Growth mechanisms and timing of emplacement of a vertically layered mafic intrusion in the feeder zone of an ocean island volcano (Fuerteventura, Canary islands)

Résumé pour le grand public L'île de Fuerteventura (Canaries) offre l'occasion rare d'observer les racines d'un volcan océanique édifié il y a 25 à 30 millions d'années et complètement érodé. On y voit de nombreux petits plutons de forme et composition variées, témoignant d'autant d'épisodes de l'activité magmatique. L'un de ces plutons, appelé PX1, présente une structure inhabituelle formée d'une alternance de bandes verticales d'épaisseur métrique à hectométrique de roches sombres de composition pyroxénilique ou gabbroïque. Les pyroxénites résultent clairement de l'accumulation de cristaux de pyroxènes et non de la simple solidification d'un magma? Se pose dès lors la question de la nature du processus qui a conduit à l'accumulation verticale de niveaux concentrés en pyroxènes. En effet, les litages pyroxénitiques classiques sont subhorizontaux, car ils résultent de l'accumulation gravitaire des cristaux séparés du magma dont ils cristalli¬sent par sédimentation. Cette étude vise à identifier et comprendre les mécanismes qui ont engendré ce Iitage minéralogique vertical et l'im¬portant volume de ces faciès cumulatifs. Nous nous sommes également intéressés aux conditions de pression et de température régnant au moment de la mise en place du pluton, ainsi qu'à sa durée de vie et à sa vitesse de refroidis¬sement. Enfin une approche géochimique nous a permis de préciser la nature de la source mantellique des magmas liés à cette activité magmatique. PX1 est en réalité un complexe filonien formé à des conditions de pression et de température de 1-2 kbar et 1050- 1100°C; sa construction a nécessité au moins 150 km3 de magma. L'alternance d'horizons gabbroïques et pyroxéniti¬ques représente des injections successives de magma sous la forme de filons verticaux, mis en place dans un contexte régional en extension. L'étude des orientations des minéraux dans ces faciès révèle que les horizons gabbroïques enregistrent l'extension régionale, alors que les pyroxénites sont générées par une compaction au sein du pluton. Ceci suggère que le régime des contraintes, qui était extensif lors de l'initiation de la mise en place de PX1, est pério¬diquement devenu compressif au sein même du pluton. Cette compression serait liée à des cycles de mise en place où la vitesse de croissance du pluton dépassait celle de l'extension régionale. La différenciation observée au sein de chaque horizon, depuis des pyroxénites riches en olivine jusqu'à des pyroxé¬nites à plagioclase interstitiel et des gabbros, ainsi que la composition géochimique des minéraux qui les constituent suggèrent que chaque filon vertical s'est mis en place à partir d'un magma de composition identique, puis a évolué indépendamment des autres en fonction du régime thermique et du régime des contraintes local. Lorsque le magma en train de cristalliser s'est trouvé en compression, le liquide résiduel a été séparé des cristaux déjà formés et extrait du système, laissant derrière lui une accumulation de cristaux dont la nature et les proportions dépendaient du stade de cristallisation atteint par le magma au moment de l'extraction. Ainsi, les niveaux de pyroxénites à olivine (premier minéral à cristalliser) ont été formés lorsque le magma correspondant était encore peu cristallisé; à l'inverse, les py¬roxénites riches en plagioclase (minéral plus tardif dans la séquence de cristallisation) et certains gabbros à caractère cumulatif résultent d'une compression tardive dans le processus de cristallisation du filon concerné. Les liquides résiduels extraits des niveaux pyroxénitiques sont rarement observés dans PX1, certaines poches et filonets de com¬position anorthositique pourraient en être les témoins. L'essentiel de ces liquides a probablement gagné des niveaux supérieurs du pluton, voire la surface du volcan. L'origine du régime compressif périodique affectant les filons en voie de cristallisation est attribuée aux injections suivantes de magma au sein du pluton, qui se sont succédées à un rythme plus rapide que la vitesse de consolidation des filons. Des datations U/Pb de haute précision sur des cristaux de zircon et de baddeleyite ainsi que40Ar/39Ar sur des cris¬taux d'amphibole révèlent une initiation de la mise en place de PX1 il y a 22.1 ± 0,7 Ma; celle-ci a duré quelque 0,48 ± 0,22 à 0,52 ± 0,29 Ma. Ce laps de temps est compatible avec celui nécessaire à la cristallisation des filons individuels, qui va de moins d'une année lors de l'initiation du magmatisme à 5 ans lors du maximum d'activité de PX1. La présence de cristaux résorbés enregistrant une cristallisation complexe suggère l'existence d'une chambre mag¬matique convective sous-jacente à PX1 et périodiquement rechargée. Les compositions isotopiques des roches étu¬diées révèlent une source mantellique profonde de type point chaud avec une contribution du manteau lithosphéri- que métasomatisé présent sous les îles Canaries. Résumé L'intrusion mafique Miocène PX1 fait partie du soubassement superficiel (0.15-0.2 GPa, 1100 °Q d'un volcan d'île océanique. La