Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.

Neogene planktonic foraminifera of DSDP Leg 41 holes

During Leg 41 Neogene sediments were recovered from five sites off northwest Africa. On the Sierra Leone Rise (Site 366), Neogene sediments consist of nanno oozes, nanno chalk, and calcareous clays 230 meters thick, resting conformably on the late Oligocene sediments. The common succession of zones occurs with two hiatuses. The lower gap corresponds to an interval around the lower/middle Miocene boundary (the Praeorbulina glomerosa and Orbulina suturalis-Globorotalia peri-pheroronda zones are absent) and the upper gap coincides with an interval around the middle/upper Miocene boundary (the Sphaeroidinellopsis sub-dehiscens-GIobigerina druryi, Globigerina nepenthes-Globorotalia siakensis and Globorotalia conlinuosa zones are missing). In the Cape Verde Basin (Site 367) deep-water Neogene turbidites (about 200-250 m thick) contain poor fauna of redeposited and sorted Cretaceous, Eocene, Oligocene, and Neogene species. On the Cape Verde Rise (Site 368) the Neogene section starts with slightly calcareous and non-calcareous clays with poor planktonic foraminifers of the lower Miocene. Later on this area was uplifted and clayey sediments have been replaced upsection in order by more shallow-water clayey nanno and nanno-foraminifer oozes and marls and pure calcareous oozes. In the middle Miocene, planktonic foraminifers are still not diverse, but since the level of the Globigerina nepenthes-Globorotalia siakensis Zone, almost all Neogene zones have been traced. The minimum thickness of the Neogene sediments is about 230 meters. On the continental slope off Spanish Sahara (Site 369) monotonous calcareous pelagic sediments of Neogene age (164 m thick) overlie the late Oligocene comformably, or with a small time gap. A set of zones beginning from the Globigerinoides primordis-Globorotaiia kugleri Zone up to the Globorotalia fohsi fohsi Zone has been revealed with a gap corresponding to the Globigerinita stainforthi and the Globigerinatella insueta-Globigerinoides irilobus zones. Above that follow sediments with heterogeneous microfauna which result from redeposition or mixing of sediments during drilling. The section ends with sediments of the late Miocene and lower Pliocene with abundant planktonic foraminifers. The latter are unconformably overlain by the Quaternary ooze. In the Morocco basin (Site 370) deep-water marls and calcareous clays of the lower Miocene contain poor assemblages of planktonic foraminifers. The middle and upper Miocene are represented by turbidites (alternation of nanno oozes, clays, siltstones, and sands) with heterogeneous microfauna. Total thickness of Neogene is up to 200 meters. In general the Neogene foraminifer microfauna of the area studied includes the majority of species which developed within the tropical-subtropical belt. The entire succession of the Miocene and Pliocene foraminifer zones occurs. The only exclusion is the Sphaeroidinellopsis subdehiscens-Globigerina druryi Zone of the middle Miocene. The distribution of species is shown on three tables. Comments are given for 47 species and subspecies of foraminifers (stratigraphic ranges, peculiarities of morphology, and ultrastructure of the shell wall).

Stratigraphic occurrence of selected marine palynomorph species recorder in the Paleogene of ODP Hole 105-647A (Table 3)

Dinoflagellate cysts were recovered throughout the Paleogene succession of Hole 647A, which contains an almost complete deep-water record of early Eocene through early late Oligocene sedimentation in the Labrador Sea. Dinoflagellate cyst biostratigraphy is in general accord with that provided by other microfossil groups and is consistent with a lower Eocene age, as determined by nannofossils, for basal sediments in Hole 647A. These sediments overlie oceanic crust of Chron 24 age. Dinocyst assemblages indicate outer neritic to oceanic conditions throughout, although the persistent occurrence of Wetzeliellaceae specimens in the lower Eocene suggests a greater influence from shelf environments during this time. Lower Eocene dinocyst assemblages are similar to coeval assemblages from the Rockall Plateau, but those from the middle to upper Eocene have mixed affinities and may be related to the intensification of the proto-Gulf Stream from middle Eocene time. Oligocene dinocyst assemblages suggest the influence of both arctic and North Atlantic wate rmasses at this site. The presence of protoperidineacean species in the upper Eocene and Oligocene may indicate increased availability of nutrients, perhaps related to increased upwelling or the effects of water-mass mixing. Productive samples are dominated by dinocysts and acritarchs, while sporomorphs are represented mainly by bisaccate pollen. Preservational differences within samples may reflect mixing of penecontemporaneous dinocyst populations during the Eocene, and all samples examined may have a considerable allochthonous component. Variability in relative abundance of many species during the Eocene may be related to fluctuating water-mass properties. A total 175 dinocyst and acritarch taxa were recorded from 53 productive samples from the Paleogene. Only one Paleogene sample was barren of palynomorphs. Of three Miocene samples processed, all were barren.

