Kinetic and mechanistic studies for the molybdenum- catalyzed oxidation of organic sulfides and olefins by t- DuO2H

This research was focussed on the effects of light, solvent and substituents in the molybdenum-catalyzed oxidation of phenylmethyl sulfides with t-Bu02H and on the effect of light in the molybdenum-catalyzed epoxidation of l-octene with t-Bu02H. It was shown that the Mo(CO)6-catalyzed oxidation of phenylmethyl sulfide with t-Bu02H~ at 35°C, proceeds 278 times faster underUV light than under laboratory lighting, whereas the Mo02(acac)2-catalyzed oxidation proceeds only 1.7 times faster under UV light than under normal laboratory lighting. The difference between the activities of both catalysts was explained by the formation of the catalytically active species, Mo(VI). The formation of the Mo(VI) species, from Mo(CO)6 was observed from the IR spectrum of Mo(CO)6 in the carbonyl region. The Mo(CO)6-catalyzed epoxidation of l-octene with t-Bu02H showed that the reaction proceeded 4.6 times faster under UV light than in the dark or under normal laboratory lighting; the rates of epoxidations were found to be the same in the dark and under normal laboratory lighting. The kinetics of the epoxidations of l-octene with t-Bu02H, catalyzed by Mo02(acac)2 were found to be complicated; after fast initial rates, the epoxidation rates decreased with time. The effect of phenylmethyl sulfide on the Mo(CO)6-catalyzed epoxidation of l-octene waS studied. It was shown that instead of phenylmethyl sulfide, phenylmethyl sulfone, which formed rapidly at 85°C, lowered the reaction rate. The epoxidation of l-octene was found to be 2.5 times faster in benzene than in ethanol. The substituent effect on the Mo02(acac)2-catalyzed oxidations of p-OH, p-CHgO, P-CH3' p-H, p-Cl, p-Br, p-CHgCO, p-HCO and P-N02 substituted phenylmethyl sulfides were studied. The oxidations followed second order kinetics for each case; first order dependency on catalyst concentration was also observed in the oxidation of p-CHgOPhSMeand PhSMe. It was found that electron-donating groups on the para position of phenylmethyl sulfide increased the rate of reaction, while electronwithdrawing groups caused the reaction rate to decrease. The reaction constants 0 were determined by using 0, 0- and 0* constants. The rate effects were paralleled by the activation energies for oxidation. The decomposition of t-Bu02H in the presence of M.o (CO)6, Mo02 (acac)2 and VO(acac)2 was studied. The rates of decomposition were found to be very small compared to the oxidation rates at high concentration of catalysis. The relative rates of the Mo02(acac)2-catalyzed oxidation of p-N02PhSMe by t-Bu02H in the presence of either p-CH30PhSMe or PhSMe clearly show that PhSMe and p-CHgOPhSMe act as co-catalysts in the oxidation of p-N02PhSMe. Benzene, mesity1ene and cyclohexane were used to determine the effect of solvent in the Mo02 (acac)2 and Mo(CO)6-catalyzed oxidation of phenylmethyl sulfide. The results showed that in the absence of hydroxylic solvent, a second molecule of t-Bu02H was involved in the transition state. The complexation of the solvent with the catalyst could not be explained.The oxidations of diphenyl sulfoxide catalyzed by VO(acac)2, Mo(CO)6 and Mo02(acac)2 showed that VO(acac)2 catalyzed the oxidation faster than Mo(CO)6 and Mo02 (acac)2_ Moreover, the Mo(CO)6-catalyzed oxidation of diphenyl sulfoxide proceeded under UV light at 35°C.

