Investigations into enhanced wax production with combustion synthesized Fischer-Tropsch catalysts

Combustion synthesized (CS) cobalt catalysts deposited over two supports, alumina and silica doped alumina (SDA), were characterized and tested for its Fischer-Tropsch (FT) activity. The properties of CS catalysts were compared to catalysts synthesized by conventional impregnation method (IWI). The CS catalysts resulted in 40-70% increase in the yield of C6+ hydrocarbons compared to MI catalysts. The FT activity for CS catalysts showed formation of long chain hydrocarbon waxes (C24+) compared to the formation of middle distillates (C-10-C-20) for IWI synthesized catalysts, indicating higher hydrocarbon chain growth probability for CS catalysts. This is ascribed to the smaller crystallite sizes, increased degree of cobalt reduction and consequentially, a higher number of active metal sites, exposed over the catalyst surface. Additionally, 12-13% increase in the overall C6+ hydrocarbon yield is realized for SDA-CS catalysts, compared to Al2O3-CS catalysts. The improved performance of CS-SDA catalysts is attributed to 48% increase in cobalt dispersion compared to Al2O3 supported CS catalysts, which is again caused by the decrease in the cobalt -support interaction for SDA supports. The metal support interactions were analyzed using XPS and H-2 TPR-TPD experiments. Combustion method produced catalysts with smaller crystallite size (17-18 nm), higher degree of reduction (similar to 92%) and higher metal dispersion (16.1%) compared to the IWI method. Despite its enhanced properties, the CS catalysts require prominently higher reduction temperatures (similar to 1100-1200 K). The hydrocarbon product analysis for Al2O3 supported catalyst showed higher paraffin wax concentrations compared to SDA supported catalysts, due to the lower surface basicity of Al2O3. This work reveals the impact of the CS catalysts and the nature of support on FT activity and hydrocarbon product spectrum. (C) 2016 Elsevier Ltd. All rights reserved.

A novel, sensitive potentiometric hydrocarbon sensor for high-vacuum applications.

A potentiometric device based on interfacing a solid electrolyte oxygen ion conductor with a thin platinum film acts as a robust, reproducible sensor for the detection of hydrocarbons in high- or ultrahigh-vacuum environments. Sensitivities in the order of approximately 5 x 10(-10) mbar are achievable under open circuit conditions, with good selectivity for discrimination between n-butane on one hand and toluene, n-octane, n-hexane, and 1-butene on the other hand. The sensor's sensitivity may be tuned by operating under constant current (closed circuit) conditions; injection of anodic current is also a very effective means of restoring a clean sensing surface at any desired point. XPS data and potentiometric measurements confirm the proposed mode of sensing action: the steady-state coverage of Oa, which sets the potential of the Pt sensing electrode, is determined by the partial pressure and dissociative sticking probability of the impinging hydrocarbon. The principles established here provide the basis for a viable, inherently flexible, and promising means for the sensitive and selective detection of hydrocarbons under demanding conditions.

One possible way to promote the bond-selective chemical-reactions by frequency-modulated lasers

It is proposed in this paper that we can use frequency-modulated (FM) lasers to realize bond-selective chemical reactions or to raise the efficiency of molecular isotope separation. Examples are given for HF molecule and the C–H bond in some hydrocarbons.

Proceedings of the Workshop on the Okhotsk Sea and Adjacent Areas [Vladivostok, June 1995]

