Metals and pesticide levels found in fish taken from Vancouver Lake: memorandum to Steve O'Brien, dated May 19, 1977

The Vancouver Lake Pilot Dredge Study revealed concentrations of certain chemicals which could be of concern: the metals copper, zinc and mercury and the pesticides lindane and aldrin were found in significant amounts. (PDF contains 1 page)

Trace metals -- a potential threat to our fishing industry

Trace metals constitute a major form of water pollutant that can adversely affect fish production. The potentially toxic metals have been identified as lead, zinc, copper, arsenic, antimony, mercury beryllium, barium, cadmium, chromium, nickel, selenium among others. Preliminary laboratory studies have been directed to the determination of traces of lead in the aquatic biota and its toxicity. There are indications that the levels reported in effluents from some of the industries may be above the tolerant limits of local fish species and organisms that make up their food. Metal pollution could become a serious problem to freshwater fisheries in the future as a result of increasing urbanization and industrialization, unless efforts are made to prevent it

Deepwater shorelines

Research has proven that Shoreline Erosion is caused by excess water contained within the shore face. This Research presents an opportunity to control erosion by managing the near shore water table. Our Research on Bogue Banks North Carolina suggests that our buildings and other impervious surfaces collect and concentrate water from storm rain runoff into the surface water table and within the critical beach front water exit point. Presently our Potable Fresh Water is supplied from deep wells located beneath an impervious layer of Marl. After our use, the Waste water is drained into the Surface Aquifer, the combined waste and storm rain water raises the Surface Aquifer water table and produces Erosion. The Deep Aquifers presently supplying our Potable Water have an unknown recharge rate, with increasing reports of Salt Water intrusion. We believe our Vital Fresh water supply system should be modified to supply Reverse Osmosis treatment plants from shallow wells. This will lower the Surface Water Table. These Shallow wells, either horizontal or vertical, might be located within the beach front, adjacent to high erosion risk properties. Beach Drains and Reverse Osmosis Water systems are new and proven technologies. By combining these technologies we can reduce or reverse Shore Erosion, ensure a safe Potable Water supply, reduce requirements for periodic beach nourishment, reduce taxes and protect our property well into the Future. (PDF contains 5 pages)

Using climate extension to assist coastal decision-makers with climate adaptation

Coastal managers need accessible, trusted, tailored resources to help them interpret climate information, identify vulnerabilities, and apply climate information to decisions about adaptation on regional and local levels. For decades, climate scientists have studied the impacts that short term natural climate variability and long term climate change will have on coastal systems. For example, recent estimates based on Intergovernmental Panel on Climate Change (IPCC) warming scenarios suggest that global sea levels may rise 0.5 to 1.4 meters above 1990 levels by 2100 (Rahmstorf 2007; Grinsted, Moore, and Jevrejeva 2009). Many low-lying coastal ecosystems and communities will experience more frequent salt water intrusion events, more frequent coastal flooding, and accelerated erosion rates before they experience significant inundation. These changes will affect the ways coastal managers make decisions, such as timing surface and groundwater withdrawals, replacing infrastructure, and planning for changing land use on local and regional levels. Despite the advantages, managers’ use of scientific information about climate variability and change remains limited in environmental decision-making (Dow and Carbone 2007). Traditional methods scientists use to disseminate climate information, like peer-reviewed journal articles and presentations at conferences, are inappropriate to fill decision-makers’ needs for applying accessible, relevant climate information to decision-making. General guides that help managers scope out vulnerabilities and risks are becoming more common; for example, Snover et al. (2007) outlines a basic process for local and state governments to assess climate change vulnerability and preparedness. However, there are few tools available to support more specific decision-making needs. A recent survey of coastal managers in California suggests that boundary institutions can help to fill the gaps between climate science and coastal decision-making community (Tribbia and Moser 2008). The National Sea Grant College Program, the National Oceanic and Atmospheric Administration's (NOAA) university-based program for supporting research and outreach on coastal resource use and conservation, is one such institution working to bridge these gaps through outreach. Over 80% of Sea Grant’s 32 programs are addressing climate issues, and over 60% of programs increased their climate outreach programming between 2006 and 2008 (National Sea Grant Office 2008). One way that Sea Grant is working to assist coastal decision-makers with using climate information is by developing effective methods for coastal climate extension. The purpose of this paper is to discuss climate extension methodologies on regional scales, using the Carolinas Coastal Climate Outreach Initiative (CCCOI) as an example of Sea Grant’s growing capacities for climate outreach and extension. (PDF contains 3 pages)

