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.

Benthic foraminiferal record of the Pleistocene uplift of the sedimentary deposits of the Burica Peninsula (Costa Rica-Panama) as a result of Cocos Ridge subduction beneath the Central American Arc

This study used paleobathymetric interpretations from benthic foraminiferal assemblages to determine the timing of the initial subduction of the Cocos Ridge beneath the Costa Rica-Panama Arc and the associated amount of uplift. Forty-seven samples from four stratigraphic sections of the Burica and the Armuelles formations yielded 217 identified species. Foraminiferal paleoecology and cluster analyses indicated paleobathymetric differences within and between the sections. Maximum and minimum uplift rates were calculated from the biochronology, elevation, paleobathymetry and estimated eustatic changes. Large decreases in paleobathymetry were mainly due to the initial middle Pleistocene subduction of the Cocos Ridge in less than 0.5 Ma. Uplift rates were uneven across the Burica Peninsula, as follows: La Vaca 4.5–0.8 m/ky, Rabo de Puerco 2.8–0.7 m/ky, San Bartolo–Chiquito 2.7–0.8 m/ky, and eastern coast 8.0–1.5 m/ky. These differences probably resulted from Cocos Ridge asymmetry and differential uplift of tectonic blocks.

The effects of manipulation of sedimentary iron and organic matter on sediment biogeochemistry and seagrasses in a subtropical carbonate environment

The microbial metabolism of organic matter (OM) in seagrass beds can create sulfidic conditions detrimental to seagrass growth; iron (Fe) potentially has ameliorating effects through titration of the sulfides and the precipitation of iron-sulfide minerals into the sediment. In this study, the biogeochemical effects of Fe availability and its interplay with sulfur and OM on sulfide toxicity, phosphorous (P) availability, seagrass growth and community structure were tested. The availability of Fe and OM was manipulated in a 2 × 2 factorial experiment arranged in a Latin square, with four replicates per treatment. The treatments included the addition of Fe, the addition of OM, the addition of both Fe and OM as well as no addition. The experiment was conducted in an oligotrophic, iron-deficient seagrass bed. Fe had an 84.5% retention efficiency in the sediments with the concentration of Fe increasing in the seagrass leaves over the course of the experiment. Porewater chemistry was significantly altered with a dramatic decrease in sulfide levels in Fe addition plots while sulfide levels increased in the OM addition treatments. Phosphorus increased in seagrass leaves collected in the Fe addition plots. Decreased sulfide stress was evidenced by heavier δ34S in leaves and rhizomes from plots to which Fe was added. The OM addition negatively affected seagrass growth but increased P availability; the reduced sulfide stress in Fe added plots resulted in elevated productivity. Fe availability may be an important determinant of the impact that OM has on seagrass vitality in carbonate sediments vegetated with seagrasses.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

Modes of sapropel formation in the eastern Mediterranean: some constraints based on pyrite properties

Pyrite formation within and directly below sapropels in the eastern Mediterranean was governed by the relative rates of sulphide production and Fe liberation and supply to the organic-rich layers. At times of relatively high [SO4]2- reduction, sulphide could diffuse downward from the sapropel and formed pyrite in underlying sediments. The sources of Fe for pyrite formation comprised detrital Fe and diagenetically liberated Fe(II) from sapropel-underlying sediments. In organic-rich sapropels, input of Fe from the water column via Fe sulphide formation in the water may have been important as well. Rapid pyrite formation at high saturation levels resulted in the formation of framboidal pyrite within the sapropels, whereas below the sapropels slow euhedral pyrite formation at low saturation levels occurred. d34S values of pyrite are -33 per mil to -50 per mil. Below the sapropels d34S is lower than within the sapropels, as a result of increased sulphide re-oxidation at times of relatively high sulphide production and concentration when sulphide could escape from the sediment. The percentage of initially formed sulphide that was re-oxidized was estimated from organic carbon fluxes and burial efficiencies in the sediment. It ranges from 34% to 80%, varying significantly between sapropels. Increased palaeoproductivity as well as enhanced preservation contributed to magnified accumulation of organic matter in sapropels.