particularité de ce pluton est l'existence d'alternances d'unités de gabbros et de pyroxénites qui met¬tent en évidence un litage magmatique vertical (NNE-SSW). Les horizons gabbroiques et pyroxénitiques sont constitués d'unités de différenciation métriques qui suggèrent tine mise en place par injections périodiques de filons verticaux de magma formant un complexe filonien. Chaque filon vertical a subi une différenciation parallèle à un front de solidification sub-vertical parallèle aux bords du filon. Les pyroxénites résultent du fractionnement et de l'accumulation d'olivine ± clinopyroxene ± plagioclase à partir d'un magma basaltique faiblement alcalin et sont interprétées comme étant des imités de différenciation tronquées dont le liquide interstitiel a été extrait par compaction. L'orientation préférentielle des clinopyroxènes dans ces pyroxe- nites (obtenues par analyse EBSD et micro-tomographique) révèle une composante de cisaillement simple dans la genèse de ces roches, ce qui confirme cette interprétation. La compaction des pyroxénites est probablement causée par a mise en place de filons de magma suivants. Le liquide interstitiel expulsé est probablement par ces derniers. Les clinopyroxènes des gabbros, montrent une composante de cisaillement pure suggérant qu'ils sont affectés par une déformation syn-magmatique parallèle aux zones de cisaillement NNE-SSW observées autour de PX1 et liées au contexte tectonique Miocène d'extension régionale. Ceci suggère que les gabbros sont liés à des taux de mise en place faibles à la fin de cycles d'activité magmatique et sont peu ou pas affectés par la compaction. L'initiation et la géométrie de PX1 sont donc contrôlées par le contexte tectonique régional d'extension alors que les taux et les volumes de magma dépendent de facteurs liés à la source. Des taux d'injection élevés résultent probable¬ment en une croissance du pluton supérieure à la place crée par cette extension. Dans ce cas de figure, la propagation des nouveaux dykes et l'inaptitude du magma à circuler à travers les anciens dykes cristallisés pourrait causer une augmentation de la pression non-lithostatique sur ces derniers, exprimée par un cisaillement simple et l'expulsion du liquide interstitiel qu'ils contiennent (documenté par les zones de collecte anorthositiques). Les compositions en éléments majeurs et traces des gabbros et pyroxenites de PX1 sont globalement homogènes et dépendent de la nature cumulative des échantillons. Cependant, de petites variations des concentrations en éléments traces ainsi que les teneurs en éléments traces des bordures de clinopyroxenes suggèrent que ces derniers ont subi un processus de rééquilibrage et de cristallisation in situ. L'homogénéité des compositions chimiques des échantillons, ainsi que la présence de grains de clinopyroxene résorbés suggère que le complexe filonien PX1 s'est mis en place au dessus d'une chambre magmatique périodiquement rechargée dans laquelle la convection est efficace. Chaque filon est donc issu d'un même magma, mais a subi une différenciation par cristallisation in situ (jusqu'à 70% de fraction¬nement) indépendamment des autres. Dans ces filons cristallisés, les minéraux cumulatifs subissent un rééquilibrage partiel avec les liquide interstitiel avant que ce dernier ne soit expulsé lors de la compaction (mettant ainsi un terme à la différenciation). Ce modèle de mise en place signifie qu'un minimum de 150Km3 de magma est nécessaire à la genèse de PX1, une partie de ce volume ayant été émis par le 'Central Volcanic Complex' de Fuerteventura. Les rapports isotopiques radiogéniques mesurés révèlent la contribution de trois pôles mantelliques dans la genèse du magma formant PX1. Le mélange de ces pôles HIMU, DMM et EM1 refléterai l'interaction du point chaud Cana¬rien avec un manteau lithosphérique hétérogène métasomatisé. Les petites variations de ces rapports et des teneurs en éléments traces au sein des faciès pourrait refléter des taux de fusion partielle variable de la source, résultant en un échantillonnage variable du manteau lithosphérique métasomatisé lors de son interaction avec le point chaud. Des datations U/Pb de haute précision (TIMS) sur des cristaux de zircon et de baddeleyite extraits de gabbros de PX1 révèlent que l'initiation de la cristallisation du magma a eu lieu il y a 22.10±0.07 Ma et que l'activité magmatique a duré un minimum de 0.48 à 0.52 Ma. Des âges 40Ar/39Ar obtenus sur amphibole sont de 21.9 ± 0.6 à 21.8 ± 0.3 Ma, identiques aux âges U/Pb. La combinaison de ces méthodes de datations, suggère que le temps maximum nécessaire à PX1 pour se refroidir en dessous de la température de fermeture de l'amphibole est de 0.8Ma. Ceci signifie que la durée de vie de PX1 est de 520 000 à 800 000 ans. La coexistence de cristaux de baddeleyite et de zircon dans un gabbro est attribuée à son interaction avec un fluide riche en C02 relâché par les carbonatites encaissantes lors du métamorphisme de contact généré par la mise en place de PX1 environ 160 000 ans après le début de sa mise en place. Les durées de vie obtenue sont en accord avec le modèle de mise en place suggérant une durée de cristallisation poux chaque filon allant de 