Geological evolution of two crustal scale shear zones. Part I. The Rand thrust complex, northwestern Mojave Desert, California. Part II. The Magdalena metamorphic core complex, north central Sonora, Mexico

The geology and structure of two crustal scale shear zones were studied to understand the partitioning of strain within intracontinental orogenic belts. Movement histories and regional tectonic implications are deduced from observational data. The two widely separated study areas bear the imprint of intense Late Mesozoic through Middle Cenozoic tectonic activity. A regional transition from Late Cretaceous-Early Tertiary plutonism, metamorphism, and shortening strain to Middle Tertiary extension and magmatism is preserved in each area, with contrasting environments and mechanisms. Compressional phases of this tectonic history are better displayed in the Rand Mountains, whereas younger extensional structures dominate rock fabrics in the Magdalena area.

In the northwestern Mojave desert, the Rand Thrust Complex reveals a stack of four distinctive tectonic plates offset along the Garlock Fault. The lowermost plate, Rand Schist, is composed of greenschist facies metagraywacke, metachert, and metabasalt. Rand Schist is structurally overlain by Johannesburg Gneiss (= garnet-amphibolite grade orthogneisses, marbles and quartzites), which in turn is overlain by a Late Cretaceous hornblende-biotite granodiorite. Biotite granite forms the fourth and highest plate. Initial assembly of the tectonic stack involved a Late Cretaceous? south or southwest vergent overthrusting event in which Johannesburg Gneiss was imbricated and attenuated between Rand Schist and hornblende-biotite granodiorite. Thrusting postdated metamorphism and deformation of the lower two plates in separate environments. A post-kinematic stock, the Late Cretaceous Randsburg Granodiorite, intrudes deep levels of the complex and contains xenoliths of both Rand Schist and mylonitized Johannesburg? gneiss. Minimum shortening implied by the map patterns is 20 kilometers.

Some low angle faults of the Rand Thrust Complex formed or were reactivated between Late Cretaceous and Early Miocene time. South-southwest directed mylonites derived from Johannesburg Gneiss are commonly overprinted by less penetrative north-northeast vergent structures. Available kinematic information at shallower structural levels indicates that late disturbance(s) culminated in northward transport of the uppermost plate. Persistence of brittle fabrics along certain structural horizons suggests a possible association of late movement(s) with regionally known detachment faults. The four plates were juxtaposed and significant intraplate movements had ceased prior to Early Miocene emplacement of rhyolite porphyry dikes.

In the Magdalena region of north central Sonora, components of a pre-Middle Cretaceous stratigraphy are used as strain markers in tracking the evolution of a long lived orogenic belt. Important elements of the tectonic history include: (1) Compression during the Late Cretaceous and Early Tertiary, accompanied by plutonism, metamorphism, and ductile strain at depth, and thrust driven? syntectonic sedimentation at the surface. (2) Middle Tertiary transition to crustal extension, initially recorded by intrusion of leucogranites, inflation of the previously shortened middle and upper crustal section, and surface volcanism. (3) Gravity induced development of a normal sense ductile shear zone at mid crustal levels, with eventual detachment and southwestward displacement of the upper crustal stratigraphy by Early Miocene time.

Elucidation of the metamorphic core complex evolution just described was facilitated by fortuitous preservation of a unique assemblage of rocks and structures. The "type" stratigraphy utilized for regional correlation and strain analysis includes a Jurassic volcanic arc assemblage overlain by an Upper Jurassic-Lower Cretaceous quartz pebble conglomerate, in turn overlain by marine strata with fossiliferous Aptian-Albian limestones. The Jurassic strata, comprised of (a) rhyolite porphyries interstratified with quartz arenites, (b) rhyolite cobble conglomerate, and (c) intrusive granite porphyries, are known to rest on Precambrian basement north and east of the study area. The quartz pebble conglomerate is correlated with the Glance Conglomerate of southeastern Arizona and northeastern Sonora. The marine sequence represents part of an isolated arm? of the Bisbee Basin.

