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.

Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Mineralogy at DSDP Leg 78A Holes

This chapter deals with the evolution of clay minerals in Cenozoic sediments from DSDP Sites 541, 542, and 543 east of the Lesser Antilles arc on and near the edge of the Barbados Ridge complex. Throughout the Miocene, smectite exceeds all other minerals at all three sites. From the Pliocene onward, however, illite becomes dominant and chlorite well-represented. Quantitative mineral differences among the three sites are significant up until the top of the Pliocene. But in the Pleistocene, the mineralogical composition becomes exactly the same at all sites. Data from the Caribbean region are used to interpret the results obtained. These involve two supply sources: (1) the adjacent islands that supply smectites and kaolinites, and (2) South America, which is the major source of illite and chlorite. The apparent northward migration of illite and chlorite on the Barbados Ridge complex and the changes reported in the quantitative distribution of the four clay minerals are most probably controlled by northerly currents along the northern coast of South America.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Characteristics and distribution of Neogene turbidites at ODP Site 108-657

Numerous and variable silty-sandy siliciclastic turbidites were observed in Neogene pelagic sediments (late Miocene to Holocene) at Site 657: (1) thick-bedded, coarse-grained and thin-bedded, fine-grained turbidites; and (2) turbidites composed of eolian dune sand and shallow-water bioclasts or of fluvial-sand or mixed sandy component assemblages. The stratigraphic distribution of these turbidites indicates five periods during which climatic conditions and material sources change. Turbidite occurrence prior to 6.2 Ma (late Miocene) is sparse; the deposits contain coarse and fine-grained turbidites with quartz grains of eolian or mixed origin suggesting the existence of arid conditions at about 8.5 and 6.5 Ma. A coarse-grained turbidite of fluvial origin, recording a humid climate, occurs at about 6.2 Ma. During the early Pliocene, turbidites are frequent (15/Ma); they contain only fine-grained sequences comprising material of mixed origin, which indicates a more humid climate perhaps. The late Pliocene starts with rare coarse-grained turbidites of wind-transported sand while the uppermost Pliocene deposits show a higher frequency of fine-grained sequences (10/0.7 Ma) composed mainly of fluvial material. During the early Pleistocene, similar high turbidite frequency was observed (20/1.3 Ma) but with a total lack of eolian supply. During the last 0.7 Ma, the frequency decreases and the sequences are characterized by highly variable sediment components that could be related to strong variations of climatic conditions. The sedimentary characteristics of turbidites are mainly controlled by sediment source and climate. The frequency must be influenced by sea-level variations, by cyclic processes of climatic origin, and possibly by variations in the continental slope morphology. Clay mineral assemblages suggest a south Saharan source of terrigenous material during the late Miocene and the Pliocene and a northwest Saharan source during the Pleistocene.

Mineralogy and geochemistry of aerosols from the Western Pacific

Aerosols collected by net method over the Western Pacific were investigated. Distribution of eolian material, its mineral and chemical compositions are controlled by the climatic and circumcontinental zonalities. It was stated that Fe and Mn were bound with mineral components of aerosols, while trace elements are bound with organogenic matter. Fluxes of aerosols and their components on the ocean surface were determined.