I REPORT OF THE PICES WORKSHOP ON THE OKHOTSK SEA AND ADJACENT AREAS (pdf, 0.1 Mb) 1. Outline of the workshop 2. Summary reports from sessions 3. Recommendations of the workshop 4. Acknowledgments II SCIENTIFIC PAPERS SUBMITTED FROM SESSIONS 1. Physical Oceanography Sessions (pdf, 4 Mb) A. Circulation and water mass structure of the Okhotsk Sea and Northwestern Pacific Valentina D. Budaeva & Vyacheslav G. Makarov Seasonal variability of the pycnocline in La Perouse Strait and Aniva Gulf Valentina D. Budaeva & Vyacheslav G. Makarov Modeling of the typical water circulations in the La Perouse Strait and Aniva Gulf region Nina A. Dashko, Sergey M. Varlamov, Young-Ho Han & Young-Seup Kim Anticyclogenesis over the Okhotsk Sea and its influence on weather Boris S. Dyakov, Alexander A. Nikitin & Vadim P. Pavlychev Research of water structure and dynamics in the Okhotsk Sea and adjacent Pacific Howard J. Freeland, Alexander S. Bychkov, C.S. Wong, Frank A. Whitney & Gennady I. Yurasov The Ohkotsk Sea component of Pacific Intermediate Water Emil E. Herbeck, Anatoly I. Alexanin, Igor A. Gontcharenko, Igor I. Gorin, Yury V. Naumkin & Yury G. Proshjants Some experience of the satellite environmental support of marine expeditions at the Far East Seas Alexander A. Karnaukhov The tidal influence on the Sakhalin shelf hydrology Yasuhiro Kawasaki On the formation process of the subsurface mixed water around the Central Kuril Islands Lloyd D. Keigwin Northwest Pacific paleohydrography Talgat R. Kilmatov Physical mechanisms for the North Pacific Intermediate Water formation Vladimir A. Luchin Water masses in the Okhotsk Sea Andrey V. Martynov, Elena N. Golubeva & Victor I. Kuzin Numerical experiments with finite element model of the Okhotsk Sea circulation Nikolay A. Maximenko, Anatoly I. Kharlamov & Raissa I. Gouskina Structure of Intermediate Water layer in the Northwest Pacific Nikolay A. Maximenko & Andrey Yu. Shcherbina Fine-structure of the North Pacific Intermediate Water layer Renat D. Medjitov & Boris I. Reznikov An experimental study of water transport through the Straits of Okhotsk Sea by electromagnetic method Valentina V. Moroz Oceanological zoning of the Kuril Islands area in the spring-summer period Yutaka Nagata Note on the salinity balance in the Okhotsk Sea Alexander D. Nelezin Variability of the Kuroshio Front in 1965-1991 Vladimir I. Ponomarev, Evgeny P. Varlaty & Mikhail Yu. Cheranyev An experimental study of currents in the near-Kuril region of the Pacific Ocean and in the Okhotsk Sea Stephen C. Riser, Gennady I. Yurasov & Mark J. Warner Hydrographic and tracer measurements of the water mass structure and transport in the Okhotsk Sea in early spring Konstantin A. Rogachev & Andrey V. Verkhunov Circulation and water mass structure in the southern Okhotsk Sea, as observed in summer, 1994 Lynne D. Talley North Pacific Intermediate Water formation and the role of the Okhotsk Sea Anatoly S. Vasiliev & Fedor F. Khrapchenkov Seasonal variability of integral water circulation in the Okhotsk Sea B. Sea ice and its relation to circulation and climate V.P. Gavrilo, G.A. Lebedev & A.P. Polyakov Acoustic methods in sea ice dynamics studies Nina M. Pestereva & Larisa A. Starodubtseva The role of the Far-East atmospheric circulation in the formation of the ice cover in the Okhotsk Sea Yoshihiko Sekine Anomalous Oyashio intrusion and its teleconnection with Subarctic North Pacific circulation, sea ice of the Okhotsk Sea and air temperature of the northern Asian continent C. Waves and tides Vladimir A. Luchin Characteristics of the tidal motions in the Kuril Straits George V. Shevtchenko On seasonal variability of tidal constants in the northwestern part of the Okhotsk Sea D. Physical oceanography of the Japan Sea/East Sea Mikhail A. Danchenkov, Kuh Kim, Igor A. Goncharenko & Young-Gyu Kim A “chimney” of cold salt waters near Vladivostok Christopher N.K. Mooers & Hee Sook Kang Preliminary results from a numerical circulation model of the Japan Sea Lev P. Yakunin Influence of ice production on the deep water formation in the Japan Sea 2. Fisheries and Biology Sessions (pdf, 2.8 Mb) A. Communities of the Okhotsk Sea and adjacent waters: composition, structure and dynamics Lubov A. Balkonskaya Exogenous succession of the southwestern Sakhalin algal communities Tatyana A. Belan, Yelena V. Oleynik, Alexander V. Tkalin & Tat’yana S. Lishavskaya Characteristics of pelagic and benthic communities on the North Sakhalin Island shelf Lev N. Bocharov & Vladimir K. Ozyorin Fishery