Geochemistry of sands and sandstones in ODP Leg 126 sites

During Ocean Drilling Program Leg 126, six sites were cored in a young backarc rift basin and its flanks (rift onset 1.1-3.56 Ma) and in the forearc basin of the Izu-Bonin Arc. In the backarc area, strata are younger than about 4.5 Ma, whereas in the forearc, ages are about 0-31 Ma in sections punctuated by important Miocene unconformities. Bulk chemical analyses of volcaniclastic turbidite sands and sandstones, derived directly from the arc, were obtained from 271 atomic absorption analyses (major elements), 253 XRF analyses (trace elements) and 16 ICP-MS analyses (trace and rare-earth elements). Of the 271 samples, 78 come from the backarc area and the remainder from the forearc. The sands and sandstones reflect the igneous compositions of their sources. Most are formed of materials derived from subalkaline, low-K andesites, and dacites, although compositions range from basalt to rhyolite. Basic and acid andesites are predominant in Oligocene rocks; in contrast, Pliocene-Pleistocene sediments were derived from acid andesitic to rhyolitic sources. The oldest sandstones, estimated to have an age of about 31 Ma, were derived from an arc tholeiitic, not boninitic, source. The 26-31 Ma sandstones furthest to the north, at Sites 787 and 792, have higher relative concentrations of Ti, Zr, and Y than do those at southern Site 793. Data from younger samples indicate that, for more than 30 m.y., the average composition of volcaniclastic sediments and volcanism near Aoga Shima was more basic than to the south, near Sumisu Jima. Using the sandstones as igneous proxies, we conclude that magmas erupted along the arc have become more depleted in light-rare-earth elements (LREE) with time. There was a major change in rare-earth-element (REE) concentrations in the late Oligocene, from essentially flat patterns (normalized La/Yb about 1-1.5) to LREE-depleted patterns (normalized La/Yb about 0.5). At the same time, Zr/Y ratios decreased from about 2-4 to about 1.5-2.5. These changes may reflect a shift in provenance, or changes in the composition of the mantle wedge beneath the arc. In the backarc area, lithic clasts and glass shards of rift-facies basalt are present in sediments as old as 2.35-3.15 Ma. Two samples of mafic sand from the backarc basin have flat REE patterns (normalized La/Yb about 1.0), like some of the <1-Ma rift lavas and unlike pre-rift sand and sandstone samples. These possibly represent the local effects of sedimentary mixing of detritus from arc and backarc eruptions because no evidence from the arc itself exists to suggest a recent change in the REE content of magmas.

Taxonomic lists and abundances of the Lower Miocene bivalve assemblages of the Vives quarry (Meilhan, SW France)

Biodiversity estimates through geological times are difficult because of taphonomic perturbations that affect sedimentary records. Pristine shell assemblages, however, allow for calibration of past diversity. Diversity structures of two exceptionally preserved Miocene bivalve assemblages are quantitatively determined, compared with recent communities and used as paleoenvironmental proxy. The extremely rich assemblages were collected in Aquitanian (Early Miocene) carbonate sands of the Vives Quarry (Meilhan, SW France). Both paleontological and sedimentological data indicate a coral patch-reef environment, which deposits were affected by transport processes. Among two samples more than 28.000 shells were counted and 135 species identified. Sample Vives 1 is interpreted as a proximal debris flow and Sample Vives 2 as a sandy shoreface/foreshore environment influenced by storms. The two Vives assemblages have a similar diversity structure despite facies differences. Rarefaction curves level off at ~600 shells. The rare species account for more than 80 % of the species pool. The high values of PIE diversity index suggest a relatively high species richness and an even distribution of abundance of the most common species within the assemblages. The fossil data are compared to death shell assemblages (family level) of a modern reefal setting (Touho area, New Caledonia). The shape of the rarefaction curves and PIE indices of Meilhan fossil assemblages compare well to modern data, especially those of deep (>10 m water depth), sandy depositional environments found downward the reef slope (slope and pass settings). In addition to primary ecological signals, the similarity of the Vives samples and the Recent deep samples derives from taphonomic processes. This assumption is supported by sedimentological and paleontological observations. Sediment transports gather allochthonous and in situ materials leading to mixing of various ecological niches. Such taphonomic processes are recorded in the diversity metrics. Environmental mixing and time-averaging of the shell assemblages disturb the preservation of local-scale diversity properties but favour the sampling of the regional-scale diversity.