1 an à 5 ans. Abstract The Miocene PX1 gabbro-pyroxenite intrusion (Fuerteventura, Canary Islands), is interpreted as the shallow-level feeder-zone (0.15-0.2 GPa and 1100-1120°C), to an ocean island volcano. The particularity of PX1 is that it displays a NNE-SSW trending vertical magmatic banding expressed by alternating gabbro and pyroxeriite sequences. The gabbro and pyroxenite sequences consist of metre-thick differentiation units, which suggest emplacement by pe¬riodic injection of magma pulses as vertical dykes that amalgamated, similarly to a sub-volcanic sheeted dyke com¬plex. Individual dykes underwent internal differentiation following a solidification front (favoured by a significant lateral/horizontal thermal gradient) parallel to the dyke edges. Pyroxenitic layers result from the fractionation and accumulation of clinopyroxene ± olivine ± plagioclase crystals from a mildly alkaline basaltic liquid and are interpre¬ted as truncated differentiation sequences, from which residual melts were extracted by compaction. Clinopyroxene mineral orientation in pyroxenites (evidenced by EBSD and micro X-ray tomography analysis) display a marked pure shear component, supporting this interpretation. Compaction and squeezing of the crystal mush is ascribed to the incoming and inflating magma pulses. The resulting expelled interstitial liquid was likely collected and erupted along with the magma flowing through the newly injected dykes. Gabbro sequences represent crystallised coalesced magma batches, emplaced at lower rates at the end of eruptive cycles, and underwent minor melt extraction as evi¬denced by clinopyroxene orientations that record a simple shear component suggesting syn-magmatic deformation parallel to observed NNF.-SSW trending shear-zones induced by the regional tensional Miocene stress-field. The initiation and geometry of PX1 is controlled by the regional extensional tectonic regime whereas rates and vo¬lumes of magma depend on source-related factors. High injection rates are likely to induce intrusion growth rates larger than could be accommodated by the regional extension. In this case, dyke tip geometry and the inability of magma to circulate through previously emplaced and crystallised dykes could result in an increase of non-lithostatic pressure on previously emplaced mushy dyke walls; generating strong pure-shear compaction and interstitial melt expulsion within the feeder-zone as recorded by the cumulitic pyroxenite bands and anorthositic collection zones. The whole-rock major and trace-element chemistry of PX1 gabbros and pyroxenites is globally homogeneous and controlled by the cumulate nature of the samples (i.e. on the modal proportions of olivine, pyroxene, plagioclase and oxides). However, small variations of whole-rock trace-element contents as well as trace-element contents of clinopyroxene rims suggest that in-situ re-equilibration and crystallisation has occurred. Additionally, the global homogeneity and presence of complex zoning of rare resorbed clinopyroxene crystals suggest that the PX1 feeder- zone overlies a periodically replenished and efficiently mixed magma chamber. Each individual dyke of magma thus originated from a compositionally constant mildly alkaline magma and differentiated independently from the others reaching up to 70% fractionation. Following dyke arrest these are affected by interaction with the trapped interstitial liquid prior to its compaction-linked expulsion (thus stopping the differentiation process). This emplacement model implies that minimum amount of approximately 150 km3 of magma is needed to generate PX1, part of it having been erupted through the overlying Central Volcanic Complex of Fuerteventura. The radiogenic isotope ratios of PX1 samples reveal the contribution on three end-members during magma genesis. This mixing of the H1MU, EMI and DMM end-members could reflect the interaction of the deep-seated Canarian mantle plume with a heterogeneous metasomatic and sepentininsed lithospheric mantle. Additionally, the observed trace-element and isotopic variations within the same fades groups could reflect varying degrees of partial melting of the source region, thus tapping more or less large areas of the metasomatised lithospheric mantle during interac¬tion with the plume. High precision ID-TIMS U/Pb zircon and baddeleyite ages from the PX1 gabbro samples, indicate initiation of magma crystallisation at 22.10 ± 0.07 Ma. The magmatic activity lasted a minimum of 0.48 to 0.52 Ma. 40Ar/39Ar amphibole ages are of 21.9 ± 0.6 to 21.8 ± 0.3, identical within errors to the U/Pb ages. The combination of the 40Ar/39Ar and U/Pb datasets imply that the maximum amount of time PX1 took to cool below amphibole Tc is 0.8 Ma, suggesting PX1 lifetime of 520 000 to 800 000 years. On top of this, the coexistence of baddeleyite and zircon in a single sample is ascribed to the interaction of PX1 with C02-rich carbonatite-derived fluids released from the host-rock carbonatites during contact metamorphism 160 000 years after PX1 initiation. These ages are in agreement with the emplacement model, implying a crystallisation time of less than 1 to 5 years for individual dykes.

