https://homepages.uc.edu/~algeot/Tribovillard-Algeo-etal-CG-2006.pdf

Trace metals as paleoredox and paleoproductivity proxies: An update

Pore systems in sedimentary carbonates are generally complex in their geometry and genesis, and commonly differ markedly from those of sandstones. Current nomenclature and classifications appear inadequate for concise description or for interpretation of porosity in sedimentary carbonates. In this article we review current nomenclature, propose several new terms, and present a classification of porosity which stresses interrelations between porosity and other geologic features. The time and place in which porosity is created or modified are important elements of a genetically oriented classification. Three major geologic events in the history of a sedimentary carbonate form a practical basis for dating origin and modification of porosity, independent of the stage of lithification. These events are (1) creation of the sedimentary framework by clastic accumulation or accretionary precipitation (final deposition), (2) passage of a deposit below the zone of major influence by processes related to and operating from the deposition surface, and (3) passage of the sedimentary rock into the zone of influence by processes operating from an erosion surface (unconformity). The first event, final deposition, permits recognition of predepositional, depositional, and post epositional stages of porosity evolution. Cessation of final deposition is the most practical basis for distinguishing primary and secondary (postdepositional) porosity. Many of the key postdepositional changes in sedimentary carbonates and their pore systems occur near the surface, either very early in burial history or at a penultimate stage associated with uplift and erosion. Porosity created or modified at these times commonly can be differentiated. On the basis of the three major events heretofore distinguished, we propose to term the early burial stage "eogenetic," the late stage "telogenetic," and the normally very long intermediate stage "mesogenetic." These new terms are also applicable to process, zones of burial, or porosity formed in these times or zones (e.g., eogenetic ceme tation, mesogenetic zone, telogenetic porosity). The proposed classification is designed to aid in geologic description and interpretation of pore systems End_Page 207------------------------------ and their carbonate host rocks. It is a descriptive and genetic system in which 15 basic porosity types are recognized: seven abundant types (interparticle, intraparticle, intercrystal, moldic, fenestral, fracture, and vug), and eight more specialized types. Modifying terms are used to characterize genesis, size and shape, and abundance of porosity. The genetic modifiers involve (1) process of modification (solution, cementation, and internal sedimentation), (2) direction or stage of modification (enlarged, reduced, or filled), and (3) time of porosity formation (primary, secondary, predepositional, depositional, eogenetic, mesogenetic, and telogenetic). Used with the basic porosity type, these genetic modifiers permit explicit designation of porosity origin and evolution. Pore shapes are classed as irregular or regular, and the latter are subdivided into equant, tubular, and platy shapes. A grade scale for size of regular-shaped pores, utilizing the average diameter of equant or tubular pores and the width of platy pores, has three main classes: micropores (< 1/16 mm), mesopores (1/16-4 mm), and megapores (4-256 mm). Megapores and mesopores are divided further into small and large subclasses. Abundance is noted by percent volume and/or by ratios of porosity types. Most porosity in sedimentary carbonates can be related specifically to sedimentary or diagenetic components that constitute the texture or fabric (fabric-selective porosity). Some porosity cannot be related to these features. Fabric selectivity commonly distinguishes pore systems of primary and early postdepositional (eogenetic) origin from those of later (telogenetic) origin that normally form after extensive diagenesis has transformed the very porous assemblage of stable and unstable carbonate minerals into a much less porous aggregate of ordered dolomite and/or calcite. Porosity in most carbonate facies, including most carbonate petroleum reservoir rocks, is largely fabric selective.

Geologic Nomenclature and Classification of Porosity in Sedimentary Carbonates

Organic carbon-rich sediments are globally developed in pelagic sedimentary sequences of Aptian-Albian and Cenomanian-Turonian age. They formed in a variety of paleo-bathymetric settings including oceanic plateaus and basins, continental margins and shelf seas. The widespread nature of these deposits suggests that they were not strictly controlled by local basin geometry but were a product of ″Oceanic Anoxic Events″ . Interpretation of these events as the result of the interplay of two major geologic and climatic factors is given. The Late Cretaceous transgression which increased the area and volume of shallow epicontinental and marginal seas and was accompanied by an increase in the production of organic carbon; and the existence of an equable global climate which reduced the supply of cold oxygenated bottom water to the world ocean. This combination of climatic and hypsographic conditions favoured the formation of an expanded oxygen-minimum layer and where this intersected the sediment-water interface, organic carbon-rich deposits could be formed, these being records of ″Oceanic Anoxic Events″ .