and oceanographic database of Okhotsk Sea Victor V. Lapko Interannual dynamics of the epipelagic ichthyocen structure in the Okhotsk Sea Valentina I. Lapshina Quantitative seasonal and year-to-year changes of phytoplankton in the Okhotsk Sea and off Kuril area of the Pacific Lyudmila N. Luchsheva Biological productivity in anomalous mercury conditions (northern part of Okhotsk Sea) Inna A. Nemirovskaya Origin of hydrocarbons in the ecosystems of coastal region of the Okhotsk Sea Tatyana A. Shatilina Elements of the Pacific South Kuril area ecosystem Vyacheslav P. Shuntov & Yelena P. Dulepova Biota of the Okhotsk Sea: Structure of communities, the interannual dynamics and current status B. Abundance, distribution, dynamics of the common fishes of the Okhotsk Sea Yuri P. Diakov Influence of some abiotic factors on spatial population dynamics of the West Kamchatka flounders (Pleuronectidae) Gordon A. McFarlane, Richard J. Beamish & Larisa M. Zverkova An examination of age estimates of walleye pollock (Theragra chalcogramma) from the Sea of Okhotsk using the burnt otolith method and implications for stock assessment and management Larisa P. Nikolenko Migration of Greenland turbot (Reinhardtius hippoglossoides) in the Okhotsk Sea Galina M. Pushnikova Fisheries impact on the Sakhalin-Hokkaido herring population Vidar G. Wespestad Is pollock overfished? C. Salmon of the Okhotsk Sea: biology, abundance and stock identification Vladimir A. Belyaev, Alexander Yu. Zhigalin Epipelagic Far Eastern sardine of the Okhotsk Sea Yuri E. Bregman, Victor V. Pushnikov, Lyudmila G. Sedova & Vladimir Ph. Ivanov A preliminary report on stock status and productive capacity of horsehair crab Erimacrus isenbeckii (Brandt) in the South Kuril Strait Natalia T. Dolganova Mezoplankton distribution in the West Japan Sea Vladimir V. Efremov, Richard L. Wilmot, Christine M. Kondzela, Natalia V. Varnavskaya, Sharon L. Hawkins & Maria E. Malinina Application of pink and chum salmon genetic baseline to fishery management Vyacheslav N. Ivankov & Valentina V. Andreyeva Strategy for culture, breeding and numerous dynamics of Sakhalin salmon populations Alla M. Kovalevskaya, Natalia I. Savelyeva & Dmitry M. Polyakov Primary production in Sakhalin shelf waters Tatyana N. Krupnova Some reasons for resource reduction of Laminaria japonica (Primorye region) Lyudmila N. Luchsheva & Anatoliy I. Botsul Mercury in bottom sediments of the northeastern Okhotsk Sea Pavel A. Luk’yanov, Natalia I. Belogortseva, Alexander A. Bulgakov, Alexander A. Kurika & Olga D. Novikova Lectins and glycosidases from marine macro and micro-organisms of Japan and Okhotsk Seas Boris A. Malyarchuk, Olga A. Radchenko, Miroslava V. Derenko, Andrey G. Lapinski & Leonid L. Solovenchuk PCR-fingerprinting of mitochondrial genome of chum salmon, Oncorhynchus keta Alexander A. Mikheev Chaos and relaxation in dynamics of the pink salmon (Oncorhynchus gorbuscha) returns for two regions Yuri A. Mitrofanov & Larisa N. Lesnikova Fish-culture of Pacific Salmons increases the number of heredity defects Larisa P. Nikolenko Abundance of young halibut along the West Kamchatka shelf in 1982-1992 Sergey A. Nizyaev Living conditions of golden king crab Lithodes aequispina in the Okhotsk Sea and near the Kuril Islands Ludmila A. Pozdnyakova & Alla V. Silina Settlements of Japanese scallop in Reid Pallada Bay (Sea of Japan) Galina M. Pushnikova Features of the Southwest Okhotsk Sea herring Vladimir I. Radchenko & Igor I. Glebov Present state of the Okhotsk herring stock and fisheries outlook Alla V. Silina & Ida I. Ovsyannikova Distribution of the barnacle Balanus rostratus eurostratus near the coasts of Primorye (Sea of Japan) Galina I. Victorovskaya Dependence of urchin Strongylocentrotus intermedius reproduction on water temperature Anatoly F. Volkov, Alexander Y. Efimkin & Valery I. Chuchukalo Feeding habits of Pacific salmon in the Sea of Okhotsk and in the Pacific waters of Kuril Islands in summer 1993 Larisa M. Zverkova & Georgy A. Oktyabrsky Okhotsk Sea walleye pollock stock status Tatyana N. Zvyagintseva, Elena V. Sundukova, Natalia M. Shevchenko & Ludmila A. Elyakova Water soluble polysaccharides of some Far-Eastern seaweeds 3. Biodiversity Program (pdf, 0.2 Mb) A. Biodiversity of island ecosystems and seasides of the North Pacific Larissa A. Gayko Productivity of Japanese scallop Patinopecten yessoensis (IAY) culture in Posieta Bay (Sea of Japan) III APPENDICES 1. List of acronyms 2. List of participants (Document pdf contains 431 pages)

