Panama City Fisheries Resources Office: FY 2008 Annual Report

HIGHLIGHTS FOR FY 2008 1. Completed the first of a two-year Gulf sturgeon population study on the Choctawhatchee River, Florida. The sub adult and adult Gulf sturgeon population was estimated at 2,800 fish. 2. Gulf sturgeon eggs were collected at three hard bottom sites in the Apalachicola River, Florida; two sites were previously confirmed spawning areas and one was a newly confirmed spawning area. 3. Documented 55 potential environmental threats to Gulf sturgeon spawning habitat in the Pea River, Florida and Alabama. 4. Assigned the Eglin AFB Road-Stream Crossing Working Group to guide the closure, repair and maintenance of roads and road stream crossings that impact threatened and endangered species. 5. Conducted 81 assessments of fish and stream invertebrates on and in watersheds surrounding Eglin AFB. 6. Provided technical support for the 5-year status review and reclassification proposed rule for the Okaloosa darter. 7. Initiated an intensive population genetic analysis of the Okaloosa darter throughout its range. Tissues from over 200 Okaloosa darters were collected and analyzed. 8. Established a GIS database to serve as a host for data from any sites sampled for mussels in Northeast Gulf of Mexico drainages. 9. Conducted habitat surveys at 115 locations in the Apalachicola River to assess the effects of drought-related mussel mortality and strandings, evaluate habitat conditions, and assess population demography. 10. A land use/aerial imagery threats assessment data analysis was completed for the Chipola River. A total of 266 impoundments/borrow pits and 471 unpaved road crossings were identified among the threats. 11. Okaloosa darters marked with elastomeric dyes were monitored in Mill Creek, Eglin AFB, to determine movement and habitat use following completion of a fish passage project. 3 12. Partners for Fish and Wildlife funded a streambank and riparian restoration project on Econfina Creek consisting of 3,900 feet of streambank fencing to exclude cattle access. One acre of riparian floodplain was planted with native trees. 13. We provided design and on-the-ground assistance for restoring surface hydrology at St. Vincent NWR. The project restored approximately 1.5 miles of tidal stream and 100 acres of wetlands. 14. A study was completed on 11 coastal streams to document large wood debris relationships with fluvial geomorphic characteristics. 15. We developed a Population Viability Analysis model for the fat threeridge mussel to determine current and future risk of extinction. 17. A Gulf Sturgeon Friends Group, “Gulf Sturgeon Preservation Society” was organized in FY 08. 18. Multiple outreach projects were completed to detail aquatic resource conservation needs and opportunities, including National Fishing Week, Earth Day, several festivals and school outreach.