The utility of sedimentary diatoms as a measure of historical lake ph

As a result of increased acid precipitation, the pH of a large number of Canadian Shield lakes has been falling. Prior to this study there was no documentation available to explain the history of lake acidification for the Algoma area lakes. In order to obtain this information the diatom inferred pH technique was developed in this study. During two field seasons, July 1981 and July 1982, short sediment cores (circa 25-30 cm) were collected from 28 study lakes located north of Lake Superior, District Algoma, Ontario. The surface sediment diatoms (0-1 cm) from each of these lakes were carefully identified, enumerated, and classified in terms of their pH indicator status. The surface sediment diatom analysis indicated that lake pH is one of the most important factors affecting the species composition and relative abundance of diatom populations. Thus diatom assemblages can be sensitive indicators of lake acidification. When Nygaard's index alpha was plotted against observed lake pH, a statistically significant relationship resulted (r=-0.89; p=

Kinetic and product studies for the oxidtion of organic sulfides and sulfoxides in the presence of transition metal complexes

Rates and products of the oxidation of diphenyl sulfide, phenyl methyl sulfide, p-chlorophenyl methyl sulfide and diphenyl sulfoxide have been determined. Oxidants included t-Bu02H alone, t-Bu02H plus molybdenum or vanadium catalysts and the molybdenum peroxo complex Mo0(02)2*HMPT. Reactions were chiefly carried out in ethanol at temperatures ranging from 20° to 65°C. Oxidation of diphenyl sulfide by t-Bu02H in absolute ethanol at 65°C followed second-order kinetics with k2 = 5.61 x 10 G M~1s"1, and yielded only diphenyl sulfoxide. The Mo(C0)g-catalyzed reaction gave both the sulfoxide and the sulfone with consecutive third-order kinetics. Rate = k3[Mo][t-Bu02H][Ph2S] + k^[Mo][t-Bu02H][Ph2S0], where log k3 = 12.62 - 18500/RT, and log k^ = 10.73 - 17400/RT. In the absence of diphenyl sulfide, diphenyl sulfoxide did not react with t-Bu02H plus molybdenum catalysts, but was oxidized by t-Bu02H-V0(acac)2. The uncatalyzed oxidation of phenyl methyl sulfide by t-Bu02H in absolute ethanol at 65°C gave a second-order rate constant, k = 3.48 x 10~"5 M^s""1. With added Mo(C0)g, the product was mainly phenyl methyl sulfoxide; Rate = k3[Mo][t-Bu02H][PhSCH3] where log k3 = 22.0 - 44500/RT. Both diphenyl sulfide and diphenyl sulfoxide react readily with the molybdenum peroxy complex, Mo0(02)2'HMPT in absolute ethanol at 35°C, yielding diphenyl sulfone. The observed features are mainly in agreement with the literature on metal ion-catalyzed oxidations of organic compounds by hydroperoxides. These indicate the formation of an active catalyst and the complexation of t-Bu02H with the catalyst. However, the relatively large difference between the activation energies for diphenyl sulfide and phenyl methyl sulfide, and the non-reactivity of diphenyl sulfoxide suggest the involvement of sulfide in the production of an active species.

Microfacies analysis of the lower paleocene beda formation in Western Concession 59 and Block 59F, Sirte Basin, Libya /

