Geochemistry and minerals at DSDP Leg 81 Holes

Three phases of volcanism have been recognized in the lower Paleogene sequence of the southwest Rockall Plateau which are related to the onset of seafloor spreading in the NE Atlantic. The earliest, Phase 1, is marked by a sequence of tholeiitic basalts and hyaloclastites which form the dipping reflector sequence in Edoras Basin. Phase 2 is characterized by tuffs and lapilli tuffs of air-fall origin, ranging in composition from basic to intermediate. They were generated by highly explosive igneous activity due to magma-water interaction, and terminate at the level of a major transgression. Subsequently, volcanism reverted to tholeiitic basalt type, producing the thin tuffs and minor basalt flows of Phase 3. Alteration of the volcanic glass and diagenesis of the tuffs and lapilli tuffs has been considerable in many cases, with a large number of diagenetic mineral phases observed, including smectite, celadonite, analcime, phillipsite, clinoptilolite, mordenite, and calcite. Although calcite is the latest observed diagenetic cement, it nevertheless occurred relatively early, in one case totally preserving basaltic glass from alteration.

Carbonate, organic carbon, pyrolysis and composition of the extracts at DSDP Holes 76-534A and 44-391

The geochemical studies of Sites 534 and 391 and their comparison allow us to improve the chemical characterization of different geological formations dating from the early Callovian to the Maestrichtian along the continental margin of eastern North America. Three of the formations are favorable for the preservation of organic matter: (1) the unnamed formation (middle Callovian to Oxfordian), (2) the Blake-Bahama Formation (Berriasian to Barremian), and (3) the Hatteras Formation (Aptian to Cenomanian). The organic matter is mainly detrital, except for a few organic-rich layers where a contribution of aquatic material occurs. In these organic-rich layers, the petroleum potential is medium to good. Maturation has not quite reached the beginning of the oil window even for the deepest organic material.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Sedimentology and origin of lower Cretaceous pelagic carbonates and redeposited clastics at DSDP Hole 76-534A

Drilling at Site 534 in the Blake-Bahama Basin recovered 268 m of Lower Cretaceous, Berriasian to Hauterivian, pelagic carbonates, together with volumetrically minor intercalations of claystone, black shales, and terrigenous and calcareous elastics. Radiolarian nannofossil pelagic carbonates accumulated in water depths of about 3300 to 3650 m, below the ACD (aragonite compensation depth) but close to the CCD (calcite compensation depth). Radiolarian abundance points to a relatively fertile ocean. In the Hauterivian and Barremian, during times of warm, humid climate and rising sea level, turbiditic influxes of both terrigenous and calcareous sediments, and minor debris flows were derived from the adjacent Blake Plateau. The claystones and black shales accumulated on the continental rise, then were redeposited onto the abyssal plain by turbidity currents. Dark organic-rich and pale organic-poor couplets are attributed to climatic variations on land, which controlled the input of terrigenous organic matter. Highly persistent, fine, parallel lamination in the pelagic chalks is explained by repeated algal "blooms." During early diagenesis, organic-poor carbonates remained oxygenated and were cemented early, whereas organic-rich intervals, devoid of burrowing organisms, continued to compact later in diagenesis. Interstitial dissolved-oxygen levels fluctuated repeatedly, but bottom waters were never static nor anoxic. The central western Atlantic in the Lower Cretaceous was thus a relatively fertile and wellmixed ocean basin.

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Geochemistry at DSDP Site 76-533