Organic Contaminant Analytical Methods of the National Status and Trends Program: 2000-2006

This document describes the analytical methods used to quantify core organic chemicals in tissue and sediment collected as part of NOAA’s National Status and Trends Program (NS&T) for the years 2000-2006. Organic contaminat analytical methods used during the early years of the program are described in NOAA Technical Memoranda NOS ORCA 71 and 130 (Lauenstein and Cantillo, 1993; Lauenstein and Cantillo, 1998) for the years 1984-1992 and 1993-1996, respectively. These reports are available from our website (http://www.ccma.nos.gov) The methods detailed in this document were utilized by the Mussel Watch Project and Bioeffects Project, which are both part of the NS&T program. The Mussel Watch Project has been monitoring contaminants in bivalves and sediments since 1986 and is the longest active national contaminant monitoring program operating in U.S. costal waters. Approximately 280 Mussel Watch sites are sampled on a biennial and decadal timescale for bivalve tissue and sediment respectively. Similarly, the Bioeffects Assessment Project began in 1986 to characterize estuaries and near coastal environs. Using the sediment quality triad approach that measures; (1) levels of contaminants in sediments, (2) incidence and severity of toxicity, and (3) benthic macrofaunal conmmunities, the Bioeffects Project describes the spatial extent of sediment toxicity. Contaminant assessment is a core function of both projects. These methods, while discussed here in the context of sediment and bivalve tissue, were also used with other matricies including: fish fillet, fish liver, nepheloid layer, and suspended particulate matter. The methods described herein are for the core organic contaminants monitored in the NS&T Program and include polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), butyltins, and organochlorines that have been analyzed consistently over the past 15-20 years. Organic contaminants such as dioxins, perfluoro compounds and polybrominated biphenyl ethers (PBDEs) were analyzed periodically in special studies of the NS&T Program and will be described in another document. All of the analytical techniques described in this document were used by B&B Laboratories, Inc, an affiliate of TDI-Brook International, Inc. in College Station, Texas under contract to NOAA. The NS&T Program uses a performance-based system approach to obtain the best possible data quality and comparability, and requires laboratories to demonstrate precision, accuracy, and sensitivity to ensure results-based performance goals and measures. (PDF contains 75 pages)

An assessment of chemical contaminants in the marine sediments of southwest Puerto Rico

This report summarizes the results of a characterization of chemical contaminants in the sediments in southwest Puerto Rico. The report is part of a project to integrate various analytical specialties to assess linkages between chemical contaminants and the condition of coral reefs. In this phase of the project, over 120 chemical contaminants were analyzed in sediments collected, including a number of organic (e.g., hydrocarbons), inorganic (e.g., metals), and biological (bacterial) compounds/analytes. The report also provides a preliminary analysis of the association between sediment contaminants and coral species richness. Overall, the levels of chemical contaminants in the study area between Guanica Bay and the town of La Parguera were fairly low. At most of the sites sampled, particularly adjacent to the town of La Parguera, concentrations of organic and inorganic contaminants were below the median values from NOAA’s National Status and Trends Program, which monitors the Nation’s coastal and estuarine waters for chemical contaminants. Elevated levels of a number of contaminant classes were seen at the two sites sampled within Guanica Bay. An initial analysis of modeled PAH (hydrocarbon) data and coral species richness (reef building species) indicated a strong negative correlation between the presence of PAHs in the sediments and coral species richness. Additional work is needed to assess possible reasons for this observed pattern. (PDF contains 126 pages).