Rahatalous

Suomen Pankin kirjaston rahatalouden kokoelma on maan kattavin ja monipuolisin rahatalouteen ja rahoitusmarkkinoihin painottunut kokoelma. Kokoelmaan kuuluu merkittävä määrä nimekkeitä, joita ei ole hankittu muihin suomalaisiin kirjastoihin. Rahatalouden kokoelma koostuu monografioista, painetuista kausijulkaisuista ja elektronisista lehtitietokannoista. Kokoelma on painottunut tieteelliseen kirjallisuuteen, joka tukee pankissa tehtävää tutkimusta. Lisäksi aineistossa on huomattava määrä yleistajuista kirjallisuutta rahatalouden eri aihealueilta. Rahatalouden kokoelmaan kuuluu monografioita n. 9000 nimekettä (joulukuu 2010). Kokoelma käsittää nimekkeitä useilta eri aihealueilta, kuten rahapolitiikka ja rahateoria (n. 900), valuutat, valuuttajärjestelmät ja valuuttakurssit (n. 1100), pankkitoiminta ja keskuspankit (n. 1300), rahoitusmarkkinat (n. 1700), yleinen talousteoria ja oppihistoria (n. 1300), talouspolitiikka ja -historia (n. 450), hyöty- ja hintateoriat (n. 300), taloudellinen kasvu ja kansantulo (n. 700), suhdanteet (n. 250), julkinen talous ja verotus (n. 400) ja ekonometria (n. 600). Lehtiä kokoelmaan kuuluu n. 300 nimekettä, joista edelleen tilataan 200 nimekettä. Osa lehdistä löytyy painettuna ja osa on käytettävissä kirjastoon hankittujen elektronisten lehtitietokantojen kautta. Kokoelma karttuu pääosin ostojen kautta ja uutta aineistoa hankitaan jatkuvasti. Kokoelmaa on kartutettu systemaattisesti 1950-luvulta lähtien, minkä vuoksi siihen kuuluu merkittävästi vanhempaa aineistoa. Kokoelmaan kuuluvista kirjoista n. 26 % on julkaistu 2000-luvulla ja n. 21 % 1990-luvulla. Varsin suuri osa kirjoista, n. 29 %, on julkaistu 1970- ja 1980-luvulla. Ennen vuotta 1950 julkaistua aineistoa on n. 10 % kokoelmasta. Aineisto on valtaosin englanninkielistä, mutta kokoelmaan kuuluu myös suomen-, ruotsin- ja saksankielisiä nimekkeitä. Monografiat on luokiteltu Suomen Pankin kirjaston oman luokitusjärjestelmän mukaan. Kokoelmaa säilytetään Suomen Pankin kirjaston tiloissa jaettuna avokokoelmaan ja varastokokoelmaan. Aineiston ensisijaisia käyttäjiä ovat pankin oma henkilökunta, mutta kirjasto on avoinna myös kaikille ulkoisille asiakkaille. Kokoelma on lainattavissa muutamia poikkeuksia lukuun ottamatta.

Optimization of parameters for fiber laser-MAG hybrid welding in shipbuilding applications

The Arctic region becoming very active area of the industrial developments since it may contain approximately 15-25% of the hydrocarbon and other valuable natural resources which are in great demand nowadays. Harsh operation conditions make the Arctic region difficult to access due to low temperatures which can drop below -50 °C in winter and various additional loads. As a result, newer and modified metallic materials are implemented which can cause certain problems in welding them properly. Steel is still the most widely used material in the Arctic regions due to high mechanical properties, cheapness and manufacturability. Moreover, with recent steel manufacturing development it is possible to make up to 1100 MPa yield strength microalloyed high strength steel which can be operated at temperatures -60 °C possessing reasonable weldability, ductility and suitable impact toughness which is the most crucial property for the Arctic usability. For many years, the arc welding was the most dominant joining method of the metallic materials. Recently, other joining methods are successfully implemented into welding manufacturing due to growing industrial demands and one of them is the laser-arc hybrid welding. The laser-arc hybrid welding successfully combines the advantages and eliminates the disadvantages of the both joining methods therefore produce less distortions, reduce the need of edge preparation, generates narrower heat-affected zone, and increase welding speed or productivity significantly. Moreover, due to easy implementation of the filler wire, accordingly the mechanical properties of the joints can be manipulated in order to produce suitable quality. Moreover, with laser-arc hybrid welding it is possible to achieve matching weld metal compared to the base material even with the low alloying welding wires without excessive softening of the HAZ in the high strength steels. As a result, the laser-arc welding methods can be the most desired and dominating welding technology nowadays, and which is already operating in automotive and shipbuilding industries with a great success. However, in the future it can be extended to offshore, pipe-laying, and heavy equipment industries for arctic environment. CO2 and Nd:YAG laser sources in combination with gas metal arc source have been used widely in the past two decades. Recently, the fiber laser sources offered high power outputs with excellent beam quality, very high electrical efficiency, low maintenance expenses, and higher mobility due to fiber optics. As a result, fiber laser-arc hybrid process offers even more extended advantages and applications. However, the information about fiber or disk laser-arc hybrid welding is very limited. The objectives of the Master’s thesis are concentrated on the study of fiber laser-MAG hybrid welding parameters in order to understand resulting mechanical properties and quality of the welds. In this work only ferrous materials are reviewed. The qualitative methodological approach has been used to achieve the objectives. This study demonstrates that laser-arc hybrid welding is suitable for welding of many types, thicknesses and strength of steels with acceptable mechanical properties along very high productivity. New developments of the fiber laser-arc hybrid process offers extended capabilities over CO2 laser combined with the arc. This work can be used as guideline in hybrid welding technology with comprehensive study the effect of welding parameter on joint quality.

