Magnitude and extent of sediment toxicity in selected estuaries of South Carolina and Georgia

Toxic chemicals can enter the marine environment through numerous routes: stormwater runoff, industrial point source discharges, municipal wastewater discharges, atmospheric deposition, accidental spills, illegal dumping, pesticide applications and agricultural practices. Once they enter a receiving system, toxicants often become bound to suspended particles and increase in density sufficiently to sink to the bottom. Sediments are one of the major repositories of contaminants in aquatic envronments. Furthermore, if they become sufficiently contaminated sediments can act as sources of toxicants to important biota. Sediment quality data are direct indicators of the health of coastal aquatic habitats. Sediment quality investigations conducted by the National Oceanic and Atmospheric Administration (NOAA) and others have indicated that toxic chemicals are found in the sediments and biota of some estuaries in South Carolina and Georgia (NOAA, 1992). This report documents the toxicity of sediments collected within five selected estuaries: Savannah River, Winyah Bay, Charleston Harbor, St. Simons Sound, and Leadenwah Creek (Figure 1). (PDF contains 292 pages)

M/V ELPIS Coral Reef Restoration Monitoring Report Monitoring Events 2004-2007 Florida Keys National Marine Sanctuary, Monroe County, Florida

This document presents the results of the first three monitoring events to track the recovery of a repaired coral reef injured by the M/V Elpis vessel grounding incident of November 11, 1989. This grounding occurred within the boundaries of what at the time was designated the Key Largo National Marine Sanctuary (NMS), now designated the Key Largo NMS Existing Management Area within the Florida Keys National Marine Sanctuary (FKNMS). Pursuant to the National Marine Sanctuaries Act (NMSA) 16 U.S.C. 1431 et seq., and the Florida Keys National Marine Sanctuary and Protection Act (FKNMSPA) of 1990, NOAA is the federal trustee for the natural and cultural resources of the FKNMS. Under Section 312 of the NMSA, NOAA has the authority to recover monetary damages for injury, destruction, or loss of Sanctuary resources, and to use the recovered monies to restore injured or lost sanctuary resources within the FKNMS. The restoration monitoring program tracks patterns of biological recovery, determines the success of restoration measures, and assesses the resiliency to environmental and anthropogenic disturbances of the site over time. To evaluate restoration success, reference habitats adjacent to the restoration site are concurrently monitored to compare the condition of restored reef areas with natural coral reef areas unimpacted by the vessel grounding. Restoration of the site was completed September 1995, and thus far three monitoring events have occurred; one in the summer of 2004, one in the summer of 2005, and the latest in the summer of 2007. The monitoring in 2004 was in the nature of a “pilot project,” or proof of concept. Only the quantitative results of the 2005 and 2007 monitoring are presented and discussed. Monitoring has consisted of assessment of the structural stability of limestone boulders used in the restoration and comparison of the coral communities on the boulders and reference areas. Corals are divided into Gorgonians, Milleporans, and Scleractinians. Coral densities at the Restored and Reference areas for the 2005 and 2007 events are compared, and it is shown that the densities of all taxa in the Restored area are greater by 2007, though not significantly so. For the Scleractinians, number and percentage of colonies by species, as well as several common biodiversity indices are provided. The greater biodiversity of the Restored area is evidenced. Also, size-class frequency distributions for Agaricia spp. (Scleractinia) are presented. These demonstrate the approaching convergence of the Restored and Reference areas in this regard. An inter-annual comparison of densities, within both areas, for all three Orders, is presented. The most noteworthy finding was the relative consistency across time for all taxa in each area. Finally, certain anomalies regarding species settlement patterns are presented. (PDF contains 48 pages.)

M/V WELLWOOD Coral Reef Restoration Monitoring Report, Monitoring Events 2004-2006. Florida Keys National Marine Sanctuary Monroe County, Florida