Geologic-hydrologic setting and surface sedimentology in the Persian Gulf

1. Morphology and sedimentation The deepest parts of the Persian Gulf lie off the Iranian coast. Several swells separate the Persian Gulf into the Western Basin, the Central Basin and the Strait of Hormuz, which leads without noticeable morphological interruption onto the Biaban Shelf; the latter gradually drops off towards the continental slope, which itself has a strongly subdivided morphology. The sediment distribution in the Western Basin runs parallel to the basin's axis to a depth of 50 -60 m. This is caused by the shallow and uniform slope of the Iranian coast into the Western Basin, by clear exposure of the area to the Shamal-Winds and by tidal currents parallel to the basin's axis. Most other parameters also show isolines parallel to the coast line. Data from the sediment analyses show a net transport which extends out along the Central Swell: coarse fraction > 63 µ, total carbonate content, carbonate in fine fractions < 2 µ, 2-6 µ and 20-63 µ, calcite-aragonite ratios in the fine fractions 2-6 µ and 20-63 µ and quartz-dolomite ratios in fine fraction 2-6 µ. At least the uppermost 10-40 m of this sediment is late Holocene. This implies sedimentation rates of several meters per 1000 years. The slope from the Iranian coast into the Central Basin (max. depth 100 m) is generally steeper, with interspersed islands and flats. Both facts tend to disturb a sediment dustribition parallel to the basin's axis over extensive areas and may preclude any such trend from being detected by the methods and sample net used. The spatial distribution of the coarse fraction, however, seems to indicate sediment transport at greater water depths perpendicular to the basin's long axis and along the steepest gradients well into the Central Basin. The flats of the Central Basin have a sediment cover distinctly different from those of the deeper basin areas. Characteristic parameters are the extremely high percentages of coarse grained sediments, total content of carbonate CO2 over 40, low total organic carbon content, (however values are high if calculated on the basis of the < 63 µ fraction), low total N-content, and low C/N ratios. These characteristics probably result from the absence of any terrigenous material being brought in as well as from exposure to wave action. Finest terrigenous material is deposited in the innermost protected part of the Hormuz Bay. In the deep channel cut into the Biaban Shelf which carries the Persian Gulf out-flow water to the Indian Ocean, no fine grained sediment is deposited as shown by grain size data. 2. Geographic settings and sedimentation Flat lands border the Arabian coast of the Persian Gulf except for the Oman region. The high and steep Zagros Mountains form the Iranian coastline. Flat topography in combination with generally low precipitation precludes fluviatile sediment being added from the South. Inorganic and biogenic carbonates accumulating under low sedimentation rates are dominant on the shallow Arabic Shelf and the slopes into the Western and Central Basins. The fluviatile sediment brought in from the Iranian side, however decisively determine the composition of the Holocene sediment cover in the Persian Gulf and on the Biaban Shelf. Holocene sediments extend 20-30 km seaward into the Western Basin and about 25 km on to the Biaban Shelf. As mentioned before, sedimentation rates are of several meters/1000 years. The rocks exposed in the hinterland influence the sediments. According to our data the Redbeds of the Zagros Mountains determine the colour of the very fine grained sediments near the Iranian Coast of the Persian Gulf. To the West of Hormuz, addition of carbonate minerals is particularly high. Dolomite and protodolomite, deposited only in this area, as well as palygorskite, have proven to be excellent trace minerals. To the East of Hormuz, the supply of terrigenous carbonates is considerably lower. Clay minerals appear to bring in inorganically bound nitrogen thus lowering the C/N ratio in these sediments especially off river mouths. 3. Climate and sedimentation The Persian Gulf is located in a climatically arid region. This directly affects sedimentation through increased wind action and the infrequent but heavy rainfalls which cause flash floods. Such flash floods could be responsible for transporting sedheats into the Central Basin in a direction perpendicular to the Gulf's axis. Eolian influx is difficult to asses from our data; however, it probably is of minor importance from the Iranian side and may add, at the most, a few centimeters of fine sediment per 1000 years. 4. Hydrology and sedimentation High water temperatures favor inorganic carbonate precipitation in southern margin of the Gulf, and probably on the flats, as well as biogenic carbonate production in general. High evaporation plus low water inflow through rivers and precipitation cause a circulation pattern that is typical for epicontinental seas within the arid climate region. Surface water flows in from the adjoining ocean, in this case the Indian Ocean and sinks to the bottom of the Persian Gulf mainly in the northern part of the Western Basin, on the "Mesopotamischer Flachschelf" ard probably in the area of the "Arabischer Flachschelf". This sinking water continually rejuvenates the bottom out-flow water. The inflowing surface water from the Indian Ocean brings organic matter into the Persian Gulf, additional nutrients are added by the "fresh" upwelling waters of the Gulf of Oman. Both nutrients and organic matter diminish very rapidly as the water moves into the Persian Gulf. This depletion of nutrients and organic matter is the reasonfor generally low organic carbon contents of the Persian Gulf sediments. The Central Swell represents a distinct boundary, to the west of which the organic carbon content are lower than to the east when sediment samples of similar grain size distribution are compared. The outflow carries well oxygenated water over the bottom of the Persian Gulf and the resulting oxidation further decreases the content of organic matter. In the Masandam-Channel and in the Biaban-Shelf channel, the outflowing water prevents deposition of fine material and transports sediment particles well beyond the shelf margin. The outflowing water remains at a depth of 200-300 m depending on its density and releases ist suspending sediment load to the ocean floor, irrespectative of the bottom morphology. This is reflected in several parameters in which the sediments from beneath the outflow differ from nearby sediments not affected by the outflowing water. High carbonate content of total samples and of the individual size fraction as well as high aragonite and dolomite contents of individual size fractions characterize the sediment beneath the outflowing water. The tidal currents, which avt more or less parallel to the Gulf's axis, favor mixing of the water masses, they rework sediments at velocities reported here. This fact enlarges to a certain degree the extent of our interfaces which are based on only a few sample points (Persian Gulf and Biaban Shelf one sample per 620 km**2, continental slope one sample per 1000 km**2). The water on the continental slope shows and oxygen minimum at 200-1200 m which favors preservation of organically-bound carbon in the sediment. The low pH-values may even permit dissolution of carbonate minerals.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.