The microbiological formation of carbonate concretions in the Upper Lias of NE England

Carbonate concretions from the Jet Rock (Upper Lias, Lower Jurassic) of NE England grew in uncompacted sediment, close to the sediment surface. Microbiological activity created isolated microenvironments in which dissolved carbonate and sulphide species were produced more rapidly than they could be dispersed by diffusion, so establishing the localised supersaturation of calcite and metastable iron sulphides. Precipitation of these minerals in the microenvironment formed a single concretion.Mass-balance calculations demonstrate that at least two different microbiological processes participated in concretionary growth. The early growth stages had an unidentifiable microbiological source of carbonate which declined in importance relative to sulphate reduction as growth proceeded. It is suggested that the diffusion of dissolved organic material was important in sustaining microbiological activity.Mineralogical zonations in the concretions result from changes in the chemistry of the microenvironment due to variations in the rates of addition/removal Ca²⁺, Fe²⁺, HCO^?₃ and HS^? by microbiological activity, the crystallization of authigenic minerals and diffusion between the microenvironment and surrounding pore waters. Such changes are of only local significance and the resulting mineralogical zonations in a concretion cannot be used to deduce successive stages of diagenesis in the whole sediment.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.     

Pathways and distances of fluid flow during low-grade metamorphism: evidence from pyrite deposits of the Cameros Basin, Spain

New geochemical and sulphur isotopic data are presented for a number of pyrite deposits from the Late Jurassic–Early Cretaceous Cameros Basin, Spain. The deposits were formed at, or close to, the peak of metamorphism and are always related to sandstone units in the mainly metapelite sequence. Iron remained immobile and conservative, pyrite iron being derived by sulphidation of chlorite in the host metapelites. Reduced sulphur, however, was supplied from two external sources: thermochemical reduction of sulphate and release of S during metamorphism of sedimentary sulphides. These sources provided isotopically heavy and light S, respectively, with variation in pyrite isotopic composition between different deposits resulting from differences in their relative importance at each site. During metamorphism, the sandstone units acted as aquifers, carrying the sulphidic pore waters to locations where permeability provided by syn-depositional fractures on a scale of 0.5–5  m allowed its interaction with the metapelites. Transport distances for sulphide during metamorphism were of the order of hundreds of metres.     

Primary versus diagenetic origin of Blue Lias rhythms (Dorset, UK): evidence from sulphur geochemistry

The question of a primary versus diagenetic origin for the limestone-shale rhythms of the Blue Lias has been addressed through a study of pyrite abundance and isotopic composition. Pyrite is relatively abundant and isotopically light in the central portions of the bioturbated limestones as compared to adjacent, less calcareous, sediment. The abundance of pyrite shows that the limestones were a focus for prolonged sulphate reduction and pyrite formation. The isotopic data indicate that bioturbation oxidized some pyrite to produce isotopically light sulphate, part of which was subsequently reduced back to pyrite before preservation by burial. Acidity generated by pyrite oxidation was buffered in the limestones by carbonate dissolution, hence supersaturation of sulphides could be maintained. By contrast, in adjacent less calcareous sediments, carbonate dissolution was unable to buffer acidity and bioturbational oxidation of pyrite formed iron-rich pore solutions. Continued sulphate reduction in the limestones acted as a sink for iron from the adjacent sediments and, with burial below the zone of bioturbation, the alkalinity so generated caused cementation of the limestones. Diagenetic cementation would be enhanced during an hiatus in sedimentation, an event which might be related to a Milankovitch forcing mechanism, but which would not be recorded in bioturbated, less calcareous sediment, thus leaving an imperfect record. Only cyclicity in pre-diagenetic sedimentation patterns may be safely related to a Milankovitch forcing mechanism as proposed by Weedon.     

Formation of syngenetic and early diagenetic iron minerals in the late Archean Mt. McRae Shale, Hamersley Basin, Australia: New insights on the patterns, controls and paleoenvironmental implications of authigenic mineral formation