Crosscutting structural relationships between the pre-Middle Cretaceous supracrustal section, younger plutons, and deformational fabrics allow the tectonic sequence to be determined. Earliest phases of a Late Cretaceous-Early Tertiary orogeny are marked by emplacement of the 78 ± 3 Ma Guacomea Granodiorite (U/Pb zircon, Anderson et al., 1980) as a sill into deep levels of the layered Jurassic series. Subsequent regional metamorphism and ductile strain is recorded by a penetrative schistosity and lineation, and east-west trending folds. These fabrics are intruded by post-kinematic Early Tertiary? two mica granites. At shallower crustal levels, the orogeny is represented by north directed thrust faulting, formation of a large intermontane basin, and development of a pronounced unconformity. A second important phase of ductile strain followed Middle Tertiary? emplacement of leucogranites as sills and northwest trending dikes into intermediate levels of the deformed section (surficial volcanism was also active during this transitional period to regional extension). Gravitational instabilities resulting from crustal swelling via intrusion and thermal expansion led to development of a ductile shear zone within the stratigraphic horizon occupied by a laterally extensive leucogranite sill. With continued extension, upper crustal brittle normal faults (detachment faults) enhanced the uplift and tectonic denudation of this mylonite zone, ultimately resulting in southwestward displacement of the upper crustal stratigraphy.

Strains associated with the two ductile deformation events have been successfully partitioned through a multifaceted analysis. R_f/Ø measurements on various markers from the "type" stratigraphy allow a gradient representing cumulative strain since Middle Cretaceous time to be determined. From this gradient, noncoaxial strains accrued since emplacement of the leucogranites may be removed. Irrotational components of the postleucogranite strain are measured from quartz grain shapes in deformed granites; rotational components (shear strains) are determined from S-C fabrics and from restoration of rotated dike and vein networks. Structural observations and strain data are compatable with a deformation path of: (1) coaxial strain (pure shear?), followed by (2) injection of leucogranites as dikes (perpendicular to the minimum principle stress) and sills (parallel to the minimum principle stress), then (3) southwest directed simple shear. Modeling the late strain gradient as a simple shear zone permits a minimum displacement of 10 kilometers on the Magdalena mylonite zone/detachment fault system. Removal of the Middle Tertiary noncoaxial strains yields a residual (or pre-existing) strain gradient representative of the Late Cretaceous-Early Tertiary deformation. Several partially destrained cross sections, restored to the time of leucogranite emplacement, illustrate the idea that the upper plate of the core complex bas been detached from a region of significant topographic relief. 50% to 100% bulk extension across a 50 kilometer wide corridor is demonstrated.

Late Cenozoic tectonics of the Magdalena region are dominated by Basin and Range style faulting. Northeast and north-northwest trending high angle normal faults have interacted to extend the crust in an east-west direction. Net extension for this period is minor (10% to 15%) in comparison to the Middle Tertiary detachment related extensional episode.

Avaliação da exposição ao metil-mercúrio na população ribeirinha da baixada cuiabana, no Pantanal Mato-Grossense, Brasil

Os efeitos tóxicos do metil-mercúrio (MeHg) em seres humanos vêm sendo amplamente discutidos, a partir de episódios de contaminação devida a ingestão frequente de peixe contaminado, em Minamata, no Japão, ou ao consumo de pão preparado com cereais tratados com fungicidas a base de metil-mercúrio, no Iraque, indicando que o metil mercúrio pode afetar o sistema nervoso central. A população ribeirinha na região do Pantanal, Brasil, é dependente do peixe, como principal fonte de alimentos e proteínas. Naquela região, o resultado de décadas de mineração de ouro, em pequena escala, foi a contaminação de muitos sistemas aquáticos com mercúrio. Consequentemente, muitas espécies de peixes possuem níveis de MeHg relativamente altos. O objetivo deste trabalho foi avaliar o nível de exposição ao MeHg entre a população ribeirinha do Pantanal. No primeiro artigo, apresentam-se os resultados da validação do método recordatório de 24 horas auto-referido, utilizando-se, como padrão-ouro, o método da pesagem, tendo-se verificado que há aproximadamente um erro de 30% ao estimar a quantidade de peixe consumido por aquela população. Um erro deste pode ser importante em se tratando do consumo de peixes carnívoros, os quais apresentam altos teores de mercúrio. No segundo artigo, ao analisar a associação entre o status neurocognitivo e a concentração de mercúrio no cabelo da população acima, os resultados indicaram que adultos expostos ao metil-mercúrio, através do consumo de peixe, podem ter déficits importantes nas medidas do desempenho neurocomportamental, sem alterações detectáveis no humor ou afetividade. Os efeitos mais importantes do mercúrio, entre os indivíduos analisados, foram detectados nos testes de velocidade e destreza da coordenação motora fina, na inibição da resposta na busca visual, e em tarefas de atenção. No terceiro artigo, considerando-se as associações observadas na concentração de mercúrio no cabelo com alguns desfechos dos testes neuro-psicológicos aplicados, calculou-se a dose-marcadora (BMD) e o limite inferior do intervalo de confiança do BMD (BMDL). Os resultados da dose marcadora e da dose de referência provisória são concordantes com os resultados estimados pelas agências de saúde internacionais.

