Stable Isotope Event Markers Near the Permo-Triassic Boundary in the Karavanke Mountains (Slovenia)

Stable isotope analyses of carbonates and organic matter from the Permo-Triassic boundary section in the Karavanke Mountains, Slovenia, indicate a further example of the “light carbon” event across the boundary. In this section the changes in carbon isotope values were a direct result of the culmination of the marine regression and associated events at the end of the Permian, which caused a drop in primary productivity, as well as related local environmental changes, with no evidence of any considerable diagenetic overprint

Recent Sediments of Makirina Cove (Northern Dalmatia, Croatia): Their Origin Viewed Through a Multidisciplinary Approach

Makirina Cove was formed by the Holocene sea-level rise which caused a marine ingression into the depression formed within Albian–Cenomanian dolomites at approximately 4.5 ka B.P. At present, Makirina Cove represents an restricted, stressed, shallow-marine (<2m) ecosystem characterized by varying seawater temperatures (0–35°C) as well as fluctuating salinities (up to 41‰) affected by seasonally enhanced evaporation, continuous freshwater supply through on-shore and submarine springs associated with the coastal karst area and surface run-off episodes. These environmental conditions have been conducive to high primary production of organic matter resulting in the formation of organic-rich deposits which contain up to 5 wt.% of organic carbon. Up to the present times, 3.5 m of sediments have been deposited indicating a relatively high sedimentation rate estimated at 0.75 m/1.0 ka in the northern central part of the Cove. The sediments are being deposited mostly as poorly sorted clayey–sandy silts. The distribution and concentration of most of the chemical elements is dependant on the mineralogical composition and granulometric features of the Makirina sediments, which show values more or less similar to those from the Central Adriatic. Accordingly, there is a positive correlation with Al and K concentrations increasing off-shore and with the depth being associated with increasing concentrations of clay minerals within the clay fraction. The same holds true for concentrations of some trace elements, especially Mo and Se which is consistent with the distribution pattern of sulphides. Selenium is preferentially enriched in authigenic pyrite and it is probably the major source of Se in the Makirina Cove sediments. The concentrations of Ca, Mg and Sr decrease off-shore and they are linked to the composition of the surrounding carbonate rocks. The saturation indices show that the water is supersaturated with respect to carbonates enabling the precipitation of authigenic amorphous or crystalline carbonate phases from the pore water in the upper segment of the sediment column. According to the oxygen isotopic (δ18O) composition, molluscs precipitated their carbonate shells mostly during warmer periods (May to November) at or near isotopic equilibrium with their ambient waters. The carbon isotopic δ13C composition of mollusc carbonate shells is environmentally affected due to oxidation and decomposition of organic matter as well as influxes of fresh water into the Cove, indicating their formation out of the predicted isotopic equilibrium with atmospheric CO2. Palynological and organic carbon isotopic (δ13C) composition shows that the sedimentary organic matter (SOM) is 70–90% lipid- and hydrogen-rich and on average 2/3 marine derived (mainly phytoplankton, bacteria and marine macrophytes) and 1/3 terrestrially derived (mainly woody tissue). The variations in composition of SOM have been noted as a function of the distance from the shore. The type and the preservation state of SOM and pyrite as well as the measurements of Eh, pH, total alkalinity, dissolved inorganic carbon (DIC) and the enrichment of redox-sensitive trace elements, indicate oxygen-depleted depositional conditions and that the sediment is highly reductive even in the uppermost segment at the sediment/water interface. According to the results obtained from the applied methods, the features of Makirina sediments strongly reflect the given depositional conditions within this restricted, stressed, shallow-marine environment where these organic-rich sediments originate, and may therefore serve as a calibration standard in further investigations

Recent Sediments of Makirina Cove (Northern Dalmatia, Croatia): Their Origin Viewed Through a Multidisciplinary Approach

