Ecological condition of coastal ocean waters along the U.S. Western Continental Shelf: 2003

Executive Summary: The western National Coastal Assessment (NCA-West) program of EPA, in conjunction with the NOAA National Ocean Service (NOS), conducted an assessment of the status of ecological condition of soft sediment habitats and overlying waters along the western U.S. continental shelf, between the target depths of 30 and 120 m, during June 2003. NCA-West and NOAA/NOS partnered with the West Coast states (Washington (WA), Oregon (OR), and California (CA)), and the Southern California Coastal Water Research Project (SCCWRP) Bight ’03 program to conduct the survey. A total of 257 stations were sampled from Cape Flattery, WA to the Mexican border using standard methods and indicators applied in previous coastal NCA projects. A key study feature was the incorporation of a stratified-random sampling design with stations stratified by state and National Marine Sanctuary (NMS) status. Each of the three states was represented by at least 50 random stations. There also were a total of 84 random stations located within NOAA’s five NMSs along the West Coast including the Olympic Coast NMS (OCNMS), Cordell Bank NMS (CBNMS), Gulf of Farallones NMS (GFNMS), Monterey Bay NMS (MBNMS), and Channel Islands NMS (CINMS). Collection of flatfish via hook-and-line for fish-tissue contaminant analysis was successful at 50 EMAP/NCA-West stations. Through a collaboration developed with the FRAM Division of the Northwest Fisheries Science Center, fish from an additional 63 stations in the same region and depth range were also analyzed for fish-tissue contaminants. Bottom depth throughout the region ranged from 28 m to 125 m for most stations. Two slightly deeper stations from the Southern California Bight (SCB) (131, 134 m) were included in the data set. About 44% of the survey area had sediments composed of sands (< 20% silt-clay), about 47% was composed of intermediate muddy sands (20-80% silt-clay), and about 9% was composed of muds (> 80% silt-clay). The majority of the survey area (97%) had relatively low percent total organic carbon (TOC) levels of < 2%, while a small portion (< 1%) had high TOC levels (> 5%), in a range potentially harmful to benthic fauna. Salinity of surface waters for 92% of the survey area were > 31 psu, with most stations < 31 psu associated with the Columbia River plume. Bottom salinities ranged only between 31.6 and 34.4 psu. There was virtually no difference in mean bottom salinities among states or between NMS and non-NMS stations. Temperatures of surface water (range 8.5 -19.9 °C) and bottom water (range 5.8 -14.7 °C) averaged several degrees higher in CA in comparison to WA and OR. The Δσt index of watercolumn stratification indicated that about 31% of the survey area had strong vertical stratification of the water column. The index was greatest for waters off WA and lowest for CA waters. Only about 2.6 % of the survey area had surface dissolved oxygen (DO) concentrations ≤ 4.8 mg/L, and there were no values below the lower threshold (2.3 mg/L) considered harmful to the survival and growth of marine animals. Surface DO concentrations were higher in WA and OR waters than in CA, and higher in the OC NMS than in the CA sanctuaries. An estimated 94.3% of the area had bottom-water DO concentrations ≤ 4.8 mg/L and 6.6% had concentrations ≤ 2.3 mg/L. The high prevalence of DO from 2.3 to 4.8 mg/L (85% of survey area) is believed to be associated with the upwelling of naturally low DO water across the West Coast shelf. Mean TSS and transmissivity in surface waters (excluding OR due to sample problems) were slightly higher and lower, respectively, for stations in WA than for those in CA. There was little difference in mean TSS or transmissivity between NMS and non-NMS locations. Mean transmissivity in bottom waters, though higher in comparison to surface waters, showed little difference among geographic regions or between NMS and non-NMS locations. Concentrations of nitrate + nitrite, ammonium, total dissolved inorganic nitrogen (DIN) and orthophosphate (P) in surface waters tended to be highest in CA compared to WA and OR, and higher in the CA NMS stations compared to CA non-sanctuary stations. Measurements of silicate in surface waters were limited to WA and CA (exclusive of the SCB) and showed that concentrations were similar between the two states and approximately twice as high in CA sanctuaries compared to OCNMS or nonsanctuary locations in either state. The elevated nutrient concentrations observed at CA NMS stations are consistent with the presence of strong upwelling at these sites at the time of sampling. Approximately 93% of the area had DIN/P values ≤ 16, indicative of nitrogen limitation. Mean DIN/P ratios were similar among the three states, although the mean for the OCNMS was less than half that of the CA sanctuaries or nonsanctuary locations. Concentrations of chlorophyll a in surface waters ranged from 0 to 28 μg L-1, with 50% of the area having values < 3.9 μg L-1 and 10% having values > 14.5 μg L-1. The mean concentration of chlorophyll a for CA was less than half that of WA and OR locations, and concentrations were lowest in non-sanctuary sites in CA and highest at the OCNMS. Shelf sediments throughout the survey area were relatively uncontaminated with the exception of a group of stations within the SCB. Overall, about 99% of the total survey area was rated in good condition (<5 chemicals measured above corresponding effect range low (ERL) concentrations). Only the pesticides 4,4′-DDE and total DDT exceeded corresponding effect range-median (ERM) values, all at stations in CA near Los Angeles. Ten other contaminants including seven metals (As, Cd, Cr, Cu, Hg, Ag, Zn), 2-methylnaphthalene, low molecular weight PAHs, and total PCBs exceeded corresponding ERLs. The most prevalent in terms of area were chromium (31%), arsenic (8%), 2-methylnaphthalene (6%), cadmium (5%), and mercury (4%). The chromium contamination may be related to natural background sources common to the region. The 2-methylnaphthalene exceedances were conspicuously grouped around the CINMS. The mercury exceedances were all at non-sanctuary sites in CA, particularly in the Los Angeles area. Concentrations of cadmium in fish tissues exceeded the lower end of EPA’s non-cancer, human-health-risk range at nine of 50 EMAP/NCA-West and nine of 60 FRAM groundfish-survey stations, including a total of seven NMS stations in CA and two in the OCNMS. The human-health guidelines for all other contaminants were only exceeded for total PCBs at one station located in WA near the mouth of the Columbia River. Benthic species richness was relatively high in these offshore assemblages, ranging from 19 to 190 taxa per 0.1-m2 grab and averaging 79 taxa/grab. The high species richness was reflected over large areas of the shelf and was nearly three times greater