Electron microprobe results of clay minerals from samples of the Frankenwald and the Thüringer Wald

Late Devonian (Frasnian) pillow basalts from the Frankenwald and Thüringer Wald within the Saxothuringian zone in Germany were found to contain abundant putative biogenic filaments, indicating that the volcanic rocks once harbored microbial life. The mineralized filaments are found in calcite-filled amygdules (former vesicles), where they started to form on internal surfaces of vesicles after seawater ingress. The filaments postdate an early fibrous carbonate cement but predate later equant calcite spar, revealing syngenetic formation. A biogenic origin of filaments is indicated by their size and morphology resembling modern microorganisms, their independence of crystal faces and cleavage plans, complex branching patterns, and internal segmentation. The filamentous microorganisms represent cryptoendoliths that lived in structural cavities of the basalt. They became preserved upon microbial clay authigenesis similar to the encrustation of modern prokaryotes in iron-rich environments. Filaments consist of clay minerals with the endmember composition berthierine-chamosite and illite-glauconite. Based on the discovery of fossilized filamentous microorganisms in Late Devonian pillow basalts of the Saxothurigian zone that are similar to filaments previously found in Middle Devonian pillow basalts of the Rhenohercynian zone, it is apparent that cryptoendolithic life was more widespread than previously recognized. Structural cavities within seafloor basalt may thus represent a common, perhaps universal niche for life in the oceanic crust.

Geochemistry, minerals and b-parameter at DSDP Leg 70 Holes

Clay minerals recovered from the Galapagos hydrothermal mounds (Holes 506C, 507D, and 509B) are mainly iron-rich nontronite-like minerals enriched in potassium. Nontronites from Hole 509B show a distinct tendency to become micaceous toward the lower beds of clay sediments. Mn-crusts consist mainly of todorokite or a mixture of todorokite and nontronite. Minerals of clay and Mnrich sediments in the mounds originated from hydrothermal solutions of uncertain origin. Pelagic oozes from hydrothermal mounds and from areas between mounds (Hole 506D) consist mainly of calcite. In the carbonate beds on or near the hydrothermal mounds an admixture of smectite is often found.

Chemistry of very young basalts from ODP Hole 106-648B

Basalts in Hole 648B, located in the rift valley of the Mid-Atlantic Ridge at 23°N in crust estimated to be less than 100,000 years old, are mainly fresh, but small amounts of secondary phases are found on fracture surfaces and in alteration halos within the rocks. The halos are defined by dark bands 1-4 mm thick that have developed parallel to fracture surfaces or pillow margins and which in some cases have migrated some centimeters into the rock. The dark bands are the principal locus of secondary phases. The secondary phases are olive-green and yellow protoceladonites, of composition and structure intermediate between celadonite and iron-rich saponite, red (Mn-poor) to opaque (Mn-rich) iron oxyhydroxides, mixtures of protoceladonite and iron oxyhydroxide, and rare manganese oxides. These phases occur mainly as linings or fillings of open spaces in the basalt within the dark bands. Sulfides and intersertal glass are the only primary phases that can be seen to have been altered. Where dark bands have migrated into the rock, the rock behind the advancing band is almost devoid of secondary phases, implying redissolution. The potassium and magnesium in the secondary phases could have been supplied from ambient seawater. The aluminum in the protoceladonites must have been derived from local reaction of intergranular glass. The source of iron and silica could have been intergranular glass or low temperature mineralizing solutions of the type responsible for the formation of deposits of manganese oxides and iron oxyhydroxides and silicates on the seafloor.

(Table 1) Composition of basal sediments collected during DSDP Leg 16

Iron-rich sediments chemically similar to those forming at present on the crest of the East Pacific Rise have been found just above basement at widely separated drill sites in the eastern equatorial Pacific, including three sites of Leg 16 of the Deep Sea Drilling Project. These sediments were probably formed when the basement was at the crest of this rise and have moved to their present location as a result of sea-floor spreading.

