Mineral, chemical and isotopic compositions of altered rocks at ODP Sites 193-1188 and 193-1189

During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges. The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite+/-illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310°C; (2) chlorite+/-mixed-layer clay alteration at temperatures of 230°C; (3) chlorite and illite alteration; (4) illite and chlorite+/-illite mixed-layer alteration at temperatures of 250-260°C; and (5) illite+/-chlorite alteration at 290-300°C. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at ~250°C, overprinted by quartz veining at 350°C. In contrast, four alteration zones occur in Hole 1189B: (1) illite+/-chlorite alteration formed at ~300°C; (2) chlorite+/-illite alteration at 235°C; (3) chlorite+/-illite and mixed layer clay alteration; and (4) chlorite+/-illite alteration at 220°C. Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples. Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (<10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence.

(Appendix) Relative abundance of planktonic foraminifera in ODP Site 138-846 late Quaternary sediments

High-resolution records of d18O and relative abundances of planktonic foraminifers were generated for ODP Leg 138 Site 846 for the past 800 k.y., with an average sampling interval of 3.6 k.y. The time scale was constructed by correlating the benthic d18O record to the SPECMAP and ODP Site 677 d18O time scales using the mapping function technique of Martinson et al. (1981). Our observations show that variations in the foraminiferal assemblages, although influenced by dissolution, are interpretable in terms of changing characteristics of upper ocean waters. Carbonate dissolution as indicated by fragmentation of planktonic foraminifers shows concentrated variance that is coherent with d18O at the 100 and 41 k.y. orbital periods. At these periods, maximum dissolution occurs during interglacial extremes. This finding differs from previous studies that have indicated that in this region percent carbonate minimum lags global ice volume minimum. N. dutertrei and dextral N. pachyderma dominate the assemblages, but do not show consistent relationships relative to glacial-interglacial cycles. However, less abundant species G. ruber, G. menardii, G. glutinata and G. sacculifer show positive and G. bulloides negative correlation with the d18O record. Q-mode factor analysis of the Site 846 assemblages and comparison with modern assemblages suggest the following. Prior to and during interglacials, the area was considerably warmer and more subtropical than at present; during glacials, the area was colder than at present with greater upwelling and advection off the eastern boundary, and possibly a stronger Peru Current; the equatorial ôcool tongueö was also possibly stronger.

Late Miocene to Quaternary planktonic foraminifera of ODP SIte 114-704

The planktonic foraminiferal zonation of Jenkins and Srinivasan (1986), which was defined for the southwestern sector of the temperate South Pacific Ocean, was successfully extended to the temperate sequences at Site 704. The zonation is based on first and last appearances of globorotalids, principally Globoconella species, which are indigenous to temperate surface-water masses. Most of the first and last appearances at ODP Site 704 are diachronous with those in the warmer temperate to subtropical South Atlantic, North Atlantic, and South Pacific oceans. The upper Miocene, upper Pliocene, and Quaternary sequences are punctuated by frequent incursions of subantarctic and polar assemblages of planktonic foraminifers. I assume that the appearance of an assemblage dominated by sinistral Neogloboquadrina pachyderma means that the Polar Front has migrated northward, but I do not know its position north or south of the site based on this preliminary work. The upper Miocene sequence contains five incursions between 6.5 and 5 Ma and the upper Pliocene and Quaternary sequence contains 16 events since 2.47 Ma. These are minimum estimates because the number of observed events will probably increase with higher sample density and use of quantitative methods to reveal more subtle events.