than levels observed in estuarine samples along the West Coast (e.g NCA-West estuarine mean of 26 taxa/grab). Mean species richness was highest off CA (94 taxa/grab) and lower in OR and WA (55 and 56 taxa/grab, respectively). Mean species richness was very similar between sanctuary vs. non-sanctuary stations for both the CA and OR/WA regions. Mean diversity index H′ was highest in CA (5.36) and lowest in WA (4.27). There were no major differences in mean H′ between sanctuary vs. nonsanctuary stations for both the CA and OR/WA regions. A total of 1,482 taxa (1,108 to species) and 99,135 individuals were identified region-wide. Polychaetes, crustaceans and molluscs were the dominant taxa, both by percent abundance (59%, 17%, 12% respectively) and percent species (44%, 25%, 17%, respectively). There were no major differences in the percent composition of benthic communities among states or between NMSs and corresponding non-sanctuary sites. Densities averaged 3,788 m-2, about 30% of the average density for West Coast estuaries. Mean density of benthic fauna in the present offshore survey, averaged by state, was highest in CA (4,351 m-2) and lowest in OR (2,310 m-2). Mean densities were slightly higher at NMS stations vs. non-sanctuary stations for both the CA and OR/WA regions. The 10 most abundant taxa were the polychaetes Mediomastus spp., Magelona longicornis, Spiophanes berkeleyorum, Spiophanes bombyx, Spiophanes duplex, and Prionospio jubata; the bivalve Axinopsida serricata, the ophiuroid Amphiodia urtica, the decapod Pinnixa occidentalis, and the ostracod Euphilomedes carcharodonta. Mediomastus spp. and A. serricata were the two most abundant taxa overall. Although many of these taxa have broad geographic distributions throughout the region, the same species were not ranked among the 10 most abundant taxa consistently across states. The closest similarities among states were between OR and WA. At least half of the 10 most abundant taxa in NMSs were also dominant in corresponding nonsanctuary waters. Many of the abundant benthic species have wide latitudinal distributions along the West Coast shelf, with some species ranging from southern CA into the Gulf of Alaska or even the Aleutians. Of the 39 taxa on the list of 50 most abundant taxa that could be identified to species level, 85% have been reported at least once from estuaries of CA, OR, or WA exclusive of Puget Sound. Such broad latitudinal and estuarine distributions are suggestive of wide habitat tolerances. Thirteen (1.2%) of the 1,108 identified species are nonindigenous, with another 121 species classified as cryptogenic (of uncertain origin), and 208 species unclassified with respect to potential invasiveness. Despite uncertainties of classification, the number and densities of nonindigenous species appear to be much lower on the shelf than in the estuarine ecosystems of the Pacific Coast. Spionid polychaetes and the ampharetid polychaete Anobothrus gracilis were a major component of the nonindigenous species collected on the shelf. NOAA’s five NMSs along the West Coast of the U.S. appeared to be in good ecological condition, based on the measured indicators, with no evidence of major anthropogenic impacts or unusual environmental qualities compared to nearby nonsanctuary waters. Benthic communities in sanctuaries resembled those in corresponding non-sanctuary waters, with similarly high levels of species richness and diversity and low incidence of nonindigenous species. Most oceanographic features were also similar between sanctuary and non-sanctuary locations. Exceptions (e.g., higher concentrations of some nutrients in sanctuaries along the CA coast) appeared to be attributable to natural upwelling events in the area at the time of sampling. In addition, sediments within the sanctuaries were relatively uncontaminated, with none of the samples having any measured chemical in excess of ERM values. The ERL value for chromium was exceeded in sediments at the OCNMS, but at a much lower percentage of stations (four of 30) compared to WA and OR non-sanctuary areas (31 of 70 stations). ERL values were exceeded for arsenic, cadmium, chromium, 2- methylnaphthalene, low molecular weight PAHs, total DDT, and 4,4′-DDE at multiple sites within the CINMS. However, cases where total DDT, 4,4′-DDE, and chromium exceeded the ERL values were notably less prevalent at CINMS than in non-sanctuary waters of CA. In contrast, 2-methylnaphthalene above the ERL was much more prevalent in sediments at the CINMS compared to non-sanctuary waters off the coast of CA. While there are natural background sources of PAHs from oil seeps throughout the SCB, this does not explain the higher incidence of 2-methylnaphthalene contamination around CINMS. Two stations in CINMS also had levels of TOC (> 5%) potentially harmful to benthic fauna, though none of these sites exhibited symptoms of impaired benthic condition. This study showed no major evidence of extensive biological impacts linked to measured stressors. There were only two stations, both in CA, where low numbers of benthic species, diversity, or total faunal abundance co-occurred with high sediment contamination or low DO in bottom water. Such general lack of concordance suggests that these offshore waters are currently in good condition, with the lower-end values of the various biological attributes representing parts of a normal reference range controlled by natural factors. Results of multiple linear regression, performed using full model procedures to test for effects of combined abiotic environmental factors, suggested that latitude and depth had significant influences on benthic variables regionwide. Latitude had a significant inverse influence on all three of the above benthic variables, i.e. with values increasing as latitude decreased (p< 0.01), while depth had a significant direct influence on diversity (p < 0.001) and inverse effect on density (p <0.01). None of these variables varied significantly in relation to sediment % fines (at p< 0.1), although in general there was a tendency for muddier sediments (higher % fines) to have lower species richness and diversity and higher densities than coarser sediments. Alternatively, it is possible that for some of these sites the lower values of benthic variables reflect symptoms of disturbance induced by other unmeasured stressors. The indicators in this study included measures of stressors (e.g., chemical contaminants, eutrophication) that are often associated with adverse biological impacts in shallower estuarine and inland ecosystems. However, there may be other sources of humaninduced stress in these offshore systems (e.g., bottom trawling) that pose greater risks to ambient living resources and which have not been captured. Future monitoring efforts in these offshore areas should include indicators of such alternative sources of disturbance. (137pp.) (PDF contains 167 pages)

