Macerals in sediments

The study of particulate organic matter (OM) in Arctic Ocean sediments from the Late Cretaceous to the Eocene (IODP Expedition 302) has revealed detailed information about the aquatic/marine OM fluxes, biological sources, preservation and export of terrestrial material. Here, we present detailed data from maceral analysis, vitrinite reflectance measurements and organic geochemistry. During the Campanian/Paleocene, fluxes of land-derived OM are indicated by reworked and oxidized macerals (vitrinite, inertinite) and terrigenous liptinite (cutinite, sporinite). In the Early Eocene, drastic environmental changes are indicated by peaks in aquatic OM (up to 40-45%, lamalginite, telalginite, liptodetrinite, dinoflagellate cysts) and amorphous OM (up to 50% bituminite). These events of increased aquatic OM flux, similar to conditions favoring black shale deposition, correlate with the global d13C events "Paleocene/Eocene Thermal Maximum" (PETM) and "Elmo-event". Freshwater discharge and proximity of the source area are documented by freshwater algae material (Pediastrum, Botryococcus) and immature land-plant material (corphuminite, textinite). We consider that erosion of coal-bearing sediments during transgression time lead to humic acids release as a source for bituminite deposited in the Early Eocene black shales.

Rock eval analysis of organic matter in sediment core 159-959D

The Cretaceous Equatorial Atlantic Gateway between the Central and South Atlantic basins is of interest not only for paleoceanographic and paleoclimatic studies, but also because it provided particularly favourable conditions for the accumulation and preservation of organic-rich sediments. Deposition of carbonaceous sediments along the Côte d'Ivoire-Ghana Transform Margin (Ocean Drilling Program Leg 159) was intimately linked to the plate tectonic and paleoceanographic evolution of this gateway. Notably, the formation of a marginal basement ridge on the southeastern border of the transform margin provided an efficient shelter of the landward Deep Ivorian Basin against erosive and potentially oxidizing currents. Different subsidence histories across the transform margin were responsible for the development of distinct depositional settings on the crest and on both sides of the basement ridge. Whereas the southern, oceanward flank of the basement ridge was characterized by rapid, continuous deepening since last Albian-early Cenomanian, marine sedimentation on the northern, landward flank was interrupted by a period of uplift and erosion in the late Albian, and rapid subsidence started after the early Coniacian. Organic-rich sediments occur throughout almost the entire Cretaceous section, but hydrogen-rich marine black shales were exclusively recovered from core sections above an uplift-related unconformity. These black shales formed when separation of Africa and South America was sufficient to allow permanent oceanic midwater exchange after the late Albian. Four periods of black shale accumulation are recovered, some of them are correlated with the global oceanic anoxic events: in the last Albian-earliest Cenomanian, at the Cenomanian-Turronian boundary, during the middle Coniacian-early Campanian, and in the mid-Maastrichtian. These periods were characterized by increasing carbon flux to the seafloor, induced by enhanced palaeoproductivity and intensified supply of terrestrial organic matter. Black shale depostion appears to be intimately linked to periods of rising or maximum eustatic sea level and to the expansion of the oxygen minimum zone, as indicated by foraminiferal biofacies. Intervals between black shales units, in contrast, indicate a shrinking oxygen minimum zone and enhanced detrital flux rates, probably related to lowering sea level. Upper Cretaceous detritral limestones with high porosities may provide excellent hydrocarbon reservoirs, alsthough their areal extent appears to be limited. Palaeogene porcellanites, capped by Neogene pelagic marls and clays, extend over a wider area and max provide another target for hydrocarbon exploration.