Timing and chemistry of fluid-flow events in the Lawn Hill Platform, Northern Australia

Mudrocks and carbonates of the Isa superbasin in the Lawn Hill platform in northern Australia host major base metal sulfide mineralization, including the giant strata-bound Century Zn-Pb deposit. Mineral paragenesis, stable isotope, and K-Ar dating studies demonstrate that long-lived structures such as the Termite Range fault acted as hot fluid conduits several times during the Paleoproterozoic and Mesoproterozoic in response to major tectonic events. Illite and chlorite crystallinity studies suggest the southern part of the platform has experienced higher temperatures (up to 300 degrees C) than similar stratigraphic horizons in the north. The irregular downhole variation of illite crystallinity values provides further information oil the thermal regime in the basin and shows that clay formation was controlled not only by temperature increase with depth but also by high water/rock ratios along relatively permeable zones. K-Ar dating of illite, in combination with other data, may indicate three major thermal events in the central and northern Lawn Hill platform Lit 1500, 1440 to 1400, and 1250 to 1150 Ma. This study did not detect the earlier Century base metal mineralizing event at 1575 Ma. 1500 Ma ages are recorded only in the south and correspond to the age of the Late Isan orogeny and deposition of the Lower Roper superbasin. They may reflect exhumation of a provenance region. The 1440 to 1300 Ma ages are related to fault reactivation and a thermal pulse at similar to 1440 to 1400 Ma possibly accompanied by fluid flow, with subsequent enhanced cooling possibly due to thermal relaxation or further crustal exhumation. The youngest thermal and/or fluid-flow event at 1250 to 1150 Ma is recorded mainly to the cast of the Tern-lite Range fault and may be related to the assembly of the Rodinian supercontinent. Fluids in equilibrium with illite that formed over a range of temperatures, at different times in different parts of the platform. have relatively uniform oxygen isotope compositions and more variable hydrogen isotope compositions (delta O-18 = 3.5-9.7 parts per thousand V-SMOW; delta D = -94 to -36 parts per thousand V-SMOW). The extent of the 180 enrichment and the variably depleted hydrogen isotope compositions suggest the illite interacted with deep-basin hypersaline brines that were composed of evaporated seawater and/or highly evolved meteoric water. Siderite is the most abundant iron-rich gangue phase in the Century Zn-Pb deposit, which is surrounded by all extensive ferroan carbonate alteration halo. Modeling suggests that the ore siderite formed at temperatures of 120 degrees to 150 degrees C, whereas siderite and ankerite in the alteration halo formed at temperatures of 150 degrees to 180 degrees C. The calculated isotopic compositions of the fluids are consistent with O-18-rich basinal brines and mixed inorganic and organic carbon Sources (6180 = 3-10 parts per thousand V-SMOW, delta C-13 = -7 to -3 parts per thousand V-PDB). in the northeast Lawn Hill platform carbonate-rich rocks preserve marine to early diagenetic carbon and oxygen isotope compositions, whereas ferroan carbonate cements in siltstones and shales in the Desert Creek borehole are O-18 and C-13 depleted relative to the sedimentary carbonates. The good agreement between temperature estimates from illite crystallinity and organic reflectance (160 degrees-270 degrees C) and inverse correlation with carbonate delta O-18 values indicates that organic maturation and carbonate precipitation in the northeast Lawn Hill platform resulted from interaction with the 1250 to 1150 Ma fluids. The calculated isotopic compositions of the fluid are consistent with evolved basinal brine (delta O-18 = 5.1-9.4 parts per thousand V-SMOW; delta C-13 = -13.2 to -3.7 parts per thousand V-PDB) that contained a variable organic carbon component from the oxidation and/or hydrolysis of organic matter in the host sequence. The occurrence of extensive O-18- and C-13-depleted ankerite and siderite alteration in Desert Creek is related to the high temperature of the 1250 to 1150 Ma fluid-flow event in the northeast Lawn Hill platform, in contrast to the lower temperature fluids associated with the earlier Century Zn-Pb deposit in the central Lawn Hill platform.