This document presents the results of the first two monitoring events to track the recovery of a repaired coral reef injured by the M/V Wellwood vessel grounding incident of August 4, 1984. This grounding occurred within the boundaries of what at the time was designated the Key Largo National Marine Sanctuary (NMS), now designated the Key Largo NMS Existing Management Area within the Florida Keys National Marine Sanctuary (FKNMS). Pursuant to the National Marine Sanctuaries Act (NMSA) 16 U.S.C. 1431 et seq., and the Florida Keys National Marine Sanctuary and Protection Act (FKNMSPA) of 1990, NOAA is the federal trustee for the natural and cultural resources of the FKNMS. Under Section 312 of the NMSA, NOAA has the authority to recover monetary damages for injury, destruction, or loss of Sanctuary resources, and to use the recovered monies to restore injured or lost sanctuary resources within the FKNMS. The restoration monitoring program tracks patterns of biological recovery, determines the success of restoration measures, and assesses the resiliency to environmental and anthropogenic disturbances of the site over time. To evaluate restoration success, reference habitats adjacent to the restoration site are concurrently monitored to compare the condition of restored reef areas with “natural” coral reef areas unimpacted by the vessel grounding or other injury. Restoration of the site was completed on July 22, 2002, and thus far two monitoring events have occurred; one in the Fall of 2004, and one in the Summer/Fall of 2006. The monitoring has consisted of: assessment of the structural stability of restoration modules and comparison of the coral recruitment conditions of the modules and reference sites. Corals are divided into Gorgonians, Milleporans, and Scleractinians and (except where noted) recruits are defined as follows: Gorgonians—maximum size (height) 150 mm at first monitoring event, 270 mm at second; Milleporans—maximum size (height) 65 mm at first event, 125 mm at second; Scleractinians—maximum size (greatest diameter) 50 mm at second event (only one species was size-classed at first event, at smaller size). Recruit densities at the restored and reference areas for each event are compared, as are size-class frequency distributions. For the Scleractinians, number and percentage of recruits by species, as well as several common biodiversity indices are provided. Finally, a qualitative comparison of recruit substrate settlement preference is indicated. Generally, results indicate that restored areas are converging on reference areas, based on almost all parameters examined, with one noted exception. Further monitoring is planned and the trends are anticipated to continue; close attention will be paid to the indicated anomaly. (PDF contains 63 pages.)

M/V CONNECTED Coral Reef Restoration Monitoring Report, Monitoring Events 2004-2005. Florida Keys National Marine Sanctuary Monroe County, Florida

This document presents the results of the monitoring of a repaired coral reef injured by the M/V Connected vessel grounding incident of March 27, 2001. This grounding occurred in Florida state waters within the boundaries of the Florida Keys National Marine Sanctuary (FKNMS). The National Oceanic and Atmospheric Administration (NOAA) and the Board of Trustees of the Internal Improvement Trust Fund of the State of Florida, (“State of Florida” or “state”) are the co-trustees for the natural resources within the FKNMS and, thus, are responsible for mediating the restoration of the damaged marine resources and monitoring the outcome of the restoration actions. The restoration monitoring program tracks patterns of biological recovery, determines the success of restoration measures, and assesses the resiliency to environmental and anthropogenic disturbances of the site over time. The monitoring program at the Connected site was to have included an assessment of the structural stability of installed restoration modules and biological condition of reattached corals performed on the following schedule: immediately (i.e., baseline), 1, 3, and 6 years after restoration and following a catastrophic event. Restoration of this site was completed on July 20, 2001. Due to unavoidable delays in the settlement of the case, the “baseline” monitoring event for this site occurred in July 2004. The catastrophic monitoring event occurred on August 31, 2004, some 2 ½ weeks after the passage of Hurricane Charley which passed nearby, almost directly over the Dry Tortugas. In September 2005, the year one monitoring event occurred shortly after the passage of Hurricane Katrina, some 70 km to the NW. This report presents the results of all three monitoring events. (PDF contains 37 pages.)

M/V JACQUELYN L Coral Reef Restoration Monitoring Report, Monitoring Events 2004-2005. Florida Keys National Marine Sanctuary Monroe County, Florida

This document presents the results of the monitoring of a repaired coral reef injured by the M/V Jacquelyn L vessel grounding incident of July 7, 1991. This grounding occurred in Florida state waters within the boundaries of the Florida Keys National Marine Sanctuary (FKNMS). The National Oceanic and Atmospheric Administration (NOAA) and the Board of Trustees of the Internal Improvement Trust Fund of the State of Florida, (“State of Florida” or “state”) are the co-trustees for the natural resources within the FKNMS and, thus, are responsible for mediating the restoration of the damaged marine resources and monitoring the outcome of the restoration actions. The restoration monitoring program tracks patterns of biological recovery, determines the success of restoration measures, and assesses the resiliency to environmental and anthropogenic disturbances of the site over time. The monitoring program at the Jacquelyn L site was to have included an assessment of the structural stability of installed restoration modules and biological condition of reattached corals performed on the following schedule: immediately (i.e., baseline), 1, 3, and 6 years after restoration and following a catastrophic event. Restoration of this site was completed on July 20, 2000. Due to unavoidable delays in the settlement of the case, the “baseline” monitoring event for this site occurred in July 2004. The catastrophic monitoring event occurred on August 31, 2004, some 2 ½ weeks after the passage of Hurricane Charley which passed nearby, almost directly over the Dry Tortugas. In September 2005, the year one monitoring event occurred shortly after the passage of Hurricane Katrina, some 70 km to the NW. This report presents the results of all three monitoring events. (PDF contains 31 pages.)

