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.

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.

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Stable isotope composition of carbonates in the Tyrrhenian Sea

The Messinian evaporitic succession recovered at ODP Sites 652, 653, and 654 in the Tyrrhenian Sea was generated under various environmental conditions which ranged from brackish to hypersaline, as deduced from the sedimentary facies and stable isotope compositions of the carbonate and sulfate deposits. Water in the basins had to be shallow to undergo such rapid and large geochemical variations. The marine influence was omnipresent in the basin at least during the deposition of sulfate evaporites; seawater or marine brines might have been supplied either by direct input into evaporitic lagoons as at Sites 653 and 654, or by subterraneous infiltration in marginal areas as at Site 652. Episodes of severe dilution by continental waters occurred frequently throughout Messinian times in the more basinal areas at Sites 653 and 654, while a fresh water body was standing permanently at Site 652. The high heat flow present at Site 652 was responsible for a major late authigenesis of iron-rich dolomites, which was initiated during the subsidence of the basin and ended before Pliocene.

Strontium isotopic ratios of evaporites of the Tyrrhenian Sea

Strontium isotopic ratios of gypsums recovered from upper Miocene (Messinian) evaporites at ODP Leg 107 Holes 652A, 653B, and 654A (Tyrrhenian Sea) are lower than expected. The values for the Messinian balatino-like gypsum, single gypsum crystals, and anhydrites range from 0.70861 to 0.70886 and are approximately 25 * 10**-5 less than would be expected for evaporites precipitated from Messinian seawater (0.70891-0.70902). Pre-evaporitic planktonic foraminifers from Hole 654A show variable degrees of dolomitization and 87Sr/86Sr values that irregularly decrease upward from normal marine values approximately 81m below the lowest evaporite occurrence. This suggests diagenetic alteration by advecting interstitial water with a low 87Sr/86Sr ratio or that the lower Sr isotopic ratios for the Messinian evaporites could have resulted from a greater influence of fresh water on the Sr isotopic composition of the desiccating Tyrrhenian Sea. Fluctuations of the 87Sr/86Sr-ratio for evaporites in the sedimentary cycles recognized for Holes 653B and 654A, the generally low Sr isotopic ratio of river water entering the Mediterranean Sea, and the presence of dwarf marine microfossils suggest that the 87Sr/86Sr ratio of the evaporites responded to hydrologic variations in a very restricted basin with variable rates of marine and fresh water input. The strontium isotopic ratios of the Messinian anhydrites from the proposed lacustrine sequence at Hole 652A fall in the same range as the marine evaporites from Holes 654A and 653B. This suggests a common or similar origin of the brines at the three locations. The complex depositional and hydrologic conditions in the Mediterranean during the Messinian salinity crisis preclude the use of Sr isotopic values from the evaporites for stratigraphic correlation and dating. They are, however, very useful in the interpretation of the depositional history of the basin. General calculations assuming a closed system suggest that the 87Sr/86Sr ratio of Messinian seawater (-0.7090) could be reduced to that of the evaporites (-0.7087) by mixing with fresh water (e.g., Nile River) in times of 10**4 to 10**5 yr.

Mineralogy and geochemistry of latest Miocene deposits in the Tyrrhenian Sea

Late Miocene sediments from ODP Sites 652 and 654, drilled on the Sardinian margin in the Western Tyrrhenian Sea, are investigated through mineralogical, micromorphological, geochemical, and microgeochemical analyses. Clay associations appear to be little controlled by conditions of deposition, and largely depend on pre- and post-depositional conditions. The sedimentary series from Central Mediterranean gives very different geodynamic information, according to the sector considered. While relatively stable conditions, like those encountered in Caltanissetta Basin, Sicily, favor the mineralogical expression of warm-temperate and subarid Messinian climate, the Eastern Sardinia margin (Site 654) clay suites mainly reflect the transition from tectonically active to relaxed conditions. The series deposited at the foot of the same margin above a thinner crust (Site 652) experienced the effects of burial diagenesis, enhanced by strong geothermal gradient.

The occurrence and significance of Pleistocene and Upper Pliocene sapropels

Numerous sapropels and sapropelic strata from Upper Pliocene and Pleistocene hemipelagic sediments of the Tyrrhenian Sea show that intermittent anoxia, possibly related to strongly increased biological productivity, was not restricted to the eastern Mediterranean basins and may be a basin-wide result of Late Pliocene-Pleistocene climatic variability. Even though the sapropel assemblage of the Tyrrhenian Sea clearly originates from multiple processes such as deposition under anoxic conditions or during spikes in surface water productivity and lateral transport of organic-rich suspensates, many "pelagic sapropels" have been recognized. Stratigraphic ages calculated for the organic-rich strata recovered during ODP Leg 107 indicate that the frequency of sapropel formation increased from the lowermost Pleistocene to the base of the Jaramillo magnetic event, coinciding with a period when stable isotope records of planktonic foraminifera indicate the onset of climatic cooling in the Mediterranean. A second, very pronounced peak in sapropel formation occurred in the Middle to Late Pleistocene (0.73-0.26 Ma). Formainifers studied in three high-resolution sample sets suggest that changes in surface-water temperature may have been responsible for establishing anoxic conditions, while salinity differences were not noted in the faunal assemblage. However, comparison of sapropel occurrence at Site 653 with the oxygen isotopic record of planktonic foraminifers established by Thunell et al. (1990, doi:10.2973/odp.proc.sr.107.155.1990) indicates that sapropel occurrences coincide with negative d18O excursions in planktonic foraminifers in thirteen of eighteen sapropels recognized in Hole 653A. A variant of the meltwater hypothesis accepted for sapropel formation in the Late Pleistocene eastern Mediterranean may thus be the cause of several "anoxic events" in the Tyrrhenian as well. Model calculations indicate that the amount of oxygen advection from Western Mediterranean Deep Water exerts the dominant control on the oxygen content in deep water of the Tyrrhenian Sea. Inhibition of deep-water formation in the northern Adriatic and the Balearic Basin by increased meltwater discharge and changing storm patterns during climatic amelioration may thus be responsible for sapropel formation in the Tyrrhenian Sea.