/pdf/cretaceous-oceanic-anoxic-events-causes-and-consequences-40gx0ik083.pdf

Cretaceous oceanic anoxic events: causes and consequences

The climatic cycles with subsequent glacial and intergalcial periods have had a great impact on the distribution and evolution of species. Using genetic analytical tools considerably increased our understanding of these processes. In this review I therefore give an overview of the molecular biogeography of Europe. For means of simplification, I distinguish between three major biogeographical entities: (i) "Mediterranean" with Mediterranean differentiation and dispersal centres, (ii) "Continental" with extra-Mediterranean centres and (iii) "Alpine" and/or "Arctic" with recent alpine and/or arctic distribution patterns. These different molecular biogeographical patterns are presented using actual examples. Many "Mediterranean" species are differentiated into three major European genetic lineages, which are due to glacial isolation in the three major Mediterranean peninsulas. Postglacial expansion in this group of species is mostly influenced by the barriers of the Pyrenees and the Alps with four resulting main patterns of postglacial range expansions. However, some cases are known with less than one genetic lineage per Mediterranean peninsula on the one hand, and others with a considerable genetic substructure within each of the Mediterranean peninsulas, Asia Minor and the Maghreb. These structures within the Mediterranean sub-centres are often rather strong and in several cases even predate the Pleistocene. For the "Continental" species, it could be shown that the formerly supposed postglacial spread from eastern Palearctic expansion centres is mostly not applicable. Quite the contrary, most of these species apparently had extra-Mediterranean centres of survival in Europe with special importance of the perialpine regions, the Carpathian Basin and parts of the Balkan Peninsula. In the group of "Alpine" and/or "Arctic" species, several molecular biogeographical patterns have been found, which support and improve the postulates based on distribution patterns and pollen records. Thus, genetic studies support the strong linkage between southwestern Alps and Pyrenees, northeastern Alps and Carpathians as well as southeastern Alps and the Dinaric mountain systems, hereby allowing conclusions on the glacial distribution patterns of these species. Furthermore, genetic analyses of arctic-alpine disjunct species support their broad distribution in the periglacial areas at least during the last glacial period. The detailed understanding of the different phylogeographical structures is essential for the management of the different evolutionary significant units of species and the conservation of their entire genetic diversity. Furthermore, the distribution of genetic diversity due to biogeographical reasons helps understanding the differing regional vulnerabilities of extant populations.

/pdf/molecular-biogeography-of-europe-pleistocene-cycles-and-46aecy9ypa.pdf

Molecular biogeography of Europe: Pleistocene cycles and postglacial trends

Various types of carbonate platforms are characterized by distinctive profiles, facies, and evolutionary sequences. Ramps may be homoclinal or distally steepened, and may have fringing or barrier shoal-water complexes of ooid-pellet sands or skeletal banks. Homoclinal ramps pass seaward into deeper water without major break in slope, and lack deep-water breccias. Distally steepened ramps may be low energy, and characterized by widespread, shallow, subwave-base mud blankets, or high energy with coastal beach/dune complexes and widespread skeletal sand blankets. Slope facies may contain abundant breccias of slope-derived clasts. Rimmed shelves have relatively flat tops, and marked break in slopes at the high energy, shallow-shelf edge where they pass into deep water. Such shelves may be aggraded with peritidal facies extending over much of the shelf, or incipiently drowned, depending on magnitude of sea level fluctuations. They may be accretionary, or bypass types that include gullied slope, escarpment, and high-relief erosional forms. Intrashelf basins occur on some shelves, controlling distribution of reservoir and source beds. Isolated platforms are surrounded by deeper water and may be located on rifted continental margins, or on submarine volcanoes. Most have high-relief rimmed margins. Platforms that have been subjected to rapid sea level rise may be incipiently drowned, and characterized by raised rims, elevated patch or pinnacle reefs, and widespread subwave-base carbonate or fine clastic blankets. Completely drowned shelves develop where the shelf is submerged to subphotic depths, terminating shallow water deposition, and commonly resulting in blanketing of the shelf by deeper water facies. Some margins show extensive down-to-basin faulting that is contemporaneous with carbonate deposition, or associated with thick prograding clastic sequences. The various types of platforms change in response to variations in sedimentation, subsidence or sea level rise, and may form distinctive evolutionary sequences. The relatively few models presented appear to accommodate most geological examples, some of which contain major reservoir facies.

Carbonate Platform Facies Models

A history of geodynamic evolution of the Mediterranean leading to the salinity crisis is outlined, based on the ‘desiccated deep-basin model’. An accurate portrayal of the crisis is presented, based on data from new drilling and studies of on-land geology.