The rock sequence of the Tertiary Beda Formation of S. W. concession 59 and 59F block in Sirte Basin of Libya has been subdivided into twelve platformal carbonate microfacies. These microfacies are dominated by muddy carbonates, such as skeletal mudstones, wackestones, and packstones with dolomites and anhydrite. Rock textures, faunal assemblages and sedimentary structures suggest shallow, clear, warm waters and low to moderate energy conditions within the depositional shelf environment. The Beda Formation represents a shallowing-upward sequence typical of lagoonal and tidal flat environments marked at the top by sabkha and brackish-water sediments. Microfossils include benthonic foraminifera, such as miliolids, Nummulites, - oerculina and other smaller benthonics, in addition to dasycladacean algae, ostracods, molluscs, echinoderms, bryozoans and charophytes. Fecal pellets and pelloids, along with the biotic allochems, contributed greatly to the composition of the various microfacies. Dolomite, where present, is finely crystalline and an early replacement product. Anhydrite occurs as nodular, chickenwire and massive textures indicating supratidal sabkha deposition. Compaction, micr it i zat ion , dolomit izat ion , recrystallization, cementation, and dissolution resulted in alteration and obliteration of primary sedimentary structures of the Beda Formation microfacies. The study area is located in the Gerad Trough which developed as a NE-SW trending extensional graben. The Gerad trough was characterized by deep-shallow water conditions throughout the deposition of the Beda Formation sediments. The study area is marked by several horsts and grabens; as a result of extent ional tectonism. The area was tectonically active throughout the Tertiary period. Primary porosity is intergranular and intragranular, and secondary processes are characterized by dissolution, intercrystalline, fracture and fenestral features. Diagenesis, through solution leaching and dolomitization, contributed greatly to porosity development. Reservoir traps of the Beda Formation are characterized by normal fault blocks and the general reservoir characteristics/properties appear to be facies controlled.

Sedimentology and taphonomy of storm-generated shell beds from the Verulam formation (Ordovician), Lakefield and Gamebridge quarries, Southern Ontario, Canada /

The Verulam Formation (Middle Ordovician) at the Lakefield Quarry and Gamebridge Quarry, southern Ontario, is comprised of five main lithofacies. These include shoal deposits consisting of Lithofacies 1, winnowed crinoidal grainstones and, shelf deposits consisting of: Lithofacies 2, wackestones, packstones, grainstones, and rudstones; Lithofacies 3, laminated calcisiltites; Lithofacies 4, nodular wackestones and mudstones; and, Lithofacies 5, laminated mudstones and shales. The distribution of the lithofacies was influenced by variations in storm frequency and intensity during a relative sea level fall. Predominant convex-up attitudes of concavo-convex shells within shell beds suggest syndepositional reworking during storm events. The bimodal orientations of shell axes on the upper surfaces of the shell beds indicates deposition under wave-generated currents. The sedimentary features and shell orientations indicate that the shell beds were deposited during storm events and not by the gradual accumulation of shelly material. Cluster and principal component analysis of relative abundance data of the taxa in the shell beds, interbedded nodular wackestones and mudstones, and laminated mudstones and shales, indicates one biofacies comprised of three main assemblages: a strophomenid (Sowerbyelladominated) assemblage, a transitional mixed strophomenid-atrypid assemblage and an atrypid (Zygospira-dominatQd) assemblage. The occurrence of the strophomenid, the strophomenid-atrypid and atrypid assemblages were controlled by storm-driven allogenic taphonomic feedback.

Structural studies and gabbro mylonitization within the Barton Bay Deformation Zone, Geraldton, Ontario /

Structures related to ductile siMple shear parallel to the Bankf ield-Tonbill Fault, define a 5km wide zone, the Barton Bay Deformation Zone. Structures present within this zone Include; simple shear fabrics S, C and C , asymmetric Z shaped folds with rotated axes, boudinage and pinch and swell structures and a subhorlzontal extension llneation. The most highly deformed rock is a gabbro mylonite which occurs in the fault zone. The deformation of this gabbro has been traced in stages from a protomylonite to an ultramylonite In which feldspar and chlorite grainslze has been reduced from over 100 microns to as little as 5 microns. Evidence from the mylonite and the surrounding structure indicates that deformation within the Barton Bay Deformation Zone is related to a regional simple shear zone, the Bankf ield-Tombill Fault. Movement along this shear zone was in a south over north oblique strike slip fashion with a dextral sense of displacement.

Kinetic studies of the effect of organic sulphides on the oxidation of other sulphides /

The rates of oxidation of three Organic sulphides viz. methyl phenyl sulphide, (P), p -me thoxyphenyl methyl sulphide (M) and methyl p-nitrophenyl sulphide (N). have been obtained in ethanol using MoO-(acac)- as catalyst and Bu OOH as the oxidizing agent. A Hammett plot gave a rho value of -2.1 and the activation energies for the oxidation of P, M and N were estimated to be 63.60, 40.12 and 197.46 Kj mol respectively. The effect of organic sulphide on the oxidation of another sulphide was also ascertained. Positive and negative deviations were observed from the expected slope.