Sediment Quality in Puget Sound Year 3 - Southern Puget Sound

As a component of a three-year cooperative effort of the Washington State Department of Ecology and the National Oceanic and Atmospheric Administration, surficial sediment samples from 100 locations in southern Puget Sound were collected in 1999 to determine their relative quality based on measures of toxicity, chemical contamination, and benthic infaunal assemblage structure. The survey encompassed an area of approximately 858 km2, ranging from East and Colvos Passages south to Oakland Bay, and including Hood Canal. Toxic responses were most severe in some of the industrialized waterways of Tacoma’s Commencement Bay. Other industrialized harbors in which sediments induced toxic responses on smaller scales included the Port of Olympia, Oakland Bay at Shelton, Gig Harbor, Port Ludlow, and Port Gamble. Based on the methods selected for this survey, the spatial extent of toxicity for the southern Puget Sound survey area was 0% of the total survey area for amphipod survival, 5.7% for urchin fertilization, 0.2% for microbial bioluminescence, and 5- 38% with the cytochrome P450 HRGS assay. Measurements of trace metals, PAHs, PCBs, chlorinated pesticides, other organic chemicals, and other characteristics of the sediments, indicated that 20 of the 100 samples collected had one or more chemical concentrations that exceeded applicable, effects-based sediment guidelines and/or Washington State standards. Chemical contamination was highest in eight samples collected in or near the industrialized waterways of Commencement Bay. Samples from the Thea Foss and Middle Waterways were primarily contaminated with a mixture of PAHs and trace metals, whereas those from Hylebos Waterway were contaminated with chlorinated organic hydrocarbons. The remaining 12 samples with elevated chemical concentrations primarily had high levels of other chemicals, including bis(2-ethylhexyl) phthalate, benzoic acid, benzyl alcohol, and phenol. The characteristics of benthic infaunal assemblages in south Puget Sound differed considerably among locations and habitat types throughout the study area. In general, many of the small embayments and inlets throughout the study area had infaunal assemblages with relatively low total abundance, taxa richness, evenness, and dominance values, although total abundance values were very high in some cases, typically due to high abundance of one organism such as the polychaete Aphelochaeta sp. N1. The majority of the samples collected from passages, outer embayments, and larger bodies of water tended to have infaunal assemblages with higher total abundance, taxa richness, evenness, and dominance values. Two samples collected in the Port of Olympia near a superfund cleanup site had no living organisms in them. A weight-of-evidence approach used to simultaneously examine all three “sediment quality triad” parameters, identified 11 stations (representing 4.4 km2, 0.5% of the total study area) with sediment toxicity, chemical contamination, and altered benthos (i.e., degraded sediment quality), 36 stations (493.5 km2, 57.5% total study area) with no toxicity or chemical contamination (i.e., high sediment quality), 35 stations (274.1 km2, 32.0% total study area) with one impaired sediment triad parameter (i.e., intermediate/high sediment quality), and 18 stations (85.7km2, 10.0% total study area) with two impaired sediment parameters (i.e., intermediate/degraded quality sediments). Generally, upon comparison, the number of stations with degraded sediments based upon the sediment quality triad of data was slightly greater in the central Puget Sound than in the northern and southern Puget Sound study areas, with the percent of the total study area degraded in each region decreasing from central to north to south (2.8, 1.3 and 0.5%, respectively). Overall, the sediments collected in Puget Sound during the combined 1997-1999 surveys were among the least contaminated relative to other marine bays and estuaries studied by NOAA using equivalent methods. (PDF contains 351 pages)

Magnitude and extent of chemical contamination and toxicity in sediments of Biscayne Bay and vicinity