Pirometamorfismo em calcários da formação Jandaíra, bacia potiguar, nordeste do Brasil

The present study aims the characterization of thermally affected carbonate rocks from Jandaíra Formation in contact with Paleogene and Neogene basic intrusions in the region of the Pedro Avelino and Jandaíra municipalities (RN), northeastern Brazil. For this study, field, petrographic, x-ray diffraction, electron microprobe, and whole rock litogeochemistry data of carbonates were undertaken. The thermally unaffected limestones are classified like wackstones, grainstones and packstones. They may constitute carbonates grains of benthic foraminifera, echinoderm spines, ostracods, algae, corals, bivalves, gastropods, peloids and intraclasts. The porosities are classified like vug, intraparticle, interparticle, intercrystal and moldic types. The major minerals are calcite, ankerite and dolomite; the detrital are montmorillonite, pyrite, limonite, quartz and microcline. The thermally affected limestones are very coarse to very fine-grained and light to dark gray color. The fossiliferous components totally disappear, and the porosity tends to disappear. With the data obtained, it can be inferred that the carbonate protoliths would be calciferous to dolomitic limestones, both with small amount of clay minerals. Crystalline carbonates from dolomitic protolith have rhombohedral calcite and iron oxides / hydroxides, making the rocks much darker. The carbonates from calciferous protolith have a wide variation of grain size according to the recrystallization degree, increasing toward contact with the basic bodies. In this group, it was identified the minerals lizardite and spinel in weakly to moderately affected samples, and spinel and spurrite in strongly affected rocks, as well as calcite, that occur everywhere. The geological context (shallow level diabase intrusions), the crystallization of the pyrometamorphic minerals spurrite and olivine, and comparison with diagrams from the literature allow estimating temperatures and pressures around 1050-1200 °C and 0.5-1.0 kbar, respectively, for PTOTAL=PCO2. The post-intrusion cooling would have afforded the releasing of metasomatic / hydrothermal fluids, allowing the opening of the metamorphic system, with possible contribution of chemical elements from host units (sandstones, shales) and from basic intrusions. This would induce hydration of previous phases, allowing the formation of serpentine, chlorite and brucite. The results discussed here reveal the strong influence of the heat from basic intrusions within the sedimentary pile. Whereas in the offshore portion of the basin occur sills with up to 1000 m thickness, the understanding of pyrometamorphism might be useful for understanding and measuring the thermally affected rocks.

Pirometamorfismo em calcários da formação Jandaíra, bacia potiguar, nordeste do Brasil

The present study aims the characterization of thermally affected carbonate rocks from Jandaíra Formation in contact with Paleogene and Neogene basic intrusions in the region of the Pedro Avelino and Jandaíra municipalities (RN), northeastern Brazil. For this study, field, petrographic, x-ray diffraction, electron microprobe, and whole rock litogeochemistry data of carbonates were undertaken. The thermally unaffected limestones are classified like wackstones, grainstones and packstones. They may constitute carbonates grains of benthic foraminifera, echinoderm spines, ostracods, algae, corals, bivalves, gastropods, peloids and intraclasts. The porosities are classified like vug, intraparticle, interparticle, intercrystal and moldic types. The major minerals are calcite, ankerite and dolomite; the detrital are montmorillonite, pyrite, limonite, quartz and microcline. The thermally affected limestones are very coarse to very fine-grained and light to dark gray color. The fossiliferous components totally disappear, and the porosity tends to disappear. With the data obtained, it can be inferred that the carbonate protoliths would be calciferous to dolomitic limestones, both with small amount of clay minerals. Crystalline carbonates from dolomitic protolith have rhombohedral calcite and iron oxides / hydroxides, making the rocks much darker. The carbonates from calciferous protolith have a wide variation of grain size according to the recrystallization degree, increasing toward contact with the basic bodies. In this group, it was identified the minerals lizardite and spinel in weakly to moderately affected samples, and spinel and spurrite in strongly affected rocks, as well as calcite, that occur everywhere. The geological context (shallow level diabase intrusions), the crystallization of the pyrometamorphic minerals spurrite and olivine, and comparison with diagrams from the literature allow estimating temperatures and pressures around 1050-1200 °C and 0.5-1.0 kbar, respectively, for PTOTAL=PCO2. The post-intrusion cooling would have afforded the releasing of metasomatic / hydrothermal fluids, allowing the opening of the metamorphic system, with possible contribution of chemical elements from host units (sandstones, shales) and from basic intrusions. This would induce hydration of previous phases, allowing the formation of serpentine, chlorite and brucite. The results discussed here reveal the strong influence of the heat from basic intrusions within the sedimentary pile. Whereas in the offshore portion of the basin occur sills with up to 1000 m thickness, the understanding of pyrometamorphism might be useful for understanding and measuring the thermally affected rocks.