Geochemistry and stable isotope record of black shales and inoceramids from the Demerara Rise

The bulk rock geochemistry and inoceramid isotopic composition from Cenomanian to Santonian, finely laminated, organic-rich black shales, recovered during Ocean Drilling Program Leg 207 on Demerara Rise (western tropical North Atlantic), suggest persistent anoxic (free H2S) conditions within the sediments and short-term variations within a narrow range of anoxic to episodically dysoxic bottom waters over a ~15 Ma time interval. In addition to being organic-rich, the 50-90 m thick sections examined exhibit substantial bulk rock enrichments of Si, P, Ba, Cu, Mo, Ni, and Zn relative to World Average Shale. These observations point to high organic burial fluxes, likely driven by high primary production rates, which led to the establishment of intensely sulfidic pore waters and possibly bottom waters, as well as to the enrichments of Cr, Mo, U, and V in the sediments. At the same time, the irregular presence of benthic inoceramids and foraminifera in this facies demonstrates that the benthic environment could not have been continuously anoxic. The d13C and d15N values of the inoceramid shell organics provide no evidence of chemosymbiosis and are consistent with pelagic rain as being a significant food source. Demerara Rise inoceramids also exhibit well-defined, regularly spaced growth lines that are tracked by d13C and d18O variations in shell carbonate that cannot be simply explained by diagenesis. Instead, productivity variations in surface waters may have paced the growth of the shells during brief oxygenation events suitable for benthic inoceramid settlement. These inferences imply tight benthopelagic coupling and more dynamic benthic conditions than generally portrayed during black shale deposition. By invoking different temporal scales for geochemical and paleontological data, this study resolves recent contradictory conclusions (e.g., sulfidic sedimentary conditions versus dysoxic to suboxic benthic waters) drawn from studies of either sediment geochemistry or fossil distributions alone on Demerara Rise. This variability may be relevant for discussions of black shales in general.

Cretaceous nannofossils of southeast France

The Aptian-lower Albian succession of the Vocontian Basin (SE France) consists of marine hemipelagic sediments including several black shale horizons. The latter are partly of regional and partly of global distribution. This sedimentary succession records the nannoplankton evolution of the Aptian-early Albian interval and thus provides an excellent opportunity to calibrate the calcareous nannofossil record with Tethyan ammonite and planktic foraminiferal biostratigraphy. The calcareous nannofossil biostratigraphy presented in this paper supports previous zonations, but it also provides a much higher resolution and thus improves the correlation of different black shale horizons on a supraregional scale. Up to 23 major (supraregionally significant) and minor (regionally significant) first and last occurrences of calcareous nannofossil taxa are recognized. Nannoconid abundances decrease rapidly in the upper Lower Aptian (nannoconid crisis I, NCI) and in the middle Upper Aptian (nannoconid crisis II, NCII). Both decreases correlate with carbonate-platform drowning events. The upper Lower Aptian interval above the NCI is characterized by high abundances of large specimens of Assipetra infracretacea and Rucinolithus terebrodentarius probably of supraregional significance. The uppermost Aptian-Lower Albian is characterized by high abundances of the calcareous nannoplankton taxon Repagulum parvidentatum, reflecting boreal influence on the Tethyan Realm. This suggests a temporary decrease in surface-water temperatures in the Vocontian Basin.

Geologic screening report for evaluation of eastern gas shales in Pennsylvania /

Cover title: Evaluation of Devonian shale potential in Pennsylvania.

The distribution and properties of the shales of South Carolina

Mode of access: Internet.

Clays and shales of Washington,

Mode of access: Internet.

Special reports on the mineral resources of Great Britain.

v.31 Ball clays -- v.32 Granites of Scotland -- v.33 Synopsis of the mineral resources of Scotland -- v.34 Rock wool -- v. 35 Limestones of Scotland -- v.36 Cambro-Ordovician limestones and dolomites of the Ord and Torran areas, SKye and the Kishorn area, Ross-Shire -- v.37 Limestones of Scotland : chemical analyses and petrography

Metalliferous black shales and related ore deposits : program and abstracts : 1988 meeting of the United States Working Group of International Geological Correlation Program Project 254 /

Mode of access: Internet.

A. Geology and mineral paragenesis of the Pea Ridge Iron Ore Mine, Washington County, Missouri : origin of the rare-earth-element- and goldbearing breccia pipes /

Includes bibliographical references.