Geochemistry of metasedimentary units of the Cambro-Ordovician Ross Orogen in North Victoria Land and Oates Land, Antarctica

Metasediments in the three early Palaeozoic Ross orogenic terranes in northern Victoria Land and Oates Land (Antarctica) are geochemically classified as immature litharenites to wackes and moderately mature shales. Highly mature lithotypes with Chemical Index of Weathering values of >=95 are typically absent. Geochemical and Rb-Sr and Sm-Nd isotope results indicate that the turbiditic metasediments of the Cambro-Ordovician Robertson Bay Group in the eastern Robertson Bay Terrane represent a very homogeneous series lacking significant compositional variations. Major variations are only found in chemical parameters which reflect differences in degree of chemical weathering of their protoliths and in mechanical sorting of the detritus. Geochemical data, 87Sr/ 86Sr t=490 Ma ratios of 0.7120 - 0.7174, epsilonNd, t=490 Ma values of -7.6 to -10.3 and single-stage Nd-model ages of 1.7 - 1.9 Ga are indicative of an origin from a chemically evolved crustal source of on average late Palaeoproterozoic formation age. There is no evidence for significant sedimentary infill from primitive "ophiolitic" sources. Metasediments of the Middle Cambrian Molar Formation (Bowers Terrane) are compositionally strongly heterogeneous. Their major and trace element data and Sm-Nd isotope data (epsilonNd, t=500 Ma values of -14.3 to -1.2 and single-stage Nd-model ages of 1.7 - 2.1 Ga) can be explained by mixing of sedimentary input from an evolved crustal source of at least early Palaeoproterozoic formation age and from a primitive basaltic source. The chemical heterogeneity of metasediments from the Wilson Terrane is largely inherited from compositional variations of their precursor rocks as indicated by the Ni vs TiO2 diagram. Single-stage Nd-model ages of 1.6 -2.2 Ga for samples from more western inboard areas of the Wilson Terrane (epsilonNd, t=510 Ma -7.0 to -14.3) indicate a relatively high proportion of material derived from a crustal source with on average early Palaeoproterozoic formation age. Metasedimentary series in an eastern, more outboard position (epsilonNd, t=510 Ma -5.4 to -10.0; single-stage Nd model ages 1.4 - 1.9) on the contrary document stronger influence of a more primitive source with younger formation ages. The chemical and isotopic characteristics of metasediments from the Bowers and Wilson terranes can be explained by variable contributions from two contrasting sources: a cratonic continental crust similar to the Antarctic Shield exposed in Georg V Land and Terre Adélie some hundred kilometers west of the study area and a primitive basaltic source probably represented by the Cambrian island-arc of the Bowers Terrane. While the data for metasediments of the Robertson Bay Terrane are also compatible with an origin from an Antarctic-Shield-type source, there is no direct evidence from their geochemistry or isotope geochemistry for an island-arc component in these series.

(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Element analyses and isotope composition of basalts from the West Valley segment, Juan de Fuca Ridge, northeast Pacific

The 50 km-long West Valley segment of the northern Juan de Fuca Ridge is a young, extension-dominated spreading centre, with volcanic activity concentrated in its southern half. A suite of basalts dredged from the West Valley floor, the adjacent Heck Seamount chain, and a small near-axis cone here named Southwest Seamount, includes a spectrum of geochemical compositions ranging from highly depleted normal (N-) MORB to enriched (E-) MORB. Heck Seamount lavas have chondrite-normalized La/Sm en -0.3, 87Sr/86Sr = 0.70235 - 0.70242, and 206Pb/204Pb = 18.22 - 18.44, requiring a source which is highly depleted in trace elements both at the time of melt generation and over geologic time. The E-MORB from Southwest Seamount have La/Sm en -1.8, 87Sr/86Sr = 0.70245 - 0.70260, and 206Pb/204Pb = 18.73 - 19.15, indicating a more enriched source. Basalts from the West Valley floor have chemical compositions intermediate between these two end-members. As a group, West Valley basalts from a two-component mixing array in element-element and element-isotope plots which is best explained by magma mixing. Evidence for crustal-level magma mixing in some basalts includes mineral-melt chemical and isotopic disequilibrium, but mixing of melts at depth (within the mantle) may also occur. The mantle beneath the northern Juan de Fuca Ridge is modelled as a plum-pudding, with "plums" of enriched, amphibole-bearing peridotite floating in a depleted matrix (DM). Low degrees of melting preferentially melt the "plums", initially removing only the amphibole component and producing alkaline to transitional E-MORB. Higher degrees of melting tap both the "plums" and the depleted matrix to yield N-MORB. The subtly different isotopic compositions of the E-MORBs compared to the N-MORBs require that any enriched component in the upper mantle was derived from a depleted source. If the enriched component crystallized from fluids with a DM source, the "plums" could evolve to their more evolved isotopic composition after a period of 1.5-2.0 Ga. Alternatively, the enriched component could have formed recently from fluids with a lessdepleted source than DM, such as subducted oceanic crust. A third possibility is that enriched material might be dispersed as "plums" throughout the upper mantle, transported from depth by mantle plumes.