M/V WAVE WALKER Coral reef restoration baseline monitoring report – 2004 Florida Keys National Marine Sanctuary, Monroe County, Florida

This document presents the results of baseline monitoring of a repaired coral reef injured by the M/V Wave Walker vessel grounding incident of January 19, 2001. This grounding occurred in Florida state waters within the boundaries of the Florida Keys National Marine Sanctuary (FKNMS). The National Oceanic and Atmospheric Administration (NOAA) and the Board of Trustees of the Internal Improvement Trust Fund of the State of Florida, (“State of Florida” or “state”) are the co-trustees for the natural resources within the FKNMS. This report documents the efficacy of the restoration effort, the condition of the restored reef area two year and four months post-effort, and provides a picture of surrounding reference areas, so as to provide a basis for future comparisons by which to evaluate the long-term success of the restoration. (PDF contains 25 pages.)

Panama City Fisheries Resources Office: FY 2003 Annual Report

HIGHLIGHTS FOR FY 2003 1. Continued a 3-year threatened Gulf sturgeon population estimate in the Escambia River, Florida and conducted presence-absence surveys in 4 other Florida river systems and 1 bay. 2. Five juvenile Gulf sturgeon collected, near the mouth of the Choctawhatchee River, Florida, were equipped with sonic tags and monitored while over-wintering in Choctawhatchee Bay. 3. Continued to examine Gulf sturgeon marine habitat use. 4. Implemented Gulf Striped Bass Restoration Plan by coordinating the 20th Annual Morone Workshop, leading the technical committee, transporting broodfish, and coordinating the stocking on the Apalachicola-Chattahoochee-Flint (ACF) river system. 5. Over 73,000 Phase II Gulf striped bass were marked with sequential coded wire tags and stocked in the Apalachicola River. Post-stocking evaluations were conducted at 31 sites. 6. Three stream fisheries assessment s were completed to evaluate the fish community at sites slated for habitat restoration by the Partners for Fish and Wildlife Program (PFW). 7. PFW program identified restoration needs and opportunities for 10 areas. 8. Developed an Unpaved Road Evaluation Handbook. 9. Completed restoration of Chipola River Greenway, Seibenhener Streambank Restoration, Blackwater River State Forest, and Anderson Property. 10. Assessments for fluvial geomorphic conditions for design criteria were completed for 3 projects. 11. Geomorphology in Florida streams initiated development of Rosgen regional curves for Northwest Florida for use by the Florida Department of Transportation. 12. Developed a Memorandum of Understanding between partners for enhancing, protecting, and restoring stream, wetland, and upland habitat in northwest Florida 13. Completed aquatic fauna and fish surveys with new emphasis on integration of data from reach level into watershed and landscape scale and keeping database current. 14. Compliance based sampling of impaired waterbodies on Eglin Air Force Base in conjunction with Florida Department of Environmental Protection for Total Maximum Daily Load development support. 15. Surveyed 20 sites for the federally endangered Okaloosa darter, provided habitat descriptions, worked with partners to implement key recovery tasks and set priorities for restoration. 16. Worked with partners to develop a freshwater mussel survey protocol to provide standard operating procedures for establishing the presence/absence of federally listed mussel species within a Federal project area. 17. GIS database was created to identify all known freshwater mussel records from the northeast Gulf ecosystem. 18. Completed recovery plan for seven freshwater mussels and drafted candidate elevation package for seven additional mussels. Developed proposals to implement recovery plan. 19. Worked with Corps of Engineers and State partners to develop improved reservoir operating policies to benefit both riverine and reservoir fisheries for the ACF river system. 20. Multiple outreach projects were completed to detail aquatic resources conservation opportunities. 21. Multiple stream restoration and watershed management projects initiated or completed (see Appendix A).

