Chemistry of orthopyroxenes, clinopyroxenes, and spinels of ODP Hole 103-637A peridotites

Mineral compositions of the plagioclase-bearing ultramafic tectonites dredged and cored seaward of the continental slope of the Galicia margin (Leg 103, Site 637) were compared to mineral compositions from onshore low-pressure ultramafic bodies (southeastern Ronda, western Pyrenees, and Lizard Point), on the basis of standardized (30-s counting time) probe analyses. The comparison was extended to some plagioclase-free harzburgites related to ophiolites (Santa Elena in Costa Rica, north Oman, and the Humboldt body in New Caledonia) on the basis of new analytical data and data from the literature. The behavior of Cr, Na, Al, Mg, Fe, Ni, and Ti in olivine, pyroxenes, and spinel was examined in order to distinguish between the effects of partial melting and mineral facies change, from the spinel to plagioclase stability fields. The peridotite from the Galicia margin appears slightly depleted in major incompatible elements and experienced a minor partial melting. However, it experienced large scale but heterogeneous recrystallization in the plagioclase field. These features are very similar to those observed in Ronda, whereas in the western Pyrenees the minerals exemplify a very minor partial-melting event (or none at all) and have retained compositions corresponding to those of the relatively high-pressure Seiland sub facies. The minerals from the Lizard Point peridotite have characteristics (low Mg/(Mg + Fe) ratio; high Cr/(Cr + Al) ratio in spinel) more related to cumulate from a differentiated tholeiitic melt than related to ophiolitic tectonite. Diffusion profiles of Al and Cr across pyroxenes and spinel show that recrystallization features occurred at different speeds or temperatures in the different bodies. The pyroxenes from Ronda would have experienced recrystallization about 14 times faster than the peridotite from the Galicia margin. The western Pyrenean lherzolites also experienced rapid recrystallization; nevertheless, because they are of a different mineral facies, the data are not directly comparable to that from Ronda and Galicia. The harzburgite at Santa Elena as well as a xenolith from alkali basalt exemplify rapid cooling characterized by very weak re-equilibration. Recrystallization speed is related to emplacement speed in the present geological environment. The slow-rising Galicia margin peridotite was emplaced by thinning of the lithospheric subcontinental mantle near an incipient mid-oceanic ridge. The fast-rising peridotites from Ronda and the western Pyrenees were hot diapirs emplaced from the asthenosphere along transcurrent faults, possibly related to the opening of the Atlantic Ocean.

Chemistry of pore water and solids, formation factors and salt-corrected porosities of DSDP Site 68-503

Recent discoveries relating to the circulation of fluids within the oceanic crust include the finding of both important fluxes of elements and isotopes into the oceans by ridge-crest hydrothermal convection and important fluxes of heat out of the oceanic crust by convection at ridge crests and at some distance from ridge crests. In the present chapter, I present isotopic, chemical, and physical data from sediments and pore waters of Deep Sea Drilling Project (DSDP) Holes 503A and 503B. These results are modeled in terms of pore-water diffusion, advection, and production to ascertain the relative contribution of these processes at this location, 7.5 m.y. removed from ridge-crest hydrothermal activity. The observations made here contribute to the understanding of chemical and heat transport in oceanic crust of moderate age.

Chemistry of igneous rocks of DSDP Leg 30 holes

Igneous rock units were encountered at four of the five sites drilled on Leg 30 of the Deep Sea Drilling Project. These units uncluded a diabase sill at Site 285, a basalt underlain by a gabbro at 286, two basalt flows at 287, and a basalt flow at 289. Site 285 is located approximately in the center of the South Fiji Basin, Site 286 is adjacent to a filled portion of the New Hebrides Trench, Site 287 is adjacent to a basement high in the Coral Sea Basin, and Sites 288 and 289 are located on the Ontong-Java Plateau north of the Solomon Islands (Figure 1). Figure 2 presents generalized lithologic columns for the igneous rock units found at these sites. When a unit number is given, e.g., Site 286, Unit 4 basalt, this number conforms with the unit number assigned to it in the overall stratigraphic sequence of that hole as defined in the individual Site Reports in this volume. Unless otherwise stated, depths are given as measured from the sediment-igneous rock contact rather than the mudline.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Interstitial water chemistry at DSDP Leg 82 Holes

Interstitial waters were collected at only two sites during Leg 82, Sites 558 and 563. Only very small changes in dissolved calcium and magnesium occur, presumably resulting from reactions in the underlying basement basalts. Dissolved strontium profiles indicate maxima, which can be understood in terms of carbonate recrystallization processes. Data on Sr/Ca in carbonates cannot be used to estimate the extent of recrystallization that has occurred in these sediments.