Contaminant trends in US National Estuarine Research Reserves

Inputs of toxic chemicals provide one of the major types of anthropogenic stress threatening our Nation's coastal and estuarine waters. To assess this threat, the National Oceanic and Atmospheric Administration's (NOAA’s) National Status and Trends (NS&T) Program Mussel Watch Project monitors the concentrations of more than 70 toxic chemicals in sediments and on the whole soft-parts of mussels and oysters at over 300 sites around the U.S. Twenty of the 25 designated areas that comprise NOAA's National Estuarine Research Reserve System (NERRS) have one or more Mussel Watch monitoring sites. Trace elements and organic contaminants were quantified including As, Ag, Cd, Cu, Hg, Ni, Pb, Zn, ΣPCBs, ΣPAHs, DDT and its metabolites, and butyltins. The Mussel Watch sites located in or near the 20 Reserves provide for both status and trends. Generally the Reserves have trace element and organic contaminant concentrations that are at or below the median concentration determined for all NS&T Mussel Watch monitoring data. Trends were derived using the Spearman-rank correlation coefficient. It was possible to determine if trends exist for sites at which six or more years of data are available. Generally no trends were found for trace elements but when trends were found they were usually decreasing. The same general conclusion holds for organic contaminants but more decreasing trends were found than for trace elements. The greatest number of decreasing trends were found for tributyltin and its metabolites. (PDF contains 203 pages)

