Geochemistry of labile organic matter in sediments and interstitial waters of ODP Sites 107-651 and 107-653

Sediment and interstitial water from Sites 651 and 653 (ODP Leg 107) were investigated by organic geochemical methods to characterize labile organic compound classes (amino compounds and carbohydrates) and to evaluate their progressive diagenetic and thermal degradation in deep-sea sediments. Downhole distribution of dissolved organic carbon (DOC) appears related to redox zones associated with bacterial activity and of diagenetic recrystallization of biogenic tests and not so much to organic matter concentrations in ambient sediments. DOC ranges from 250 to 8300 µmol/L (3-100.1 ppm). Amino acids contribute 10%-0.3% of DOC; carbohydrates range from 78 to 5 µmol/L. Rate of degradation of amino acids by thermal effects and/or bacterial activity at both sites (significantly different in sedimentation rates: average 41 cm/1000 yr in the top 300 m at Site 651, average 3.9 cm/1000 yr in the Pliocene/Quaternary sequence at Site 653 to 220 mbsf) is more dependent on exposure time rather than on the depth within the sediment column. Variability in neutral, acidic, and basic amino acid fractions of total amino acids (with a range of 1.1-0.02 µmol/g sediment; up to 2.5% of organic carbon) varies with carbonate content and by differences in thermal stability of amino acids. Distribution patterns of monosaccharides are interpreted to result from differences in organic matter sources, sedimentation rates, and the degree of organic matter decomposition prior to and subsequent to burial. Total particulate carbohydrates range from 1.82 to 0.21 µmol/g sediment and contribute about 8% to the sedimentary organic matter. Investigation of trace metals in the interstitial waters did not show any correlation of either DOC, amino compounds, or carbohydrates.

Calcareous nannofossils of ODP Leg 107 holes

This paper summarizes the nannoplankton biostratigraphy and the paleoenvironmental interpretations obtained from Leg 107 in the Tyrrhenian Sea. Marine sediments are ranging in age from late Tortonian to Recent. The Mediterranean as a semiclosed adjacent sea of the Atlantic is strongly controlled by paleoceanographic changes in the Atlantic which are related to the global climatic evolution. This influence of the Atlantic is more pronounced in the western than in the eastern Mediterranean. The occurrence of sapropels and sapropelic layers also in the western Mediterranean was shown for the first time.

Pliocene-Pleistocene stable isotope record of ODP Site 107-653

Planktonic foraminiferal oxygen and carbon isotope analyses from Tyrrhenian Sea Ocean Drilling Program (ODP) Site 653 provide a continuous record of the Pliocene-Pleistocene paleoceanographic history of the Mediterranean. Long-term trends in oxygen isotopes primarily reflect changes in global climatic conditions, with a more local or regional signal superimposed on this record. For example, significant enrichments in 18O due to decreases in surface water temperature and/or increases in continental ice volume occurred at 3.1, 2.7, 2.1, 1.6, and 0.4 Ma. In contrast to most open-ocean results, the early Pliocene 6lsO record of Site 653 exhibits high-amplitude fluctuations indicative of very unstable climatic conditions in this region. Another unique aspect of this Mediterranean d18Orecord is the pronounced cooling at the Pliocene/Pleistocene boundary. The carbon isotope record for Site 653 also exhibits high-amplitude variability throughout the Pliocene-Pleistocene. This variability most probably reflects changes in the carbon isotopic composition of the source of Mediterranean surface waters.

Pleistocene-Pliocene strontium-isotope ratios of ODP Site 107-653 (Table 1)

Strontium isotopic determinations were made on samples from the Pliocene-Pleistocene sequence recovered at ODP Hole 653A, the proposed "deep-sea type section" for the Mediterranean region. Biostratigraphic correlations can be combined with the patterns of variations in the 87Sr/86Sr values to delineate the following: (1) the earliest Pliocene (MP11 to basal MP12 zones) is distinguished by fluctuations in the ratio, probably related to the unstable paleoceanographic conditions following the Zanclean flooding and initial in-filling of the Mediterranean after the Messinian desiccation, (2) during most of the Pliocene between approximately 4.5 and 2.4 Ma (MP12 to MP15 zones) the 87Sr/86Sr values remain relatively constant, producing a plateau in the strontium isotope-depth curve for this period, and (3) beginning at approximately 2.4 Ma (across the MP15/MP16 boundary) and continuing into the latest Pleistocene, the 7Sr/86Sr values increase significantly but show fluctuations that have both positive and negative slopes. The presence of a plateau in the curve generated for the Mediterranean type section duplicates in greater detail the late Neogene results reported by DePaolo (1986, doi:10.1130/0091-7613(1986)14<103:DROTNS>2.0.CO;2). The virtual lack of change in the ratio between 4.5 and 2.4 Ma essentially eliminates strontium isotopes as a high-resolution correlation method for this period. The fluctuations in the ratio beginning at 2.4 Ma may be a reflection of major climatic changes occurring in the latest Pliocene-Pleistocene. The relationship between glacial-interglacial cycles and seawater 87Sr/86Sr values suggested by DePaolo (1986) and Capo and DePaolo (1987) is uncertain but should be tested as significant increases and decreases in 87Sr/86Sr of seawater have apparently occurred since 2.4 Ma.