Panama City Fisheries Resources Office: FY 2006 Annual Report

HIGHLIGHTS FOR FY 2006 1. Captured and tagged 475 Gulf sturgeons in five Florida rivers and one bay. 2. Documented Gulf sturgeon marine movement and habitat use in the Gulf of Mexico. 3. Assisted the National Oceanic and Atmospheric Administration (NOAA) with the collection of Gulf sturgeon, implantation of acoustic tags, and monitoring of fish in a study to examine movement patterns and habitat use in Pensacola and Choctawhatchee bays post-Hurricane Ivan. 4. Provided technical assistance to Jon “Bo” Sawyer in completing a study – Summer Resting Areas of the Gulf Sturgeon in the Conecuh/Escambia River System, Alabama-Florida – for acquiring a Degree of Master of Science at Troy University, Alabama. 5. Coordinated tagging and data collection with NOAA observers aboard trawlers while collecting Gulf sturgeon during dredging operations in the coastal Gulf of Mexico. 6. Hosted the 7th Annual Gulf Sturgeon Workshop. 7. Implemented Gulf Striped Bass Restoration Plan by coordinating the 23rd Annual Morone Workshop, leading the technical committee, transporting broodfish, coordinating the stocking on the Apalachicola-Chattahoochee-Flint (ACF) river system, and evaluating post-stocking success. 8. Continued updating and managing the Freshwater Mussel Survey Database, a Geographic Information System (GIS) database, for over 800 unique sites in the Northeast Gulf (NEG) drainages in Alabama (AL), Georgia (GA), and Florida (FL). 9. Formed a recovery implementation team for listed mussels in the ACF river basin and oversaw grant cooperative agreements for 14 listed and candidate freshwater mussels in the NEG watersheds. 10. Initiated a project in the Apalachicola River to relocate mussels stranded as a result of drought conditions, and calculate river flows at which mussels would be exposed. 11. Initiated a project in Sawhatchee Creek, Georgia to determine the status of threatened and endangered (T&E) freshwater mussels and target restoration projects, population assessments, and potential population augmentation to lead toward recovery of the listed species. 12. Initiated a study to determine the age and growth of the endangered fat threeridge mussel (Amblema neislerii). 13. Provided technical assistance to the Panama City Ecological Services office for a biological opinion on the operations of Jim Woodruff Lock and Dam and its effects on the listed species and designated and proposed critical habitat in the Apalachicola River, Florida. 14. Assisted with a multi-State, inter-agency team to develop a management plan to restore the Alabama shad in the ACF river system. 15. Conducted fishery surveys on Tyndall AFB, Florida and Ft. Benning, Georgia and completed a report with recommendations for future recreational fishery needs. 16. Provided fishery technical assistance to four National Wildlife Refuges (NWR) (i.e., Okefenokee NWR, Banks Lake NWR, St. Vincent NWR, and St. Marks NWR). 17. Initiated an Aquatic Resources and Recreation Fishing Survey on Department of Defense facilities located in Region 4. 18. Identified 130 road-stream crossings on Eglin AFB for rehabilitation and elimination of sediment imputs. 19. Continued the Aquatics Monitoring Program at Eglin AFB to assess techniques that determine current status and sustainability of aquatic habitat and develop a measure to determine quality or degradation of habitat. 20. Assisted Eglin AFB Natural Resource managers in revising the installation’s Integrated Natural Resources Management Plan (INRMP) and its associated component plans. 21. Coordinated recovery efforts for the endangered Okaloosa darter including population/life history surveys, stream restoration, and outreach activities. 22. Initiated a comprehensive status review of the Okaloosa darter with analyses performed to assess available habitat, preferred habitats, range expansions/reductions/fragmentations, population size, and probability of extinction. 23. Assisted the Gulf Coastal Plain Ecosystem Partnership and the Florida Fish and Wildlife Conservation Commission (FWC) under a Memorandum of Agreement to develop conservation strategies, implement monitoring and assessment programs, and secure funds for aquatic management programs in six watersheds in northwest Florida and southeast Alabama. 24. Entered into a cooperative agreement with the U.S. Air Force to encourage the conservation and rehabilitation of natural resources at Hurlburt Field, Florida. 25. Multiple outreach projects were completed to detail aquatic resources’ conservation needs and opportunities; including National Fishing Week, Earth Day, several festivals, and school outreach.