Pleistocene and upper Pliocene sapropels in the Tyrrhenian Sea, Mediterranean Sea

A most significant finding of the ODP Leg 107 drilling campaign was the recovery of at least 56 distinct sapropel intervals in upper Pliocene to Pleistocene sediments of six sites drilled in the Tyrrhenian Sea. Except for 3 repots of disturbed organic-rich sediments - recovered in Core 201 of the Swedish Deep-Sea Expedition, in Core 2R-1,107 cm of Site 373 (Leg 13 DSDP) and at Site 373, Core 1-2,O-5 cm of DSDP Leg 42A - sapropels had previously only been described from the eastern Mediterranean and the Black Sea. Scientific deep-sea drilling in the Tyrrhenian Sea during DSDP Legs 13 and 42A apparently missed most of these deposits due to spot coring and rotary drilling techniques; high sedimentation rates may have precluded recovery by conventional gravity coring devices. The recovery of multiple layers of sapropels and sapropelic sediments in the Tyrrhenian Sea demonstrates that oceanographic conditions conducive to sapropel formation were not confined to the Black Sea and eastern Mediterranean, but occurred sporadically and possibly simultaneously in the entire Mediterranean during the Pliocene and Pleistocene. In the light of this finding, previous models of sapropel genesis may need reconsideration. In this paper, we present some initial data on the Tyrrhenian sapropels and suggest some implications of their massive occurrence in the western Mediterranean realm. We end by outlining possible causes for deposition of sapropels in an attempt to revive the interest in sapropels and their paleoceanographic significance.

Composition of Messinian sediments from the Tyrrhenian Sea

The data base for this study is represented by essentially nonevaporitic Messinian sediments recovered at ODP Sites 654, 653, 652, and 656 along the eastern Sardinian margin, and of the overlying early Pliocene oozes. Grain-size distribution, carbonate content, and microscopic observation of the sand size fractions were investigated. Messinian paleoenvironments, documented in the western Tyrrhenian Sea (ODP Sites 654 and 653), provide additional evidence supporting the deep basin desiccation model. A sharp lithologic contrast between early Pliocene pelagic oozes and latest Messinian conformable gypsiferous silts supports this model. The "lago-mare" biofacies was only occasionally observed in the shallowest site and is limited to the topmost part of the Messinian. Sites 652 and 656, lying in the deeper part of the Tyrrhenian and located on the downthrown side of an important eastward dipping fault system known as "Faglia centrale" are characterized by terrigenous sedimentation, with partly recycled minor evaporites. Of special interest is Site 652, where the thickness of the (probable) Messinian is 530 m. Sedimentary characters indicate a permanently subaqueous but nonmarine environment, with turbidites accumulating in a rapidly subsiding basin. According to the model proposed, this basin was fed by continental waters during times of maximum evaporitic draw-down, with temporary marine incursions from the west or southwest when the water level was higher. A basement ridge separated the evaporating pond from this endoreic lake located on the opposite (eastern) margin of the Tyrrhenian Basin, which was then limited to its western part. Post-Messinian reactivation of the "Faglia centrale" is necessary to account for the inversion of the relief.

Geochemistry of basal dolomitic and Fe-Mn sediments from the Tyrrhenian Sea

In the Tyrrhenian Sea (Western Mediterranean), unusual reddish, soft to lithified, dolomitic sediments up to 45 m thick overlie igneous crust at the base of thick Pliocene-Quaternary deep-sea sediment successions in the Marsili (Site 650) and Vavilov (Site 651) basins. These sediments also overlie the Gortani Ridge, a basaltic Seamount near the base of the Sardinian continental margin (Site 655). At both basinal sites (650, 651), the lowest sediments are dolomitic, with manganese oxide (MnO) segregations. Whole-rock X-ray diffraction indicates abundant dolomite and quartz, with subordinate calcite, illite (authigenic), feldspar and minor kaolinite, chlorite, and anhydrite. Chemical analyses show strong enrichment in magnesium oxide (MgO) and MnO relative to shale or deep-sea clay. Mg and Mn correlate positively and exhibit decreasing concentrations up the succession in the Marsili Basin (Site 650). The following scenario is proposed: peridotites were exposed on the seafloor in the Vavilov Basin (Site 651) and then eroded, depositing talc in local fine-grained dolomitic sediments within the igneous basement. After local magmatism ended, the igneous basement at each site subsided rapidly (about 800 m/m.y.) and was blanketed with calcareous and clay-rich oozes. During early diagenesis (from isotopic evidence; McKenzie et al., this volume) tepid fluids, of modified seawater composition, reacted with and dolomitized the overlying deep-sea sediments. At Site 651 additional Mg may have been extracted from asthenosphere peridotite cored at shallow depths (about 100 m). One can hypothesize that fluids rich in Mg and Mn were flushed from the igneous basement, triggered by extensional faulting and local tilting during subsidence of the basement, and that these fluids then dolomitized the base of the overlying sediment succession. Late tectonic movements in the Vavilov Basin (Site 651) fractured already lithified dolomitic sediments and more reducing (? hydrothermal) fluids locally remobilized Fe and Mn and corroded dolomite crystals.