ALBERT

Notes: The sedimentology, mineralogy and pore fluid chemistry of seven cores from the Holocene sediments of Florida Bay were studied to determine the physical processes and diagenetic reactions affecting the sediments. The cores were taken in a transect from a shallow mudbank onto a small adjacent island, Jimmy Key. Steady state models of pore fluid chemistry are used to estimate the rates of various reactions.In the mudbank sediments, little carbonate mineral diagenesis is taking place. No change in sediment mineralogy is detectable and pore water profiles of Ca2+, Mg2+ and Sr2+ show only minor variation. Chloride concentrations indicate substantial biological mixing of seawater from the bay into the sediments in one of the cores. Pore water analyses of sulphate and alkalinity show only a low degree of sulphate depletion and a decreasing extent of sulphate reduction downcore. Models of sulphate reduction in the mudbank show that there is substantial chemical exchange between the sediment pore fluids and water from the bay probably as a result of bio-irrigation. The sulphate and alkalinity data also suggest that the underlying Pleistocene rocks contain water of near normal seawater composition.Stratigraphic analysis and δ13C analyses of the organic carbon in the sediments of the island cores show that the sediments were primarily deposited in a subtidal mudbank setting; only the upper 20–30 cm is supratidal in origin. Nevertheless, island formation had a significant effect on pore fluid chemistry and the types of diagenetic reactions throughout the sediment column. Chloride in the sediment pore fluids is more than twice the normal seawater concentrations over most of the depth of the cores. The constant, elevated chloride concentrations indicate that hypersaline fluids which formed in ponds on the island are advected downward through the sediments. Models of the chloride profiles yield an estimate of 2·5 cm yr−1 as a minimum advective velocity. Changes in pore water chemistry with depth are interpreted as indicating the following sequence of reactions: (1) minor high-Mg calcite dissolution and low-Mg calcite precipitation, from 0 to 35 cm; (2) Ca- or Mg-sulphate dissolution and low-Mg calcite precipitation, from 5 to 35 cm; (3) dolomite or magnesite precipitation together with sulphate reduction, from 35 to 55 cm; and (4) little reaction below 55 cm. In addition, one or more as yet unidentified reactions must be taking place from 5 to 55 cm depth as an imbalance in possible sources and sinks of alkalinity is observed. The imbalance could be explained if chloride is not completely conservative. Despite the pore fluid chemical evidence for diagenetic reactions involving carbonate minerals, no changes in sediment mineralogy were detected in X-ray diffraction analyses, probably because of the comparatively young age of the island.

Notes: Dark grey, bituminous dolostones interbedded with marine-derived anhydrite horizons occur in the Triassic Reichenhall Formation of western Austria. Fossils are rare and indicate a hostile, hypersaline depositional environment. The dolomites are finely crystalline, fairly stoichiometric, well ordered and non-ferroan. Closely spaced samples (94 in total) of individual dolomite units have been analysed for their carbon and oxygen isotopic composition. The data indicate surprisingly low δ18O values (-5.7 to -2.1%0 PDB), whereas the δ13C values are comparable to the contemporary Triassic seawater (+0.2 to +2.6%0 PDB). Sedimentological evidence, including (i) lack of any evidence for extensive dissolution, (ii) distinct oxygen and carbon isotope ratios of individual dolomite units, (iii) covariance of carbon and oxygen isotopes within some dolomite layers and (iv) inclusions of celestite in dolomite, indicates a nearly closed system after early diagenesis. Combining this information with water-rock interaction calculations suggests that the lightest oxygen isotope compositions are the result of freshwater influx into the basin during very early dolomite formation. A secondary factor may be dolomite recrystallization at elevated temperatures during burial.

Notes: Dolomites from the upper calcareous-siliceous member of the Miocene Monterey Formation exposed west of Santa Barbara, California, were analysed for geochemical, isotopic and crystallographic variation. The data clearly document the progressive recrystallization of dolomite during burial diagenesis in marine pore fluids.Recrystallization is recognized by the following compositional and crystallographic variations. Dolomites have decreasing δ18O and δ13C compositions, decreasing Sr contents and increasing Mg contents with increasing burial depths and temperatures from east to west in the study area. δ18O values vary from 5·3‰ in the east to − 5·5‰ PDB in the west and are interpreted to reflect the greater extent and higher temperature of dolomite recrystallization in the west. δ13C values correlate with δ18O and decrease from 13·6‰ in the east to − 8·7‰ PDB in the west. Sr concentrations correlate positively with δ18O values and decrease from a mean of 750 ppm in the east to a mean of 250 ppm in the west. Mol% MgCO3 values inversely correlate with δ18O values and increase from a minimum of 41·0 in the east to a maximum of 51·4 in the west.Rietveld refinements of powder X-ray diffraction data indicate that the more recrystallized dolomites have more contracted unit cells and increased cation ordering. The fraction of the Ca sites in the dolomites that are occupied by Ca atoms increases slightly with the approach to stoichiometry. The fraction of the Mg sites occupied by Mg atoms strongly correlates with mol% MgCO3. Even in early diagenetic, non-stoichiometric dolomites, there is little substitution of Mg in Ca sites. During recrystallization, the amount of Mg substituting for Ca in Ca sites decreases even further. Most of the disorder in the least recrystallized, non-stoichiometric dolomites is related to substitution of excess Ca on Mg sites.

Notes: The Upper Permian Gröden Formation of the Northern Calcareous Alps (Austria) is composed of alluvial fan and playa lake sediments that were deposited in intramontane basins. A conspicuous feature of these redbeds is the abundance of magnesite in the form of nodules and discrete layers in mudstones as well as intergranular cement in sandstones. Sedimentological observations indicate that the bulk of these carbonates formed during early diagenesis and were probably syndepositional. Petrographically, most magnesites consist of micrite or, less commonly, microspar. An early non-ferroan magnesite is post-dated by later stage ferroan magnesites. Nodules consisting of recrystallized, sparry magnesite were observed only at one location. The general absence of relics of a non-magnesite precursor mineral and the occurrence of shrinkage features suggest that the fine grained magnesites formed by transformation of a hydrated magnesium carbonate mineral, e.g. hydromagnesite. Carbon, oxygen, sulphur and strontium isotope ratios in conjunction with sedimentological criteria support a model of (hydro)magnesite precipitation in an inland playa lake system, which was fed by run-off from the surrounding hinterland. The scarcity of evaporites and the dominance of magnesite over calcite and dolomite suggest that the playa lake brines were low in sulphate and had high Mg/Ca ratios. The source for the high magnesium concentrations is thought to be the weathering of Devonian dolostones and associated massive magnesite deposits in the catchment area.