Lead and strontium isotope composition, mass accumulation rates and rare earth elements of selected samples from DSDP Sites 92-597 to 92-601

Most of the Pb isotope data for the Leg 92 metalliferous sediments (carbonate-free fraction) form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts (MORB) toward the field for Mn nodules. These arrays are directed closely to the average values of Mn nodules, the composition of which reflects the Pb isotope composition of seawater (Reynolds and Dasch, 1971). Since the Leg 92 samples are almost devoid of continentally derived detritus, it can be inferred that the more radiogenic end-member is seawater. The less radiogenic end-member lies in the very middle of the MORB field, and hence can be considered to reflect the Pb isotope composition of typical ocean-ridge basalt. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb from the two different end-member sources. According to this model, eight samples from Sites 599 to 601 contain 50 to 100% basaltic Pb. Five of these samples have compositions that are identical within the uncertainty of the analyses. We use the average of these five values to define our unradiogenic end-member in the linear mixing model. The ratios used for this average are 206Pb/204Pb = 18.425 ± 0.010; 207Pb/204Pb = 15.495 ± 0.018; 208Pb/204Pb = 37.879 ± 0.068. These values should approximate the average Pb isotope composition of discharging hydrothermal solutions, and therefore also that of the basaltic crust, over the period of time represented by these samples ( 4 m.y., from 4 to 8 Ma). Sr isotope ratios show a significant range of values, from 0.7082 to 0.7091. The lower ratios are well outside the value of 0.70910 ± 6 for modern-day seawater (Burke et al., 1982). However, most values correspond very closely to the curve of 87Sr/86Sr versus age for seawater, with older samples having progressively lower 87Sr/86Sr ratios. The simplest explanation for this progressive reduction is that recrystallization of the abundant biogenic carbonate in the sediments released older seawater Sr which was incorporated into ferromanganiferous phases during diagenesis. Leg 92 metalliferous sediments have total rare earth element (REE) contents that range on a carbonate-free basis from 131 to 301 ppm, with a clustering between 167 and 222 ppm. The patterns have strong negative Ce anomalies. Samples from Sites 599 to 601 display a slight but distinct enrichment in the heavy REE relative to the light REE, whereas those from Sites 597 to 598 show almost no heavy REE enrichment. The former patterns (those for Sites 599 to 601) are interpreted as indicating moderate diagenetic alteration of metalliferous sediments originating at the EPR axis; the latter reflect more complete diagenetic modification.

Geochemistry of igneous rocks recovered from a transect across the Mariana Trough, arc, fore-arc, and trench, at DSDP Leg 60 Holes and DM17

Major and trace element analyses are presented for 110 samples from the DSDP Leg 60 basement cores drilled along a transect across the Mariana Trough, arc, fore-arc, and Trench at about 18°N. The igneous rocks forming breccias at Site 453 in the west Mariana Trough include plutonic cumulates and basalts with calc-alkaline affinities. Basalts recovered from Sites 454 and 456 in the Mariana Trough include types with compositions similar to normal MORB and types with calc-alkaline affinities within a single hole. At Site 454 the basalts show a complete compositional transition between normal MORB and calc-alkaline basalts. These basalts may be the result of mixing of the two magma types in small sub-crustal magma reservoirs or assimilation of calc-alkaline, arc-derived vitric tuffs by normal MORB magmas during eruption or intrusion. A basaltic andesite clast in the breccia recovered from Site 457 on the active Mariana arc and samples dredged from a seamount in the Mariana arc are calc-alkaline and similar in composition to the basalts recovered from the Mariana Trough and West Mariana Ridge. Primitive island arc tholeiites were recovered from all four sites (Sites 458-461) drilled on the fore-arc and arc-side wall of the trench. These basalts form a coherent compositional group distinct from the Mariana arc, West Mariana arc, and Mariana Trough calc-alkaline lavas, indicating temporal (and perhaps spatial?) chemical variations in the arc magmas erupted along the transect. Much of the 209 meters of basement cored at Site 458 consists of endiopside- and bronzite-bearing, Mg-rich andesites with compositions related to boninites. These andesites have the very low Ti, Zr, Ti/Zr, P, and rare-earthelement contents characteristic of boninites, although they are slightly light-rare-earth-depleted and have lower MgO, Cr, Ni, and higher CaO and Al2O3 contents than those reported for typical boninites. The large variations in chemistry observed in the lavas recovered from this transect suggest that diverse mantle source compositions and complex petrogenetic process are involved in forming crustal rocks at this intra-oceanic active plate margin.