The toxicity of sediments in Biscayne Bay and many adjoining tributaries was determined as part of a bioeffects assessments program managed by NOAA’s National Status and Trends Program. The objectives of the survey were to determine: (1) the incidence and degree of toxicity of sediments throughout the study area; (2) the spatial patterns (or gradients) in chemical contamination and toxicity, if any, throughout the study area; (3) the spatial extent of chemical contamination and toxicity; and (4) the statistical relationships between measures of toxicity and concentrations of chemicals in the sediments. The survey was designed to characterize sediment quality throughout the greater Biscayne Bay area. Surficial sediment samples were collected during 1995 and 1996 from 226 randomly-chosen locations throughout nine major regions. Laboratory toxicity tests were performed as indicators of potential ecotoxicological effects in sediments. A battery of tests was performed to generate information from different phases (components) of the sediments. Tests were selected to represent a range in toxicological endpoints from acute to chronic sublethal responses. Toxicological tests were conducted to measure: reduced survival of adult amphipods exposed to solid-phase sediments; impaired fertilization success and abnormal morphological development in gametes and embryos, respectively, of sea urchins exposed to pore waters; reduced metabolic activity of a marine bioluminescent bacteria exposed to organic solvent extracts; induction of a cytochrome P-450 reporter gene system in exposures to solvent extracts; and reduced reproductive success in marine copepods exposed to solid-phase sediments. Contamination and toxicity were most severe in several peripheral canals and tributaries, including the lower Miami River, adjoining the main axis of the bay. In the open basins of the bay, chemical concentrations and toxicity generally were higher in areas north of the Rickenbacker Causeway than south of it. Sediments from the main basins of the bay generally were less toxic than those from the adjoining tributaries and canals. The different toxicity tests, however, indicated differences in severity, incidence, spatial patterns, and spatial extent in toxicity. The most sensitive test among those performed on all samples, a bioassay of normal morphological development of sea urchin embryos, indicated toxicity was pervasive throughout the entire study area. The least sensitive test, an acute bioassay performed with a benthic amphipod, indicated toxicity was restricted to a very small percentage of the area. Both the degree and spatial extent of chemical contamination and toxicity in this study area were similar to or less severe than those observed in many other areas in the U.S. The spatial extent of toxicity in all four tests performed throughout the bay were comparable to the “national averages” calculated by NOAA from previous surveys conducted in a similar manner. Several trace metals occurred in concentrations in excess of those expected in reference sediments. Mixtures of substances, including pesticides, petroleum constituents, trace metals, and ammonia, were associated statistically with the measures of toxicity. Substances most elevated in concentration relative to numerical guidelines and associated with toxicity included polychlorinated biphenyls, DDT pesticides, polynuclear aromatic hydrocarbons, hexachloro cyclohexanes, lead, and mercury. These (and other) substances occurred in concentrations greater than effects-based guidelines in the samples that were most toxic in one or more of the tests. (PDF contains 180 pages)

Survey of sediment quality in Sabine Lake, Texas and vicinity

The toxicity of sediments in Sabine Lake, Texas, and adjoining Intracoastal Waterway canals was determined as part of bioeffects assessment studies managed by NOAA’s National Status and Trends Program. The objectives of the survey were to determine: (1) the incidence and degree of toxicity of sediments throughout the study area; (2) the spatial patterns (or gradients) in chemical contamination and toxicity, if any, throughout the study area; (3) the spatial extent of chemical contamination and toxicity; and (4) the statistical relationships between measures of toxicity and concentrations of chemicals in the sediments. Surficial sediment samples were collected during August, 1995 from 66 randomly-chosen locations. Laboratory toxicity tests were performed as indicators of potential ecotoxicological effects in sediments. A battery of tests was performed to generate information from different phases (components) of the sediments. Tests were selected to represent a range in toxicological endpoints from acute to chronic sublethal responses. Toxicological tests were conducted to measure: reduced survival of adult amphipods exposed to solid-phase sediments; impaired fertilization success and abnormal morphological development in gametes and embryos, respectively, of sea urchins exposed to pore waters; reduced metabolic activity of a marine bioluminescent bacteria exposed to organic solvent extracts; and induction of a cytochrome P-450 reporter gene system in exposures to solvent extracts of the sediments. Chemical analyses were performed on portions of each sample to quantify the concentrations of trace metals, polynuclear aromatic hydrocarbons, and chlorinated organic compounds. Correlation analyses were conducted to determine the relationships between measures of toxicity and concentrations of potentially toxic substances in the samples. Based upon the compilation of results from chemical analyses and toxicity tests, the quality of sediments in Sabine Lake and vicinity did not appear to be severely degraded. Chemical concentrations rarely exceeded effects-based numerical guidelines, suggesting that toxicant-induced effects would not be expected in most areas. None of the samples was highly toxic in acute amphipod survival tests and a minority (23%) of samples were highly toxic in sublethal urchin fertilization tests. Although toxic responses occurred frequently (94% of samples) in urchin embryo development tests performed with 100% pore waters, toxicity diminished markedly in tests done with diluted pore waters. Microbial bioluminescent activity was not reduced to a great degree (no EC50 <0.06 mg/ml) and cytochrome P-450 activity was not highly induced (6 samples exceeded 37.1 ug/g benzo[a]pyrene equivalents) in tests done with organic solvent extracts. Urchin embryological development was highly correlated with concentrations of ammonia and many trace metals. Cytochrome P450 induction was highly correlated with concentrations of a number of classes of organic compounds (including the polynuclear aromatic hydrocarbons and chlorinated compounds). (PDF contains 51 pages)