Geology of the Rankin Inlet area, Northwest Territories /

The Rankin Inlet area, on the west shore of Hudson Bay in the Northwest Territories, is in the Churchill Structural Province. Metamorphosed volcanic and sedimentary rocks, previously mapped as Archean and part of the Kaminak Group, underlie most of the area. The Rankin Inlet Group consists of greywacke, with minor conglomeratic greywacke, quartzite and dolomite, overlain by massive and pillowed basaltic flows. Gabbro sills intrude the sediments near the base of the volcanic sequence and three serpentinite sills outcrop at the base of the volcanic sequence. The sediments are in fault-contact with quartz monzonite to the south and were intruded by granitic rocks to the northwest. Two periods of folding were defined by the mapping. The first generation folds are recumbent isoclinal folds, with northwest-trending and northeast-dipping axial planes, formed through gravitational sliding. The second generation folds are symmetrically disposed about the axis of the granitic intrusion and have east-southeast trending and nearly vertical axial planes. Whole-rock analysis of 64 rock samples indicates that metasomatic alteration accompanied the intrusion of both the granitic rocks and the serpentinite. The volcanic rocks, gabbro and serpentinite were derived from a magma of oceanic tholeiitic affinities. The stratigraphic sequence and chemistry of the volcanic rocks of the Rankin Inlet Group indicate that this assemblage is correlative with the Hurwitz Group rather than the Kaminak Group and is therefore Aphebian in age.

Petrography and geochemistry of the McArthur Township area, Ontario /

The McArthur Township area in the Archean Abitibi Belt of northeast Ontario contains northwesterly trending volcanic rocks which are located on a limb of a large syncline. The axial trace of the syncline passes through the adjacent Douglas Township. The Archean volcanic rocks and associated sedimentary rocks are intruded and deformed by two large plutons and a few smaller hypabyssal intrusions. A petrographic and geochemical study of the Precambrian rocks exposed 1n the study area was undertaken in order to investigate the metamorphic grade and geochemical characteristics of the rocks. All the samples were studied with the microscope and analysis of 20 major and trace elements were determined on a selection of the less altered specimens by x-ray fluorescence. Three different periods of igneous activity have occurred in the study area. The first two periods were dominated by volcanic extrusive rocks accompanied by gabbroic sills. The third cycle is the diapiric intrusion of the granitic plutons and subsequent metamorphism of the older rocks to the low to medium grade. Two periods of sedimentation are also recognized in the study area which occurred after the first and second cycle of volcanism. Chemically, the lavas are subdivided into three main associations: (1) The komatiitic association is characterized by high MgO, high Ni, low Ti02 and a low FeO*/(FeO* + MgO) ratio. They occupy the base of each volcanic cycle and some of the flows exhibit spinifex textures. (2) The tholeiitic association displays distinct iron and titanium enrichment trends in the intermediate membersor -i r (3) The calc-alkaline association contains low FeO* and TI02 and high Ni contents relative to modern calc-alkaline types. They are formed at the end of each cycle of volcanism and overlie the tholeiitic flows. All three associations of the first volcanic cycle are exposed in the study area, while the second cycle is represented by a komatiltic sequence. The volcanic rocks were possibly formed by multiple partial melting of the Archean mantle to produce parental magmas under various P - T conditions.

