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.

Sm-Nd isotope and Mn/Ca ratios for cleaned Neogloboquadrina pachyderma from ODP Hole 105-647A (Table 1)

The neodymium (Nd) isotope composition of ancient seawater is a potentially useful tracer of changes in continental inputs and ocean circulation on timescales of a few ka. Here we present the first Nd isotope record for seawater using sedimentary foraminifera cleaned using standard oxidative-reductive techniques. The data, along with Mn/Ca ratios, suggest that cleaned foraminifera provide a reliable record of Nd in seawater and hold out the prospect of using Nd in foraminifera to examine changes in seawater that accompany glacial-interglacial climatic cycles. The principal potential problem to be overcome with the use of forams as records of trace elements in ancient seawater is their diagenetic Fe-Mn coatings. These contain large amounts of Nd and other trace elements but can be cleaned off using highly reducing reagents. Mn(Ca ratios for the majority of the cleaned sedimentary foraminifera analysed here lie within the range (10-100 µmol/mol) that has yielded success in studies of transition elements in forams. Mass-balance modelling suggests that for residual Mn/Ca ratios <100 µmol/mol, Nd added to the foram in the coating will never shift the measured Nd isotope composition significantly away from the seawater value acquired by the foram test in the water column. Additionally, Nd concentrations measured in cleaned sedimentary foraminifera are comparable with those for a modern sample that has never encountered diagenetic fluids. Finally, core-top planktonic foraminifera for two sites have Nd isotope compositions that are identical to local surface seawater. The data we present here for Labrador Sea forams over the past 2.5 m.y. are interpreted in terms of changes in the seawater isotopic composition. The data show a pronounced shift from epsilon-Nd values of ~-12 to ~-19 in the period 2.5-1.5 Ma. This change is interpreted to result from the initiation of Northern Hemisphere glaciation and the increased derivation of Labrador Sea Nd via ice-rafting from Archaean terranes in central Canada. In combination with stable isotope and foraminiferal relative species abundance data, the new Nd data are consistent with the surface hydrography of the Labrador Sea being dominated by a fluctuating balance between cold, polar waters containing unradiogenic Nd and warm, subtropical waters containing more radiogenic Nd. The major change in Labrador Sea Nd that is observed in the past 2.5 Ma can, on its own, account for the change in the Nd isotope composition of North Atlantic Deep Water over the same time period.

Mesozooplankton and phytoplankton time series of the Baltic Monitoring Program (BMP)

Within the monitoring programme of the Helsinki Commission (HELCOM) the mesozooplankton of the Bornholm Basin (ICES subdivision 25, station BMP-K2) was sampled by the WP-2 net (lOOfJm) 5-8 times a year in 1988-1992. Abundance, biomass, secondary production and productivity (P/B) were given for mesozooplankton groups and copepod species. Environmental factors recorded were temperature, chlorophyll a and primary production. Within copepods, the dominant species were Temora longicornis and Pseudocalanus minutus with yearly peak values of 40-50% of the monthly copepod numbers and biomasses. The annual production of Temora longicornis was highest (6.5g C/m**2/y). The biomass of all copepods was at its maximum in June (mean = 2.25g C/m**2), especially in 1992 (3.65g C/m**2). The differences between results from two methods used to calculate the production of copepods were greatest in June and July. The cladocerans were only important in summer and the appendicularians only in spring. The productivity (P/B) of the appendicularians was highest of all mesozooplankton groups. Numbers and the biomass of the meroplankton were one or two orders of magnitude below the holoplanktic groups.

Petrophysical measurement of ODP Leg 122 and 123 samples (Tables 1, 2)