Chemical composition and fluxes of deep sea suspended matter within and over the 9°50'N hydrothermal field, EPR

Results of geochemical studies of suspended matter from the water mass over the hydrothermal field at 9°50'N on the East Pacific Rise are reported. The suspended matter was sampled in background waters, in the buoyant plume, and in the near-bottom waters. Contents of Si, Al, P, Corg, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the elements in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters trace elements are associated with Fe, Zn, and Cu (probably, with their sulfides formed during mixing of hydrothermal fluids with seawater). Chemical composition of sediment matter precipitated in a sediment trap was similar to the near-bottom suspended matter.

Calculated sea surface temperatures of two sediment cores

The reconstruction of ocean history employs a large variety of methods with origins in the biological, chemical, and physical sciences, and uses modern statistical techniques for the interpretation of extensive and complex data sets. Various sediment properties deliver useful information for reconstructing environmental parameters. Those properties that have a close relationship to environmental parameters are called ''proxy variables'' (''proxies'' for short). Proxies are measurable descriptors for desired (but unobservable) variables. Surface water temperature is probably the most important parameter for describing the conditions of past oceans and is crucial for climate modelling. Proxies for temperature are: abundance of microfossils dwelling in surface waters, oxygen isotope composition of planktic foraminifers, the ratio of magnesium or strontium to calcium in calcareous shells or the ratio of certain organic molecules (e.g. alkenones produced by coccolithophorids). Surface water salinity, which is important in modelling of ocean circulation, is much more difficult to reconstruct. At present there is no established method for a direct determination of this parameter. Measurements associated with the paleochemistry of bottom waters to reconstruct bottom water age and flow are made on benthic foraminifers, ostracodes, and deep-sea corals. Important geochemical tracers are d13C and Cd/Ca ratios. When using benthic foraminifers, knowledge of the sediment depth habitat of species is crucial. Reconstructions of productivity patterns are of great interest because of important links to current patterns, mixing of water masses, wind, the global carbon cycle, and biogeography. Productivity is reflected in the flux of carbon into the sediment. There are a number of fluxes other than those of organic carbon that can be useful in assessing productivity fluctuations. Among others, carbonate and opal flux have been used, as well as particulate barite. Furthermore, microfossil assemblages contain clues to the intensity of production as some species occur preferentially in high-productivity regions while others avoid these. One marker for the fertility of sub-surface waters (that is, nutrient availability) is the carbon isotope ratio within that water (13C/12C, expressed as d13C). Carbon isotope ratios in today's ocean are negatively correlated with nitrate and phosphate contents. Another tracer of phosphate content in ocean waters is the Cd/Ca ratio. The correlation between this ratio and phosphate concentrations is quite well documented. A rather new development to obtain clues on ocean fertility (nitrate utilization) is the analysis of the 15N/14N ratio in organic matter. The fractionation dynamics are analogous to those of carbon isotopes. These various ratios are captured within the organisms growing within the tagged water. A number of reconstructions of the partial pressure of CO2 have been attempted using d13C differences between planktic and benthic foraminifers and d13C values of bulk organic material or individual organic components. To define the carbon system in sea water, two elements of the system have to be known in addition to temperature. These can be any combination of total CO2 , alkalinity, or pH. To reconstruct pH, the boron isotope composition of carbonates has been used. Ba patterns have been used to infer the distribution of alkalinity in past oceans. Information relating to atmospheric circulationand climate is transported to the ocean by wind or rivers, in the form of minerals or as plant andanimal remains. The most useful tracers in this respect are silt-sized particles and pollen.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

Oxygen isotope concentrations of minerals from the upper kilometer of the ocean crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in 18O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 have delta 18O values generally ranging from +6.1 to +8.5? SMOW (mean= +7.0?), although minor zeolite-rich samples range up to 12.7?. Rocks depleted in 18O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6?, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4?, respectively. Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10-100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios (~1), and hydrothermal fluids probably contained mantle-derived CO2. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient (~2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and 18O enrichment of fluids, resulting in local increases in delta 18O of rocks which had been previously depleted in 18O during prior axial metamorphism.