Genesis and distribution of Mississippi Valley-type ore assemblages in Middle Silurian strata, Niagara Peninsula, Ontario /

Presently non-commercial occurrences of Mississippi Valley-type ore assemblages in the Middle Silurian strata of the Niagara Peninsula have been studied. Based on this detailed study, a new poly-stage genetic model is proposed which relates ore mineralization in carbonate environments to the evolution of the sedimentary basin. Sulphide ore mineralization occurred during two episodes: 1. During the late diagenesis stage, which is characterized by compaction-maturation of the sediments, the initial mineralization took place by upward and outward movement of connate waters. Metals were probably supplied from all the sediments regardless of their specific lithologies. However, clay minerals were possibly the main contributors. The possible source of sulphur was from petroleum-type hydrocarbons presently mixed with the sediments at the site of ore deposition. Evidence for this is the fact that the greatest abundance of ore minerals is in petroliferous carbonates. The hydrocarbons probably represent liquids remaining after upward migration to the overlying Guelph-Salina reservoirs. The majority of sphalerite and galena formed during this period, as well as accessory pyrite, marcasite, chalcopyrite, chalcocite, arsenopyrite, and pyrrhotite; and secondary dolomite, calcite, celestite, and gypsum. 2. During the presently ongoing surface erosion and weathering phase, which is marked by the downward movement of groundwater, preexisting sulphides were probably remobilized, and trace amounts of lead and zinc were leached from the host material, by groundwaters. Metal sulphides precipitated at, or below, the water table, or where atmospheric oxygen could raise the Eh of groundwaters to the point where soluble metal complexes are unstable and native sulphur co-precipitates with sphalerite and galena. This process, which can be observed today, also results in the transport and deposition of the host rock material. Breakdown of pre-existing sulphide and sulphate, as well as hydrocarbon present in the host rock, provided sulphur necessary for sulphide precipitation. The galena and sphalerite are accompanied by dolomite, calcite, gypsum, anglesite, native sulphur and possibly zincite.

Structural, stratigraphic and geochemical studies of the Horwood Peninsula - Gander Bay Area, Northeast Newfoundland /

The Horwood Peninsula - Gander Bay area is located at NE Newfoundland in the Botwood Zone (Williams et a1., 1974) or in the Dunnage Zone (Williams, 1979) of the Central Mobile Belt of the Newfoundland Appalachians. The area is underlain by Middle Ordovician to possible Lower Silurian rocks of the Davidsville and Indian Islands Groups, respectively. Three conformable formations named informally : the Mafic Volcanic Formation, the Greywacke and Siltstone Formation and the Black Slate Formation, have been recognized in the Davidsville Group. The Greywacke and the Black Slate Formations pass locally into a Melange Formation. From consideration of regional structure and abundant locally-derived mafic volcanic olisto- 1iths in the melange, it is considered to have originated by gravity sliding rather than thrusting. Four formations have been recognized in the Indian Islands Group. They mainly contain silty slate and phyllite, grey cherty siltstone, green to red micaceous siltstone and limestone horizons. Repetition of lithological units by F1 folding are well-demonstrated in one of formations in this Group. The major structure in this Group on the Horwood Peninsula is interpreted to be a synclinal complex. The lithology of this Group is different from the Botwood Group to the west and is probably Late Ordovician and/or Early Silurian in age. The effects of soft-sediment deformation can be seen from the lower part of the Davidsville Group to the middle part of the Indian Islands Group indicating continuous and/or episodic slumping and sliding activities throughout the whole area. However, no siginificant depOSitional and tectonic break that could be assigned to the Taconian Orogeny has been recognized in this study. Three periods of tectonic deformation were produced by the Acadian Orogeny. Double boudinage in thin dikes indicates a southeast-northwest sub-horizontal compression and main northeast-southwest sub-horizontal extension during the D1 deformation. A penetrative, axial planar slaty cleavage (Sl) and tight to isocJ.ina1 F1 folds are products of this deformation. The D2 and D3 deformations formed S2 and S3 fabrics associated with crenulations and kink bands which are well-shown in the slates and phyllites of the Indian Islands Group. The D2 and D3 deformations are the products of vertical and northeast-southwest horizontal shortening respectively. The inferred fault between the Ordovician slates (Davidsville Group) and the siltstones (Indian Islands Group) suggested by Williams (1963, 1964b, 1972, 1978) is absent. Formations can be followed without displacement across this inferred fault. Chemically, the pillow lavas, mafic agglomerates, tuff beds and diabase dikes are subdivided into three rock suites : (a) basaltic komatiite (Beaver Cove Assemblage), (b) tholeiitic basalt (diabase dikes), (c) alkaline basalt (Shoal Bay Assemblage). The high Ti02 , MgO, Ni contents and bimodal characteristic of the basaltic komatiite in the area are comparable to the Svartenhuk Peninsula at Baffin Bay and are interpreted to be the result of an abortive volcano-tectonic rift-zone in a rear-arc basin. Modal and chemical analyses of greywackes and siltstones show the trend of maturity of these rocks increasing from poorly sorted Ordovician greywackes to fairly well-sorted Silurian siltstones. Rock fragments in greywackes indicate source areas consisting of plagiogranite, low grade metamorphic rocks and ultramafic rocks. Rare sedimentary structures in both Groups indicate a southeasterly provenance. Trace element analyses of greywackes also reveal a possible island-arc affinity.

