Sediment core fossils in ancient Lake Ohrid: testing for faunal change since the Last Interglacial

Ancient Lake Ohrid is probably of early Pleistocene or Pliocene origin and amongst the few lakes in the world harbouring an outstanding degree of endemic biodiversity. Although there is a long history of evolutionary research in Lake Ohrid, particularly on molluscs, a mollusc fossil record has been missing up to date. For the first time, gastropod and bivalve fossils are reported from the basal, calcareous part of a 2.6 m long sediment succession (core Co1200) from the north-eastern part of Lake Ohrid. Electron spin resonance (ESR) dating of mollusc shells from the same stratigraphic level yielded an age of 130 ± 28 ka. Lithofacies III sediments, i.e. a stratigraphic subdivision comprising the basal succession of core Co1200 between 181.5–263 cm, appeared solid, greyish-white, and consisted almost entirely of silt-sized endogenic calcite (CaCO3>70%) and intact and broken mollusc shells. Here we compare the faunal composition of the thanatocoenosis with recent mollusc associations in Lake Ohrid. A total of 13 mollusc species (9 gastropod and 4 bivalve species) could be identified within Lithofacies III sediments. The value of sediment core fossils for reconstructing palaeoenvironmental settings was evaluated and the agreement between sediment and palaeontological proxies was tested. The study also aims at investigating major faunal changes since the Last Interglacial and searching for signs of extinction events. The combined findings of the ecological study and the sediment characteristics suggest deposition in a shallow water environment during the Last Interglacial. The fossil fauna exclusively included species also found in the present fauna, i.e. no extinction events are evident for this site since the Last Interglacial. The thanatocoenosis showed the highest similarity with recent Intermediate Layer (5–25 m water depth) mollusc assemblages. The demonstrated existence of a mollusc fossil record in Lake Ohrid sediment cores also has great significance for future deep drilling projects. It can be hoped that a more far reaching mollusc fossil record will then be obtained, enabling insight into the early evolutionary history of Lake Ohrid.

Th and U isotopes, dose rates and ages of marine shells and sediment of core GIK14350, north Germany

The ESR dating method was applied to marine shells taken from a sediment core from Dagebüll, Schleswig-Holstein. Four samples from two different depths of the core (17.5 m and 25-26 m), separated by a 2.76 meter thick clay layer (Turritella Clay), yielded identical ages within the limits of error. They indicated an assignment to the oxygen isotope stage 5, thus confirming the stratigraphic age. In addition, the ESR-ages confirm the interpretation of Lomitschka et al. (1997, doi:10.2312/meyniana.1997.49.85), that the Th/U-ages of shells below the clay layer are reliable, whereas shells located above the clay layer, which were strongly influenced by percolating groundwaters of an open system, yielded falsified Th/U-ages.

Determination of sulfite and manganese in sediments from the K/T boundary

The solid-state-physics technique of electron spin resonance (ESR) has been employed in an exploratory study of marine limestones and impact-related deposits from Cretaceous-Tertiary (KT) boundary sites including Spain (Sopelana and Caravaca), New Jersey (Bass River), the U.S. Atlantic continental margin (Blake Nose, ODP Leg 171B/1049/A), and several locations in Belize and southern Mexico within -600 km of the Chicxulub crater. The ESR spectra of SO3(1-) (a radiation-induced point defect involving a sulfite ion substitutional for CO3(2-) which has trapped a positive charge) and Mn(2+) in calcite were singled out for analysis because they are unambiguously interpretable and relatively easy to record. ESR signal strengths of calcite-related SO3(1-) and Mn(2+) have been studied as functions of stratigraphic position in whole-rock samples across the KT boundary at Sopelana, Caravaca, and Blake Nose. At all three of these sites, anomalies in SO3(1-) and/or Mn(2+) intensities are noted at the KT boundary relative to the corresponding background levels in the rocks above and below. At Caravaca, the SO3(1-) background itself is found to be lower by a factor of 2.7 in the first 30,000 years of the Tertiary relative to its steady-state value in the last 15,000 years of the Cretaceous, indicating either an abrupt and quasi-permanent change in ocean chemistry (or temperature) or extinction of the marine biota primarily responsible for fixing sulfite in the late Cretaceous limestones. An exponential decrease in the Mn(2+) concentration per unit mass calcite, [Mn(2+)], as the KT boundary at Caravaca is approached from below (1/e characteristic length =1.4 cm) is interpreted as a result of post-impact leaching of the seafloor. Absolute ESR quantitative analyses of proximal impact deposits from Belize and southern Mexico group naturally into three distinct fields in a twodimensional [SO3(1-)]-versus-[Mn(2+)] scatter plot. These fields contain (I) limestone ejecta clasts, (II) accretionary lapilli, and (III) a variety of SO3(1-) -depleted/Mn(2+) enriched impact deposits. Data for the investigated non-impact-related Cretaceous and Tertiary marine limestones (Spain and Blake Nose) fall outside of these three fields. With reference to thes enon-impact deposits, fields I, II, and III can be respectively characterized as Mn(2+) -depleted, SO3(1-) -enhanced, and SO3(1-) -depleted. It is proposed that (1) field I represents calcites from the Yucatin Platform, and that the Mn(2+) -depleted signature can be used as an indicator of primary Chicxulub ejecta in deep marine environments and (2) field II represents calcites that include a component formed in the vapor plume, either from condensation in the presence of CO2/SO3(1-) -rich vapors, or reactions between CaO and CO2/SO3 rich vapors, and that this SO3(1-) -enhanced signature can be used as an indicator of impact vapor plume deposits. Given these two propositions, the ESR data for the Blake Nose deposits are ascribed to the presence of basal coarse calcitic Chicxulub ejecta clasts, while the finer components that are increasingly represented toward the top are interpreted to contain high- SO3(1-) calcite from the vapor plume. The apparently-undisturbed Bass River deposit may contain even higher concentrations of vapor-plume calcite. None of the three components included in field III appear to be represented at distal, deep marine KT-boundary sites; this field may include several types of impact-related deposits of diverse origins and diagenetic histories.

Diagenetic alteration of organic matter in DSDP Leg 57 Holes

I analyzed Leg 57 sediments organogeochemically and spectroscopically. Organic carbon and extractable organic matter prevail from the Pliocene to the Miocene. Humic acids occur widely from the Pleistocene to the lower Miocene and one portion of the Oligocene. The absence of humic acids in Oligocene and Cretaceous samples suggests that humic acids had changed to kerogen. Visible spectroscopic data reveal that humic acids in this study have a low degree of condensed aromatic-ring system, which is a feature of anaerobic conditions during deposition, and that chlorophyll derivatives that had at first combined with humic acids moved to the solvent- soluble fraction during diagenesis. The elemental compositions of humic acids show high H/C and O/C ratios, which seem appropriate to a stage before transformation to kerogen. The relation between the linewidths and g-values on the electron spin resonance data indicates that the free radicals in humic acids are quite different from those in kerogen. The low spin concentrations of kerogen and the yields of humic acids up to the lower Miocene demonstrate that organic matter in these sediments is immature. The foregoing indicate the necessity to isolate humic acids even in ancient rocks in the study of kerogen.

Beryllium, thorium and protactinium isotope ratios in sediments from the Galapagos microplate

Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.