Organic carbon, calcium carbonate and carbon/nitrogen ratio at DSDP Leg 93 sites

A large number of samples of nonlithified and lithified sediments from Leg 93 sites were analyzed for their contents of organic carbon and calcium carbonate. An average of two samples was selected from every core for carbonate determination; organic carbon was measured in most of these samples. Nearly all of these analyses were performed on board Glomar Challenger for samples from Sites 603 and 604. Site 605 samples, plus some of the deeper samples from Hole 603B, were analyzed at the University of Michigan. The procedures used in both cases were virtually the same, and their results compared well. Organic carbon analyses were done using a Hewlett- Packard 185-B CHN Analyzer. Portions of samples selected for calcium carbonate determinations were treated with dilute HC1 to remove carbonate, washed with deionized water, and dried at 110°C. A Cahn Electrobalance was used to weight 20-mg samples of sediment for CHN analysis. Samples were combusted at 1050°C in the presence of an oxidant, and the volumes of the evolved gases determined as measures of the C, H, and N contents of sediment organic matter. Areas of gas peaks were determined and compared to those of rock standards of known carbon and nitrogen contents. These values were used to standardize instrument response so that C/N atomic ratios could be reported. Organic carbon concentrations were calculated on the basis of sediment dry weight. Hydrogen elemental analysis with the procedure used is untrustworthy because of the variable amounts of clay minerals and their hydrates, hence hydrogen values are not reported for samples analyzed by this method.

(Table 2) Oxygen and carbon isotope composition of planktonic foraminiferal species from DSDP Holes 93-603B and 93-604, and one benthic species from Hole 93-604

Holes 603C and 604 of DSDP Leg 93 were drilled on the western Atlantic continental rise at water depths of 4633 m and 2364 m, respectively. In Hole 603C, a nearly continuous, undisturbed, and complete section of Pliocene and lower Pleistocene sediments was recovered by hydraulic piston coring; in Hole 604, a section of uppermost Miocene to Pleistocene sediments was incompletely recovered by rotary coring. In order to reconstruct the Pliocene and Pleistocene history of isotopic variations, 139 oxygen and carbon isotope values were determined for planktonic and monospecific benthic foraminifer samples from these holes. Large parts of the Pleistocene history could not, however, be documented because sample intervals were large and sediments at Site 604 were redeposited. Time correlation is based on magnetostratigraphic (Hole 603C) and micropaleontologic (Hole 603C, Site 604) interpretation. Stable isotope analyses were carried out on the planktonic foraminiferal species Globigerinoides ruber, G. obliquus, and Globorotalia inflata from Hole 603C (48 analyses) and from Site 604 (48 analyses); at Site 604, the benthic foraminifer Uvigerina peregrina (43 analyses) was also studied through the section. Age calibration for Hole 603C is based on the magnetostratigraphy of Canninga et al. (1987; doi:10.2973/dsdp.proc.93.130.1987), which uses the time scale of Lowrie and Alvarez (1981).

Oligocene to Miocene stable isotope record and planktonic foraminifer biostratigraphy of the Sierra Leone Rise

We have integrated Oligocene to lower upper Miocene planktonic foraminifer biostratigraphy with benthic foraminifer (Cibicidoides spp.) stable isotope records for two sites drilled on opposite sides of the Sierra Leone Rise in the eastern equatorial Atlantic Ocean. Deep Sea Drilling Project Site 366 (2853 m present water depth; 2200-2800 m paleodepth) recovered an Oligocene to upper Miocene record with a minor unconformity in the "middle" Oligocene and a condensed middle Miocene section. Ocean Drilling Program Site 667 (3529 m present depth; 3000-3500 m paleodepth) recovered an apparently continuous "middle" Oligocene to lower middle Miocene record and a similar condensed middle Miocene section. The Oligocene to lower Miocene sections were deposited at similar sedimentation rates (~11-16 m/m.y.). Stable isotope stratigraphy proved to be useful in establishing intra- and interbasinal correlations. In addition to the well-known earliest Oligocene and middle Miocene S180 increases, a distinct d18O increase occurred near the Oligocene/Miocene boundary. Carbon isotope variations provide similar potential for improving correlations; for example, a d13C increase occurred near the Oligocene/Miocene boundary in concert with increased d18O values. There was little d13C difference between the western Atlantic and eastern Atlantic basins during the late Oligocene and most of the middle Miocene; in contrast, eastern basin d13C values were slightly lower than those in the western basins during the earliest Oligocene (about 35-33 Ma) and early Miocene (about 22-18 Ma).