Densidade, genética e saúde populacional como ferramentas para propor um plano de controle e erradicação de invasão biológica: o caso de Callithrix aurita (Primates) no Parque Nacional da Serra dos Órgãos, RJ, Brasil

A introdução de espécies em locais fora de sua distribuição natural é uma preocupação importante na conservação da biodiversidade. A espécie Callithrix aurita é endêmica das regiões de floresta de altitude da Mata Atlântica do Sudeste do Brasil. Os critérios mais relevantes que a enquadram como espécie ameaçada de extinção são: destruição do habitat, incapacidade de adaptação a florestas secundárias degradadas, declínio populacional, distribuição restrita e introdução de espécies exóticas invasoras. Estes critérios, aliados à evidente raridade, explicam a sua inclusão na Lista Oficial de Espécies da Fauna Brasileira Ameaçadas de Extinção. Os objetivos do trabalho são: estimar o tamanho populacional de C. aurita, C. penicillata e seus híbridos no Parque Nacional da Serra dos Órgãos, avaliar a hibridação entre as espécies por caracteres morfológicos e laboratoriais, verificar o estado de saúde e confirmar a participação de C. aurita na paternidade dos animais capturados, propor um plano de erradicação e de controle de invasão de C. penicillata no Parque. Os tamanhos populacionais das duas espécies de primatas foram estimados através do método Distance Sampling. Um total de sete sagüis foi capturado com armadilhas de captura viva para a contenção física e química e posterior realização dos procedimentos. Para o hemograma, as dosagens bioquímicas e as análises genéticas, o sangue foi recolhido em um tubo de ensaio contendo anticoagulante e mantido em temperatura de refrigeração até o momento da manipulação / processamento das amostras. Callithrix aurita parece estar bem preservada apenas na área do Parque correspondente ao trecho situado no município de Petrópolis. As análises citogenéticas e moleculares dos híbridos são uma ferramenta útil para confirmar se há ou não hibridação, identificando as espécies envolvidas e verificando se há tendência nos retrocruzamentos. Pode-se sugerir que existe uma tendência à diferenciação das espécies e identificação de indivíduos híbridos pelo padrão hematológico e bioquímico, a ser confirmada com uma amostragem maior de animais da espécie C. aurita, preferencialmente da mesma localidade e nas mesmas condições. No caso de C. aurita, as principais recomendações para sua conservação incluem pesquisas para o registro de outras populações em áreas de distribuição livres de invasão, para que se possa avaliar as chances de recuperação populacional e sobrevivência da espécie. A criação de novas Unidades de Conservação deve ser estimulada, assim como estudos mais aprofundados sobre a espécie nos locais já conhecidos de ocorrência, além de um programa seguro de criação em cativeiro.