Sampling and analytical methods of the National Status and Trends Program Mussel Watch Project: 1993-1996 Update

Polycyclic aromatic hydrocarbons, butyltins, polychlorinated biphenyls, DDT and metabolites, other chlorinated pesticides, trace and major elements, and a number of measures of contaminant effects are quantified in bivalves and sediments collected as part of the NOAA National Status and Trends (NS&T) Program. This document contains descriptions of some of the sampling and analytical protocols used by NS&T contract laboratories from 1993 through 1996. (PDF contains 257 pages)

Chemical contaminants, pathogen exposure and general health status of live and beach-cast Washington sea otters (Enhydra lutris kenyoni)

Analyses of blood and liver samples from live captured sea otters and liver samples from beachcast sea otter carcasses off the remote Washington coast indicate relatively low exposure to contaminants, but suggest that even at the low levels measured, exposure may be indicated by biomarker response. Evidence of pathogen exposure is noteworthy - infectious disease presents a potential risk to Washington sea otters, particularly due to their small population size and limited distribution. During 2001 and 2002, 32 sea otters were captured, of which 28 were implanted with transmitters to track their movements and liver and blood samples were collected to evaluate contaminant and pathogen exposure. In addition, liver samples from fifteen beachcast animals that washed ashore between 1991 and 2002 were analyzed to provide historical information and a basis of reference for values obtained from live otters. The results indicate low levels of metals, butyltins, and organochlorine compounds in the blood samples, with many of the organochlorines not detected except polychlorinated biphenyls (PCBs), and a few aromatic hydrocarbons detected in the liver of the live captured animals. Aliphatic hydrocarbons were measurable in the liver from the live captured animals; however, some of these are likely from biogenic sources. A significant reduction of vitamin A storage in the liver was observed in relation to PCB, dibutyltin and octacosane concentration. A significant and strong positive correlation in vitamin A storage in the liver was observed for cadmium and several of the aliphatic hydrocarbons. Peripheral blood mononuclear cell (PBMC) cytochrome P450 induction was elevated in two of 16 animals and may be potentially related to aliphatic and aromatic hydrocarbon exposure. Mean concentration of total butyltin in the liver of the Washington beach-cast otters was more than 15 times lower than the mean concentration reported by Kannan et al. (1998) for Southern sea otters in California. Organochlorine compounds were evident in the liver of beach-cast animals, despite the lack of large human population centers and development along the Washington coast. Concentrations of PCBs and chlordanes (e.g., transchlordane, cis-chlordane, trans-nonachlor, cis-nonachlor and oxychlordane) in liver of Washington beach-cast sea otters were similar to those measured in Aleutian and California sea otters, excluding those from Monterey Bay, which were higher. Mean concentrations of 1,1,1,- trichloro-2,2-bis(p-chlorophyenyl)ethanes (DDTs) were lower, and mean concentrations of cyclohexanes (HCH, e.g., alpha BHC, beta BHC, delta BHC and gamma BHC) were slightly higher in Washington beach-cast otters versus those from California and the Aleutians. Epidemiologically, blood tests revealed that 80 percent of the otters tested positive for morbillivirus and 60 percent for Toxoplasma, the latter of which has been a significant cause of mortality in Southern sea otters in California. This is the first finding of positive morbillivirus titers in sea otters from the Northeast Pacific. Individual deaths may occur from these diseases, perhaps more so when animals are otherwise immuno-compromised or infected with multiple diseases, but a population-threatening die-off from these diseases singly is unlikely while population immunity remains high. The high frequency of detection of morbillivirus and Toxoplasma in the live otters corresponds well with the cause of death of stranded Washington sea otters reported herein, which has generally been attributable to infectious disease. Washington’s sea otter population continues to grow, with over 1100 animals currently inhabiting Washington waters; however, the rate of growth has slowed over recent years. The population has a limited distribution and has not yet reached its carrying capacity and as such, is still considered at high risk to catastrophic events. (PDF contains 189 pages)

Hydrocarbon sensors for oil spill prevention and response, Seward, Alaska, April 8th-10th, 2008: workshop proceedings