Panama City Fisheries Resources Office: FY 2005 Annual Report

HIGHLIGHTS FOR FY 2005 1. Assisted with a study to assess hurricane impacts to Gulf sturgeon critical foraging habitat. 2. Documented Gulf sturgeon marine movement and habitat use in the Gulf of Mexico. 3. Documented Gulf sturgeon spawning with the collection of fertilized eggs in the Apalachicola River, Florida. 4. Documented Gulf sturgeon spawning with the collection of fertilized eggs in the Yellow River, Florida. 5. Assisted with benthic invertebrate survey at Gulf sturgeon marine foraging grounds. 6. Implemented Gulf Striped Bass Restoration Plan by coordinating the 22nd Annual Morone Workshop, leading the technical committee, transporting broodfish, and coordinating the stocking on the Apalachicola-Chattahoochee-Flint (ACF) river system. 7. Over 87,000 Phase II Gulf striped bass were marked with sequential coded wire tags and stocked in the Apalachicola River. Post-stocking evaluations were conducted at 45 sites in the fall and spring and 8 thermal refuges in the summer. 8. Completed fishery surveys on 4 ponds on Eglin AFB totaling 53 acres, and completed a report with recommendations for future recreational fishery needs. 9. Completed final report for aquatic monitoring at Eglin AFB from 1999 to 2004. 10. Completed a field collection of the endangered Okaloosa darter to be incorporated into a status review to be completed in FY06. 11. Provided technical assistance to the Region 4 National Wildlife Refuge (NWR) program on changes to the fishery conservation targets for the region. Also provided technical assistance to four NWRs (i.e., Okefenokee NWR, Banks Lake NWR, St. Vincent NWR, and St. Marks NWR) relative to hurricanes and recreational fishing. 12. A draft mussel sampling protocol was tested in wadeable streams in Northwest Florida and southwest Georgia, and an associated field guide, poster, and Freshwater Mussel Survey Protocol and Identification workshop were completed in FY05. 13. Implemented recovery plan and candidate conservation actions for 14 listed and candidate freshwater mussels in the Northeast Gulf Watersheds. 14. Initiated or completed multiple stream restoration and watershed management projects. A total of 7.5 stream miles were restored for stream fishes, and 11 miles of coastline were enhanced for sea turtle lighting. A total of 630 acres of wetlands and 2,401 acres of understory habitat were restored. 15. Conducted a watershed assessment to develop a threats analysis for prioritizing restoration, protection, and enhancement to natural resources of Spring Creek, Georgia and Canoe Creek, Florida. 16. Continued the formation of an Unpaved Road Interagency Team of Federal, State, and local agencies in Northwest Florida to promote stream protection and restoration from unpaved road sediment runoff. Began the development of a technical committee agreement. 17. Conducted Alabama Unpaved Road Inventory within the Northeast Gulf Ecosystem. Data collection will be completed during FY06. 18. Finalized the development of two North Florida hydrophysiographic regional curves for use by the Florida Department of Transportation (DOT) and others involved with stream restoration and protection. Initiated the development of the Alabama Coastal Plain Riparian Reference Reach and Regional Curves for use by the Alabama Department of Environmental Management (ADEM). 19. Provided technical assistance in collecting data, analysis, and thesis formulation with Troy University, Alabama, to identify the influence of large woody debris in southeastern coastal plain streams. 20. Completed pre- and post-restoration fish community monitoring at several restoration projects including Big Escambia Creek, Magnolia Creek, and Oyster Lake, Florida. 21. Established a watershed partnership for the Chipola River in Alabama and Florida and expanded development and participation in the Spring Creek Watershed Partnership, Georgia. 22. Continued to identify barriers which inhibit the movement of aquatic species within the Northeast Gulf Ecoregion. 23. Completed a report on road crossing structures in Okaloosa darter streams to guide the closure/repair/maintenance of roads to contribute to recovery of the endangered species. In cooperation with Three Rivers RC&D Council, fish passage sites identified in the report were prioritized for restoration. 24. Monitored Aquatic Nuisance Species in the Apalachicola River and tested the sterility of exotic grass carp. 25. Multiple outreach projects were completed to detail aquatic resources conservation needs and opportunities. Participated in National Fishing Week event, several festivals, and school outreach.