Heavy metal pollution in sediments at shipbreaking area of Bangladesh

The research was carried out to assess the trace metal concentration in sediments of ship breaking area in Bangladesh. The study areas were separated into Ship breaking Zone and Reference Site for comparative analysis. Metals like Iron ( Fe) was found at 11932 to 41361.71µg.g-1 in the affected site and 3393.37 µg.g-1 in the control site. Manganese (Mn) varied from 2.32 to 8.25 µg.g-1 in the affected site where as it was recorded as 1.8 µg.g-1 in the control area. Chromium(Cr), Nickel (Ni), Zinc(Zn) and Lead (Pb) were also varied from 22.89 to 86.72 µg.g-1; 23.12 to 48.6;83.78 to 142.85 and 36.78 to 147.83 µg.g-1 respectively in the affected site whereas these were recorded as 19; 3.98; 22.22 and 8.82 µg.g-1 in the control site. Copper (Cu); Cadmium (Cd) and Mercury (Hg) concentration were varied from 21.05 to 39.85; 0.57 to 0.94 and 0.05 to 0.11 µg.g-1 in the affected site and 33.0; 0.115 and 0.01 µg.g-1 in the control site. It may conclude that heavy metal pollution in sediments at ship breaking area of Bangladesh is at alarming stage.

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).

Caracterização geológica da ocorrência de óleo na Formação Rio Bonito associada a um modelo não convencional de geração

O trabalho teve como escopo a caracterização geológica, em termos estruturais e estratigráficos, do sistema petrolífero responsável pela ocorrência de óleos encontrados na Formação Rio Bonito, na região carbonífera de Santa Catarina. Atualmente, especula-se que a assinatura geoquímica destes óleos relaciona-se à Formação Irati associado a um modelo não convencional de geração, vinculando a maturação térmica à intrusão de diabásio, devido a um soterramento insuficiente da rocha geradora. Como a Formação Irati encontra-se posicionada estratigraficamente acima da Formação Rio Bonito, o sistema está associado a um forte controle estrutural para o modelo de migração. A preparação de um mapa geológico integrado para a área de estudo envolvendo dados geológicos de campo, dados aeromagnetométricos e informações de furos de sondagem permitiu um entendimento mais aprofundado do arcabouço tectônico-estratigráfico da região. Seções geológicas mostraram a presença de falhas de grandes rejeitos que promoveram um sistema de Horsts e Grabens relacionados às NE-SW e secundariamente a falhas E-W, que permitiram a colocação da Formação Irati em contato lateral ou em um posicionamento abaixo da Formação Rio Bonito. A partir das seções cronoestratigráficas elaboradas foi possível reconhecer prováveis selos, trapas estratigráficos e estruturais, associados ao sistema petrolífero Irati-Rio Bonito. A análise geoquímica (isótopos e biomarcadores) dos óleos coletados na Formação Rio Bonito apontaram que os mesmos estão associadas aos folhelhos do Membro Assistência da Formação Irati, por possuírem uma razão pristano/fitano menor que 1, gamacerano, e a presença de isoprenóides pentametileicosano (i-25) e esqualano (i-30). A partir de análises geoquímicas realizadas em extratos orgânicos extraídos de folhelhos da Formação Irati intrudidos por diabásio, obteve-se valores da relação entre biomarcadores correspondentes e valores de Ro que indicam que foi alcançado o pico de geração de óleo. Contudo, não há registro na área de estudo de um soterramento suficiente que favorecesse essa situação, levando-nos, assim, a acreditar em um modelo de geração não convencional, por meio da intrusão de diabásio nas rochas geradoras. O arcabouço estrutural e os óleos estudados na região sugerem um processo migratório de sudoeste para o nordeste, ao longo de um sistema de falhas NE-SW, encontradas na região, que foram geradas anteriormente ou concomitantemente ao derrame basáltico associado à Formação Serra Geral.

Avaliação da sorção de Cu (II) e Hg (II) pela Sargassum sp modificado com epicloridrina

É crescente o aumento da preocupação do homem com a contaminação de ambientes aquáticos uma vez que da subsistência dos mesmos depende o bem estar de todos. Ao mesmo tempo em que cresce a preocupação tem aumentado a quantidade de pesquisas em busca de tecnologias alternativas ao tratamento e remediação de efluentes aquosos contaminados pelas mais diversas substâncias incluindo os metais pesados. Nas últimas décadas, tem crescido o número de trabalhos avaliando a capacidade de sorção e a viabilidade da utilização de biossorventes de baixo custo na captação de íons metálicos e um desses materiais são as biomassas de algas pardas. Dentre os vários gêneros existentes no planeta o território brasileiro é rico na macroalga do gênero Sargassum. Muito embora a composição dessas biomassas varie o principal constituinte das mesmas é o ácido algínico e seus sais alcalinos na forma de um copolímero linear, homopolimérico, com unidades do ácido manurônico, (M), (1-4)-β-D- ligado e seu epímero em C-5 nos resíduos α-L-gulurônicos, (G), respectivamente, covalentemente ligados entre si em sequencias diferenciadas ou em blocos. Os monômeros podem aparecer em blocos homopoliméricos consecutivos, resíduos G (unidades G), resíduos consecutivos M (unidades M), pequenas unidades alternadas M e G (blocos MG), ou em blocos aleatoriamente organizados. A proposta dessa dissertação é realizar a modificação do copolímero existente na biomassa com epicloridrina, avaliar e comparar a captação de íons Cu (II) e Hg (II) pela biomassa da alga Sargassum sp., com a biomassa não modificada e resultados publicados na literatura