The tribology of linear tape recording systems

This thesis is devoted to the tribology at the head~to~tape interface of linear tape recording systems, OnStream ADRTM system being used as an experimental platform, Combining experimental characterisation with computer modelling, a comprehensive picture of the mechanisms involved in a tape recording system is drawn. The work is designed to isolate the mechanisms responsible for the physical spacing between head and tape with the aim of minimising spacing losses and errors and optimising signal output. Standard heads-used in ADR current products-and prototype heads- DLC and SPL coated and dummy heads built from a AI203-TiC and alternative single-phase ceramics intended to constitute the head tape-bearing surface-are tested in controlled environment for up to 500 hours (exceptionally 1000 hours), Evidences of wear on the standard head are mainly observable as a preferential wear of the TiC phase of the AI203-TiC ceramic, The TiC grains are believed to delaminate due to a fatigue wear mechanism, a hypothesis further confirmed via modelling, locating the maximum von Mises equivalent stress at a depth equivalent to the TiC recession (20 to 30 nm). Debris of TiC delaminated residues is moreover found trapped within the pole-tip recession, assumed therefore to provide three~body abrasive particles, thus increasing the pole-tip recession. Iron rich stain is found over the cycled standard head surface (preferentially over the pole-tip and to a lesser extent over the TiC grains) at any environment condition except high temperature/humidity, where mainly organic stain was apparent, Temperature (locally or globally) affects staining rate and aspect; stain transfer is generally promoted at high temperature. Humidity affects transfer rate and quantity; low humidity produces, thinner stains at higher rate. Stain generally targets preferentially head materials with high electrical conductivity, i.e. Permalloy and TiC. Stains are found to decrease the friction at the head-to-tape interface, delay the TiC recession hollow-out and act as a protective soft coating reducing the pole-tip recession. This is obviously at the expense of an additional spacing at the head-to-tape interface of the order of 20 nm. Two kinds of wear resistant coating are tested: diamond like carbon (DLC) and superprotective layer (SPL), 10 nm and 20 to 40 nm thick, respectively. DLC coating disappears within 100 hours due possibly to abrasive and fatigue wear. SPL coatings are generally more resistant, particularly at high temperature and low humidity, possibly in relation with stain transfer. 20 nm coatings are found to rely on the substrate wear behaviour whereas 40 nm coatings are found to rely on the adhesive strength at the coating/substrate interface. These observations seem to locate the wear-driving forces 40 nm below the surface, hence indicate that for coatings in the 10 nm thickness range-· i,e. compatible with high-density recording-the substrate resistance must be taken into account. Single-phase ceramic as candidate for wear-resistant tape-bearing surface are tested in form of full-contour dummy-heads. The absence of a second phase eliminates the preferential wear observed at the AI203-TiC surface; very low wear rates and no evidence of brittle fracture are observed.

Volcanogenic mineralisation in the limestone lake area, Saskatchewan, Canada

This thesis describes the geology, geochemistry and mineralogy of a Lower Proterozoic, metamorphosed volcanogenic Cu-Zn deposit, situated at the western end of the Flin Flon greenstone belt. Stratabound copper mineralisation occurs in silicified and chloritoid-bearing alteration assemblages within felsic tuffs and is mantled by thin (< 3m) high-grade sphalerite layers. Mineralisation is underlain by garnet-hornblende bearing Lower Iron Formation (LIF), and overlain by garnet-grunerite bearing Upper Iron Formation (UIF). Distinctive trace element trends, involving Ti and Zr, in mineralised and footwall felsic tuffs are interpreted to have formed by fractionation associated with a high-level magma chamber in a caldera-type environment. Discrimination diagrams for basaltic rocks are interpreted to indicate their formation in an environment similar to that of recent, primitive, tholeiitic island arcs. Microprobe studies of key mineral phases demonstrate large and small scale chemical variations in silicate phases related to primary lithological, rather than metamorphic, controls. LIF is characterised by alumino-ferro-tschermakite and relatively Mn-poor, Ca-rich garnets, whereas UIF contains manganoan grunerite and Mn-rich garnets. Metamorphic mineral reactions are considered and possible precursor assemblages identified for garnet-, and chloritoid-bearing rocks. Chloritoid-bearing rocks are interpreted as the metamorphosed equivalents of iron-rich feeder zones formed near the surface. The iron-formations are thought to represent iron-rich sediments formed on the sea floor formed from the venting of the ore fluids. Consideration of various mineral assemblages leads to an estimate for peak metamorphic conditions of 450-500oC and > 4Kb total pressure. Comparisons with other volcanogenic deposits indicate affinities with deposits of `Mattabi-type' from the Archean of Ontario. An extrapolation of the main conclusions of the thesis to adjacent areas points to the presence of a number of geologically similar localities with potential for mineralisation.