The capillary-pressure characteristics of 22 samples of lithified post-Paleozoic Indian-Ocean carbonates were compared to published data from older carbonate rocks (lower Paleozoic Hunton Group of Texas and Oklahoma). The Indian-Ocean samples are considerably more porous than are the Paleozoic samples, yet all of the Indian-Ocean samples fit readily into a descriptive petrofacies scheme previously established for the Hunton Group. The Indian-Ocean samples may be assigned to four petrophysical facies (petrofacies) based on the shapes of their capillary-pressure curves, their pore-throat-size distributions, their estimated recovery efficiency values (for nonwetting fluids), and the visual characteristics of their pore systems, as observed with a scanning-electron microscope. Petrofacies assignments for the Indian-Ocean samples are as follows. Petrofacies I includes six samples collected from the coarse basal portions of event deposits (primarily turbidites). These samples have large throats, leptokurtic throat-size distributions, low- to moderate recovery efficiency values, concave cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies II includes two sedimentologically dissimilar samples that have medium-size throats, platykurtic throat-size distributions, moderate- to-high recovery efficiency values, gently sloping cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies III includes two polymictic sandstones and a skeletal packstone that have small throats, polymodal throat-size distributions, moderate recovery efficiency values, gently sloping cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies IV includes 11 samples, mostly recrystallized neritic carbonates, that have small throats, leptokurtic throat-size distributions, high recovery efficiency values, convex cumulative-intrusion capillary-pressure curves, and low porosity values. Comparison of petrofacies assignment to core-, thin-section-, and smear-slide data, and to inferred depositional setting, suggests that pore systems in most samples from Holes 765C and 766A result from primary depositional features, whereas pore systems in samples from Hole 761C and one sample from Hole 765C have been strongly influenced by diagenetic processes. For Hole 761C, prediction of petrophysical parameters should be most successful if based on diagenetic facies patterns. By contrast, the distribution of favorable reservoir facies and of permeability barriers in less highly altered rocks collected from Holes 765C and 766A is related to depositional patterns. Recovery efficiency is inversely related to both porosity and median throat size for the present data set. This relationship is similar to that observed for carbonates of the lower Paleozoic Hunton Group and the Ordovician Ellenburger dolomite, but opposite of that observed for some other ancient carbonates. The coarse deposits of the massive basal units of turbidites are petrophysically distinct and form a coherent petrophysical group (Petrofacies I) with substantial reservoir potential. Two samples assigned to Petrofacies I have extremely large throats (median throat size at least 4 ?m, and at least six times that of any other sample) and therefore high permeability values. These two samples come from thin, coarse turbidites that lack or have poorly developed fine divisions and are interpreted to have been deposited on channeled suprafan lobes in a proximal mid-fan setting. The restriction of extremely high permeability values to a single depositional facies suggests that careful facies mapping of deep-sea fans in a deliberate search for such coarse turbidites could dramatically enhance the success of exploration for aquifers or hydrocarbon reservoirs. Such reservoirs should have substantial vertical heterogeneity. They should have high lateral permeability values but low vertical permeability values, and reservoir sections should include numerous thin units having widely differing petrophysical characteristics.

Chemical and mineral compositions of sediments from ODP Site 127-797

In order to reconstruct past variations in the aeolian dust (Kosa) contribution to the Japan Sea, and to establish a direct link between terrestrial and marine climatic records, we have applied statistical procedures to distinguish and quantify detrital subcomponents within the detrital fraction of the late Quaternary hemipelagic sediments in the Japan Sea. Q-mode factor analysis with varimax and oblique rotation of the factors followed by multiple-regression analysis between mineral composition and factor loadings was conducted using six ''detrital'' elements. Four detrital subcomponents were defined, which are attributed to Kosa derived from ''typical'' loess, Kosa from ''weathered'' loess, and fine and coarse arc-derived detritus, respectively, based on comparisons with the chemical and mineral compositions of probable source materials. Using these detrital subcomponents, the variation in Kosa fraction was reconstructed for the last 200 ky. The results reveal millennial-scale as well as glacial-interglacial scale variations in Kosa contribution. Especially, millennial-scale variability of Kosa contribution suggests the presence of high frequency variation in summer monsoon precipitation in the central to east Asia during the last 200 ky.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

Sedimentological and paleomagnetic investigations on two gravity cores and ODP sites 113-690 and 693 off Kapp Norvegia, Antarctic continental margin