Bulk X-ray mineralogy of 47 hemipelagic mud and clay samples from the Blake Outer Ridge has revealed that the sediments contain low magnesian calcite, calcian dolomite, ferroan dolomite, and magnesian siderite. Dolomite and siderite are authigenic and occur as rhombohedrons scattered through the sediments, whereas calcite is mostly biogenic. Pliocene dolomitic lenses are made up of interlocking polyhedral grains of ferroan dolomite. The contents of authigenic dolomite and siderite are 3 to 8% in carbonate sediments and 70 to 89% in dolomitic lenses. Dolomite occurs largely in the cores above 192 m sub-bottom depth, whereas siderite occurs in the cores below 87 m. The distribution and occurrence of dolomite and siderite have determined the diagenetic zonation of carbonates as Zone I (dolomitic zone, top-90 m), Zone II (transition zone, 90-180 m), and Zone III (sideritic zone, 180 m-bottom). Measurements of major and minor elements in the untreated total sediment samples and the insoluble residues after digestion in acid-reducing solution have revealed that the soluble fraction concentrates carbonates and ferromanganese associations (Ca, Mg, Sr, Fe, and Mn). Typical "hydrogenous elements" (Co, Cu, Ni, and V) are more concentrated in the insoluble residues rather than in the soluble fraction; the concentrations of these four elements are low and comparable to modern offshore mud, probably because the Site 533 sediments were deposited at a high rate of sedimentation. The contents of Fe2O3 and MnO are somewhat high for rapidly accumulated mud, particularly in the Pliocene sediments (8.09 and 0.26%, respectively, on a Carbonate-free basis). The high Fe and Mn contents are mainly due to the high contribution of the leacheable nonlithogenous fraction; leacheable Fe and Mn originate in the ferromanganese oxide accumulated on the seafloor. Only a small amount of ferric oxide was converted to iron sulfide in the surficial part of Zone I. Most ferromanganese oxide was reduced and precipitated as ferroan dolomite and magnesian siderite in Zones II and III under high alkalinity and high pH conditions in the organic-matter-rich sediments. Fe2+ and Mn2+ in the deeper sediments beneath Zone III possibly migrated upward and concentrated as siderite in Zone III, hence resulting in high contents of Fe and Mn in the Pliocene sediments. Analysis of carbonate zonation on the Blake Outer Ridge has revealed that the zonation is subparallel to the bedding plane rather than to the present seafloor. The sediments at Site 103 on the flank region of the Ridge are lacking Zone I and most of Zone II, probably the result of erosion of the most of the Pleistocene and Pliocene sediments by the enhanced bottom currents during the Pleistocene.

Grain-size distribution, carbon and calcium carbonate at DSDP Leg 63 Holes

Sand-silt-clay distribution was determined at Scripps on samples collected at the time the cores were split and described. The sediment classification used here is that of Shepard (1954); sand, silt, and clay boundaries are determined on the basis of the Wentworth (1922) scale. Thus the sand, silt, and clay fractions are composed of particles whose diameters range from 2000 to 62.5 µm, 62.5 to 3.91 µm, and less than 3.91 µm, respectively. This classification is applied regardless of sediment type and origin.

Minerals and geochemistry of DSDP Hole 81-552A

The acid insoluble coarse fractions of the glacial-interglacial sequence of Hole 552A in the NE Atlantic are made up of varying amounts of terrigenous detritus, biogenic silica, and pyroclastic material, principally volcanic glass. Volcanic ash content varies significantly over the entire interval, and the three North Atlantic ash horizons of Ruddiman and Glover (1972) can be recognized satisfactorily. The terrigenous detritus is of mixed metamorphic-basaltic type and probably originated on the Greenland landmass

Geochemistry of Lau Backarc Basin sediments

Major and minor (Mn, Sr, Ba, V, Cr, Ni, Co, Zn, Cu, Zr, Y, Sc) elements and mineralogic compositions were determined on bulk sediments collected during Ocean Drilling Program Leg 135. Three classes of sediment samples from holes drilled in the Lau Basin are discriminated by mineralogy and major element data. Samples labeled Class 1 are significantly enriched in biogenic calcite and occur predominantly in the northern part of the basin (Sites 834-835), whereas those of Class 3 are mostly enriched in volcanogenic material and are predominant in the central part of the basin (Sites 836-839). The minor element composition records the effects of the hydrothermal activity on the sediments. In the northern area of the basin (Sites 834-835), sedimentation is characterized by higher accumulation rates of the carbonate and hydrothermal fractions. These sediments are probably reworked predominantly, transported in the water column, and then settled locally. Thus, ponded sediments are probably responsible to this high accumulation rates. Diagenetic processes altered the volcanic material to a grade corresponding to the stability of phillipsite. In the central area of the basin (Sites 836-839), sedimentation is characterized by the action of bottom currents preferentially reworking the carbonate and hydrothermal fractions. Volcanogenic accumulation rates are greater at these sites than in the northern Lau Basin. Alteration of volcanic material is more important deeper in the holes and records authigenesis of clay rich in Fe-Mg, most likely smectite. Locally, clay minerals have apparently incorporated Cr and other ore-forming elements.