Interstitial-water chemistry of ODP Leg 113 sites

Variations in the distribution of major elements and stable oxygen isotopes in ODP Leg 113 pore water are not related to lithology and thus appear to be controlled by minor constituents. Petrographic observations and geochemical considerations indicate that alteration of calc-alkalic volcanic material dispersed in the sediment is an important process. A diagenetic reaction is constructed that involves transformation of volcanic glass into smectite, zeolite (represented by phillipsite), chert, and iron sulfide. Mass balance calculations reveal that alteration of less than 10% (volume) of volcanogenic material may account for the observed depletion of magnesium, potassium, and 18O and enrichment of calcium. Alteration of this amount of volcanic glass produces less than 4% (volume) of smectite and zeolite. Hence, mass balance is obtained without having to invoke unreasonable large amounts of volcanic matter or interactions between seawater and basement.

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.

Chemistry of minerals of ODP Hole 103-637A peridotites

The Galicia margin lies northwest of the Iberian Peninsula and is a passive ocean margin with thin sedimentary cover. Altered peridotite was recovered from ODP Site 637, on the north-trending ridge at the western edge of the margin, near the oceanic/continental crust boundary. The altered ultramafics were originally clinopyroxene-rich upper mantle harzburgites and are now extensively serpentinized (>85%) and cut by very late-stage carbonate veins. Despite pervasive late, low-temperature alteration, evidence of early, high-temperature alteration remains. Alteration is apparent as (1) amphibole rims on clinopyroxene (>800°C), (2) hornblende + tremolite (450° to 800°C), (3) breakdown of hornblende to form tremolite + chlorite (<450°C), (4) zoned Cr-spinels, (5) hydration of orthopyroxene and olivine to serpentine, (6) serpentine veins, (7) replacement of pyroxene and olivine by calcite, and (8) calcite veins and vugs. Both the relict igneous and the high-temperature alteration minerals (amphiboles) show evidence of brittle deformation. Subsequent low-temperature alteration veins and minerals are deformed only in faulted and brecciated zones. This textural evidence suggests that the low-temperature alteration occurred after emplacement of the ultramafics at the surface. Serpentine fills tension fractures in orthopyroxene, and both serpentine and calcite fill tension cracks in olivine. The high-temperature alterations in these samples are similar to those found in oceanic fracture zone and ophiolite ultramafics. This widespread occurrence of high-temperature alteration suggests that hot fluids were pervasive in these ultramafic blocks. Localization of high-temperature alteration close to large carbonate veins suggests channelization of the late, low-temperature fluids. Earlier hydrations (e.g., high-temperature alterations and serpentinization) were pervasive.

Water chemistry of lakes from the Antarctic

This paper reviews Japanese limnological studies mainly in the McMurdo and Syowa oases, with special emphasis on the nutrient distribution. Generally, the chemical composition of the major ionic components in the coastal lakes and ponds is similar to that in seawater, while that in inland Dry Valley lakes and ponds of the McMurdo Oasis is abundant in calcium, magnesium and sulfate ions. The former can be explained by the direct influences of sea salts, while the latter is mainly attributable to the accumulation of atmospheric salts. Most saline lakes are meromictic. Dissolved oxygen concentrations in the upper layers are saturated or supersaturated, but the bottom layers are anoxic and often hydrogen sulfide occurs. The concentrations of nutrients vary largely not only among the lakes but also with depth. Silicate-Si, which is generally abundant in all freshwater and saline lakes, may be due to erosions of soils and rocks. Nitrite-N concentrations in both freshwater and saline lakes are generally low. Nitrate-N concentrations in the oxic layers of the inland saline lakes in the McMurdo Oasis arc often high, but not high in the coastal saline lakes of the Syowa and Vestfold oases. The abundance of phosphate-P and ammonium-N in the bottom stagnant layers of saline lakes can be explained by the accumulation of microbially released nutrients due to the decomposition of organic substances. Nutrients are supplied mainly from meltstreams in the catchment areas, and are proved to play an important role in primary production.

Pore-water chemistry at DSDP Leg 70 Holes

Geological and geophysical data collected during Deep Sea Drilling Project (DSDP) Leg 70 indicate that hydrothermal solutions are upwelling through the sediments of the mounds hydrothermal field (Sites 506, 507, and 509) and downwelling in the low heat-flow zone to the south (Site 508). Pore-water data are compatible with these conclusions. Pore waters at mounds sites are enriched in Ca and depleted in Mg relative to both seawater and Site 508 pore waters. These anomalies are believed to reflect prior reaction of the interstitial waters with basement rocks. The mounds solutions are also enriched in iron, which is probably hydrothermal and en route to forming nontronite. Concentrations of Si and NH3 in mounds pore water increase upcore as a result of the addition of dissolving biogenic debris to ascending hydrothermal solutions. Some low heat-flow pore-water samples (Site 508) are enriched in Ca and depleted in Mg. These anomalies likely reflect the presence of pockets of hydrothermal solutions in areas otherwise dominated by downwelling bottom water.

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

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