Panama City Fisheries Resources Office: FY 2004 Annual Report

HIGHLIGHTS FOR FY 2004 1. Completed the second of a 3-year Gulf sturgeon population estimate on the Escambia River, Florida. 2. Completed the first of a 2-year Gulf sturgeon population estimate on the Apalachicola River, Florida. 3. Conducted Gulf sturgeon presence-absence surveys in three other Florida river systems. 4. Documented Gulf sturgeon marine habitat use in the near shore waters of the Gulf of Mexico. 5. Identified environmental threats to Gulf sturgeon spawning habitat in the Choctawhatchee River, Florida. 6. Initiated a study to document Gulf sturgeon spawning with the collection of fertilized eggs in the Yellow River, Florida. 7. Implemented Gulf Striped Bass Restoration Plan by coordinating the 21st Annual Morone Workshop, leading the technical committee, transporting broodfish, and coordinating the stocking on the Apalachicola-Chattahoochee-Flint (ACF) river system. 8. Over 86,000 Phase II Gulf striped bass were marked with sequential coded wire tags and stocked in Lake Seminole and the Apalachicola River. Post-stocking evaluations were conducted at 31 sites. 9. Drafted updates to Apalachicola-Chattahoochee-Flint Striped Bass Restoration and Evaluation Five-Year Plan with partners. 10. Fishery surveys were conducted on Tyndall Air Force Base and St. Marks and St. Vincent National Wildlife Refuges. 11. Habitat evaluations and population surveys were completed at 153 Okaloosa darter stream sites. 12. Aquatic insect biomonitoring and identification of over 39,000 individual aquatic macroinvertebrates was completed and provided to Eglin Air Force Base. 13. Ten years of fishery data from Okefenokee and Banks Lake National Wildlife Refuges was analyzed with recommendations incorporated into the refuge Comprehensive Conservation Plan. 14. A draft mussel sampling protocol was tested in wadeable streams in northwest Florida and southwest Georgia. 15. Implemented recovery plan and candidate conservation actions for 14 listed and candidate freshwater mussels in the Northeast Gulf Watersheds. 16. Worked with partners in developing the Spring Creek Watershed Partnership in the Flint River basin, Georgia. 17. Multiple stream restoration and watershed management projects were initiated or completed. A total of 6.8 stream miles were restored for stream fishes, along with 56.4 miles of coastline were enhanced for sea turtle lighting. A total of 135 acres of wetlands and 58 acres of understory habitat were restored. 18. Multiple outreach projects were completed to detail aquatic resources conservation needs and opportunities. Participated in National Fishing Week event, BASS ProShops event, several festivals, and school outreach.

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).

Documentaci??n geom??trica de un yacimiento arqueol??gico de gran extensi??n. El ejemplo de Contrebia Leukade (La Rioja)

[ES] La investigaci??n hist??rica en yacimientos arqueol??gicos de grandes dimensiones, requiere de un soporte gr??fico con base geom??trica en el que puedan ser referenciados los hallazgos, reflejadas las ??pocas hist??ricas, planificadas las intervenciones, dise??adas las soluciones constructivas o restauradoras, definidas las zonas afectadas de protecci??n, etc. Al mismo tiempo, la medida supone una parte importante de la propia documentaci??n de los restos arqueol??gicos, que aporta informaci??n cuantitativa de la forma, dimensiones y disposici??n espacial del conjunto del yacimiento y de cada uno de sus elementos constitutivos. La investigaci??n se ve enriquecida por el enlace de las bases de datos gr??ficos y alfanum??ricos. La posterior difusi??n de resultados, tanto a nivel t??cnico como popular, se ven beneficiados por un soporte geom??trico consistente y sobre todo planificado.

Sequence specific complexation of b DNA at sites containing g,c base pairs

A series of eight related analogs of distamycin A has been synthesized. Footprinting and affinity cleaving reveal that only two of the analogs, pyridine-2- car box amide-netropsin (2-Py N) and 1-methylimidazole-2-carboxamide-netrops in (2-ImN), bind to DNA with a specificity different from that of the parent compound. A new class of sites, represented by a TGACT sequence, is a strong site for 2-PyN binding, and the major recognition site for 2-ImN on DNA. Both compounds recognize the G•C bp specifically, although A's and T's in the site may be interchanged without penalty. Additional A•T bp outside the binding site increase the binding affinity. The compounds bind in the minor groove of the DNA sequence, but protect both grooves from dimethylsulfate. The binding evidence suggests that 2-PyN or 2-ImN binding induces a DNA conformational change.