Calcium carbonate, organic carbon, sediment description and hydrogen and oxygen index at DSDP Sites 93-603, 93-605, 93-604 and 95-603

The organic matter contents of sediments and rocks sampled during DSDP Leg 93 have been characterized by CHN and Rock-Eval analyses. Most samples from Sites 604 and 605 on the New Jersey continental slope and from Site 603 on the Hatteras outer continental rise contained less than 0.5% organic carbon. Some Neogene samples from the slope contained 1 to 2% organic carbon, and Cretaceous samples from the outer rise were as rich as 13.6% organic carbon by weight. Thin layers of black claystones of Santonian, Cenomanian, and Albian age were found interbedded in organiccarbon- lean, bioturbated, turbiditic claystones. Similar layers of turbiditic black marlstones were interspersed among Neocomian limestones and sandstones. Although the organic matter in many of the samples appeared to be detrital continental material, according to Rock-Eval and C/N values, Cenomanian black shales, in particular, contained substantial proportions of marine-derived organic matter.

Calcareous nannofossil abundance and datums of ODP Leg 189 sites

Quaternary sediments were recovered at all five sites drilled during Ocean Drilling Program (ODP) Leg 189 in the Tasmanian Gateway. Two of these sites lie north of the present-day Subtropical Front (STF), and three sites lie south of the STF. Quaternary sediments recovered at Sites 1168, 1170, 1171, and 1172 were studied in detail to determine the calcareous nannofossil biostratigraphy and construct an age model for these sediments. The Pliocene/Pleistocene boundary was identified by the last occurrence (LO) of Discoaster brouweri at Site 1172 and approximated by the LO of Calcidiscus macintyrei at the other sites because of a lack of discoasterids. A hiatus encompassing the entire Helicosphaera sellii Zone was tentatively identified at Sites 1168 and 1172 by the coincident LOs of C. macintyrei and H. sellii. Similar hiatuses have been noted at ODP Site 1127 on the Great Australian Bight, Deep Sea Drilling Project Site 282 off the Tasman subcontinent, and ODP Site 1165 in Prydz Bay, Antarctica.

Morphological variability of Globorotalia menardii in DSDP Sites 68-502 and 68-503

Variability in the test of Globorotalia menardii during the past 8 million years has been investigated at DSDP Site 502A (Caribbean Sea) and DSDP Site 503A (Eastern Equatorial Pacific). Measurements were made of spire height (delta x), maximum diameter (delta y), the tangent angles of the upper and lower peripheral keels (phi 1, phi 2, respectively), the number of chambers in the final whorl, and the area of the silhouette in keel view. Four morphotypes alpha, beta, gamma, and delta were distinguished. Morphotype alpha was found in strata ranging in age from the Late Miocene through the Holocene. It shows a continuous increase in delta x and delta y until the Late Pleistocene. During and after the final closure of the ancient Central American Seaway (between 2.4 Ma and 1.8 Ma) there was a rapid increase in the area of the test in keel view. At the Caribbean Sea site, morphotype beta evolved during the past 0.22 Ma. It is less inflated than alpha and has a more delicate test. In the morphospace of delta x vs. delta y, morphotypes alpha and beta can be distinguished by a separation line delta y = 3.2 * delta x - 160 (delta x and delta y in µm). Plots of morphotype alpha are below that line, those of beta are above it. Morphotype alpha is taken to be Globorotalia menardii menardii Parker, Jones & Brady (1865) and includes G. menardii 'A' Bolli (1970). Morphotype beta is identified as G. menardii cultrata (d'Orbigny). Morphotypes gamma and delta are extinct Upper Miocene to Pliocene forms which evolved from morphotype alpha. They have a narrower phi 1 angle and more chambers (>=7) than morphotype alpha commonly with 5 to 6 chambers (7 in transitional forms). In contemporaneous samples morphotype delta can be distinguished from gamma by a smaller value of phi 1 and 8 or more chambers in the final whorl. Morphotype gamma is taken to be G. limbata (Fornasini, 1902) and includes the junior synonym G. menardii 'B' Bolli (1970). Morphotype delta is G. multicamerata Cushman & Jarvis (1930). With the exception of the Late Pleistocene development of G. menardii cultrataonly in the Caribbean the morphological changes of G. menardii at DSDP Sites 502A and 503A are similar. The development from the ancestral G. menardii menardii of the G. limbata - G. multicamerata lineage during the Pliocene and of G. menardii cultrata during the Late Pleistocene suggests responses at the two sites to a changing palaeoceanography during and after the formation of the Isthmus of Panama.