Determination of source finiteness and depth of large earthquakes

In this thesis, a method to retrieve the source finiteness, depth of faulting, and the mechanisms of large earthquakes from long-period surface waves is developed and applied to several recent large events.

In Chapter 1, source finiteness parameters of eleven large earthquakes were determined from long-period Rayleigh waves recorded at IDA and GDSN stations. The basic data set is the seismic spectra of periods from 150 to 300 sec. Two simple models of source finiteness are studied. The first model is a point source with finite duration. In the determination of the duration or source-process times, we used Furumoto's phase method and a linear inversion method, in which we simultaneously inverted the spectra and determined the source-process time that minimizes the error in the inversion. These two methods yielded consistent results. The second model is the finite fault model. Source finiteness of large shallow earthquakes with rupture on a fault plane with a large aspect ratio was modeled with the source-finiteness function introduced by Ben-Menahem. The spectra were inverted to find the extent and direction of the rupture of the earthquake that minimize the error in the inversion. This method is applied to the 1977 Sumbawa, Indonesia, 1979 Colombia-Ecuador, 1983 Akita-Oki, Japan, 1985 Valparaiso, Chile, and 1985 Michoacan, Mexico earthquakes. The method yielded results consistent with the rupture extent inferred from the aftershock area of these earthquakes.

In Chapter 2, the depths and source mechanisms of nine large shallow earthquakes were determined. We inverted the data set of complex source spectra for a moment tensor (linear) or a double couple (nonlinear). By solving a least-squares problem, we obtained the centroid depth or the extent of the distributed source for each earthquake. The depths and source mechanisms of large shallow earthquakes determined from long-period Rayleigh waves depend on the models of source finiteness, wave propagation, and the excitation. We tested various models of the source finiteness, Q, the group velocity, and the excitation in the determination of earthquake depths.

The depth estimates obtained using the Q model of Dziewonski and Steim (1982) and the excitation functions computed for the average ocean model of Regan and Anderson (1984) are considered most reasonable. Dziewonski and Steim's Q model represents a good global average of Q determined over a period range of the Rayleigh waves used in this study. Since most of the earthquakes studied here occurred in subduction zones Regan and Anderson's average ocean model is considered most appropriate.

Our depth estimates are in general consistent with the Harvard CMT solutions. The centroid depths and their 90 % confidence intervals (numbers in the parentheses) determined by the Student's t test are: Colombia-Ecuador earthquake (12 December 1979), d = 11 km, (9, 24) km; Santa Cruz Is. earthquake (17 July 1980), d = 36 km, (18, 46) km; Samoa earthquake (1 September 1981), d = 15 km, (9, 26) km; Playa Azul, Mexico earthquake (25 October 1981), d = 41 km, (28, 49) km; El Salvador earthquake (19 June 1982), d = 49 km, (41, 55) km; New Ireland earthquake (18 March 1983), d = 75 km, (72, 79) km; Chagos Bank earthquake (30 November 1983), d = 31 km, (16, 41) km; Valparaiso, Chile earthquake (3 March 1985), d = 44 km, (15, 54) km; Michoacan, Mexico earthquake (19 September 1985), d = 24 km, (12, 34) km.

In Chapter 3, the vertical extent of faulting of the 1983 Akita-Oki, and 1977 Sumbawa, Indonesia earthquakes are determined from fundamental and overtone Rayleigh waves. Using fundamental Rayleigh waves, the depths are determined from the moment tensor inversion and fault inversion. The observed overtone Rayleigh waves are compared to the synthetic overtone seismograms to estimate the depth of faulting of these earthquakes. The depths obtained from overtone Rayleigh waves are consistent with the depths determined from fundamental Rayleigh waves for the two earthquakes. Appendix B gives the observed seismograms of fundamental and overtone Rayleigh waves for eleven large earthquakes.

Invariants, Lie-Bäcklund operators and Bäcklund transformations

This thesis is mainly concerned with the application of groups of transformations to differential equations and in particular with the connection between the group structure of a given equation and the existence of exact solutions and conservation laws. In this respect the Lie-Bäcklund groups of tangent transformations, particular cases of which are the Lie tangent and the Lie point groups, are extensively used.

In Chapter I we first review the classical results of Lie, Bäcklund and Bianchi as well as the more recent ones due mainly to Ovsjannikov. We then concentrate on the Lie-Bäcklund groups (or more precisely on the corresponding Lie-Bäcklund operators), as introduced by Ibragimov and Anderson, and prove some lemmas about them which are useful for the following chapters. Finally we introduce the concept of a conditionally admissible operator (as opposed to an admissible one) and show how this can be used to generate exact solutions.

