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.

Elemental abundance and water content at DSDP Leg 86 Holes

X-ray fluorescence analyses of 1143 samples from Site 576 (32°21.4'N, 164°16.5'E) and 539 samples from Site 578 (33°55.6'N, 151°37.7'E) for the elements Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, Ba, and S show consistent trends from Si-rich surficial deposits to dark brown clays rich in Mn, Fe, P, and Ti in early Cenozoic sections. These data sets form the basis for a detailed paleogeochemical stratigraphy of North Pacific "red" clays.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Stable isotope record of Cibicidoides spp. from Late Miocene sediments of the Southern Ocean

Deepwater circulation plays an important role in climate modulation through its redistribution of heat and salt and its control of atmospheric CO2. Oppo and Fairbanks (1987, doi:10.1016/0012-821X(87)90183-X) showed that the Southern Ocean is an excellent monitor of deepwater circulation changes for two reasons: (1) the Southern Ocean is a mixing reservoir for incoming North Atlantic Deep Water and recirculated water from the Pacific and Indian oceans; and (2) the nutrient/delta13C tracers of deepwater are not significantly changed by surficial processes within the Southern Ocean. We can extend these principles to the late Miocene because tectonic changes in the Oligocene and early and middle Miocene developed near-modern basinal configurations. However, on these time scales, changes in the oceanic carbon reservoir and mean ocean nutrient levels also affect the delta13C differences between ocean basins. From 9.8 to 9.3 Ma, Southern Ocean delta13C values oscillated between high North Atlantic values and low Pacific values. The Southern Ocean recorded delta13C values similar to Pacific values from 9.2 to 8.9 Ma, reflecting a low contribution of Northern Component Water (NCW). The delta13C differences between the NCW and Pacific Outflow Water (POW) end-members were low from 8.9 to 8.0 Ma, making it difficult to discern circulation patterns. NCW production may have completely shutdown at 8.6 Ma, allowing Southern Component Water (SCW) to fill the North Atlantic and causing the delta13C values in the North Atlantic, Pacific, and Southern oceans to converge. Deepwater delta13C patterns resembling the modern distributions evolved by 7.0 Ma: delta13C values were near 1.0 per mil in the North Atlantic; 0.0 per mil in the Pacific; and 0.5 per mil in the Southern Ocean. Development of near-modern delta13C distributions by 7.0 Ma resulted not only from an increase in NCW flux but also from an increase in deepwater nutrient levels. Both of these processes increased the delta13C difference between the North Atlantic and Pacific oceans. Deepwater circulation patterns similar to today's operated as early as 9.8 Ma, but were masked by the lower nutrient/delta13C differences. During the late Miocene, 'interglacial' intervals prevailed during intervals of NCW production, while 'glacial' intervals occurred during low NCW production.

Helium isotope ratios and sedimentation rate models of ODP holes

A continuous age model for the brief climate excursion at the Paleocene-Eocene boundary has been constructed by assuming a constant flux of extraterrestrial 3He (3He[ET]) to the seafloor. 3He[ET] measurements from ODP Site 690 provide quantitative evidence for the rapid onset (surficial carbon budget at this time. These observations support astronomically calibrated age models indicating extremely rapid release of isotopically light carbon, possibly from seafloor methane hydrate, as the proximal cause of the event. However, the 3He[ET] technique indicates a previously unrecognized and extreme increase in sedimentation rate coincident with the return of climate proxies to pre-event values. The 3He[ET]-based age model thus suggests a far more rapid recovery from the climatic perturbation than previously proposed or predicted on the basis of the modern carbon cycle, and so may indicate additional or accelerated mechanisms of carbon removal from the ocean-atmosphere system during this period. 3He[ET] was also measured at ODP Site 1051 to test the validity of the Site 690 chronology. Comparison of these data sets seems to require removal of several tens of kyr of sediment within the climatic excursion at Site 1051, an observation consistent with sediment structures and previous age modeling efforts. The Site 1051 age model shows a ~30 kyr period in which climate proxies return toward pre-event values, after which they remain invariant for ~80 kyr. If this rise represents the recovery interval identified at Site 690, then the 3HeET-based age models of the two sites are in good agreement. However, alternative interpretations are possible, and work on less disrupted sites is required to evaluate the reliability of the proposed new chronology of the climate excursion. Regardless of these details, this work shows that the 3HeET technique can provide useful independent evidence for the development and testing of astronomically calibrated age models.