Structural studies in the Southern Province, South of Sudbury, Ontario

Rocks correlated with the Hough Lake and Quirke Lake Groups of the Huronian Supergroup form part of a northeasterly trending corridor that separates 1750 Ma granitic intrusive rocks of the Chief Lake batholith from the 1850 Ma mafic intrusive rocks of the Sudbury Igneous Complex. This corridor is dissected by two major structural features; the Murray Fault Zone (MFZ) and the Long Lake Fault (LLF). Detailed structural mapping and microstructural analysis indicates that the LLF, which has juxtaposed Huronian rocks of different deformation style and metamorphism grade, was a more significant plane of dislocation than the MFZ. The sense of displacement along the LLF is high angle reverse in which rocks to the southeast have been raised relative to those in the northwest. South of the LLF Huronian rocks underwent ductile defonnation at amphibolite facies conditions. The strain was constrictional, defined by a triaxial strain ellipsoid in which X > Y > z. Calculations of a regional k value were approximately 1.3. Penetrative ductile defonnation resulted in the development of a preferred crystallographic orientation in quartz as well as the elongation of quartz grains to fonn a regional southeast-northwest trending, subvertical lineation. Similar lithologies north of the LLF underwent dominantly brittle deformation under greenschist facies conditions. Deformation north of the LLF is characterized by the thrusting of structural blocks to form angular discordances in bedding orientation which were previously interpreted as folds. Ductile deformation occurred between 1750 and 1238 Ma and is correlated with a regional period of south over north reverse faulting that effected much of the southern Sudbury region. Post dating the reverse faulting event was a period of sedimentation as a conglomerate unit was deposited on vertically bedded Huronian rocks. Rocks in the study area were intruded by both mafic and felsic dykes. The 1238 Ma mafic dykes appear to have been offset during a period of dextral strike slip displacement along the major fault'). Indirect evidence indicates that this event occurred after the thrusting at 950 to 1100 Ma associated with the Grenvillian Orogeny.

The determination of sinigrin in Brassica, and investigations into the use of allyl-isothiocyanate as a nematicide

The goal of this thesis was to study factors related to the development of Brassica juncea as a sustainable nematicide. Brassica juncea is characterized by the glycoside (glucosinolate) sinigrin. Various methods were developed for the determination of sinigrin in Brassica juncea tissue extracts. Sinigrin concentrations in plant tissues at various stages of growth were monitored. Sinigrin enzymatically breaks down into allylisothiocyanate (AITC). AITC is unstable in aqueous solution and degradation was studied in water and in soil. Finally, the toxicity of AITC against the root-lesion nematode (Pratylenchus penetrans) was determined. A method was developed to extract sinigrin from whole Brassica j uncea tissues. The optimal time of extraction wi th boiling phosphate buffer (0.7mM, pH=6.38) and methanol/water (70:30 v/v) solutions were both 25 minutes. Methanol/water extracted 13% greater amount of sinigrin than phosphate buffer solution. Degradation of sinigrin in boiling phosphate buffer solution (0.13%/minute) was similar to the loss of sinigrin during the extraction procedure. The loss of sinigrin from boiling methanol/water was estimated to be O.Ol%/minute. Brassica juncea extract clean up was accomplished by an ion-pair solid phase extraction (SPE) method. The recovery of sinigrin was 92.6% and coextractive impurities were not detected in the cleaned up extract. Several high performance liquid chromatography (HPLC) methods were developed for the determination of sinigrin. All the developed methods employed an isocratic mobile phase system wi th a low concentration of phosphate buffer solution, ammonium acetate solution or an ion-pair reagent solution. A step gradient system was also developed. The method involved preconditioning the analytical column with phosphate buffer solution and then switching the mobile phase to 100% water after sample injection.Sinigrin and benzyl-glucosinolate were both studied by HPLC particle beam negative chemical ionization mass spectrometry (HPLCPB- NCI-MS). Comparison of the mass spectra revealed the presence of fragments arising from the ~hioglucose moiety and glucosinolate side-chain. Variation in the slnlgrin concentration within Brassica juncea plants was studied (Domo and Cutlass cuItivars). The sinigrin concentration in the top three leaves was studied during growth of each cultivar. For Cutlass, the minimum (200~100~g/g) and maximum (1300~200~g/g) concentrations were observed at the third and seventh week after planting, respectively. For Domo, the minimum (190~70~g/g) and maximum (1100~400~g/g) concentrations were observed at the fourth and eighth week after planting, respectively. The highest sinigrin concentration was observed in flower tissues 2050±90~g/g and 2300±100~g/g for Cutlass and Domo cultivars, respectively. Physical properties of AITC were studied. The solubility of AITC in water was determined to be approximately 1290~g/ml at 24°C. An HPLC method was developed for the separation of degradation compounds from aqueous AITC sample solutions. Some of the degradation compounds identified have not been reported in the literature: allyl-thiourea, allyl-thiocyanate and diallyl-sulfide. In water, AITC degradation to' diallyl-thiourea was favored at basic pH (9.07) and degradation to diallyl-sulfide was favored at acidic pH (4 . 97). It wap necessary to amend the aqueous AITC sample solution with acetonitrile ?efore injection into the HPLC system. The acetonitrile amendment considerably improved AITC recovery and the reproducibility of the results. The half-life of aqueous AITC degradation at room temperature did not follow first-order kinetics. Beginning with a 1084~g/ml solution, the half-life was 633 hours. Wi th an ini tial AITC concentration of 335~g/ml the half-life was 865 hours. At 35°C the half-life AITC was 76+4 hours essentially independent of the iiisolution pH over the range of pH=4.97 to 9.07 (1000~g/ml). AITC degradation was also studied in soil at 35°C; after 24 hours approximately 75% of the initial AITC addition was unrecoverable by water extraction. The ECso of aqueous AITC against the root-lesion nematode (Pratylenchus penetrans) was determined to be approximately 20~g/ml at one hour exposure of the nematode to the test solution. The toxicological study was also performed with a myrosinase treated Brassica juncea extract. Myrosinase treatment of the Brassica juncea extract gave nearly quantitative conversion of sinigrin into AITC. The myrosinase treated extract was of the same efficacy as an aqueous AITC solution of equivalent concentration. The work of this thesis was focused upon understanding parameters relevant to the development of Brassica juncea as a sustainable nematicide. The broad range of experiments were undertaken in support of a research priority at Agriculture and Agri-Food Canada.