Stable isotope ratios and paleoceanaographic reconstructions from sediment cores 80-548 and 161-978A

Largely continuous millennial-scale records of benthic d18O, Mg/Ca-based temperature, and salinity variations in bottom waters were obtained from Deep Sea Drilling Project Site 548 (eastern Atlantic continental margin south of Ireland, 1250 m water depth) for the period between 3.7 and 3.0 million years ago. This site monitored mid-Pliocene changes in Mediterranean Outflow Water (MOW) documented by continuously high Nd values between -10.7 and -9. Site 978 (Alboran Sea, 1930 m water depth) provides a complementary record of bottom water variability in the westernmost Mediterranean Sea, which is taken to represent MOW composition at its source. Both sites are marked by a singular and persistent rise in bottom water salinities by 0.7-1.4 psu and in densities by ~1 kg m-3 from 3.5 to 3.3 Ma, which is matched by an average 3 °C increase in bottom water temperatures at Site 548. This event suggests the onset of strongly enhanced deep-water convection in the Mediterranean Sea and a related strengthened MOW flow, which implies a major aridification of the Mediterranean source region. In harmony with model suggestions, the enhanced MOW flow has possibly intensified Upper North Atlantic Deep Water formation.

Geochemical and isotopic composition of Bransfield Basin Lavas collected during SONNE cruise SO155

Bransfield Basin is an actively extending marginal basin separating the inactive South Shetland arc from the northern Antarctic Peninsula. Rift-related volcanism is widespread throughout the central Bransfield Basin, but the wider eastern Bransfield Basin was previously unsampled. Lavas recovered from the eastern subbasin form three distinct groups: (1) Bransfield Group has moderate large-ion lithophile element (LILE) enrichment relative to normal mid-ocean ridge basalt (NMORB), (2) Gibbs Group has strong LILE enrichment and is restricted to a relic seamount interpreted as part of the South Shetland arc, and (3) fresh alkali basalt was recovered from the NE part of the basin near Spanish Rise. The subduction-related component in Bransfield and Gibbs Group lavas is a LILE-rich fluid with radiogenic Sr, Nd, and Pb isotope compositions derived predominantly from subducting sediment. These lavas can be modeled as melts from Pacific MORB source mantle contaminated by up to 5% of the subduction-related component. They further reveal that Pacific mantle, rather than South Atlantic mantle, has underlain Bransfield Basin since 3 Ma. Magma productivity decreases abruptly east of Bridgeman Rise, and lavas with the least subduction component outcrop at that end. Both the eastward decrease in subduction component and occurrence of young alkali basalts require that subduction-modified mantle generated during the lifetime of the South Shetland arc has been progressively removed from NE to SW. This is inconsistent with previous models suggesting continued slow subduction at the South Shetland Trench but instead favors models in which the South Scotia Ridge fault has propagated westward since 3 Ma generating transtension across the basin.