In Chapter II we establish the group nature of all separable solutions and conserved quantities in classical mechanics by analyzing the group structure of the Hamilton-Jacobi equation. It is shown that consideration of only Lie point groups is insufficient. For this purpose a special type of Lie-Bäcklund groups, those equivalent to Lie tangent groups, is used. It is also shown how these generalized groups induce Lie point groups on Hamilton's equations. The generalization of the above results to any first order equation, where the dependent variable does not appear explicitly, is obvious. In the second part of this chapter we investigate admissible operators (or equivalently constants of motion) of the Hamilton-Jacobi equation with polynornial dependence on the momenta. The form of the most general constant of motion linear, quadratic and cubic in the momenta is explicitly found. Emphasis is given to the quadratic case, where the particular case of a fixed (say zero) energy state is also considered; it is shown that in the latter case additional symmetries may appear. Finally, some potentials of physical interest admitting higher symmetries are considered. These include potentials due to two centers and limiting cases thereof. The most general two-center potential admitting a quadratic constant of motion is obtained, as well as the corresponding invariant. Also some new cubic invariants are found.

In Chapter III we first establish the group nature of all separable solutions of any linear, homogeneous equation. We then concentrate on the Schrodinger equation and look for an algorithm which generates a quantum invariant from a classical one. The problem of an isomorphism between functions in classical observables and quantum observables is studied concretely and constructively. For functions at most quadratic in the momenta an isomorphism is possible which agrees with Weyl' s transform and which takes invariants into invariants. It is not possible to extend the isomorphism indefinitely. The requirement that an invariant goes into an invariant may necessitate variants of Weyl' s transform. This is illustrated for the case of cubic invariants. Finally, the case of a specific value of energy is considered; in this case Weyl's transform does not yield an isomorphism even for the quadratic case. However, for this case a correspondence mapping a classical invariant to a quantum orie is explicitly found.

Chapters IV and V are concerned with the general group structure of evolution equations. In Chapter IV we establish a one to one correspondence between admissible Lie-Bäcklund operators of evolution equations (derivable from a variational principle) and conservation laws of these equations. This correspondence takes the form of a simple algorithm.

In Chapter V we first establish the group nature of all Bäcklund transformations (BT) by proving that any solution generated by a BT is invariant under the action of some conditionally admissible operator. We then use an algorithm based on invariance criteria to rederive many known BT and to derive some new ones. Finally, we propose a generalization of BT which, among other advantages, clarifies the connection between the wave-train solution and a BT in the sense that, a BT may be thought of as a variation of parameters of some. special case of the wave-train solution (usually the solitary wave one). Some open problems are indicated.

Most of the material of Chapters II and III is contained in [I], [II], [III] and [IV] and the first part of Chapter V in [V].

Habitat enhancing marine structures: Creating habitat in urban waters

Although maritime regions support a large portion of the world’s human population, their value as habitat for other species is overlooked. Urban structures that are built in the marine environment are not designed or managed for the habitat they provide, and are built without considering the communities of marine organisms that could colonize them (Clynick et al., 2008). However, the urban waterfront may be capable of supporting a significant proportion of regional aquatic biodiversity (Duffy-Anderson et al., 2003). While urban shorelines will never return to their original condition, some scientists think that the habitat quality of urban waterfronts could be significantly improved through further research and some design modifications, and that many opportunities exist to make these modifications (Russel et al., 1983, Goff, 2008). Habitat enhancing marine structures (or HEMS) are a potentially promising approach to address the impact of cities on marine organisms including habitat fragmentation and degradation. HEMS are a type of habitat improvement project that are ecologically engineered to improve the habitat quality of urban marine structures such as bulkheads and docks for marine organisms. More specifically, HEMS attempt to improve or enhance the physical habitat that organisms depend on for survival in the inter- and sub-tidal waterfronts of densely populated areas. HEMS projects are targeted at areas where human-made structures cannot be significantly altered or removed. While these techniques can be used in suburban or rural areas restoration or removal is preferred in these settings, and HEMS are resorted to only if removal of the human-made structure is not an option. Recent research supports the use of HEMS projects. Researchers have examined the communities found on urban structures including docks, bulkheads, and breakwaters. Complete community shifts have been observed where the natural shoreline was sandy, silty, or muddy. There is also evidence of declines in community composition, ecosystem functioning, and increases in non-native species abundances in assemblages on urban marine structures. Researchers have identified two key differences between these substrates including the slope (seawalls are vertical; rocky shores contain multiple slopes) and microhabitat availability (seawalls have very little; rocky shores contain many different types). In response, researchers have suggested designing and building seawalls with gentler slopes or a combination of horizontal and vertical surfaces. Researchers have also suggested incorporating microhabitat, including cavities designed to retain water during low tide, crevices, and other analogous features (Chapman, 2003; Moreira et al., 2006) (PDF contains 4 pages)