Unimodality of wave amplitude in the northern Hemisphere

A novel statistic for local wave amplitude of the 500-hPa geopotential height field is introduced. The statistic uses a Hilbert transform to define a longitudinal wave envelope and dynamical latitude weighting to define the latitudes of interest. Here it is used to detect the existence, or otherwise, of multimodality in its distribution function. The empirical distribution function for the 1960-2000 period is close to a Weibull distribution with shape parameters between 2 and 3. There is substantial interdecadal variability but no apparent local multimodality or bimodality. The zonally averaged wave amplitude, akin to the more usual wave amplitude index, is close to being normally distributed. This is consistent with the central limit theorem, which applies to the construction of the wave amplitude index. For the period 1960-70 it is found that there is apparent bimodality in this index. However, the different amplitudes are realized at different longitudes, so there is no bimodality at any single longitude. As a corollary, it is found that many commonly used statistics to detect multimodality in atmospheric fields potentially satisfy the assumptions underlying the central limit theorem and therefore can only show approximately normal distributions. The author concludes that these techniques may therefore be suboptimal to detect any multimodality.

Calculating the ocean's mean dynamic topography from a mean sea surface and a geoid

In principle the global mean geostrophic surface circulation of the ocean can be diagnosed by subtracting a geoid from a mean sea surface (MSS). However, because the resulting mean dynamic topography (MDT) is approximately two orders of magnitude smaller than either of the constituent surfaces, and because the geoid is most naturally expressed as a spectral model while the MSS is a gridded product, in practice complications arise. Two algorithms for combining MSS and satellite-derived geoid data to determine the ocean’s mean dynamic topography (MDT) are considered in this paper: a pointwise approach, whereby the gridded geoid height field is subtracted from the gridded MSS; and a spectral approach, whereby the spherical harmonic coefficients of the geoid are subtracted from an equivalent set of coefficients representing the MSS, from which the gridded MDT is then obtained. The essential difference is that with the latter approach the MSS is truncated, a form of filtering, just as with the geoid. This ensures that errors of omission resulting from the truncation of the geoid, which are small in comparison to the geoid but large in comparison to the MDT, are matched, and therefore negated, by similar errors of omission in the MSS. The MDTs produced by both methods require additional filtering. However, the spectral MDT requires less filtering to remove noise, and therefore it retains more oceanographic information than its pointwise equivalent. The spectral method also results in a more realistic MDT at coastlines. 1. Introduction An important challenge in oceanography is the accurate determination of the ocean’s time-mean dynamic topography (MDT). If this can be achieved with sufficient accuracy for combination with the timedependent component of the dynamic topography, obtainable from altimetric data, then the resulting sum (i.e., the absolute dynamic topography) will give an accurate picture of surface geostrophic currents and ocean transports.

The basic ingredients of the North Atlantic storm track. Part I: land-sea contrast and orography

Understanding and predicting changes in storm tracks over longer time scales is a challenging problem, particularly in the North Atlantic. This is due in part to the complex range of forcings (land–sea contrast, orography, sea surface temperatures, etc.) that combine to produce the structure of the storm track. The impact of land–sea contrast and midlatitude orography on the North Atlantic storm track is investigated through a hierarchy of GCM simulations using idealized and “semirealistic” boundary conditions in a high-resolution version of the Hadley Centre atmosphere model (HadAM3). This framework captures the large-scale essence of features such as the North and South American continents, Eurasia, and the Rocky Mountains, enabling the results to be applied more directly to realistic modeling situations than was possible with previous idealized studies. The physical processes by which the forcing mechanisms impact the large-scale flow and the midlatitude storm tracks are discussed. The characteristics of the North American continent are found to be very important in generating the structure of the North Atlantic storm track. In particular, the southwest–northeast tilt in the upper tropospheric jet produced by southward deflection of the westerly flow incident on the Rocky Mountains leads to enhanced storm development along an axis close to that of the continent’s eastern coastline. The approximately triangular shape of North America also enables a cold pool of air to develop in the northeast, intensifying the surface temperature contrast across the eastern coastline, consistent with further enhancements of baroclinicity and storm growth along the same axis.