Pliocene-Pleistocene biostratigraphy in the Tyrrhenian Sea

The distribution of stratigraphically important calcareous nannofossils and planktonic foraminifera has been investigated in the Pliocene-Pleistocene sequences of ODP Sites 652, 653, and 654 (Tyrrhenian Sea-western Mediterranean). Semiquantitative and quantitative methods have been used, and an optimum relative sequence of bioevents based on the calcareous plankton groups has been established. About 30 bioevents in an interval of 5.0 m.y. are considered widely traceable in the area and reasonably synchronous. On the basis of those events, a correlation among the three investigated sequences is presented.

Late Pliocene stable oxygen isotope record of the Mediterranean Sea

Detailed pollen analyses and oxygen isotope records of three foraminiferal species, Globigerina bulloides, Uvigerina peregrina and Cibicides pachyderma, from the Semaforo and Vrica composite sections (Crotone, southern Italy) have been compared to the global climatic changes depicted by late Pliocene-early Pleistocene foraminiferal d18O records of Site 607 in the North Atlantic, and Hole 653A in the Tyrrhenian basin, West Mediterranean. Major overturns in the mid-altitude vegetation are shown near isotopic stages 82, 60, 58 and 50, at about 2.03 Ma, 1.6 Ma and 1.37 Ma according to the Raymo et al. (1989, doi:10.1029/PA004i004p00413) and Ruddiman et al. (1989, doi:10.1029/PA004i004p00353) timescales. At the same dates, glacial 18O maxima either became higher or display step increases in the western Mediterranean or in the open ocean as well. This suggests that size increases of Northern Hemisphere ice sheets were the driving factor for regional or local marine and continental environmental changes within the Mediterranean basin. Near isotopic stages 62-60, close to the conventional Plio-Pleistocene boundary, the climatic conditions severed enough within the Mediterranean basin to modify the continental environment, as depicted by a sudden increase of Artemisia percentages, while the first significant southward migration of the North Polar Front may have been recorded by an influx of left coiling Neogloboquadrina pachyderma in the central Mediterranean. It also appears that 'Boreal Guests' entered the Mediterranean during phases of 18O enrichment of foraminiferal calcite. There does not seem to be any discrepancy between the climatic concept of the Pliocene-Pleistocene boundary and its chronostratigraphic definition.

Plio-Pleistocene benthic foraminifera of the Tyrrhenian Sea

Benthic foraminifers from Site 652, Site 653 (Hole 653A), and Site 654 of Leg 107 (Tyrrhenian Sea, Western Mediterranean), which penetrated with more or less good recovery the Plio-Pleistocene stratigraphic interval, were studied in a total of 699 close-spaced samples. A total number of 269 species have been classified and their quantitative distribution in each sample is reported. The benthic foraminifers assemblage is more diversified in Site 654, less diversified in Site 652. Less than a half of the benthic foraminifers species listed from Plio-Pleistocene Italian land sections are present in the coeval deep-sea Tyrrhenian record, in which shallow water species are missing and Nodosarids are poorly represented. A very few species have comparable stratigraphic distribution in the three deep-sea sequences and in Italian land sections when compared against calcareous plankton biostratigraphy. In the same three sites, the first appearance levels of several species are younger and younger, and last appearance levels are earlier and earlier from Site 654 to Site 653 and Site 652. Five biostratigraphic events, biochronologically evaluated and occurring at the same level in the deepsea Tyrrhenian record and in several land sections, have been selected as zonal boundaries of the proposed benthic foraminifers biostratigraphic scheme. The Plio-Pleistocene interval has been subdivided into four biozones and one subzone, recognizable both in the deep-sea and land-based sequences. The Cibicidoides (?) italicus assemblage zone stretches from the base of the Pliocene to the extinction level of the zonal marker, biochronologically evaluated at 2.9 Ma. The Cibicidoides robertsonianus interval zone stretches from the Cibicidoides (?) italicus extinction level to the Pliocene Mediterranean FO of Gyroidinoides altiformis, evaluated at 2.4 Ma. The Gyroidinoides altiformis interval zone stretches from the Mediterranean Pliocene FO of the zonal marker to the appearance level of Articulina tubulosa, evaluated at 1.62 Ma. The Articulina tubulosa assemblage zone stretches from the appearance level of the zonal marker to the Recent. In the Articulina tubulosa biozone, the Hyalinea baltica subzone is proposed. The appearance level of Hyalinea baltica is evaluated at 1.35 Ma, well above the Plio-Pleistocene boundary as defined in the Vrica stratotype section.