Various algorithms for optimization and learning in adaptive systems

This thesis discusses various methods for learning and optimization in adaptive systems. Overall, it emphasizes the relationship between optimization, learning, and adaptive systems; and it illustrates the influence of underlying hardware upon the construction of efficient algorithms for learning and optimization. Chapter 1 provides a summary and an overview.

Chapter 2 discusses a method for using feed-forward neural networks to filter the noise out of noise-corrupted signals. The networks use back-propagation learning, but they use it in a way that qualifies as unsupervised learning. The networks adapt based only on the raw input data-there are no external teachers providing information on correct operation during training. The chapter contains an analysis of the learning and develops a simple expression that, based only on the geometry of the network, predicts performance.

Chapter 3 explains a simple model of the piriform cortex, an area in the brain involved in the processing of olfactory information. The model was used to explore the possible effect of acetylcholine on learning and on odor classification. According to the model, the piriform cortex can classify odors better when acetylcholine is present during learning but not present during recall. This is interesting since it suggests that learning and recall might be separate neurochemical modes (corresponding to whether or not acetylcholine is present). When acetylcholine is turned off at all times, even during learning, the model exhibits behavior somewhat similar to Alzheimer's disease, a disease associated with the degeneration of cells that distribute acetylcholine.

Chapters 4, 5, and 6 discuss algorithms appropriate for adaptive systems implemented entirely in analog hardware. The algorithms inject noise into the systems and correlate the noise with the outputs of the systems. This allows them to estimate gradients and to implement noisy versions of gradient descent, without having to calculate gradients explicitly. The methods require only noise generators, adders, multipliers, integrators, and differentiators; and the number of devices needed scales linearly with the number of adjustable parameters in the adaptive systems. With the exception of one global signal, the algorithms require only local information exchange.

Improving the chances for developing coastal country success in adapting to climate change

There is an unequivocal scientific consensus that increases in greenhouse gases in the atmosphere drive warming temperatures of air and sea, and acidification of the world’s oceans from carbon dioxide absorbed by the oceans. These changes in turn can induce shifts in precipitation patterns, sea level rise, and more frequent and severe extreme weather events (e.g. storms and sea surge). All of these impacts are already being witnessed in the world’s coastal regions and are projected to intensify in years to come. Taken together, these impacts are likely to result in significant alteration of natural habitats and coastal ecosystems, and increased coastal hazards in low-lying areas. They can affect fishers, coastal communities and resource users, recreation and tourism, and coastal infrastructure. Approaches to planned adaptation to these impacts can be drawn from the lessons and good practices from global experience in Integrated Coastal Management (ICM). The recently published USAID Guidebook on Adapting to Coastal Climate Change (USAID 2009) is directed at practitioners, development planners, and coastal management professionals in developing countries. It offers approaches for assessing vulnerability to climate change and climate variability in communities and outlines how to develop and implement adaptation measures at the local and national levels. Six best practices for coastal adaptation are featured in the USAID Guidebook on Adapting to Coastal Climate Change and summarized in the following sections. (PDF contains 3 pages)

Seismic structure above and below the core-mantle boundary

Seismic structure above and below the core-mantle boundary (CMB) has been studied through use of travel time and waveform analyses of several different seismic wave groups. Anomalous systematic trends in observables document mantle heterogeneity on both large and small scales. Analog and digital data has been utilized, and in many cases the analog data has been optically scanned and digitized prior to analysis.