TOC, TN, and sedimentary d15N and d13C ratios of sediment core SO201-2-85

We present high-resolution records of sedimentary nitrogen (d15Nbulk) and carbon isotope ratios (d13Cbulk) from piston core SO201-2-85KL located in the western Bering Sea. The records reflect changes in surface nitrate utilization and terrestrial organic matter contribution in submillennial resolution that span the last 180 kyr. The d15Nbulk record is characterized by a minimum during the penultimate interglacial indicating low nitrate utilization (~62-80%) despite the relatively high export production inferred from opal concentrations along with a significant reduction in the terrestrial organic matter fraction (mterr). This suggests that the consumption of the nitrate pool at our site was incomplete and even more reduced than today (~84%). d15Nbulk increases from Marine Isotope Stage (MIS) 5.4 and culminates during the Last Glacial Maximum, which indicates that nitrate utilization in the Bering Sea was raised during cold intervals (MIS 5.4, 5.2, 4) and almost complete during MIS 3 and 2 (~93-100%). This is in agreement with previous hypotheses suggesting that stronger glacial stratification reduced the nutrient supply from the subeuphotic zone, thereby increasing the iron-to-nutrient ratio and therefore the nitrate utilization in the mixed surface layer. Large variations in d15Nbulk were also recorded from 180 to 130 ka BP (MIS 6), indicating a potential link to insolation and sea-level forcing and its related feedbacks. Millennial-scale oscillations were observed in d15Nbulk and d13Cbulk that might be related to Greenland interstadials.

Chemical and mineral composition of rocks from the Philippine Sea

The book is devoted to geology of the Philippine Sea floor. This region is studied most extensively among other marginal seas of the Pacific Ocean. Rocks of the sedimentary and basalt layers within this sea have been studied during five legs of D/S Glomar Challenger. International geological expedition on board R/V Dmitry Mendeleev carried out according to the Project ''Ophiolites of Continents and Comparable Rocks of the Ocean Floor''obtained unique collection of rocks from the second and third layers of the ocean crust in the Philippine Sea. The book provides detailed petrographic and geochemical description of igneous and sedimentary formations from the Philippine Sea and compares them with rocks of the continental ophiolite association. An analysis of structure and history of the ocean crust formation in the region is based on all known geological information. The main periods of tectonic movement activation and nature of their manifestations within the sea are shown.

(Table 3) Isotopic composition of pyrite sulfur and carbonate carbon in carbonate nodules and host sediments from Core DM9-666, Gulf of California

Isotopic-geochemical study revealed presence of mantle He (3He/4He up to 223x10**-8) in gases from mud volcanoes of Eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations of carbon isotopic composition d13C in CH4 and CO2 and chemical composition of gas and water at temporally constant 3He/4He ratio indicate their relation with crustal processes. Unusual direct correlations of 3He/4He ratio with concentrations of He and CH4 and 40Ar/36Ar ratio can be explained by generation of gas in the Cenozoic sequence of the Middle Kura basin.

Chemical composition of bottom sediments and sedimentary rocks from the Pilippine Sea

Data on chemical composition of bottom sediments from some polygons in the Philippine Sea are reported. Areal and vertical variability of major and trace element contents in bottom sediments is analyzed for clarifying sedimentation features and diagenetic migration of the elements in the upper part of the sedimentary sequence.