During April 8th-10th, 2008, the Aliance for Coastal Technology (ACT) partner institutions, University of Alaska Fairbanks (UAF), Alaska SeaLife Center (ASLC), and the Oil Spill Recovery Institute (OSRI) hosted a workshop entitled: "Hydrocarbon sensors for oil spill prevention and response" in Seward, Alaska. The main focus was to bring together 29 workshop participants-representing workshop managers, scientists, and technology developers - together to discuss current and future hydrocarbon in-situ, laboratory, and remote sensors as they apply to oil spill prevention and response. [PDF contains 28 pages] Hydrocarbons and their derivatives still remain one of the most important energy sources in the world. To effectively manage these energy sources, proper protocol must be implemented to ensure prevention and responses to oil spills, as there are significant economic and environmental costs when oil spills occur. Hydrocarbon sensors provide the means to detect and monitor oil spills before, during, and after they occur. Capitalizing on the properties of oil, developers have designed in-situ, laboratory, and remote sensors that absorb or reflect the electromagnetic energy at different spectral bands. Workshop participants identified current hydrocarbon sensors (in-situ, laboratory, and remote sensors) and their overall performance. To achieve the most comprehensive understanding of oil spills, multiple sensors will be needed to gather oil spill extent, location, movement, thickness, condition, and classification. No single hydrocarbon sensor has the capability to collect all this information. Participants, therefore, suggested the development of means to combine sensor equipment to effectively and rapidly establish a spill response. As the exploration of oil continues at polar latitudes, sensor equipment must be developed to withstand harsh arctic climates, be able to detect oil under ice, and reduce the need for ground teams because ice extent is far too large of an area to cover. Participants also recognized the need for ground teams because ice extent is far too large of an area to cover. Participants also recognized the need for the U.S. to adopt a multi-agency cooperation for oil spill response, as the majority of issues surounding oil spill response focuses not on the hydrocarbon sensors but on an effective contingency plan adopted by all agencies. It is recommended that the U.S. could model contingency planning based on other nations such as Germany and Norway. Workshop participants were asked to make recommendations at the conclusion of the workshop and are summarized below without prioritization: *Outreach materials must be delivered to funding sources and Congressional delegates regarding the importance of oil spill prevention and response and the development of proper sensors to achieve effective response. *Develop protocols for training resource managers as new sensors become available. *Develop or adopt standard instrument specifications and testing protocols to assist manufacturers in further developing new sensor technology. *As oil exploration continues at polar latitudes, more research and development should be allocated to develop a suite of instruments that are applicable to oil detection under ice.

Der PAH-Metabolit 1-Hydroxypyren in der Galle von Klieschen (Limanda limanda) aus Nord- und Ostsee

Due to their carcinogenic properties, polycyclic aromatic hydrocarbons (PAH) are important environmental contaminants which may lead to increased levels of neoplastic aberrations in fish liver. To measure the PAH contamination of fish, concentrations of PAH metabolites were determined in the bile. The main metabolite 1-hydroxypyrene was determined in concentrations from < 0.8 to 189 ng/ml in bile of dab caught in the North Sea and the Baltic Sea re-spectively. The concentrations are comparable to levels of 1-hydroxypyrene measured in cod and herring from the Baltic Sea. The highest concentrations in dab bile were measured in fish from the inner German Bight and the Kiel Bight.

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Hydrogen-Atom Transfer Photochemistry of Tetrakis(µ-pyrophosphito)diplatinate(II)

In many senses, the hydrogen-atom transfer reactions observed with the triplet excited state of pyrophosphito-bridged platinum(II) dimers resemble the reactions of organic ketone nπ* states. The first two chapters describe our attempts to understand the reactivity differences between these two chromophores. Reactivity of the metal dimers is strongly regulated by the detailed nature of the ligands that ring the axial site, the hydrogen-abstraction center. A hydrogen-bonded network linking the ligands facilitates H-atom transfer quenching with alcohols through the formation of a hydrogen-bonded complex between the alcohol and a dimer. For substrates of equal C-H bond strength that lack a hydroxyl group (e.g., benzyl hydrocarbons), the quenching rate is several orders of magnitude slower.

The shape and size of the axial site, as determined by the ligands, also discriminate among quenchers by their steric characteristics. Very small quenchers quench slowly because of high entropies of activation, while very large ones have large enthalpic barriers. The two effects find a balance with quenchers of "just the right size."

The third chapter discusses the design of a mass spectrometer that uses positron annihilation to ionize neutral molecules. The mass spectrometer creates positron-molecule adducts whose annihilation produces fragmentation products that may yield information on the bonding of positrons in such complexes.