Differential travel times of S - SKS are shown to be an excellent diagnostic of anomalous lower mantle shear velocity (V s) structure. Wavepath geometries beneath the central Pacific exhibit large S- SKS travel time residuals (up to 10 sec), and are consistent with a large scale 0(1000 km) slower than average V_s region (≥3%). S - SKS times for paths traversing this region exhibit smaller scale patterns and trends 0(100 km) indicating V_s perturbations on many scale lengths. These times are compared to predictions of three tomographically derived aspherical models: MDLSH of Tanimoto [1990], model SH12_WM13 of Suet al. [1992], and model SH.10c.17 of Masters et al. [1992]. Qualitative agreement between the tomographic model predictions and observations is encouraging, varying from fair to good. However, inconsistencies are present and suggest anomalies in the lower mantle of scale length smaller than the present 2000+ km scale resolution of tomographic models. 2-D wave propagation experiments show the importance of inhomogeneous raypaths when considering lateral heterogeneities in the lowermost mantle.

A dataset of waveforms and differential travel times of S, ScS, and the arrival from the D" layer, Scd, provides evidence for a laterally varying V_s velocity discontinuity at the base of the mantle. Two different localized D" regions beneath the central Pacific have been investigated. Predictions from a model having a V_s discontinuity 180 km above the CMB agree well with observations for an eastern mid-Pacific CMB region. This thickness differs from V_s discontinuity thicknesses found in other regions, such as a localized region beneath the western Pacific, which average near 280 km. The "sharpness" of the V_s jump at the top of D", i.e., the depth range over which the V_s increase occurs, is not resolved by our data, and our data can in fact may be modeled equally well by a lower mantle with the increase in V_s at the top of D" occurring over a 100 krn depth range. It is difficult at present to correlate D" thicknesses from this study to overall lower mantle heterogeneity, due to uncertainties in the 3-D models, as well as poor coverage in maps of D" discontinuity thicknesses.

P-wave velocity structure (V_p) at the base of the mantle is explored using the seismic phases SKS and SPdKS. SPdKS is formed when SKS waves at distances around 107° are incident upon the CMB with a slowness that allows for coupling with diffracted P-waves at the base of the mantle. The P-wave diffraction occurs at both the SKS entrance and exit locations of the outer core. SP_dKS arrives slightly later in time than SKS, having a wave path through the mantle and core very close to SKS. The difference time between SKS and SP_dKS strongly depends on V_p at the base of the mantle near SK Score entrance and exit points. Observations from deep focus Fiji-Tonga events recorded by North American stations, and South American events recorded by European and Eurasian stations exhibit anomalously large SP_dKS - SKS difference times. SKS and the later arriving SP_dKS phase are separated by several seconds more than predictions made by 1-D reference models, such as the global average PREM [Dziewonski and Anderson, 1981] model. Models having a pronounced low-velocity zone (5%) in V_p in the bottom 50-100 km of the mantle predict the size of the observed SP_dK S-SKS anomalies. Raypath perturbations from lower mantle V_s structure may also be contributing to the observed anomalies.

Outer core structure is investigated using the family of SmKS (m=2,3,4) seismic waves. SmKS are waves that travel as S-waves in the mantle, P-waves in the core, and reflect (m-1) times on the underside of the CMB, and are well-suited for constraining outermost core V_p structure. This is due to closeness of the mantle paths and also the shallow depth range these waves travel in the outermost core. S3KS - S2KS and S4KS - S3KS differential travel times were measured using the cross-correlation method and compared to those from reflectivity synthetics created from core models of past studies. High quality recordings from a deep focus Java Sea event which sample the outer core beneath the northern Pacific, the Arctic, and northwestern North America (spanning 1/8th of the core's surface area), have SmKS wavepaths that traverse regions where lower mantle heterogeneity is pre- dieted small, and are well-modeled by the PREM core model, with possibly a small V_p decrease (1.5%) in the outermost 50 km of the core. Such a reduction implies chemical stratification in this 50 km zone, though this model feature is not uniquely resolved. Data having wave paths through areas of known D" heterogeneity (±2% and greater), such as the source-side of SmKS lower mantle paths from Fiji-Tonga to Eurasia and Africa, exhibit systematic SmKS differential time anomalies of up to several seconds. 2-D wave propagation experiments demonstrate how large scale lower mantle velocity perturbations can explain long wavelength behavior of such anomalous SmKS times. When improperly accounted for, lower mantle heterogeneity maps directly into core structure. Raypaths departing from homogeneity play an important role in producing SmKS anomalies. The existence of outermost core heterogeneity is difficult to resolve at present due to uncertainties in global lower mantle structure. Resolving a one-dimensional chemically stratified outermost core also remains difficult due to the same uncertainties. Restricting study to higher multiples of SmKS (m=2,3,4) can help reduce the affect of mantle heterogeneity due to the closeness of the mantle legs of the wavepaths. SmKS waves are ideal in providing additional information on the details of lower mantle heterogeneity.