Makirina Cove was formed by the Holocene sea-level rise which caused a marine ingression into the depression formed within Albian–Cenomanian dolomites at approximately 4.5 ka B.P. At present, Makirina Cove represents an restricted, stressed, shallow-marine (<2m) ecosystem characterized by varying seawater temperatures (0–35°C) as well as fluctuating salinities (up to 41‰) affected by seasonally enhanced evaporation, continuous freshwater supply through on-shore and submarine springs associated with the coastal karst area and surface run-off episodes. These environmental conditions have been conducive to high primary production of organic matter resulting in the formation of organic-rich deposits which contain up to 5 wt.% of organic carbon. Up to the present times, 3.5 m of sediments have been deposited indicating a relatively high sedimentation rate estimated at 0.75 m/1.0 ka in the northern central part of the Cove. The sediments are being deposited mostly as poorly sorted clayey–sandy silts. The distribution and concentration of most of the chemical elements is dependant on the mineralogical composition and granulometric features of the Makirina sediments, which show values more or less similar to those from the Central Adriatic. Accordingly, there is a positive correlation with Al and K concentrations increasing off-shore and with the depth being associated with increasing concentrations of clay minerals within the clay fraction. The same holds true for concentrations of some trace elements, especially Mo and Se which is consistent with the distribution pattern of sulphides. Selenium is preferentially enriched in authigenic pyrite and it is probably the major source of Se in the Makirina Cove sediments. The concentrations of Ca, Mg and Sr decrease off-shore and they are linked to the composition of the surrounding carbonate rocks. The saturation indices show that the water is supersaturated with respect to carbonates enabling the precipitation of authigenic amorphous or crystalline carbonate phases from the pore water in the upper segment of the sediment column. According to the oxygen isotopic (δ18O) composition, molluscs precipitated their carbonate shells mostly during warmer periods (May to November) at or near isotopic equilibrium with their ambient waters. The carbon isotopic δ13C composition of mollusc carbonate shells is environmentally affected due to oxidation and decomposition of organic matter as well as influxes of fresh water into the Cove, indicating their formation out of the predicted isotopic equilibrium with atmospheric CO2. Palynological and organic carbon isotopic (δ13C) composition shows that the sedimentary organic matter (SOM) is 70–90% lipid- and hydrogen-rich and on average 2/3 marine derived (mainly phytoplankton, bacteria and marine macrophytes) and 1/3 terrestrially derived (mainly woody tissue). The variations in composition of SOM have been noted as a function of the distance from the shore. The type and the preservation state of SOM and pyrite as well as the measurements of Eh, pH, total alkalinity, dissolved inorganic carbon (DIC) and the enrichment of redox-sensitive trace elements, indicate oxygen-depleted depositional conditions and that the sediment is highly reductive even in the uppermost segment at the sediment/water interface. According to the results obtained from the applied methods, the features of Makirina sediments strongly reflect the given depositional conditions within this restricted, stressed, shallow-marine environment where these organic-rich sediments originate, and may therefore serve as a calibration standard in further investigations

Sulfur (³⁴S/³²S) isotope composition of gypsum and implications for deep cave formation on the Nullarbor Plain, Australia

Large deep caves with little relation to surface topography are distinctive karst features on the Nullarbor Plain of Australia. The presence of gypsum deposits and chemoautotrophic bacteria within the caves have been suggested as evidence for cave formation and (or) enlargement via sulfuric acid speleogenesis. To test this hypothesis, the stable sulfur isotope compositions (δ34S) of both cave gypsum and surface gypsum were measured. Analyses yielded relatively high, positive δ34S values from both cave gypsum and surface gypsum, arguing against gypsum genesis via microbial chemoautotrophy, and more broadly, sulfuric acid speleogenesis. Instead, the gypsum is interpreted as forming via evaporation of seawater during the Quaternary

Determination of high resolution pore water profiles of trace metals in sediments of the Rupel River (Belgium) using DET (Diffusive Equilibrium in Thin Films) and DGT (Diffusive Gradients in Thin Films) techniques

The techniques of diffusional equilibrium in thin films (DET) and diffusional gradients in thin films (DGT) were used to obtain high resolution pore water profiles of total dissolved and labile trace (mobilizable) metals in the sediments of the Rupel River, Belgium. DGT measures labile metal species in situ by immobilizing them on a resin gel after diffusion through a diffusive gel whereas for DET an equilibrium is established between the DET gel and the pore water. Concentrations of Pb and Zn obtained by DGT were in good agreement with the results obtained by centrifugation, and thus were well buffered by rapid equilibrium with the solid phase, whereas Fe, Mn and Cd were very tightly bound to the sediment phase and large differences were observed between the labile and the total metal concentrations. Cu, Zn, Co and Ni show intermediated behavior.Good correlations were found between the profiles of As and Fe and Mn and Co for DET as well as DGT showing a close link between the geochemical behavior of these elements. Cu, Zn, Pb and Cd are also influenced by the reductive mobilization of Fe and Mn oxides but are also closely linked to the bacterial degradation of organic matter in the surface sediments as to the precipitation of metal sulfides in the deeper layers