Mechanism of uptake of the catecholic (7)-α-formamido cephalosporin BRL 41897A by klebsiella pneumoniae

The catecholic cephalosporin BRL 41897 A is resistant to β-lactamases and is taken up by bacteria via the iron transport system. The uptake of this antibiotic in E.coli uses the Fiu and Cir outer membrane proteins, whereas in P. aerugtnosa it enters via the pyochelin transport system. In this thesis mutants of K. pneumoniae resistant to BRL 41897A were isolated using TnphoA mutagenesis and used to study the mechanism of uptake of BRL 41897A by K. pneumoniae. The activity of BRL 41897A towards the parent strain (M10) was increased in iron depleted media, whereas no significant differences in the resistant (KSL) mutants were observed. Three mutants (KSL19, KSL38and KSL59) produced decreased amounts of certain iron-regulated outer membrane proteins. The uptake of 55Fe-BRL 41897A by M10 in iron-deficient medium was higher than in iron-rich medium. This result indicated the involvement of an iron transport system in the uptake of BRL 41897A by K. pneumoniae. Uptake by the KSL mutants in iron-deficient culture was higher than that by M10. This result, supported by analysis of outer membrane and periplasmic proteins of the KSL mutants, indicates that loss of one outer membrane protein can be compensated by over expression of other outer membrane and/or periplasmic proteins. However, the increased uptake of BRL 41897A by the KSL mutants did not reflect increased activity towards these strains, indicating that there are defects in the transport of BRL 41897A resulting in failure to reach the penicillin binding protein target sites in the cytoplasmic membrane. Southern blotting of chromosomal digests and sequencing in one mutant (KSL19) showed that only one copy of TnphoA was inserted into its chromosome. A putative TnphoA inserted gene in KSL19, designated kslA, carrying a signal sequence was identified. Transformation of a fragment containing the kslA gene into KSL19 cells restored the sensitivity to BRL 41897A to that of the parent strain. Data base peptide sequence searches revealed that the kslA gene in the KSL19 has some amino acid homology with the E. coli ExbD protein, which is involved in stabilisation of the TonB protein. 

Annotated record and chemical composition of ferromanganese concretions and crusts sampled from the lakes and streams of Norway

The main objective of the project was to develop a geochemical method for exploration of ores associated with granitic rocks. Fe and Mn oxidates were sampled in streambeds and lakes from 129 localities in Southeastern Norway. 65 of these localities are situated in the northern Oslo Graben. The samples were examined mineralogically and chemically by a variety of methods. Geochemical maps of the element content in oxidates show regional distribution patterns for several elements. Sampling and analysis of oxidates can be used in exploration for mineralizations such as the Skrukkelia Mo-deposit in the northern Oslo Graben. New anomalies (especially for Zn and W) have been detected. Appendix I contains a description of samples, chemical and mineralogical determinations performed on the samples, backscattered electron image-, X-ray image- and scanning electron image pictures of the oxidate preparates. Appendix II contains spectral plots, point analysis with the microprobe, X-ray diffractograms, analytical results, correlation coefficient matrix, scatterplots, frequency distributions and information on data storage. Appendix III containS maps of the element content in oxidates.

Annotated record of the detailed examination of ferromanganese concretions from the Svalbard shelf in the Barents Sea

Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

(Tables, page 17-18), Chemical composition of ferromanganese concretions of the lakes of Northern Savolax in Eastern Finland

This paper discusses the occurrence of manganese-rich concretions in the lakes of Northern Savolax in Eastern Finland. The samples were collected in the summer of 1905 and left to dry for 2 months at room temperature. The quantity of H2O mentionned in the analysis was obtained by dessication at 155°C. The amount of Mn is calulated as MnO2 although other valences might be present in the samples. The contents in CO2 and organic substances was not determined. J. Aschan determined that as a general rule, in Finland the manganese rich lake deposits are rather associated with soft bottom sediments while the iron rich deposits are more assocaited with hard or sandy bottoms.