Paleolimnology of selected Precambrian Shield lakes /

The analysis of fossil diatoms and Mallomonas assemblages in a 2.85 m sediment core revealed that a series of distinct floristic changes have occurred in the development of Found Lake, a small Shield lake in southern Ontario. Climatic and vegetational changes in the lake's watershed were closely associated with successional changes in the lake's biota. Nutrients released by the deciduous component of the Found Lake watershed appeared to be especially important in determining diatom and Mallomonas standing crop. The top 20 cm of sediment of 3 ,Shield lakes was then investigated using close interval (1 cm) analyses of diatoms, Mallomonas scales, pollen grains and sedimentary phosphorus. Found and Jake Lake are adjacent to Highway 60, whereas Delano Lake has been undisturbed and was used as a control. Dramatic changes in the diatom and Mallomonas communities were recorded in the Found and Jake Lake stratigraphies and could be closely associated with known historical events. Increased turbidity and nutrient enrichment were believed responsible for these successional changes. In addition, diatom and Mallomonas standing crop increased substantially following road construction in Found Lake's drainage basin. Meanwhile, no. sharp changes in diatom or Mallomonas communities were recorded in the recent sediments of the control (Delano) lake. The use£ulness o£ Synuracean scales as paleoindicators, as well as the importance o£ sectioning cores at close intervals during transition periods in a laker's development, was stressed.

A geochemical and petrological study of volcanic rocks in the Beardmore-Geraldton Archaean Greenstone Belt, Northwestern Ontario

Three repetitive sequences of northward youngIng, east striking, linear, volcano-sedimentary units are found in the late Archaean BeardmoreGeraldton greenstone belt, situated within the Wabigoon subprovince of the Superior Province of northwestern Ontario. The volcanic components are characterised by basaltic flows that are pillowed at the top and underlain by variably deformed massive flows which may In part be intrusive. Petrographic examination of the volcanic units indicates regional metamorphism up to greenschist facies (T=3250 C - 4500 C, P=2kbars) overprinted by a lower amphibolite facies thermal event (T=5750 C, P=2kbars) confined to the south-eastern portion of the belt. Chemical element results suggest olivine, plagioclase and pyroxene are the main fractionating mineral phases. Mobility studies on the varIOUS chemical elements indicate that K, Ca, Na and Sr are relatively mobile, while P, Zr, Ti, Fet (total iron = Fe203) and Mg are relatively immobile. Discriminant diagrams employing immobile element suggests that the majority of the samples are of oceanic affinity with a minor proportion displaying an island arc affinity. Such a transitional tectonic setting IS also refle.cted in REE data where two groups of volcanic samples are recognised. Oceanic tholeiites are LREE depleted with [La/Sm] N = 0.65 and a relatively flat HREE profile with [Sm/Yb] N = 1.2. Island arc type basalts (calc-alkaline) are LREE enriched, with a [La/Sm] N = 1.6, and a relatively higher fractionated HREE profile with [Sm/Yb] N = 1.9. Petrogenetic modelling performed on oceanIC tholeiites suggests derivation from a depleted spinel lherzolite source which undergoes 20% partial melting. Island arc type basalts can be derived by 10% partial melting of a hypothetical amphibolitised oceanic tholeiite source. The majority of the volcanic rocks in the Beardmore-Geraldton Belt are interpreted to represent fragments of oceanic crust trapped at a consuming plate margin. Subsequent post accretionary intrusion of gabbroic rocks (sensu lato) with calc-alkaline affinity is considered to result in the apparent hybrid tectonic setting recognized for the BGB.