Photoelectrochemistry of GaAs and Si liquid junctions

A quantitative study has been performed on the stability of GaAs surfaces in a 0.10 M K₂Se-0.01 M K₂Se₂ aqueous solution. In this electrolyte, n-type GaAs electrodes displayed significant photocorrosion in competition with faradaic charge transfer to Se^2-. Chemisorption of group VIIIB metal ions onto the GaAs surfaces yielded improved current-voltage behavior of the GaAs photoanodes, and also resulted in a significant reduction in photocorrosion. This behavior implies that the chemisorbed metal ions act to increase the rate of hole transfer to the Se^2- species. Related experiments on n-GaAs, pGaAs, and Sn-doped In₂O₃ electrodes in Te^2-/- aqueous solutions have also been performed.

The majority carrier (electrons) transfer rate constant at a highly doped n⁺-Si/Co(Cp)₂Cl-methanol junction has been measured directly using the chronoamperometry electrochemical technique. The reduction reaction rate of Co(Cp)₂+ was 0.03 cm-s^-1 at the Si electrode, and was more than 100 times slower than at a hanging mercury electrode. The slower rate was attributed to the smaller optical and static dielectric constants, and the lower density of electrons of the semiconductor. The experimental results were compared to the Marcus theory of charge transfer.

The unique properties of high purity Si/liquid junctions have been investigated under illumination conditions in which the photogenerated carrier concentration exceeds the dopant concentration. Under these high injection conditions, negligible electric fields exist at the semiconductor/liquid interface, and carrier motion is driven by diffusion. Studies of the current-voltage properties of the Si in methanol solutions containing various redox couples suggested that high efficiency photoelectrochemical cells could be established through selective collection of carriers at the semiconductor/liquid junction. The quasi-Fermi levels of electrons and holes were measured directly against the solution potential. Steady-state and transient photovoltage measurements, and theoretical modeliug of the carrier transport, generation, and recombination dynamics indicated that the quasi-Fermi levels were flat across the semiconductor sample. The recombination velocities at the Si/liquid junctions have also been measured, and were shown to vary with the solution potential following the Shockley-Read-Hall theory on recombination.

Carbon-13 magnetic resonance spectroscopy

High-resolution, natural-abundance ¹³C spectra have been obtained from a wide variety of organic compounds; ¹³C chemical shifts and coupling constants have been correlated with other molecular properties.

Geminal and vicinal, carbon-proton couplings in benzene and the five- and six-membered aromatic heterocycles have been related to the corresponding proton-proton couplings in substituted ethylenes. The carbon-proton coupling constants in benzene are J_CCH = + 1.0, J_CCCH = +7.4 and J_CCCH = -1.1 Hz. Extended Hückel wavefunctions are uniformly poor in explaining the long-range, carbon-proton couplings in aromatic systems.

Couplings between carbon and elements other than hydrogen have been observed in proton decoupled ¹³C spectra. All of the carbons in fluorobenzene and 1-fluoronaphthalene, but only six of the carbons in 2-fluoronaphthalene are coupled to the fluorine. One-bond, carbon-phosphorus coupling in trialkylphosphines is negative, while one-bond, carbon-phosphorus coupling in tetra-alkylphosphonium ions is positive. Atoms which do not use hybrid orbitals to form bonds to carbon (F, P(III), Se, Te) may have negative, one-bond coupling constants because of the failure of the average energy approximation. One-bond couplings between carbon and carbon, silicon, tin, lead and mercury appear to be explainable in terms of an effective nuclear charge and the s-bond order of the metal. Couplings between carbon and nitrogen and phosphorus (IV) have significant negative contributions to the Fermi contact coupling expression, though, within one series, correlations with s-bond order may be valid. Carbon-carbon coupling in cyclopropane derivatives (10-15 Hz) is consistent with a high degree of p character in the interior orbitals. Some two- and three-bond carbon-carbon coupling constants have also been observed.

