentrations of related cholanic acids and some of their conjugated derivatives were studied. The results suggested that the driving force for the interaction between the cholanic acid anion and histones is the lowering of the activity coefficient of the cholanic acid anion which occurs when it is partially removed from solution by interaction with hydrophobic regions of the positively charged histones.

The role of histones in the structure of chromatin has been studied by comparing the effects of selective removal of histones from chromatin by increasing concentrations of DOC with those caused by NaCl (removes histone I at lowest concentrations, while higher concentrations remove histones II, III, and IV). Properties studied included thermal denaturation, sedimentation velocity, flow dichroism, relaxation times of molecules oriented in a flow field, and the irreversible disruption of a 130 S, cross-linked component of sheared chromatin. The data indicated that none of the structural or chemical parameters with which these properties are correlated show a dependence on the presence of one particular histone fraction.

The template activity (ability to prime a 0.2 M KC1 DNA-dependent RNA synthesis system catalyzed by E. coli RNA polymerase) increases from that of native chromatin (approximately 25 per cent of that pure DNA) to that of pure DNA in a fashion which shows a nearly linear relationship to the amount of histone coverage of the template. The precipitability of partially dehistonized chromatin samples in 0.15 M NaCl shows a large dependence on the presence of histone I.

I. The crystal structure of a new dimer of triphenylfluorocyclobutadiene. II. A low temperature refinement of the cyanuric triazide structure

I. THE CRYSTAL STRUCTURE OF A NEW DIMER OF TRIPHENYLFLUOROCYCLOBUTADIENE

The crystal structure of thermal isomer of the “head-to-head” dimer of triphenylfluorocyclobutadiene was determined by the direct method. The Σ₂ relationship involving the low angle reflections with the largest E’s were found and solved for the signs by the symbolic method of Zachariasen. The structure was seen in the electron density map and the E-map, and was refined antisotropically by the method of least squares. The residual R was 0.065.

The structure is a gem-difluorohexaphenyldihydropentalene. All of the phenyl groups are planar as it is the cyclopentadiene ring of the dihydropentalene skeleton. Overcrowding at the position of the flourines causes some deviations from the normal bond angles in the cyclopentene ring.

The list of observed and calculated structure factors on pages 32-34 will not be legible on the microfilm. Photographic copies may be obtained from the California Institute of Technology.

II. A LOW TEMPERATURE REFINEMENT OF THE CYANURIC TRIAZIDE STRUCTURE

The structure of cyanuric triazide was refined anisotropically by the method of least squares. Three-dimensional intensity data, which has been collected photographically with MoK_α radiation at -110˚C, were used in the refinement. The residual R was reduced to 0.081.

The structure is completely planar, and there is no significant bond alternation in the cyanuric ring. The packing of the molecules causes the azide groups to deviate from linearity by 8 degrees.