In order to understand this sequence specific complexation better, the Ackers quantitative footprinting method for measuring individual site affinity constants has been extended to small molecules. MPE•Fe(II) cleavage reactions over a 10^5 range of free ligand concentrations are analyzed by gel electrophoresis. The decrease in cleavage is calculated by densitometry of a gel autoradiogram. The apparent fraction of DNA bound is then calculated from the amount of cleavage protection. The data is fitted to a theoretical curve using non-linear least squares techniques. Affinity constants at four individual sites are determined simultaneously. The distamycin A analog binds solely at A•T rich sites. Affinities range from 10^(6)- 10^(7)M^(-1) The data for parent compound D fit closely to a monomeric binding curve. 2-PyN binds both A•T sites and the TGTCA site with an apparent affinity constant of 10^(5) M^(-1). 2-ImN binds A•T sites with affinities less than 5 x 10^(4) M^(-1). The affinity of 2-ImN for the TGTCA site does not change significantly from the 2-PyN value. At the TGTCA site, the experimental data fit a dimeric binding curve better than a monomeric curve. Both 2-PyN and 2-ImN have substantially lower DNA affinities than closely related compounds.

In order to probe the requirements of this new binding site, fourteen other derivatives have been synthesized and tested. All compounds that recognize the TGTCA site have a heterocyclic aromatic nitrogen ortho to the N or C-terminal amide of the netropsin subunit. Specificity is strongly affected by the overall length of the small molecule. Only compounds that consist of at least three aromatic rings linked by amides exhibit TGTCA site binding. Specificity is only weakly altered by substitution on the pyridine ring, which correlates best with steric factors. A model is proposed for TGTCA site binding that has as its key feature hydrogen bonding to both G's by the small molecule. The specificity is determined by the sequence dependence of the distance between G's.

One derivative of 2-PyN exhibits pH dependent sequence specificity. At low pH, 4-dimethylaminopyridine-2-carboxamide-netropsin binds tightly to A•T sites. At high pH, 4-Me_(2)NPyN binds most tightly to the TGTCA site. In aqueous solution, this compound protonates at the pyridine nitrogen at pH 6. Thus presence of the protonated form correlates with A•T specificity.

The binding site of a class of eukaryotic transcriptional activators typified by yeast protein GCN4 and the mammalian oncogene Jun contains a strong 2-ImN binding site. Specificity requirements for the protein and small molecule are similar. GCN4 and 2-lmN bind simultaneously to the same binding site. GCN4 alters the cleavage pattern of 2-ImN-EDTA derivative at only one of its binding sites. The details of the interaction suggest that GCN4 alters the conformation of an AAAAAAA sequence adjacent to its binding site. The presence of a yeast counterpart to Jun partially blocks 2-lmN binding. The differences do not appear to be caused by direct interactions between 2-lmN and the proteins, but by induced conformational changes in the DNA protein complex. It is likely that the observed differences in complexation are involved in the varying sequence specificity of these proteins.

Studies of molecular bonding, interactions and decomposition reactions on the (001) surface of ruthenium

The interactions of N₂, formic acid and acetone on the Ru(001) surface are studied using thermal desorption mass spectrometry (TDMS), electron energy loss spectroscopy (EELS), and computer modeling.

Low energy electron diffraction (LEED), EELS and TDMS were used to study chemisorption of N₂ on Ru(001). Adsorption at 75 K produces two desorption states. Adsorption at 95 K fills only the higher energy desorption state and produces a (√3 x √3)R30° LEED pattern. EEL spectra indicate both desorption states are populated by N₂ molecules bonded "on-top" of Ru atoms.

Monte Carlo simulation results are presented on Ru(001) using a kinetic lattice gas model with precursor mediated adsorption, desorption and migration. The model gives good agreement with experimental data. The island growth rate was computed using the same model and is well fit by R(t)^m - R(t₀)^m = At, with m approximately 8. The island size was determined from the width of the superlattice diffraction feature.