Substituent effects of hydroxyl groups on the ¹³C chemical shifts of continuous-chain alkanes depend both on steric and electronic factors. The hydroxyl substituent effects in the long-chain, primary alcohols are α = -48.3, β = -10.2, and γ = +6.0 ppm. The upfield γ effect is attributed to steric crowding in the gauche conformations. Additivity of the hydroxyl and carbonyl and alkyl substituent effects in alkyl-substituted cyclohexanols and cyclohexanones has been demonstrated.

Spontaneous and stimulated light emission due to radiative recombination in forward biased lead telluride P-N junctions

Since the discovery in 1962 of laser action in semiconductor diodes made from GaAs, the study of spontaneous and stimulated light emission from semiconductors has become an exciting new field of semiconductor physics and quantum electronics combined. Included in the limited number of direct-gap semiconductor materials suitable for laser action are the members of the lead salt family, i.e . PbS, PbSe and PbTe. The material used for the experiments described herein is PbTe . The semiconductor PbTe is a narrow band- gap material (E_g = 0.19 electron volt at a temperature of 4.2°K). Therefore, the radiative recombination of electron-hole pairs between the conduction and valence bands produces photons whose wavelength is in the infrared (λ ≈ 6.5 microns in air).

The p-n junction diode is a convenient device in which the spontaneous and stimulated emission of light can be achieved via current flow in the forward-bias direction. Consequently, the experimental devices consist of a group of PbTe p-n junction diodes made from p –type single crystal bulk material. The p - n junctions were formed by an n-type vapor- phase diffusion perpendicular to the (100) plane, with a junction depth of approximately 75 microns. Opposite ends of the diode structure were cleaved to give parallel reflectors, thereby forming the Fabry-Perot cavity needed for a laser oscillator. Since the emission of light originates from the recombination of injected current carriers, the nature of the radiation depends on the injection mechanism.

The total intensity of the light emitted from the PbTe diodes was observed over a current range of three to four orders of magnitude. At the low current levels, the light intensity data were correlated with data obtained on the electrical characteristics of the diodes. In the low current region (region A), the light intensity, current-voltage and capacitance-voltage data are consistent with the model for photon-assisted tunneling. As the current is increased, the light intensity data indicate the occurrence of a change in the current injection mechanism from photon-assisted tunneling (region A) to thermionic emission (region B). With the further increase of the injection level, the photon-field due to light emission in the diode builds up to the point where stimulated emission (oscillation) occurs. The threshold current at which oscillation begins marks the beginning of a region (region C) where the total light intensity increases very rapidly with the increase in current. This rapid increase in intensity is accompanied by an increase in the number of narrow-band oscillating modes. As the photon density in the cavity continues to increase with the injection level, the intensity gradually enters a region of linear dependence on current (region D), i.e. a region of constant (differential) quantum efficiency.

Data obtained from measurements of the stimulated-mode light-intensity profile and the far-field diffraction pattern (both in the direction perpendicular to the junction-plane) indicate that the active region of high gain (i.e. the region where a population inversion exists) extends to approximately a diffusion length on both sides of the junction. The data also indicate that the confinement of the oscillating modes within the diode cavity is due to a variation in the real part of the dielectric constant, caused by the gain in the medium. A value of τ ≈ 10^-9 second for the minority- carrier recombination lifetime (at a diode temperature of 20.4°K) is obtained from the above measurements. This value for τ is consistent with other data obtained independently for PbTe crystals.

Data on the threshold current for stimulated emission (for a diode temperature of 20. 4°K) as a function of the reciprocal cavity length were obtained. These data yield a value of J’_th = (400 ± 80) amp/cm² for the threshold current in the limit of an infinitely long diode-cavity. A value of α = (30 ± 15) cm^-1 is obtained for the total (bulk) cavity loss constant, in general agreement with independent measurements of free- carrier absorption in PbTe. In addition, the data provide a value of n_s ≈ 10% for the internal spontaneous quantum efficiency. The above value for n_s yields values of t_b ≈ τ ≈ 10^-9 second and t_s ≈ 10^-8 second for the nonradiative and the spontaneous (radiative) lifetimes, respectively.