Elimination of the Greenland Ice Sheet in a High CO2 Climate

Projections of future global sea level depend on reliable estimates of changes in the size of polar ice sheets. Calculating this directly from global general circulation models (GCMs) is unreliable because the coarse resolution of 100 km or more is unable to capture narrow ablation zones, and ice dynamics is not usually taken into account in GCMs. To overcome these problems a high-resolution (20 km) dynamic ice sheet model has been coupled to the third Hadley Centre Coupled Ocean-Atmosphere GCM (HadCM3). A novel feature is the use of two-way coupling, so that climate changes in the GCM drive ice mass changes in the ice sheet model that, in turn, can alter the future climate through changes in orography, surface albedo, and freshwater input to the model ocean. At the start of the main experiment the atmospheric carbon dioxide concentration was increased to 4 times the preindustrial level and held constant for 3000 yr. By the end of this period the Greenland ice sheet is almost completely ablated and has made a direct contribution of approximately 7 m to global average sea level, causing a peak rate of sea level rise of 5 mm yr-1 early in the simulation. The effect of ice sheet depletion on global and regional climate has been examined and it was found that apart from the sea level rise, the long-term effect on global climate is small. However, there are some significant regional climate changes that appear to have reduced the rate at which the ice sheet ablates.

The full-spectrum correlated-k method for longwave atmospheric radiative transfer using an effective Planck function

The correlated k-distribution (CKD) method is widely used in the radiative transfer schemes of atmospheric models and involves dividing the spectrum into a number of bands and then reordering the gaseous absorption coefficients within each one. The fluxes and heating rates for each band may then be computed by discretizing the reordered spectrum into of order 10 quadrature points per major gas and performing a monochromatic radiation calculation for each point. In this presentation it is shown that for clear-sky longwave calculations, sufficient accuracy for most applications can be achieved without the need for bands: reordering may be performed on the entire longwave spectrum. The resulting full-spectrum correlated k (FSCK) method requires significantly fewer monochromatic calculations than standard CKD to achieve a given accuracy. The concept is first demonstrated by comparing with line-by-line calculations for an atmosphere containing only water vapor, in which it is shown that the accuracy of heating-rate calculations improves approximately in proportion to the square of the number of quadrature points. For more than around 20 points, the root-mean-squared error flattens out at around 0.015 K/day due to the imperfect rank correlation of absorption spectra at different pressures in the profile. The spectral overlap of m different gases is treated by considering an m-dimensional hypercube where each axis corresponds to the reordered spectrum of one of the gases. This hypercube is then divided up into a number of volumes, each approximated by a single quadrature point, such that the total number of quadrature points is slightly fewer than the sum of the number that would be required to treat each of the gases separately. The gaseous absorptions for each quadrature point are optimized such that they minimize a cost function expressing the deviation of the heating rates and fluxes calculated by the FSCK method from line-by-line calculations for a number of training profiles. This approach is validated for atmospheres containing water vapor, carbon dioxide, and ozone, in which it is found that in the troposphere and most of the stratosphere, heating-rate errors of less than 0.2 K/day can be achieved using a total of 23 quadrature points, decreasing to less than 0.1 K/day for 32 quadrature points. It would be relatively straightforward to extend the method to include other gases.

Precipitation and latent heating distributions from satellite passive microwave radiometry. Part I: improved method and uncertainties

A revised Bayesian algorithm for estimating surface rain rate, convective rain proportion, and latent heating profiles from satellite-borne passive microwave radiometer observations over ocean backgrounds is described. The algorithm searches a large database of cloud-radiative model simulations to find cloud profiles that are radiatively consistent with a given set of microwave radiance measurements. The properties of these radiatively consistent profiles are then composited to obtain best estimates of the observed properties. The revised algorithm is supported by an expanded and more physically consistent database of cloud-radiative model simulations. The algorithm also features a better quantification of the convective and nonconvective contributions to total rainfall, a new geographic database, and an improved representation of background radiances in rain-free regions. Bias and random error estimates are derived from applications of the algorithm to synthetic radiance data, based upon a subset of cloud-resolving model simulations, and from the Bayesian formulation itself. Synthetic rain-rate and latent heating estimates exhibit a trend of high (low) bias for low (high) retrieved values. The Bayesian estimates of random error are propagated to represent errors at coarser time and space resolutions, based upon applications of the algorithm to TRMM Microwave Imager (TMI) data. Errors in TMI instantaneous rain-rate estimates at 0.5°-resolution range from approximately 50% at 1 mm h−1 to 20% at 14 mm h−1. Errors in collocated spaceborne radar rain-rate estimates are roughly 50%–80% of the TMI errors at this resolution. The estimated algorithm random error in TMI rain rates at monthly, 2.5° resolution is relatively small (less than 6% at 5 mm day−1) in comparison with the random error resulting from infrequent satellite temporal sampling (8%–35% at the same rain rate). Percentage errors resulting from sampling decrease with increasing rain rate, and sampling errors in latent heating rates follow the same trend. Averaging over 3 months reduces sampling errors in rain rates to 6%–15% at 5 mm day−1, with proportionate reductions in latent heating sampling errors.