Nutritional and anti-nutritional analyses of Azolla africana Desv. and Spirodela polyrrhiza L. Schleiden as feedstuffs for fish production

The chemical composition of Azolla africana and Spirodela polyrrhiza cultivated in earthen ponds were determined. Crude protein contents of the samples were 28.9~c0.6 and 25.6~c0.2% dry matter for A. africana and S. polyrrhiza respectively. Dry matter, crude fibre and lipid contents of A. africana were higher (P<0.05) than values obtained for S. polyrrhiza. Mineral analyses showed that S. polyrrhiza contained higher levels of Na, S, Ca, Mg and Fe than A. africana. Except for Ca content in S. polyrrhiza, heavy metals (Ni and Zn) accumulation in Azolla were very high. There were no wide differences in the individual amino acid indexes except for methionine. Some anti-nutritional factors were determined. Cyanide, tannin and phytin contents of fresh weed samples were higher than sun-dried samples. A. africana contained more cyanide and tannin than S. polyrrhiza both in fresh and sun-dried forms

Transport of pollutants through the water and subsurface soil using simulated acid rain

The mobility of heavy metals (Zn, Cd, Pb and Ni) was studied in the laboratory acidic leaching two different soils around Ibadan with simulated acid rain. The sampling was carried out from two different sites viz: Orogun and Ilupeju respectively. For Orogun site a depth of 128cm was reached (consisting of four horizons). Different length of polyvinyl chloride (PVC) pipes were cut for different soil horizon depth as observed on the field. The PVC pipes were packed with requires masses of soil. This is then leached using simulated acid rain of different pH of 2.0, 4.0, 6.0 and 8.0 after spiking with known volume of standard solution of metals of interest. It was found that simulated acid rain enhanced the mobility of metals in solution. The pH, Cation Exchange capacity, % clay and organic matter were found to contributed majority to the mobility of metals. Generally as observed, the mobility of metal was to follow the order Zn>Ni>Pb>Cd as the soil is becoming more acidic

Evaluation of the body burdens of heavy metals in five commercially important fishes from different locations in Kainji Lake

The level and distribution of some heavy metals viz Cadmium, Lead, Copper Zinc, and Cobalt in five commercially important fishes, water and sediments at three different locations in Kainj Lake were determined using standard methods. The results show that the ranges of heavy metals mu g/g in fishes in Dam site Laotian are: Cd (0.05~c0.01-20~c01), (Pb(ND-1.12 plus or minus )1), Cu (0.81~c25-2.93~c06), Zn (20.89 arrow right .15-36.78~c2.97), Co(0.08~c01-0.27~c02); in cover Dam, the ranges are Cd (0.04~c02-0.16~c0.2), Pb (nd-02~c01), Cu(0.75~c05-2.61~c13), Zn(15.70~c1.55-32.23~c2.70), Co(0.04~c02-0.25~c0.01) and in Yuna they are Cd (0.05~c01-0.14~c02), Pb (nd-0.32~c01), Cu (0.23~c07-2.70~c05), Zn(15.50 plus or minus `.35-25.62~c2.47), Co(0.07~c02-23~c0.01). The metals concentration (mg/l) in the water sample from Dam site, cover dam and Yuna respectively are Cd(0.007~c001,. 004~c001 and 0.005~001), Pb(013~c001, ND and ND), Cu(.055~c008.030~c007, 05 plus or minus .010), Zn(0.13~c01, 0.060 plus or minus .0055) and Co (.026 plus or minus .022 plus or minus .004, .024 plus or minus .004), while the metals concentration ( mu g/g) in sediments sample from Dam site, cover dam and Yuna are respectively Cd(.05 plus or minus .01, .02 plus or minus .01), Pb(16.00~c1.00, ND and 9.33~c1.01), Cu(24.00~c1.34, 4.26 plus or minus .91 and 11.08~c1.32), Zn(42.00~c1.00, 35~c10 and 38.00 plus or minus .45), Co(15.00~c1.17, 8.69~c1.21 and 10.91~c44). The concentrations of the tested heavy metals are within the acceptable standards of WHO (1987a)