Composition of minerals from peridotides at the Mid-Atlantic Ridge, 13°N

Peridotites (diopside-bearing harzburgites) found at 13°N of the Mid-Atlantic Ridge fall into two compositional groups. Peridotites P1 are plagioclase-free rocks with minerals of uniform composition and Ca-pyroxene strongly depleted in highly incompatible elements. Peridotites P2 bear evidence of interaction with basic melt: mafic veinlets; wide variations in mineral composition; enrichment of minerals in highly incompatible elements (Na, Zr, and LREE); enrichment of minerals in moderately incompatible elements (Ti, Y, and HREE) from P1 level to abundances 4-10 times higher toward the contacts with mafic aggregates; and exotic mineral assemblages Cr-spinel + rutile and Cr-spinel + ilmenite in peridotite and pentlandite + rutile in mafic veinlets. Anomalous incompatible-element enrichment of minerals from peridotites P2 occurred at the spinel-plagioclase facies boundary, which corresponds to pressure of about 0.8-0.9 GPa. Temperature and oxygen fugacity were estimated from spinel-orthopyroxene-olivine equilibria. Peridotites P1 with uniform mineral composition record temperature of the last complete recrystallization at 940-1050°C and FMQ buffer oxygen fugacity within the calculation error. In peridotites P2, local assemblages have different compositions of coexisting minerals, which reflects repeated partial recrystallization during heating to magmatic temperatures (above 1200°C) and subsequent reequilibration at temperatures decreasing to 910°C and oxygen fugacity significantly higher than FMQ buffer (delta log fO2 = 1.3-1.9). Mafic veins are considered to be a crystallization product from basic melt enriched in Mg and Ni via interaction with peridotite. The geochemical type of melt reconstructed by the equilibrium with Ca-pyroxene is defined as T-MORB: (La/Sm)_N~1.6 and (Ce/Yb) )_N~2.3 that is well consistent with compositional variations of modern basaltic lavas in this segment of the Mid-Atlantic Ridge, including new data on quenched basaltic glasses.

Heavy minerals from Paleogene sediments at DSDP Leg 81 Holes

Five heavy mineral associations occur in the Paleocene and Eocene sediments recovered during Leg 81 of the Deep Sea Drilling Project (DSDP) in the SW Rockall area. Association 1, consisting of augite, iddingsite, and olivine, was derived from the basaltic rocks of the northern part of the Rockall Plateau. Association 2 consists of epidote group minerals, including piedmontite, and amphiboles of actinolite, actinolitic hornblende, and magnesio-hornblende compositions, and was derived from the metamorphic basement of south Greenland. Association 3 comprises garnet, augite, apatite, and edenitic and pargasitic amphiboles and has a provenance in the southern Rockall Plateau. Associations 4 (garnet, apatite, edenitic/pargasitic amphiboles) and 5 (garnet, apatite) are intrastratal solution derivatives of Association 3, with successive removal of first pyroxene and then amphibole with increasing depth of burial. Throughout the SW Rockall Plateau area there is a significant change in the spectrum of the above assemblages in the lower part of the Eocene. This change has been noted at Sites 403, 404, 553, and 555 and is defined by the last appearance of Association 2. This level therefore marks the cessation of sediment supply from southern Greenland and is the result of the final separation of Rockall and Greenland immediately prior to magnetic Anomaly 24.

Biogenic silica in ODP Hole 105-647A

Eocene to Holocene sediments from Ocean Drilling Program (ODP) Site 647 (Leg 105) in the southern Labrador Sea, approximately 200 km south of the Gloria Drift deposits, were investigated for their biogenic silica composition. Three sections of different diagenetic alteration products of primary siliceous components could be distinguished: (1) opal-A was recorded in the Miocene and the early Oligocene time intervals with strongly corroded siliceous skeletons in the Miocene and mostly well preserved biogenic opal in the early Oligocene; (2) opal-CT precipitation occurs between 250-440 meters below seafloor (mbsf) (earliest Oligocene to late Eocene); (3) between 620-650 mbsf (early/middle Eocene), biogenic opal was transformed to clay minerals by authigenesis of smectites. Using accumulation rates of biogenic opal, paleoproductivity was estimated for the early Oligocene to late Eocene interval. A maximum productivity of biogenic silica probably occurred between 35.5 and 34.5 Ma (early Oligocene). No evidence for opal sedimentation during most of middle Eocene was found. However, at the early/middle Eocene boundary (around 52 Ma), increased opal fluxes were documented by diagenetic alteration products of siliceous skeletons.