A section through the late Archean Mt. McRae Shale comprising, in ascending order, a lower shale interval (LSI), a banded iron formation (BIF), an upper shale (USI) and a carbonate (C1) has been analyzed for total Fe and Al contents and authigenic Fe present as carbonate, oxide, sulfide and silicate phases. The authigenic mineralogy is controlled by the episodic addition of Fe from hydrothermal activity and removal of Fe by sulfide, relative to rates of clastic sedimentation. The LSI and BIF have mean Fe_T/Al values of 2 and 5, respectively, that record iron enrichment from hydrothermal sources. Iron was precipitated primarily as siderite accompanied by Fe-rich chlorite from anoxic bottom waters rich in dissolved Fe. Pyrite formation was probably limited by the availability of sulfate, which was present at low concentrations and became rapidly depleted. The USI has generally lower Fe_T/Al values (0.6-1.3), similar to those found in Paleozoic shales, with the exception of one interval where enrichment may reflect either a weak hydrothermal source or the operation of an iron shuttle. This interval contains authigenic Fe predominantly as pyrite, where high values for DOP (>0.8) indicate the existence of a water column that became rich in dissolved sulfide (euxinic) when sulfate concentrations increased due to a transient or secular increase in ocean/atmosphere oxygenation. High concentrations of dissolved sulfide maintained low concentrations of dissolved Fe, which allowed only minor amounts of Fe to be precipitated as carbonates and silicates. The USI also has elevated concentrations of organic matter that most probably reflect increased productivity and likely limited euxinia to midportions of the water column on the basin margin. The carbonate C1 represents a basinal chemistry where sulfide has been removed and Fe_T/Al values are ∼1 indicating that hydrothermal activity again produced dissolved Fe-rich bottom waters. Detailed iron speciation of the Mt. McRae Shale can be used to recognize spatial and temporal variations in iron and sulfur inputs to the late Archean Hamersley Basin, just prior to the Paleoproterozoic rise in atmospheric oxygenation, and our refined methods have relevance to all Fe-rich deposits.     

Bioavailable iron in the Southern Ocean: the significance of the iceberg conveyor belt

Productivity in the Southern Oceans is iron-limited, and the supply of iron dissolved from aeolian dust is believed to be the main source from outside the marine reservoir. Glacial sediment sources of iron have rarely been considered, as the iron has been assumed to be inert and non-bioavailable. This study demonstrates the presence of potentially bioavailable Fe as ferrihydrite and goethite in nanoparticulate clusters, in sediments collected from icebergs in the Southern Ocean and glaciers on the Antarctic landmass. Nanoparticles in ice can be transported by icebergs away from coastal regions in the Southern Ocean, enabling melting to release bioavailable Fe to the open ocean. The abundance of nanoparticulate iron has been measured by an ascorbate extraction. This data indicates that the fluxes of bioavailable iron supplied to the Southern Ocean from aeolian dust (0.01–0.13 Tg yr^-1) and icebergs (0.06–0.12 Tg yr^-1) are comparable. Increases in iceberg production thus have the capacity to increase productivity and this newly identified negative feedback may help to mitigate fossil fuel emissions.     

Contributions from glacially derived sediment to the global iron (oxyhydr)oxide cycle: Implications for iron delivery to the oceans

Estimates of glacial sediment delivery to the oceans have been derived from fluxes of meltwater runoff and iceberg calving, and their sediment loads. The combined total (2900 Tg yr⁻¹) of the suspended sediment load in meltwaters (1400 Tg yr⁻¹) and the sediment delivered by icebergs (1500 Tg yr⁻¹) are within the range of earlier estimates. High-resolution microscopic observations show that suspended sediments from glacial meltwaters, supraglacial, and proglacial sediments, and sediments in basal ice, from Arctic, Alpine, and Antarctic locations all contain iron (oxyhydr)oxide nanoparticles, which are poorly crystalline, typically ∼5 nm in diameter, and which occur as single grains or aggregates that may be isolated or attached to sediment grains. Nanoparticles with these characteristics are potentially bioavailable. A global model comparing the sources and sinks of iron present as (oxyhydr)oxides indicates that sediment delivered by icebergs is a significant source of iron to the open oceans, beyond the continental shelf. Iceberg delivery of sediment containing iron as (oxyhydr)oxides during the Last Glacial Maximum may have been sufficient to fertilise the increase in oceanic productivity required to drawdown atmospheric CO₂ to the levels observed in ice cores.     

Burial of organic carbon and pyrite sulfur in sediments over phanerozoic time: a new theory

In present day marine sediments, almost all of which are deposited in normal oxygenated seawater, rates of burial of organic carbon (C) and pyrite sulfur (S) correlate positively and bear a constant ratio to one another (C/S ～- 3 on a weight basis). By contrast, calculations, based on the isotopic model of Garrels and Lerman (1981), indicate that at various times during the Phanerozoic the worldwide burial ratio must have been considerably different than the present day value. This ratio change is caused by the requirement that, increases in the worldwide mass of organic carbon must be accompanied by equivalent decreases in the mass of sedimentary pyrite sulfur, in order to maintain a roughly constant level of O₂ in the atmosphere. Such apparently contradictory behavior can be explained if the locus of major organic carbon burial has shifted over time from normal marine environments, as at present, to non-marine freshwater, or to euxinic environments, in the geologic past. A shift to predominantly freshwater burial can help explain predicted high C/S ratios in Permo-Carboniferous sediments, and a shift to euxinic environments can help explain predicted low C/S ratios during the early Paleozoic. It is demonstrated that the three environments today exhibit distinguishably different average C/S ratios.