Oligocene to Quaternary sediments were recovered from the Antarctic continental margin in the eastern Weddell Sea during ODP Leg 113 and Polarstern expedition ANT-VI. Clay mineral composition and grain size distribution patterns are useful for distinguishing sediments that have been transported by ocean currents from those that were ice-rafted. This, in turn, has assisted in providing insights about the changing late Paleogene to Neogene sedimentary environment as the cryosphere developed in Antarctica. During the middle Oligocene, increasing glacial conditions on the continent are indicated by the presence of glauconite sands, that are interpreted to have formed on the shelf and then transported down the continental slope by advancing glaciers or as a result of sea-level lowering. The dominance of illite and a relatively high content of chlorite suggest predominantly physical weathering conditions on the continent. The high content of biogenic opal from the late Miocene to the late Pliocene resulted from increased upwelling processes at the continental margin due to increased wind strength related to global cooling. Partial melting of the ice-sheet occurred during an early Pliocene climate optimum as is shown by an increasing supply of predominantly current-derived sediment with a low mean grain size and peak values of smectite. Primary productivity decreased at ~ 3 Ma due to the development of a permanent sea-ice cover close to the continent. Late Pleistocene sediments are characterized by planktonic foraminifers and biogenic opal, concentrated in distinct horizons reflecting climatic cycles. Isotopic analysis of AT. pachyderma produced a stratigraphy which resulted in a calculated sedimentation rate of 1 cm/k.y. during the Pleistocene. Primary productivity was highest during the last three interglacial maxima and decreased during glacial episodes as a result of increasing sea-ice coverage.

Geochemical data for drilled powder samples from two fossil Porites corals from Integrated Ocean Drilling Program Expedition 310

Fossil corals are unique archives of past seasonal climate variability, providing vital information about seasonal climate phenomena such as ENSO and monsoons. However, submarine diagenetic processes can potentially obscure the original climate signals and lead to false interpretations. Here we demonstrate the potential of laser ablation ICP-MS to rapidly detect secondary aragonite precipitates in fossil Porites colonies recovered by Integrated Ocean Drilling Program (IODP) Expedition 310 from submerged deglacial reefs off Tahiti. High resolution (100 µm) measurements of coralline B/Ca, Mg/Ca, S/Ca, and U/Ca ratios are used to distinguish areas of pristine skeleton from those afflicted with secondary aragonite. Measurements of coralline Sr/Ca, U/Ca and oxygen isotope ratios, from areas identified as pristine, reveal that the seasonal range of sea surface temperature in the tropical south Pacific during the last deglaciation (14.7 and 11 ka) was similar to that of today.

Clay mineralogy of ODP Site 131-808 sediments

Drill core recovered at Ocean Drilling Program Site 808 (Leg 131) proves that the wedge of trench sediment within the central region of the Nankai Trough comprises approximately 600 m of hemipelagic mud, sandy turbidites, and silty turbidites. The stratigraphic succession thickens and coarsens upward, with hemipelagic muds and volcanic-ash layers of the Shikoku Basin overlain by silty and sandy trench-wedge deposits. Past investigations of clay mineralogy and sand petrography within this region have led to the hypothesis that most of the detritus in the Nankai Trough was derived from the Izu-Honshu collision zone and transported southwestward via axial turbidity currents. Shipboard analyses of paleocurrent indicators, on the other hand, show that most of the ripple cross-laminae within silty turbidites of the outer marginal trench-wedge facies are inclined to the north and northwest; thus, many of the turbidity currents reflected off the seaward slope of the trench rather than moving straight down the trench axis. Shore-based analyses of detrital clay minerals demonstrate that the hemipelagic muds and matrix materials within sandy and silty turbidites are all enriched in illite; chlorite is the second-most abundant clay mineral, followed by smectite. In general, the relative mineral percentages change relatively little as a function of depth, and the hemipelagic clay-mineral population is virtually identical to the turbidite-matrix population. Comparisons between different size fractions (<2 µm and 2-6 µm) show modest amounts of mineral partitioning, with chlorite content increasing in the coarser fraction and smectite increasing in the finer fraction. Values of illite crystallinity index are consistent with conditions of advanced anchimetamorphism and epimetamorphism within the source region. Of the three mica polytypes detected, the 2M1 variety dominates over the 1M and 1Md polytypes; these data are consistent with values of illite crystallinity. Measurements of mica bo lattice spacing show that the detrital illite particles were eroded from a zone of intermediate-pressure metamorphism. Collectively, these data provide an excellent match with the lithologic and metamorphic character of the Izu-Honshu collision zone. Data from Leg 131, therefore, confirm the earlier interpretations of detrital provenance. The regional pattern of sediment dispersal is dominated by a combination of southwest-directed axial turbidity currents, radial expansion of the axial flows, oblique movement of suspended clouds onto and beyond the seaward slope of the Nankai Trough, and flow reflection back toward the trench axis.