The external quantum efficiency (n_d) for stimulated emission from diode J-2 (at 20.4° K) was calculated by using the total light intensity vs. diode current data, plus accepted values for the material parameters of the mercury- doped germanium detector used for the measurements. The resulting value is n_d ≈ 10%-20% for emission from both ends of the cavity. The corresponding radiative power output (at λ = 6.5 micron) is 120-240 milliwatts for a diode current of 6 amps.

Studies of noble gases in meteorites and in the earth

The isotopic and elemental abundances of noble gases in the solar system are investigated, using simple mixing models and mass-spectrometric measurements of the noble gases in meteorites and terrestrial rocks and minerals.

Primordial neon is modeled by two isotopically distinct components from the interstellar gas and dust. Neon from the gas dominates solar neon, which contains about ten times more ²⁰Ne than ²²Ne. Neon from the dust is represented in meteorites by neon-E, with ²⁰Ne/²²Ne less than 0.6. Isotopic variations in meteorites require neon from both dust and gas to be present. Mixing dust and gas without neon loss generates linear correlation lines on three-isotope and composition-concentration diagrams. A model for solar wind implantation predicts small deviations from linear mixing, due to preferential sputtering of the lighter neon isotopes.

Neon in meteorites consists of galactic cosmic ray spallation neon and at least two primordial components, neon-E and neon-S. Neon was measured in several meteorites to investigate these end- members. Cosmogenic neon produced from sodium is found to be strongly enriched in ²²Ne. Neon measurements on sodium-rich samples must be interpreted with care so not to confuse this source of ²²Ne with neon-E, which is also rich in ²²Ne.

Neon data for the carbonaceous chondrite Mokoia show that the end member composition of neon-Si in meteorites is ²⁰Ne/²²Ne = 13.7, the same as the present solar wind. The solar wind composition evidently has remained constant since before the compaction of Mokoia.

Ca, Al-rich inclusions from the Allende meteorite were examined for correlation between neon-E and oxygen or magnesium isotopic anomalies. ²²Ne and ³⁶Ar enrichments found in some inclusions are attributed to cosmic- ray-induced reactions on Na and Cl, not to a primordial component. Neon-E is not detectably enriched in Allende.

Measurements were made to determine the noble gas contents of various terrestrial rocks and minerals, and to investigate the cycling of noble gases between different terrestrial reservoirs. Beryl crystals contain a characteristic suite of magmatic gases including nucleogenic ²¹Ne and ²²Ne from (α,n) reactions, radiogenic ⁴⁰Ar, and fissiogenic ^131-136Xe from the decay of K and U in the continental crust. Significant concentrations of atmospheric noble gases are also present in beryl.

Both juvenile and atmospheric noble gases are found in rocks from the Skaergaard intrusion. The ratio ⁴⁰Ar/³⁶Ar (corrected for in situ decay of ⁴⁰K) correlates with δ¹⁸O in plagioclase. Atmospheric argon has been introduced into samples that have experienced oxygen-isotope exchange with circulating meteoric hydrothermal fluids. Unexchanged samples contain juvenile argon with ⁴⁰Ar/³⁶Ar greater than 6000 that was trapped from the Skaergaard magma.

Juvenile and atmospheric gases have been measured in the glassy rims of mid-ocean ridge (MOR) pillow basalts. Evidence is presented that three samples contain excess radiogenic ¹²⁹Xe and fission xenon, in addition to the excess radiogenic ⁴⁰Ar found in all samples. These juvenile gases are being outgassed from the upper-mantle source region of the MOR magma. No isotopic evidence has been found here for juvenile primordial noble gases accompanying the juvenile radiogenic gases in the MOR glasses. Large argon isotopic variations in a single specimen provide a clear indication of the late-stage addition of atmospheric argon, probably from seawater.

The Skaergaard data demonstrate that atmospheric noble gases dissolved in ground water can be transferred into crustal rocks. Subduction of oceanic crust altered by seawater can transport atmospheric noble gases into the upper mantle. A substantial portion of the noble gases in mantle derived rocks may represent subducted gases, not a primordial component as is often assumed.