An investigation into the oxidation of organic sulphides, organic selenides and simple hydrocarbons by Mortierella isabellina NRRL 1757

The work presented in this thesis is divided into three separate sections 4!> Each' 'section is involved wi th a different problem, however all three are involved with a microbial oxidation of a substrate~ A series of 'aryl substituted phenyl a.nd be,nzyl methyl sulphides were oxidized to the corre~pondi~g sulphoxides by 'Mo:rtierellai's'a'b'e'llina NRR.L17'S7 @ For this enzymic Qxidation, based on 180 labeled experiments, the oxygen atom is derived fr'orn the atmosphere and not from water. By way of an u~.traviolet analysis, the rates of oxidation, in terms of sulphox~ de appearance, were obtained and correlated with the Hatnmett p s~grna constants for the phenyl methyl sulphide series. A value of -0.67 was obtained and, is interpreted in terms of a mechanism of oxidation that involves an electrophilic attack on the sulphide sulphur by an enzymic ironoxygen activated complex and the conversion of the resulti!lg sulphur cation to sulphoxide. A series of alkyl phenyl selen~des have been incubated with the fu~gi, Aspergillus niger ATCC9l42, Aspergillus fO'etidus NRRL 337, MIIJisabellina NF.RLl757 and'He'lminth'osparium sp'ecies NRRL 4671 @l These fu?gi have been reported to be capable of carrying out the efficient oxidation of sulphide to sulphoxide, but in no case was there any evidence to supp'ort the occurrence of a microbialox,idation. A more extensive inves·t~gation was carried out with'M,e 'i's'a'b'e'l'l'i'na, this fu~gus was capable of oxidizing the correspondi~g sulphides to sulphoxi.de·s·$ Usi:ng a 1abel.edsubstra.te, [Methyl-l4c]-methyl phenyl selenide, the fate of this compound was invest~gated followi!lg an i'ncubation wi th Me isabellina .. BeSUldes th. e l4C-ana1YS1Q S-,'. a quant"ltta"lve selen'lum ana1Y"S1S was carried out with phenyl methyl selenide. These techniques indicate that thesel'enium was capable of enteri!1g thefu!1gal cell ef'ficiently but that s'ome metabolic cleav~ge of the seleni'um-carbon bond' may take plac'e Ie The l3c NMR shifts were assigned to the synthesized alkyl phenyl sulphides and selenides@ The final section involved the incubation ofethylben~ zene and p-e:rtr.hyltoluene wi th'M ~ 'isab'e'llina NRRL 17574b Followi~ g this incubation an hydroxylated product was isolated from the medium. The lH NMR and mass spectral data identify the products as I-phenylethanol and p-methyl-l-phenylethanol. Employi!lg a ch'iral shift re~gent,tri~ (3-heptafluorobutyl-dcamphorato)'- europium III, the enantiomeric puri ty of these products was invest~gated. An optical rotation measurement of I-phenylethanol was in ~greement with the results obtained with the chiral shift re~gen,te 'M.isabe'l'lina is capable of carryi~g out an hydroxylation of ethylbenzene and p-ethyltoluene at the ~ position.