Physical oceanography during five ECOMARGE cruises

The first experiment of the ECOMARGE programme (ECOsystèmes de MARGE continentale) was initiated in 1983-1984, in the Gulf of Lions (northwestern Mediterranean Sea). The objectives of the ECOMARGE-I experiment were: to quantify the transfer of particulate matter, in general, and of organic carbon, in particular, from its introduction to and formation in the waters of the continental shelf-to its consumption or sedimentation on the shelf or its transfer to the slope and deep sea; and to understand the processes involved in that transfer, consumption and sedimentation together with their variability in space and time. The results of that experiment, from 1983 to 1988, are presented in this Special Issue. The highlights of the results are summarised in this paper. These results indicate that, of the particles formed in the waters of the continental shelf and those introduced by rivers, some are deposited as sediments on the shelf. A portion is transported offshore, however, to the slope and deep sea. The Rho^ne River, in the northeastern part of the study area, is the major source of continental material; this is transported to sea in a benthic nepheloid layer and, mostly, alongshore to the southwest. Here, it largely leaves the shelf through the canyons, especially the Lacaze-Duthiers Canyon. In the offshore waters, particle concentrations and distributions show surficial, intermediate and benthic nepheloid layers. These turbid structures increase towards the southwest, corresponding to the seaward shift of the front between the coastal waters and the Liguro-Provençal cyclonic gyre, a major forcing function in the Gulf of Lions. Considering the source and fate of particles (largely biogenic from the euphotic zone and abiogenic from deeper waters) a layered system is described, which is emphasized by the concentrations of natural and artificial elements and compounds. Of the flux of particles to the Lacaze-Duthiers Canyon, on a decadal scale, about 30% (as a minimum) is estimated to be stored as sediment; the remainder is transported down-canyon, towards the deep sea. The temporal variability of processes affecting this net seaward transport, of both biogenic and abiogenic material, is from hours, days to seasonal, and probably interannual, time scales. The response of the system to these variations is rapid, with pulses of increased discharge of particles from the adjacent shelf being detected in sediment traps in the Lacaze-Duthiers Canyon in less than 16 days (the temporal resolution of the traps). Based upon the study of tracers of particulate matter and environmental factors (i.e. river discharge and climatic conditions), it appears that the contribution from the Rho^ne River and its adjacent area is maximal during the winter; at this time, the flow of the Liguro-Provençal Current also increases. In contrast, the maximum relative contribution of the adjacent southwesterly area to the flux in the Lacaze-Duthiers Canyon occurs in summer, during storm events.

Planktonic foraminifera of ODP Hole 107-654A

The late Miocene sediments of the Tyrrhenian ODP Site 654 encompass a deepening sequence which begins with glauconite shallow water sands followed by a rapid transition to deep water sediments and culminates with dolomitic mudstones associated with Messinian evaporites. The sequence compares well with the so-called 'Sahelian cycle' and with post-orogenic cycles recognized in peninsular Italy and Sicily. The studied interval, consisting of 55 m thick nannofossil oozes, belongs to the Globorotalia suterae subzone and lower part of the Globorotalia conomiozea Zone, indicating late Tortonian and early Messinian age, respectively. Biomagnetostratigraphic correlation assigns the Tortonian/ Messinian boundary an age of 6.44-6.45 Ma. In addition, six main events have been recognized, based on the range of keeled globorotaliids and coiling direction changes of keeled and unkeeled globorotaliids, which have been correlated to the geomagnetic time-scale. Comparison with North Atlantic sites and land sections of the Guadalquivir basin and northern Morocco provides good correlations with the events documented in these areas. In particular, Event IV, which predates the FO of Globorotalia conomiozea, may be used to recognize the Tortonian/Messinian boundary in extra-Mediterranean areas where G. conomiozea is missing. Variations in the distribution of different species of Globigerinoides are related to changes in the surficial marine environment. Although no clear trends can be recognized on the oxygen and carbon isotope records of Globigerinoides obliquus, the parallelism between the occurrence of low salinity species (G. sacculifer) and peaks of low 5180 values, as well as that of normal salinity species (G. obliquus) and peaks of high d18O values, suggests strong local changes of environmental conditions. The high amplitude of the fluctuations of d18O values suggests important variations in the salinity of the Tyrrhenian Sea, related to a rapidly changing water budget. The major feature of the carbon isotope record is a large decrease between 7.0 and 6.95 Ma, which therefore predates the 6.2 Ma global 'carbon shift'.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.