Some aspects of the limnology of Makwaye (Ahmadu Bello University) Lake, Samaru, Zaria

The monthly variations in the physico-chemical parameters and zooplankton abundance were followed from December, 2003 to March 2004 in Makwaye (Ahmadu Bello University Farm) Lake, Samaru, Zaria. In this lake, all physico-chemical parameters investigated showed wide variations within the months except hardness, which exhibited highly significant variation both between stations and within months. Chemical variables including Na, Mg, Zn, Pb, Fe, K and Cu showed significant variations within the months. Three groups namely Cladocera (32.62%), Rotifera (29.33%) and Copepoda (38.05%) were observed. These indicated low species richness

Structure, chemistry, and energetics of organic and inorganic adsorbates on Ga-rich GaAs and GaP(001) surfaces

The work described in this dissertation includes fundamental investigations into three surface processes, namely inorganic film growth, water-induced oxidation, and organic functionalization/passivation, on the GaP and GaAs(001) surfaces. The techniques used to carry out this work include scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Atomic structure, electronic structure, reaction mechanisms, and energetics related to these surface processes are discussed at atomic or molecular levels.

First, we investigate epitaxial Zn₃P₂ films grown on the Ga-rich GaAs(001)(6×6) surface. The film growth mechanism, electronic properties, and atomic structure of the Zn₃P₂/GaAs(001) system are discussed based on experimental and theoretical observations. We discover that a P-rich amorphous layer covers the crystalline Zn3P2 film during and after growth. We also propose more accurate picture of the GaP interfacial layer between Zn₃P₂ and GaAs, based on the atomic structure, chemical bonding, band diagram, and P-replacement energetics, than was previously anticipated.

Second, DFT calculations are carried out in order to understand water-induced oxidation mechanisms on the Ga-rich GaP(001)(2×4) surface. Structural and energetic information of every step in the gaseous water-induced GaP oxidation reactions are elucidated at the atomic level in great detail. We explore all reasonable ground states involved in most of the possible adsorption and decomposition pathways. We also investigate structures and energies of the transition states in the first hydrogen dissociation of a water molecule on the (2×4) surface.

Finally, adsorption structures and thermal decomposition reactions of 1-propanethiol on the Ga-rich GaP(001)(2×4) surface are investigated using high resolution STM, XPS, and DFT simulations. We elucidate adsorption locations and their associated atomic structures of a single 1-propanethiol molecule on the (2×4) surface as a function of annealing temperature. DFT calculations are carried out to optimize ground state structures and search transition states. XPS is used to investigate variations of the chemical bonding nature and coverage of the adsorbate species.

Chain-forming zintl antimonides as novel thermoelectric materials

Zintl phases, a subset of intermetallic compounds characterized by covalently-bonded "sub-structures," surrounded by highly electropositive cations, exhibit precisely the characteristics desired for thermoelectric applications. The requirement that Zintl compounds satisfy the valence of anions through the formation of covalent substructures leads to many unique, complex crystal structures. Such complexity often leads to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical modes in the phonon dispersion. To date, excellent thermoelectric properties have been demonstrated in several Zintl compounds. However, compared with the large number of known Zintl phases, very few have been investigated as thermoelectric materials.

From this pool of uninvestigated compounds, we selected a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked MSb₄ tetrahedra, where $M$ is a triel element. The compounds discussed in this thesis (A₅M₂Sb₆ and A₃MSb₃, where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related "chain-forming" structure types. This thesis describes the thermoelectric characterization and optimization of these phases, and explores the influence of their chemistry and structure on the thermal and electronic transport properties. Due to their large unit cells, each compound exhibits exceptionally low lattice thermal conductivity (0.4 - 0.6 W/mK at 1000 K), approaching the predicted glassy minimum at high temperatures. A combination of Density Functional calculations and classical transport models were used to explain the experimentally observed electronic transport properties of each compound. Consistent with the Zintl electron counting formalism, A₅M₂Sb₆ and A₃MSb₃ phases were found to have filled valence bands and exhibit intrinsic electronic properties. Doping with divalent transition metals (Zn²⁺ and Mn²⁺) on the M³⁺ site, or Na¹⁺ on the A³⁺ site allowed for rational control of the carrier concentration and a transition towards degenerate semiconducting behavior. In optimally-doped samples, promising peak zT values between 0.4 and 0.9 were obtained, highlighting the value of continued investigations of complex Zintl phases.