Petrography, geochemistry and structure of the Timmins area, Ontario

Regional structural analysis of the Timmins area indicates four major periods of tectonic deformation. The DI deformation is characterized by a series of isoclinal FI folds which are outlined in the study area by bedding, pillow tops and variolitic flows. The D2 deformation developed the Porcupine Syncline and refolded the Fl folds about a NE. axis. A pervasive S2 foliation developed during low grade (greenschist) regional metamorphism associated with the D2 deformation. The S2 foliation developed south of the Destor-Porcupine Break. The third phase of tectonic D3 deformation is recognized by the development of a S3 sub-horizontal crenulation cleavage which developed on the plane of the S2 foliation. No meso scopic folds are associated with this deformation. The 8 3 crenulation cleavage is observed south of the Destor-Porcupine Break. The D4 tectonic deformation is recorded as a subvertical S4 crenulation cleavage which developed on the plane of the S2 foliation and also offsets the S3 crenulation cleavage. Macroscopic F4 folds have refolded the F2 axial plane. No metamorphic recrystallization is associated with this deformation. The S4 crenulation cleavage is observed south of the Destor-Porcupine Break. Petrographic evidence indicates that the Timmins area has been subjected to pervasive regional low grade (greenschist) metamorphism which has recrystallized the original mineralogy. South of the study are~ the Donut Lake ultramafic lavas have been subjected to contact medium grade (amphibolite facies) metamorphism associated with the intrusion of the Peterlong Lake Complex. The Archean volcanic rocks of the Timmins area have been subdivided into komatiitic, tholeiitic and calcalkaline suites based on Zr, Ti0 2 and Ni. The three elements were used because of their r e lative immobility during subsequent metamorphic events. Geochemical observations in the Timmins area indicates that the composition of the Goose Lake and Donut Lake Formations are a series of peridotitic, pyroxenitic and basaltic komatiites. The Lower Schumacher Formation is a sequence of basaltic komatiites while the upper part of the Lower Schumacher Formation is an intercalated sequence of basaltic komatiites and low Ti0 2 tholeiites. The variolitic flows are felsic tholeiites in composition and geochemical evidenc e sugg ests that they developed as a n immiscible splitting of a tholeiitic magma. The Upper Schumacher Formation is a sequence of tholeiitic rocks dis p laying a mild iron enrichment. The Krist and Boomerang Formations are the felsic calc-alkaline rocks of the study area which are characteristically pyroclastic. The Redstone Fo rmation is dominantly a calc-alkali ne sequence of volcani c rocks whose minor mafic end me mbers exposed in 1t.he study hav e basaltic komatiitic compositions. Geochemical evidence sugges ts that the Keewatin-type se dimentary rocks have a composition similar to a quartz diorite or a granodiorite. Fi e l d obs ervations and petrographic evidence suggests that they were derived fr om a distal source and now repr esent i n part a turbidite sequence. The Timiskaming-type sedimentary rocks approach the c omp osi t ion of the felsic calc-alkaline rocks of the study area . The basal conglomerate in the study are a sugge s ts that th e uni t was derived fr om a proximal source. Petrographic and ge ochemical evidence suggests that the peridotitic and pyroxenitic komatiites originated as a 35-55% partial melt within the mantle, in excess of 100 Km. depth. The melt ros e as a diapir with the subsequent effusion of the ultramafic lavas, The basaltic komatiites and tholeiitic rocks originated in the mantle from lesser degrees of partial melting and fractionated in low pressure chambers. Geochemical evidence suggests a "genetic link" between the basaltic komatiites and tholeiites, The calc-alkaline rocks developed as a result of the increa.se In PO in the magma chamber. The felsic calcalkaline rocks are a late stage effusion possibly the last major volcanic eruptions in the area.