The interplay of localization and interactions in quantum many-body systems

Disorder and interactions both play crucial roles in quantum transport. Decades ago, Mott showed that electron-electron interactions can lead to insulating behavior in materials that conventional band theory predicts to be conducting. Soon thereafter, Anderson demonstrated that disorder can localize a quantum particle through the wave interference phenomenon of Anderson localization. Although interactions and disorder both separately induce insulating behavior, the interplay of these two ingredients is subtle and often leads to surprising behavior at the periphery of our current understanding. Modern experiments probe these phenomena in a variety of contexts (e.g. disordered superconductors, cold atoms, photonic waveguides, etc.); thus, theoretical and numerical advancements are urgently needed. In this thesis, we report progress on understanding two contexts in which the interplay of disorder and interactions is especially important.

The first is the so-called “dirty” or random boson problem. In the past decade, a strong-disorder renormalization group (SDRG) treatment by Altman, Kafri, Polkovnikov, and Refael has raised the possibility of a new unstable fixed point governing the superfluid-insulator transition in the one-dimensional dirty boson problem. This new critical behavior may take over from the weak-disorder criticality of Giamarchi and Schulz when disorder is sufficiently strong. We analytically determine the scaling of the superfluid susceptibility at the strong-disorder fixed point and connect our analysis to recent Monte Carlo simulations by Hrahsheh and Vojta. We then shift our attention to two dimensions and use a numerical implementation of the SDRG to locate the fixed point governing the superfluid-insulator transition there. We identify several universal properties of this transition, which are fully independent of the microscopic features of the disorder.

The second focus of this thesis is the interplay of localization and interactions in systems with high energy density (i.e., far from the usual low energy limit of condensed matter physics). Recent theoretical and numerical work indicates that localization can survive in this regime, provided that interactions are sufficiently weak. Stronger interactions can destroy localization, leading to a so-called many-body localization transition. This dynamical phase transition is relevant to questions of thermalization in isolated quantum systems: it separates a many-body localized phase, in which localization prevents transport and thermalization, from a conducting (“ergodic”) phase in which the usual assumptions of quantum statistical mechanics hold. Here, we present evidence that many-body localization also occurs in quasiperiodic systems that lack true disorder.

Catalytic conversion of nitrogen to ammonia by an iron model complex

Threefold symmetric Fe phosphine complexes have been used to model the structural and functional aspects of biological N₂ fixation by nitrogenases. Low-valent bridging Fe-S-Fe complexes in the formal oxidation states Fe(II)Fe(II), Fe(II)/Fe(I), and Fe(I)/Fe(I) have been synthesized which display rich spectroscopic and magnetic behavior. A series of cationic tris-phosphine borane (TPB) ligated Fe complexes have been synthesized and been shown to bind a variety of nitrogenous ligands including N₂H₄, NH₃, and NH₂-. These complexes are all high spin S = 3/2 and display EPR and magnetic characteristics typical of this spin state. Furthermore, a sequential protonation and reduction sequence of a terminal amide results in loss of NH₃ and uptake of N₂. These stoichiometric transformations represent the final steps in potential N₂ fixation schemes.

Treatment of an anionic FeN₂ complex with excess acid also results in the formation of some NH₃, suggesting the possibility of a catalytic cycle for the conversion of N₂ to NH₃ mediated by Fe. Indeed, use of excess acid and reductant results in the formation of seven equivalents of NH₃ per Fe center, demonstrating Fe mediated catalytic N₂ fixation with acids and protons for the first time. Numerous control experiments indicate that this catalysis is likely being mediated by a molecular species.

A number of other phosphine ligated Fe complexes have also been tested for catalysis and suggest that a hemi-labile Fe-B interaction may be critical for catalysis. Additionally, various conditions for the catalysis have been investigated. These studies further support the assignment of a molecular species and delineate some of the conditions required for catalysis.

Finally, combined spectroscopic studies have been performed on a putative intermediate for catalysis. These studies converge on an assignment of this new species as a hydrazido(2-) complex. Such species have been known on group 6 metals for some time, but this represents the first characterization of this ligand on Fe. Further spectroscopic studies suggest that this species is present in catalytic mixtures, which suggests that the first steps of a distal mechanism for N₂ fixation are feasible in this system.