Trace metals in fresh water plankton

The uptake of Cu, Zn, and Cd by fresh water plankton was studied by analyzing samples of water and plankton from six lakes in southern California. Co, Pb, Mn, Fe, Na, K, Mg, Ca, Sr, Ba, and Al were also determined in the plankton samples. Special precautions were taken during sampling and analysis to avoid metal contamination.

The relation between aqueous metal concentrations and the concentrations of metals in plankton was studied by plotting aqueous and plankton metal concentrations vs time and comparing the plots. No plankton metal plot showed the same changes as its corresponding aqueous metal plot, though long-term trends were similar. Thus, passive sorption did not completely explain plankton metal uptake.

The fractions of Cu, Zn, and Cd in lake water which were associated with plankton were calculated and these fractions were less than 1% in every case.

To see whether or not plankton metal uptake could deplete aqueous metal concentrations by measurable amounts (e.g. 20%) in short periods (e.g. less than six days), three integrated rate equations were used as models of plankton metal sorption. Parameters for the equations were taken from actual field measurements. Measurable reductions in concentration within short times were predicted by all three equations when the concentration factor was greater than 10^5. All Cu concentration factors were less than 10^5.

The role of plankton was regulating metal concentrations considered in the context of a model of trace metal chemistry in lakes. The model assumes that all particles can be represented by a single solid phase and that the solid phase controls aqueous metal concentrations. A term for the rate of in situ production of particulate matter is included and primary productivity was used for this parameter. In San Vicente Reservoir, the test case, the rate of in situ production of particulate matter was of the same order of magnitude as the rate of introduction of particulate matter by the influent stream.

Digested sludge: delineation and modeling for ocean disposal

Experimental work was performed to delineate the system of digested sludge particles and associated trace metals and also to measure the interactions of sludge with seawater. Particle-size and particle number distributions were measured with a Coulter Counter. Number counts in excess of 10¹² particles per liter were found in both the City of Los Angeles Hyperion mesophilic digested sludge and the Los Angeles County Sanitation Districts (LACSD) digested primary sludge. More than 90 percent of the particles had diameters less than 10 microns.

Total and dissolved trace metals (Ag, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were measured in LACSD sludge. Manganese was the only metal whose dissolved fraction exceeded one percent of the total metal. Sedimentation experiments for several dilutions of LACSD sludge in seawater showed that the sedimentation velocities of the sludge particles decreased as the dilution factor increased. A tenfold increase in dilution shifted the sedimentation velocity distribution by an order of magnitude. Chromium, Cu, Fe, Ni, Pb, and Zn were also followed during sedimentation. To a first approximation these metals behaved like the particles.

Solids and selected trace metals (Cr, Cu, Fe, Ni, Pb, and Zn) were monitored in oxic mixtures of both Hyperion and LACSD sludges for periods of 10 to 28 days. Less than 10 percent of the filterable solids dissolved or were oxidized. Only Ni was mobilized away from the particles. The majority of the mobilization was complete in less than one day.

The experimental data of this work were combined with oceanographic, biological, and geochemical information to propose and model the discharge of digested sludge to the San Pedro and Santa Monica Basins. A hydraulic computer simulation for a round buoyant jet in a density stratified medium showed that discharges of sludge effluent mixture at depths of 730 m would rise no more than 120 m. Initial jet mixing provided dilution estimates of 450 to 2600. Sedimentation analyses indicated that the solids would reach the sediments within 10 km of the point discharge.

Mass balances on the oxidizable chemical constituents in sludge indicated that the nearly anoxic waters of the basins would become wholly anoxic as a result of proposed discharges. From chemical-equilibrium computer modeling of the sludge digester and dilutions of sludge in anoxic seawater, it was predicted that the chemistry of all trace metals except Cr and Mn will be controlled by the precipitation of metal sulfide solids. This metal speciation held for dilutions up to 3000.

The net environmental impacts of this scheme should be salutary. The trace metals in the sludge should be immobilized in the anaerobic bottom sediments of the basins. Apparently no lifeforms higher than bacteria are there to be disrupted. The proposed deep-water discharges would remove the need for potentially expensive and energy-intensive land disposal alternatives and would end the discharge to the highly productive water near the ocean surface.

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.