The techniques, algorithms and computer programs used for simulations are documented. Coordinate schemes for indexing sites on a 2-D hexagonal lattice, programs for simulation of adsorption and desorption, techniques for analysis of ordering, and computer graphics routines are discussed.

The adsorption of formic acid on Ru(001) has been studied by EELS and TDMS. Large exposures produce a molecular multilayer species. A monodentate formate, bidentate formate, and a hydroxyl species are stable intermediates in formic acid decomposition. The monodentate formate species is converted to the bidentate species by heating. Formic acid decomposition products are CO₂, CO, H₂, H₂O and oxygen adatoms. The ratio of desorbed CO with respect to CO₂ increases both with slower heating rates and with lower coverages.

The existence of two different forms of adsorbed acetone, side-on, bonded through the oxygen and acyl carbon, and end-on, bonded through the oxygen, have been verified by EELS. On Pt(111), only the end-on species is observed. On dean Ru(001) and p(2 x 2)O precovered Ru(001), both forms coexist. The side-on species is dominant on clean Ru(001), while O stabilizes the end-on form. The end-on form desorbs molecularly. Bonding geometry stability is explained by surface Lewis acidity and by comparison to organometallic coordination complexes.

^(18)O/^(16)O and D/H studies on the interactions between heated meteoric ground waters and igneous intrusions: Western San Juan Mountains, Colorado and the Isle of Skye, Scotland

Detailed oxygen, hydrogen and carbon isotope studies have been carried out on igneous and metamorphic rocks of the Stony Mountain complex, Colorado, and the Isle of Skye, Scotland, in order to better understand the problems of hydrothermal meteoric water-rock interaction.

The Tertiary Stony Mountain stock (~1.3 km in diameter), is composed of an outer diorite, a main mass of biotite gabbro, and an inner diorite. The entire complex and most of the surrounding country rocks have experienced various degrees of ¹⁸O depletion (up to 10 per mil) due to interaction with heated meteoric waters. The inner diorite apparently formed from a low-¹⁸O magma with δ¹⁸O ≃ +2.5, but most of the isotopic effects are a result of exchange between H₂O and solidified igneous rocks. The low-¹⁸O inner diorite magma was probably produced by massive assimilation and/or melting of hydrothermally altered country rocks. The δ¹⁸O values of the rocks generally increase with increasing grain size, except that quartz typically has δ¹⁸O = +6 to +8, and is more resistant to hydrothermal exchange than any other mineral studied. Based on atom % oxygen, the outer diorites, gabbros, and volcanic rocks exhibit integrated water/rock ratios of 0.3 ± 0.2, 0.15 ± 0.1, and 0.2 ± 0.1, respectively. Locally, water/rock ratios attain values greater than 1.0. Hydrogen isotopic analyses of sericites, chlorites, biotites, and amphiboles range from -117 to -150. δD in biotites varies inversely with Fe/Fe+Mg, as predicted by Suzuoki and Epstein (1974), and positively with elevation, over a range of 600 m. The calculated δD of the mid-to-late-Tertiary meteoric waters is about -100. Carbonate δ¹³C values average -5.5 (PDB), within the generally accepted range for deep-seated carbon.

