The geochemistry of the sedimentary rocks of the Harlech Dome, North Wales

Bedrock geochemical analysis, coupled with detailed data analysis, was carried out on some 260 samples taken from two areas of 'the Harlech Dome, near Dolgellau, North Wales. This was done to determine if rocks from mineralised and non-mineralised areas could be distinguished, and to determine mineralisation types and wall rock alterations. The Northern Area, near Talsarnau, has no recorded mineralisation, while the Southern Area, near Bontddu, has been exploited for gold. The rocks sampled, in both areas, were from the Cambrian Gamlan Flags, Clogau Shales, Vigra Flags, later vein materials, and igneous intrusions. All samples were analysed, using a new rapid, atomic absorption spectrophotometric technique, for Si, AI, Fe, Cu, Ni, Zn, Pb, Sr, Hg, and Ba. In addition 60 samples were analysed by X-ray fluorescence for Mn, Ti, Ca, K, Na, P, Cr, Ce, La, S, Y , Rh, and Th. Total CO2 was determined, on selected samples, using a combustion technique. Elemental distributions, for each rock type, in each area, were· plotted, and means, standard deviations, and enrichment indices were calculated. Multivariate statistical analysis on the results distinguished a Cu-type mineralisation in the Northern area, and both Cu and Pb/Zn types in the Southern Area. It also showed the Northern Area to be less strongly mineralised than the Southern one in which both mineralisation types are associated with wall rock alteration. Elemental associations and trends due to sedimentary processes were distinguished from those related to mineralisation. Hg is related to mineralisation, and plots of factor scores, on the sampling grid, produced clusters of mineralisation related factors in areas of known mineralisation. A double Fourier Trend Analysis program, with a wavelength search routine, was developed and used to recognise sedimentary trends for Sr. Y., Rb, and Th. These trends were interpreted to represent areas of low pH and reducing conditions. They also indicate that the supply of sediment remained constant over Gamlan, Clogau, and Vigra times. The trend surface of Hg showed no association with rock type. It is shown that analysis of a small number of samples, for a carefully selected number of elements, with detailed data analysis, can provide more useful information than analysis of a large number of samples for many elements. The mineralisation is suggested to have been the result of water solutions leaching ore metals from the sedimentary rocks and redepositing them in veins.

Diagenetic processes in ore formation with special reference to the Zambian copperbelt and permian marl slate.

This thesis is concerned with the role of diagenesis in forming ore deposits. Two sedimentary 'ore-types' have been examined; the Proterozoic copper-cobalt orebodies of the Konkola Basin on the Zambian Copperbelt, and the Permian Marl Slate of North East England. Facies analysis of the Konkola Basin shows the Ore-Shale to have formed in a subtidal to intertidal environment. A sequence of diagenetic events is outlined from which it is concluded that the sulphide ores are an integral part of the diagenetic process. Sulphur isotope data establish that the sulphides formed as a consequence of the bacterial reduction of sulphate, while the isotopic and geochemical composition of carbonates is shown to reflect changes in the compositions of diagenetic pore fluids. Geochemical studies indicate that the copper and cobalt bearing mineralising fluids probably had different sources. Veins which crosscut the orebodies contain hydrocarbon inclusions, and are shown to be of late diagenetic lateral secretion origin. RbiSr dating indicates that the Ore-Shale was subject to metamorphism at 529 A- 20 myrs. The sedimentology and petrology of the Marl Slate are described. Textural and geochemical studies suggest that much of the pyrite (framboidal) in the Marl Slate formed in an anoxic water column, while euhedral pyrite and base metal sulphides formed within the sediment during early diagenesis. Sulphur isotope data confirm that conditions were almost "ideal" for sulphide formation during Marl Slate deposition, the limiting factors in ore formation being the restricted supply of chalcophile elements. Carbon and oxygen isotope data, along with petrographic observations, indicate that much of the calcite and dolomite occurring in the Marl Slate is primary, and probably formed in isotopic equilibrium. A depositional model is proposed which explains all of the data presented and links the lithological variations with fluctuations in the anoxicioxic boundary layer of the water column.