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay. minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite-smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R greater than or equal to 3) illite-smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less. illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)(sn) ratios show negative correlations with the illite content in illite-smectite and positive correlations with the delta(18)O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)(sn) ratios and illite content in illite-smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/ rock ratio conditions. Increasing HREE enrichment with delta(18)O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins. (C) 2003 Elsevier Science B.V. All rights reserved.

A redescription of Atopacanthus dentatus Hussakof and Bryant, 1918 (Acanthodii, Ischnacanthidae)

The holotype specimen of the ischnacanthid acanthodian Alopacanthus dentatus comprises most of the posterior half of a dentigerous jaw bone, rather than a fragment from the middle of the jaw as was previously believed. A new diagnosis and revised description for the taxon are based on the holotype from the Rhinestreet Shale (Frasnian) and other specimens front the North Evans and Genundewa limestones (early Frasnian) of the Genesee Formation (late Givetian-early Frasnian); all of: these dentigerous jaw bones were collected near Hamburg, New York state, U.S.A. An emended diagnosis for Atopacanthus clarifies the differences between it and other ischnacanthid genera.

Geochemistry of late Archaean stromatolites from Zimbabwe: evidence for microbial life in restricted epicontinental seas

We report comprehensive trace element and Sr-isotope data for microbial carbonates from the Archaean Mushandike limestone, Masvingo Greenstone Belt, Zimbabwe. The stromatolites have very coherent REE + Y patterns and share the essential shale-normalised characteristics of other Archaean marine precipitates (positive La and Gd anomalies, absence of a negative Cc anomaly and a strongly superchondritic Y/Ho ratio). Mixing models constrain the maximum amount of shale contamination to 0.25-1% and calculated detritus-free carbonate REE + Y systematics require precipitation from seawater. In terms of light-REE over heavy-REE depletion, however, the studied samples are very different from all other known Archaean marine precipitates. In shale-normalised plots, the Mushandike samples yield a negative slope. A very restricted, regional input source of the dissolved load is indicated because normalisation with locally occurring tonalite gneiss REE + Y data yields a pattern closely resembling typical shale-normalised Archaean marine chemical sediments. The disappearance of a negative Eu anomaly when patterns are normalised with local tonalite gneiss strengthens this interpretation. Sr-isotope ratios are strongly correlated with trace element contents and ratios, which explains the modest scatter in Sr-isotope ratios as representing (minor) clastic contamination. Importantly, even the least contaminated samples have very radiogenic initial Sr-87/Sr-86 ratios (0.7184) implying Sr input from an ancient high Rb/Sr source, such as the early Archaean gneisses of south-central Zimbabwe. A local ancient (3.5-3.8 Ga) source is also indicated by previously published Pb-isotope datasets for the Mushandike stromatolites. This is entirely compatible with the occurrence of 3.7-3.8 Ga zircons in quartzites and metapelites from comparably old greenstone belts within less than 150 km of the studied locality. Comparison of the Pb-isotope ratios of the Mushandike stromatolites with 2.7 and 2.6 Ga old stromatolites from the neighbouring, Belingwe Greenstone Belt demonstrates differences in initial isotope composition that relate to the extent of exchange with the open ocean. The development of numerous basins on old continental crust, with water masses variably restricted from the open ocean. suggests a lack of strong vertical topography on this late Archaean craton. (C) 2004 Elsevier B.V. All rights reserved.

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation, in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter-rich black shales rather than in sandstones, siltstones and organic matter-poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity-permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity-permeability and organic matter alteration, suitable for subsequent mineral precipitation. K-Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 +/- 150 (2sigma) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity-permeability creation. Those rocks lacking sufficient porosity-permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.

Rare earth element geochemistry of Late Devonian reefal carbonates, canning basin, Western Australia: Confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd-SN/Yb-SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd-SN/Yb-SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modem seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans. Copyright (C) 2004 Elsevier Ltd.