Almost all the rocks within 4 km of the central Tertiary intrusive complex of Skye are depleted in ¹⁸O. Whole-rock δ¹⁸O values of basalts (-7. 1 to +8.4), Mesozoic shales (-0.6 to + 12.4), and Precambrian sandstones (-6.2 to + 10.8) systematically decrease inward towards the center of the complex. The Cuillin gabbro may have formed from a ¹⁸O-depleted magma (depleted by about 2 per mil); δ¹⁸O of plagioclase (-7.1 to + 2.5) and pyroxene (-0.5 to + 3.2) decrease outward toward the margins of the pluton. The Red Hills epigranite plutons have δ¹⁸O quartz (-2.7 to + 7.6) and feldspar (-6.7 to + 6.0) that suggest about 3/4 of the exchange took place at subsolidus temperatures; profound disequilibrium quartz-feldspar fractionations (up to 12) are characteristic. The early epigranites were intruded as low-¹⁸O melts (depletions of up to 3 per mil) with δ¹⁸O of the primary, igneous quartz decreasing progressively with time. The Southern Porphyritic Epigranite was apparently intruded as a low-¹⁸O magma with δ¹⁸O ≃ -2.6. A good correlation exists between grain size and δ¹⁸O for the unique, high-¹⁸O Beinn an Dubhaich granite which intrudes limestone having a δ¹⁸O range of +0.5 to +20.8, and δ¹³C of -4.9 to -1.0. The δD values of sericites (-104 to -107), and amphiboles, chlorites, and biotites (-105 to -128) from the igneous rocks , indicate that Eocene surface waters at Skye had δD ≃ -90. The average water/rock ratio for the Skye hydrothermal system is approximately one; at least 2000 km³ of heated meteoric waters were cycled through these rocks.

Thus these detailed isotopic studies of two widely separated areas indicate that (1) ¹⁸O-depleted magmas are commonly produced in volcanic terranes invaded by epizonal intrusions; (2) most of the ¹⁸O-depletion in such areas are a result of subsolidus exchange (particularly of feldspars); however correlation of δ¹⁸O with grain size is generally preserved only for systems that have undergone relatively minor meteoric hydrothermal exchange; (3) feldspar and calcite are the minerals mos t susceptible to oxygen isotopic exchange, whereas quartz is very resistant to oxygen isotope exchange; biotite, magnetite, and pyroxene have intermediate susceptibilities; and (4) basaltic country rocks are much more permeable to the hydrothermal convective system than shale, sandstone, or the crystalline basement complex.

Transition metal clusters supported by multinucleating ligand frameworks as models of biological active sites

This dissertation describes efforts to model biological active sites with small molecule clusters. The approach used took advantage of a multinucleating ligand to control the structure and nuclearity of the product complexes, allowing the study of many different homo- and heterometallic clusters. Chapter 2 describes the synthesis of the multinucleating hexapyridyl trialkoxy ligand used throughout this thesis and the synthesis of trinuclear first row transition metal complexes supported by this framework, with an emphasis on tricopper systems as models of biological multicopper oxidases. The magnetic susceptibility of these complexes were studied, and a linear relation was found between the Cu-O(alkoxide)-Cu angles and the antiferromagnetic coupling between copper centers. The triiron(II) and trizinc(II) complexes of the ligand were also isolated and structurally characterized.

Chapter 3 describes the synthesis of a series of heterometallic tetranuclear manganese dioxido complexes with various incorporated apical redox-inactive metal cations (M = Na⁺, Ca²⁺, Sr²⁺, Zn²⁺, Y³⁺). Chapter 4 presents the synthesis of heterometallic trimanganese(IV) tetraoxido complexes structurally related to the CaMn₃ subsite of the oxygen-evolving complex (OEC) of Photosystem II. The reduction potentials of these complexes were studied, and it was found that each isostructural series displays a linear correlation between the reduction potentials and the Lewis acidities of the incorporated redox-inactive metals. The slopes of the plotted lines for both the dioxido and tetraoxido clusters are the same, suggesting a more general relationship between the electrochemical potentials of heterometallic manganese oxido clusters and their “spectator” cations. Additionally, these studies suggest that Ca²⁺ plays a role in modulating the redox potential of the OEC for water oxidation.

Chapter 5 presents studies of the effects of the redox-inactive metals on the reactivities of the heterometallic manganese complexes discussed in Chapters 3 and 4. Oxygen atom transfer from the clusters to phosphines is studied; although the reactivity is kinetically controlled in the tetraoxido clusters, the dioxido clusters with more Lewis acidic metal ions (Y³⁺ vs. Ca²⁺) appear to be more reactive. Investigations of hydrogen atom transfer and electron transfer rates are also discussed.

