Marks of Fire, Value and Faith. Swords with Ferrous Inlays in Finland during the Late Iron Age (ca. 700–1200 AD)

This study explores swords with ferrous inlays found in Finland and dating from the late Iron Age, ca. 700–1200 AD. These swords reflect profound changes not only in styles and fashion but also in the technology of hilts and blades. This study explores how many of these kinds of swords are known from Finland, how they were made and where, what their status was in Late Iron Age Finland, and where the Finnish finds stand in accordance with other areas of Europe. The various methods included measuring of the finds and statistics. The main method of revealing the inlaid marks was radiography due to its non-destructive nature. In cases where inlays were visible without radiography, their details were inspected via microscopy. To study the materials and manufacture of inlaid swords, a sample of them was metallographically analysed to determine the forging technologies and nature of used materials. Furthermore, the manufacture was also studied with experimental approaches. As a result, a catalogue of 151 swords with ferrous inlays was created. This number is relatively high compared with other European countries, although systematic studies have been conducted in only some countries. The inlaid motifs were classified into five distinct categories to help the classification. To summarize, almost every documented inlaid sword was unique in some respect including measurements, inlaid motifs and materials of blades and inlays. Technological variation was also present, some blades being poorer and some of higher quality in spite of the inlaid motifs. Misspelt inscriptions as well as letter-like marks were common in Finland and also in Scandinavia. Furthermore, the provenance of iron and steel used in some blades hints at Scandinavian ores. The above observations, along with the experimental results indicating the existence of multiple alternative techniques of inlaying, suggest that these swords were manufactured locally in Scandinavia, most likely in imitation of Continental European models. Inlaid swords were valued partly for their assumed functionality in combat, as evidenced by damage on some examined blades, or they were valued for their inlays, which could have had fashionable or symbolical meanings bound to local beliefs.

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.

Effect of iron on reactivity of vanillin in wine models /

Phenolic compounds are important components of grapes and wines. They have been found to have important roles in grape and wine systems and properties that are beneficial for human health. Vanillin (3-methoxy-4-hydroxybenzaldehyde) is a phenolic compound coming from the oxidative degradation of lignin in oak-barrels during the aging of wine. Vanillin is an important flavour component of wine and its concentration in wine influences significantly the aroma and flavour of wine. The concentration of vanillin in wine is affected by various factors including the presence of metal ions. In this work, by using HPLC, HPLC-MS, and MS technologies, iron (III) cations were found to affect the oxidation of vanillin in a model system of wine, and the product of the oxidation was identified as divanillin. The mechanism of the redox reaction between vanillin and Fe^"^ is thought to follow that of other phenol oxidations. Increasing the concentration of Fe ^ in the model system accelerates divanillin production. The best pH condition for the divanillin production in the system is the range of 3.0 ~ 3.5. Increasing temperature from 20°C to 40°C accelerates the divanillin production. Divanillin was found to exist in three commercial red wines in this work. Keeping the storage temperature cool and decreasing the contact of grapes and wines with iron are two major measures suggested by this work in order to decrease the oxidation of vanillin during the making and aging of wine.

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

HG 186.55-186.75-1

Domain boundaries observed between the fine grained and coarse grained sediment. The coarse grained sediment contains lineations.

HG 186.55-186.75-2

Fine grained sediment, quite structure-less.

HG 195.45-195.55 Thin Section

Dark brown sediment with clasts ranging from small to large. The grains are sub-angular. Two main domains can be seen. Both are coarse grained, but one contains larger grains and potentially more clay material. Lineations are present throughout the sample in multiple directions. Minor rotation around a few larger clasts can be seen, as well as comet structures.

HG 244.40-244.55-B Thin Section

Coarse grained sample with sub-angular to sub-rounded clasts ranging from small-large in size. Rotation structures, grain crushing and lineations were seen throughout the sample.

HG 249.40-249.55 Thin Section

Coarse grained sample with clasts ranging from small to medium. Clast shape ranges from angular to sub-angular. Lineations and rotation structures seen. Clay material and fine grained domains (darker colour) also seen.

HG 251.55-251.70

Coarse grained sample with clay stained domains. Grains range from small to medium in size and are sub-angular. Lineations, weathered grains, and minor grain stacking.

HG 257.55-257.75 Thin Section

Dark brown sediment with clasts that range from small to large. The clast shape ranges from sub-angular to sub-rounded. Lineations are abundant in this sample. Edge-to-edge grain crushing can also be seen. Darker organic rich domains are also present throughout the sample.