Sedimentary record of the western Amundsen Sea Embayment after the last glacial maximum

Reliable dating of glaciomarine sediments deposited on the Antarctic shelf since the Last Glacial Maximum (LGM) is very challenging because of the general absence of calcareous (micro-) fossils and the recycling of fossil organic matter. As a consequence, radiocarbon (14C) ages of the acid-insoluble organic fraction (AIO) of the sediments bear uncertainties that are very difficult to quantify. In this paper we present the results of three different chronostratigraphic methods to date a sedimentary unit consisting of diatomaceous ooze and diatomaceous mud that was deposited following the last deglaciation at five core sites on the inner shelf in the western Amundsen Sea (West Antarctica). In three cores conventional 14C dating of the AIO in bulk sediment samples yielded age reversals down-core, but at all sites the AIO 14C ages obtained from diatomaceous ooze within the diatom-rich unit yielded similar uncorrected 14C ages ranging from 13,517±56 to 11,543±47 years before present (yr BP). Correction of these ages by subtracting the core-top ages, which are assumed to reflect present-day deposition (as indicated by 21044 Pb dating of the sediment surface at one core site), yielded ages between ca. 10,500 and 8,400 calibrated years before present (cal yr BP). Correction of the AIO ages of the diatomaceous ooze by only subtracting the marine reservoir effect (MRE) of 1,300 years indicated deposition of the diatom-rich sediments between 14,100 and 11,900 cal yr BP. Most of these ages are consistent with age constraints between 13.0 and 8.0 ka BP for the diatom-rich unit, which we obtained by correlating the relative palaeomagnetic intensity (RPI) records of three of the sediment cores with global and regional reference curves for palaeomagnetic intensity. As a third dating technique we applied conventional 53 radiocarbon dating of the AIO included in acid-cleaned diatom hard parts that were extracted from the diatomaceous ooze. This method yielded uncorrected 14C ages of only 5,111±38 and 5,106±38 yr BP, respectively. We reject these young ages, because they are likely to be overprinted by the adsorption of modern atmospheric carbon dioxide onto the surfaces of the extracted diatom hard parts prior to sample graphitisation and combustion for 14C dating. The deposition of the diatom-rich unit in the western Amundsen Sea suggests deglaciation of the inner shelf before ca. 13 ka BP. The deposition of diatomaceous oozes on other parts of the Antarctic shelf around the same time, however, seems to be coincidental rather than directly related.

Sedimentary record of the western Amundsen Sea Embayment

The Amundsen Sea Embayment (ASE) drains approximately 35% of the West Antarctic Ice Sheet (WAIS) and is one of the most rapidly changing parts of the cryosphere. In order to predict future ice-sheet behaviour, modellers require long-term records of ice-sheet melting to constrain and build confidence in their simulations. Here, we present detailed marine geological and radiocarbon data along three palaeo-ice stream tributary troughs in the western ASE to establish vital information on the timing of deglaciation of the WAIS since the Last Glacial Maximum (LGM). We have undertaken multi-proxy analyses of the cores (core description, shear strength, x-radiographs, magnetic susceptibility, wet bulk density, total organic carbon/nitrogen, carbonate content and clay mineral analyses) in order to: (1) characterise the sedimentological facies and depositional environments; and (2) identify the horizon(s) in each core that would yield the most reliable age for deglaciation. In accordance with previous studies we identify three key facies, which offer the most reliable stratigraphies for dating deglaciation by recording the transition from a grounded ice sheet to open marine environments. These facies are: i) subglacial, ii) proximal grounding-line, and iii) seasonal open-marine. In addition, we incorporate ages from other facies (e.g., glaciomarine diamictons deposited at some distance from the grounding line, such as glaciogenic debris flows and iceberg rafted diamictons and turbates) into our deglacial model. In total, we have dated 78 samples (mainly the acid insoluble organic (AIO) fraction, but also calcareous foraminifers), which include 63 downcore and 15 surface samples. Through careful sample selection prior to dating, we have established a robust deglacial chronology for this sector of the WAIS. Our data show that deglaciation of the western ASE was probably underway as early as 22,351 calibrated years before present (cal 44 yr BP), reaching the mid-shelf by 13,837 cal yr BP and the inner shelf to within c.10-12 km of the present ice shelf front between 12,618 and 10,072 cal yr BP. The deglacial steps in the western ASE broadly coincide with the rapid rises in sea-level associated with global meltwater pulses 1a and 1b, although given the potential dating uncertainty, additional, more precise ages are required before these findings can be fully substantiated. Finally, we show that the rate of ice-sheet retreat increased across the deep (up to1,600 m) basins of the inner shelf, highlighting the importance of reverse slope and pinning points in accelerated phases of deglaciation.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.