Appendix A describes the synthesis, and metallation reactions of a new dinucleating bis(N-heterocyclic carbene)ligand framework. Dicopper(I) and dicobalt(II) complexes of this ligand were prepared and structurally characterized. A dinickel(I) dichloride complex was synthesized, reduced, and found to activate carbon dioxide. Appendix B describes preliminary efforts to desymmetrize the manganese oxido clusters via functionalization of the basal multinucleating ligand used in the preceding sections of this dissertation. Finally, Appendix C presents some partially characterized side products and unexpected structures that were isolated throughout the course of these studies.

Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

Towards a Participatory Integrated Assessment Approach for Planning and Managing Natura 2000 Network Sites

36 p.

The role of sites of special scientific interest (SSSIs) in the conservation of British rivers

This paper discusses the particular contribution of the SSSI (Sites of Special Scientific Interest) as a way of nature conservation for rivers. In 1989, the Nature Conservancy Council proposed a dual selection system for selection of rivers; either (1) "Whole river" SSSIs representing the main types of river, or rivers which show classic and representative transitions down their lengths, or (2) "Sectional" SSSIs which are shorter stretches of river with high nature conservation interest. The NCC has recently classified all SSSIs with a river interest into 4 categories: - river SSSIs, river valley SSSIs, river adds interest - where the river clearly adds biological interest to the site, and rivers of incidental interest. The overall length of river SSSIs amounts to almost 1000 km.

Municipalismo e política urbana: a Influência da União na Política Urbana Municipal

A política urbana, em seus vetores de regulação, serviços públicos e fomento, é o conjunto de princípios, diretrizes e ações que orientam a atividade econômica de urbanização, podendo determinar condutas à iniciativa privada através da função social da propriedade. Por afetar diretamente a vida das pessoas e a conformação da propriedade nas cidades, a política urbana é, por essência, municipal. A tradição da força municipalista no Brasil, que data do período imperial, ainda que em alguns momentos sufocada, manejou tornar os Municípios entes federados, assegurando- lhes, na Constituição de 1988, autonomia e atribuições, como a execução da política urbana traçada em diretrizes gerais por leis nacionais. As diretrizes nacionais para a política urbana, elaboradas em processo participativo, deveria pautar as ações da União, Estados e Municípios no tocante aos três mencionados vetores. No entanto, notando-se a quase total ausência dos Estados, verifica-se que a União, após a Constituição de 1988, rompeu com a própria ideologia de planejamento construída com a criação do Ministério das Cidades pelo Governo Lula e, atropelando o tempo de formação das diretrizes nacionais da política urbana, lançou programas de fomento a moradias e saneamento básico, cuja execução deve ser organizada pelos Municípios, que são tecnicamente frágeis e carentes de recursos para implementar a própria política urbana. Este recorte temático permite estudar a atuação mais recente da União em política urbana que, mesmo pretendendo dar conta de mazelas históricas do país, não destoa muito do período centralizador de formulação da política urbana do Regime Militar. Em Municipalismo e Política Urbana, analisa-se a influência da União na Política Urbana Municipal.

I. Spectroscopic observation of discrete sites in simple liquids. II. Infrared intensity perturbations of hydrogen halide fundamentals in liquid xenon. III. Rotation of HCl in solid rare gases.

Part I

The spectrum of dissolved mercury atoms in simple liquids has been shown to be capable of revealing information concerning local structures in these liquids.

Part II

Infrared intensity perturbations in simple solutions have been shown to involve more detailed interaction than just dielectric polarization. No correlation has been found between frequency shifts and intensity enhancements.

Part III

Evidence for perturbed rotation of HCl in rare gas matrices has been found. The magnitude of the barrier to rotation is concluded to be of order of 30 cm^(-1).