History of the Mediterranean salinity crisis

The Upper Cretaceous chalks of southern England are a thick sequence of rhythmically bedded, bioturbated coccolith micrites, deposited in an outer shelf environment in water depths which varied between 50 and 200–300 m.

The products of sea floor cementation are widely represented in the sequence, and a series of stages of progressive lithification can be recognized. These began with a pause in sedimentation and the formation of an omission surface, followed by (a) growth of discrete nodules below the sediment-water interface to form a nodular chalk, erosion of which produced intraformational conglomerates. (b) Further growth and fusion of nodules into continuous or semicontinuous layers: incipient hardgrounds. (c) Scour, which exposed the layer as a true hardground. At this stage, the exposed lithified chalk bottom was subject to boring and encrustation by a variety of organisms, whilst calcium carbonate was frequently replaced by glauconite and phosphate to produce superficial mineralized zones. In many cases, the processes of sedimentation, cementation, exposure and mineralization were repeated several times, producing composite hardgrounds built up of a series of layers of cemented and mineralized chalk, indicating a long and complex diagenetic history.

Petrographic study of early cemented chalks indicates lithification was the result of the precipitation of small crystals on and between coccoliths and coccolith fragments. By analogy with known occurrences of early lithification in Recent deeper water carbonates, the cement is believed to have been either high magnesian calcite or aragonite, and more probably the former. The vast scale of operations involved in the cementation process precludes carbonate in expelled pore fluids as the source of cement, whilst quantities of aragonite incorporated in sediment are also inadequate. This, plus the observed association of horizons of early lithification with pauses in sedimentation associated with omission surfaces suggests seawater as a source of cementing materials.

Stratigraphic studies indicate that processes of early lithification leading to hardground formation proceeded to completion in intervals to be measured in tens or hundreds of years. Regional studies suggest that early lithification characterized relatively shallow water phases associated with regional regression over the whole of the area, whilst in detail, the distribution of mature mineralized hardground complexes is strongly correlated with sedimentary thinning and condensation over small areas and the buried flanks of massifs. Early cementation in more basinal areas is typically in the form of nodular developments and incipient hardgrounds, whilst day contents in excess of a few percent appear to have inhibited early lithification.

The striking rhythmicity of hardgrounds and nodular chalks is no more than a particular expression of the overall rhythmicity of chalk sequences. The stage of early lithification reached in any instance is dependent on sediment type, the time interval represented by the associated omission surface and the degree of associated scour and erosion (if any).

Chalk hardgrounds differ from most others described in the geological literature in their widespread distribution (individual hardgrounds may cover up to 1500 km2), the presence of striking glauconite and phosphate replacements of lithified carbonate matrices, their frequently sparse epifaunas, and boring infaunas dominated by clionid sponges. These differences reflect the deeper water shelf setting of the chalk, and the more open marine, oceanic circulatory system, both strikingly different from the setting of other, shallower water hardgrounds.

Litho- and biostratigraphic variation in the chalk sequences of the area studied are summarized in an appendix.

Morphology and genesis of nodular chalks and hardgrounds in the Upper Cretaceous of southern England

Deep-Water Limestones and Radiolarites of the Alpine Jurassic

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13°S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to —20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of Sr/Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to —200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

/pdf/diagenesis-and-interstitial-water-chemistry-at-the-peruvian-38t5pu68eg.pdf

Diagenesis and interstitial-water chemistry at the Peruvian continental margin; major constituents and strontium isotopes

Indurated Globigerina-rich sediments have been recorded from more than thirty localities on sea floors around the world, between depths of 200 and 3,500 m. Many are stained by iron and manganese minerals or are associated with manganese nodules or crusts, suggesting that such lithification occurs along profiles of sedimentational equilibrium. Samples from the eastern Mediterranean and from off Barbados, here described and illustrated with photomicrographs and electron micrographs, contain high-magnesian calcite and dolomite, and show recrystallization of the micritic matrix, as well as calcitic cavity fillings. We conclude, contrary to widespread opinion, that calcite can be precipitated chemically in seawater, and that carbonate sediments can become lithified on the sea floor.

Robert E. Garrison

Papers

History of the Mediterranean salinity crisis

Morphology and genesis of nodular chalks and hardgrounds in the Upper Cretaceous of southern England

Deep-Water Limestones and Radiolarites of the Alpine Jurassic

Diagenesis and interstitial-water chemistry at the Peruvian continental margin; major constituents and strontium isotopes

Carbonate Lithification on the Sea Floor