Chemical analysis of water samples of station M1_1207, Red Sea (Table 1-3)

Two water samples and two sediment samples taken in 1965 by the R. V. "Meteor" in the area of the hot salt brine of the Atlantis II-Deep were chemically investigated, and in addition the sediment samples were subjected to X-ray and optical analysis. The investigation of the sulfur-isotope-ratios showed the same values for all water samples. This information combined with the Ca-sulfate solubility data leads us to conclude that, for the most part, the sulfate content of the salt brine resulted from mixing along the boundary with the normal seawater. In this boundary area gypsum or anhydrite is formed which sinks down to the deeper layers of the salt brine where it is redisolved when the water becomes undersaturated. In the laboratory, formation of CaS04 precipitate resulted from both the reheating of the water sample from the uppermost zone of the salt brine to the in-situ-temperature as well as by the mixing of the water sample with normal Red Sea water. The iron and manganese delivered by the hot spring is separated within the area of the salt brine by their different redox-potentials. Iron is sedimented to a high amount within the salt brine, while, as evidenced by its small amounts in all sediment samples, the more easily reducible manganese is apparently carried out of the area before sedimentation can take place. The very good layering of the salt brine may be the result of the rough bottom topography with its several progressively higher levels allowing step-like enlargements of the surface areas of each successive layer. Each enlargement results in larger boundary areas along which more effective heat transfer and mixing with the next layer is possible. In the sediment samples up to 37.18% Fe is found, mostly bound as very poorly crystallized iron hydroxide. Pyrite is present in only very small amounts. We assume that the copper is bound mostly as sulfide, while the zinc is most likely present in an other form. The sulfur-isotope-investigations indicate that the sulfur in the sediment, bound as pyrite and sulfides, is not a result of bacterical sulfate-reduction in the iron-rich mud of the Atlantis II-Deep, but must have been brought up with the hot brine.

Chemical composition of manganese micronodules from expedition VA-05/1 in the Pacific Ocean

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel "Valdivia" during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm2 effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn K alpha X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi 238Pu source. The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise. Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.

(Table 2, page 50) Toolik lake sediment chemistry (0-1 cm interval)

The sediments within Toolik Lake in arctic Alaska are characterized by extremely low rates of organic matter sedimentation and unusually high concentrations of iron and manganese. Pore water and solid phase measurements of iron, manganese, trace metals, carbon, nitrogen, phosphorus, and sulfur are consistent with the hypothesis that the reduction of organic matter by iron and manganese is the most important biogeochemical reaction within the sediment. Very low rates of dissolved oxygen consumption by the sediments result in an oxidizing environment at the sediment-water interface. This results in high retention of upwardly-diffusing iron and manganese and the formation of metal-enriched sediment. Phosphate in sediment pore waters is strongly adsorbed by the metal-enriched phases. Consequently, fluxes of phosphorus from the sediments to overlying waters are very small and contribute to the oligotrophic nature of the Toolik Lake aquatic system. Toolik Lake contains an unusual type of lacustrine sediment, and in many ways the sediments are similar to those found in oligotrophic oceanic environments.

Sediment and pore water chemistry and physical oceanography of samples obtained during Baltic Sea research cruises

Sediment samples from approximately 40 stations in the Western, middle and eastern Baltic Sea were investigated for manganese and iron content. In a series of interstitial water samples and numerous deep and surface water samples, the manganese content was likewise determined. A strong enrichment of these elements in the basin sediments was shown. In many instances, several percent manganese were present. As a maximum value, 13% was found in a 1 mm thick layer. Furthermore, a distinct decrease in manganese content with increasing sediment depth was shown in the upper 10 to 20 cm of the Sediment at almost all stations. Both phenomena may be explained by the release of manganese from the Sediment through diffusion. In the flat parts of the Baltic and those parts having good bottom water circulation, this diffusion progresses especially vigorously as a result of a steep gradient of the Mn++ concentration in the interstitial water-deep water interface. The manganese which hereby passes into the water overlying the bottom (manganese contents between 10 and 100 y Mn/l were determined in numerous deep water samples) is partly reprecipitated on the Sediment surface, and partly carried by currents into the deeper basins where it is finallv deposited. It is bound there as a manganese-rich mixed carbonate, the composition of which can be proved chemically and by x-ray methods. Iron is likewise of higher content in the basinal sediments, however, the extent of its enrichment is far less since it is less soluble than manganese under the reducing conditions in the sediments. The fine bands of manganese- and iron-rich layers in the basin sediments may likewise be explained as a result of diffusion.