Thorium and Uranium analyses of sediment core GIK12310-4, NW African continental margin (Table 1,2)

The Th content of the sediment samples from "Meteor" core GIK12310-4 (3080 m water depth, off NW Africa) on a carbonate-free basis lies around the average of 12.4 ppm and is similar to the average content of the earth crust. On the contrary, uranium was found to be up to 3.5-fold enriched in the core section between 60 and 330 cm (within the Wuerm Glacial) where reducing conditions occur, due to deposition of authigenic uranium (9 µg/cm**2 1000 yrs.). The authigenic uranium content is correlated to the organic matter content (U/Corg ratio = 6 * 10**4). On the basis of the uranium content of the oxidized section uranium was split into a detritic and an authigenic component and the amount of supported ionium was calculated. From the profile of the specific Io-cxcess activity (= Io-total - Io-supported) with depth, average sedimentation rates of 3.3 ± 0.6 cm/1000 yrs. for the warmer stages and of 5 ± 1 cm/l000 yrs. for the cooler periods were estimated.

Phosphorus geochemistry of eastern equatorial Pacific Ocean sediments

We determined phosphorus (P) concentrations in Leg 138 sediment samples from Sites 844, 846, and 851, using a sequential extraction technique to identify the P associated with five sedimentary components. Total concentrations of P (sum of the five components) ranged from 4 to 35 µmol P/g sediment, with mean values relatively similar between the three sites (11, 14, and 12 for Sites 844,846, and 851, respectively). Authigenic/biogenic P was the most important component in terms of percentage of total P (about 75%), with iron-bound P (13%), adsorbed P (2%-9%), and organic P (4%) of secondary importance; detrital P was a minor P sink (1%) in these sediments. Profiles of adsorbed P and iron-bound P show decreasing concentrations with age, indicating that these components have been affected by diagenesis and reorganization of P. A peak in iron-bound P may reflect higher fluxes of hydrothermally derived Fe to eastern equatorial Pacific Ocean sediments from 11 to 8 Ma. Lower detrital P values for western Site 851 reflect a greater distance of this site from a terrigenous source area, compared to that of Sites 844 and 846. Phosphorus mass accumulation rates (P-MARs; units of µmol P/cm**2/k.y.) were calculated using total P concentrations (not including the minor and oceanically unreactive detrital P component) and sedimentation rates and dry-bulk densities averaged over time intervals of 0.5 m.y. P-MARs generally decrease from 17 Ma to the present. Eastern transect Sites 844 and 846 display a decrease in P-MARs from about 30 to 10 in the interval from 17 to 8 Ma, while western transect Site 851 is highly variable during this interval. P-MARs increase to about 45 and stay relatively high from 8 to 6 Ma, then decrease toward the present to some of the lowest values of the record (about 10). The general trend of high P-MARs at about 6 Ma and decreasing values toward the present is correlated with other geochemical and sedimentary trends through this interval and may reflect (1) a change in net sediment and P burial, (2) a reorganization of fluxes with no change of net burial, or (3) a combination of the two.

Stable isotopes of benthic foraminifera from Site ODP 184-1146

We generated a high resolution (~8 ky) benthic record from a West Pacific marginal basin to investigate the detailed structure and spectral characteristics of deep water isotope fluctuations during the middle Miocene. The benthic record from ODP Site 1146 allows unprecedented resolution of the structure of the middle Miocene delta13C excursion, as well as tighter control on the chronology of climatic events. Spectral analysis of the variance in the delta18O and delta13C records from ODP Site 1146 reveals spectral power concentrated in the eccentricity band (400-, ~100-ky) over the time interval between 13 and 17 Ma. The amplitude evolution in the 400-ky band is strikingly similar to that of the long eccentricity in Laskar's solution. There is an abrupt switch to the obliquity band in the delta18O record at -14.9 Ma, suggesting a shift in the ocean/climate response to orbital forcing (from low latitude eccentricity to high latitude obliquity forcing). The obliquity signal is pervasive in the delta18O record until -13.9 Ma, when a sharp increase in delta18O values indicates a major climatic transition. Comparison of delta18O and delta13C profiles from DSDP Site 588 (SW Pacific Ocean), ODP Site 761 (E Indian Ocean) and ODP Site 1146 (South China Sea) reveals significantly cooler deep water in the NE Indian Ocean throughout the middle Miocene and a restricted deep water exchange between the Pacific Ocean and Indian Ocean.