A simple, coherent framework for partitioning uncertainty in climate predictions

A simple and coherent framework for partitioning uncertainty in multi-model climate ensembles is presented. The analysis of variance (ANOVA) is used to decompose a measure of total variation additively into scenario uncertainty, model uncertainty and internal variability. This approach requires fewer assumptions than existing methods and can be easily used to quantify uncertainty related to model-scenario interaction - the contribution to model uncertainty arising from the variation across scenarios of model deviations from the ensemble mean. Uncertainty in global mean surface air temperature is quantified as a function of lead time for a subset of the Coupled Model Intercomparison Project phase 3 ensemble and results largely agree with those published by other authors: scenario uncertainty dominates beyond 2050 and internal variability remains approximately constant over the 21st century. Both elements of model uncertainty, due to scenario-independent and scenario-dependent deviations from the ensemble mean, are found to increase with time. Estimates of model deviations that arise as by-products of the framework reveal significant differences between models that could lead to a deeper understanding of the sources of uncertainty in multi-model ensembles. For example, three models are shown diverging pattern over the 21st century, while another model exhibits an unusually large variation among its scenario-dependent deviations.

Advancements in the estimation of ice particle fall speeds using laboratory and field measurements

Accurate estimates for the fall speed of natural hydrometeors are vital if their evolution in clouds is to be understood quantitatively. In this study, laboratory measurements of the terminal velocity vt for a variety of ice particle models settling in viscous fluids, along with wind-tunnel and field measurements of ice particles settling in air, have been analyzed and compared to common methods of computing vt from the literature. It is observed that while these methods work well for a number of particle types, they fail for particles with open geometries, specifically those particles for which the area ratio Ar is small (Ar is defined as the area of the particle projected normal to the flow divided by the area of a circumscribing disc). In particular, the fall speeds of stellar and dendritic crystals, needles, open bullet rosettes, and low-density aggregates are all overestimated. These particle types are important in many cloud types: aggregates in particular often dominate snow precipitation at the ground and vertically pointing Doppler radar measurements. Based on the laboratory data, a simple modification to previous computational methods is proposed, based on the area ratio. This new method collapses the available drag data onto an approximately universal curve, and the resulting errors in the computed fall speeds relative to the tank data are less than 25% in all cases. Comparison with the (much more scattered) measurements of ice particles falling in air show strong support for this new method, with the area ratio bias apparently eliminated.

Changes to Indian Ocean subantarctic mode water in a coupled climate model as CO2 forcing increases

Subantarctic mode water (SAMW) has been shown to be a good indicator of anthropogenic climate change in coupled climate models. SAMW in a coupled climate model and the response of modeled SAMW to increasing CO2 are examined in detail. How SAMW adjusts from climatological values toward a new equilibrium in the coupled model, with different climatological temperature and salinity properties, is shown. The combined formation rate of SAMW and Antarctic intermediate water is calculated as approximately 18 Sv (Sv ≡ 106 m3 s−1) in the Indian sector of the Southern Ocean, slightly lower than climatological values would suggest. When forced with increasing CO2, SAMW is produced at a similar rate but at lower densities. This result suggests that the rate of heat uptake in this part of the ocean will be unchanged by anthropogenic forcing. The important signal in the response of SAMW is the shift to colder and fresher values on isopycnals that is believed to be related to changes in thermodynamic surface forcing. It is shown that, given uniform forcing, SAMW is expected to enhance the signal relative to other water masses. Independent increases in surface heating or freshwater forcing can produce changes similar to those observed, but the two different types of forcing are distinguishable using separate forcing experiments, hodographs, and passive anomaly tracers. The changes in SAMW forced by increasing CO2 are dominated by surface heating, but changes to freshwater fluxes are also important.

The effects of the RAW filter on the climatology and forecast skill of the SPEEDY model

In a recent study, Williams introduced a simple modification to the widely used Robert–Asselin (RA) filter for numerical integration. The main purpose of the Robert–Asselin–Williams (RAW) filter is to avoid the undesired numerical damping of the RA filter and to increase the accuracy. In the present paper, the effects of the modification are comprehensively evaluated in the Simplified Parameterizations, Primitive Equation Dynamics (SPEEDY) atmospheric general circulation model. First, the authors search for significant changes in the monthly climatology due to the introduction of the new filter. After testing both at the local level and at the field level, no significant changes are found, which is advantageous in the sense that the new scheme does not require a retuning of the parameterized model physics. Second, the authors examine whether the new filter improves the skill of short- and medium-term forecasts. January 1982 data from the NCEP–NCAR reanalysis are used to evaluate the forecast skill. Improvements are found in all the model variables (except the relative humidity, which is hardly changed). The improvements increase with lead time and are especially evident in medium-range forecasts (96–144 h). For example, in tropical surface pressure predictions, 5-day forecasts made using the RAW filter have approximately the same skill as 4-day forecasts made using the RA filter. The results of this work are encouraging for the implementation of the RAW filter in other models currently using the RA filter.