(Table 2) Chemical composition of quenched glasses from the Mohns and Knipovich Ridges

The aim of this project was a petrogeochemical study of igneous rocks in the areas of the Mohns and Knipovich Ridges, both being the northern extensions of the Mid-Atlantic Ridge (MAR), using data available for quenching glass samples collected during Cruises 36 and 38 of R/V Akademic Mstislav Keldysh and during Cruise 15 of R/V Professor Logachev. Results of igneous rock studying from the Mohns and Knipovich Ridges at the background of evolution of the total North Atlantic Province, which had been identified earlier from tectonic and geophysical data, showed that igneous rocks of the Knipovich Ridge can be ranked as shallow tholeiites, primary melts of which were relatively rich in Na and Si and poor in Fe. This type of magma is characteristic of colder regions of the oceanic lithosphere. Its occurrence in the Knipovich Ridge and its potential propagation up to the Gakkel Ridge suggest that igneous rocks of this region originated under conditions of passive spreading in contrast to the MAR region in vicinity of Iceland and Azores, where substantial contribution of hotter material of a rising plume contributed to formation of the oceanic crust. The North Atlantic Ocean is the youngest province in terms of ocean-floor opening. Geologically and geophysically it is one of well studied regions of the World Ocean. Nevertheless some basic key items of its origin still remain to be clarified. In 1975 Scatler et al. proved specifics of this region manifested in growth of the gravity field, and also in relative height of the ocean floor in the region of 33-70°N, which was associated by them with rise of the hotter mantle, as compared with common regions of the Mid-Atlantic Ridge. Later this view was confirmed by character of magmatism, which differed in depth of generation and by melting degree of the resulting primary magma. Uniqueness of the North Atlantic region was also proved by the fact that this region was marked by extensive geochemical anomalies associated with Azores, Iceland, and Jan Mayen. All of these data allow to consider the northern part of the MAR (north of 33°N) as an united global geotectonic province. The Mohns and Knipovich Ridges located north of Iceland locate at the northern end of this province. This is the least known region. Therefore, new data for ridge areas of 73-77°N are needed for more complete geologic history of the Arctic Basin. The aim of this study was to carry out a complex comparison of magmatism at the Mohns and Knipovich Ridges with magmatism at large segments of the MAR northern province and to reconstruct mechanisms of primary magma formation, as well as conditions of their fractionation. This paper was based on results of studying quenched glasses, which reflect evolution of melt in the course of its formation.

Stable carbon and oxygen isotope record of Cretaceous planktonic foraminifera from DSDP (Table 1)

The Cretaceous Heterohelix moremani (Cushman) was the only biserial planktonic foraminiferal species from its first appearance in the late Albian up to the Cenomanian/Turonian boundary. Within that time, it increased gradually in abundance relative to other planktonic foraminifera in five Circum-North Atlantic sections. It is generally rare in upper Albian sediments, common in most of the Cenomanian and very abundant in sediments representing the latest Cenomanian Oceanic Anoxic Event. Short-term variations on the overall abundance trend correlate with positive excursions in the bulk carbonate delta13C record. Maximum rain rates of H. moremani during OAE2 show that this species was an opportunist that did well in extreme conditions, but its overall distribution indicates that it is not necessarily a marker for very high palaeoproductivity environments. Stable oxygen and carbon isotope measurements on foraminiferal species indicate that H. moremani was a surface water dweller at least in part of its geographic range, but incorporated 13C out of equilibrium with ambient seawater. It is depleted in delta13C relative to other planktonic foraminifera, which is attributed to vital effects related to its opportunistic character.

Chemistry of sulfide deposites of ODP Site 106-649

The Snake Pit active hydrothermal field was discovered at 23°22'N on the Mid-Atlantic Ridge during ODP Leg 106. Among the ten holes drilled in the mound at the foot of an active chimney, only three (649B, 649F, and 649G) had substantial recovery, and produced cores of unconsolidated hydrothermal deposit made up of porous sulfide fragments with minor talc pellets and biological debris, and a few pieces of brassy massive sulfides. Eight representative samples from the 6.5-m-long core from Hole 649B were analyzed for bulk chemistry, both by XRF (major elements) and NAA (trace elements). Major elements average compositions show high Fe (36 wt%), S (37 wt%), and Cu (12 wt%) contents, and minor Zn (6.7 wt%), reflecting a mostly high-temperature deposit. Trace elements are characterized by a high Au content (600 ppb) which could express the maturity of the mound. Mineralogical assemblages show evidence of sequential precipitation, and absence of equilibrium. Major sulfide phases are pyrrhotite, pyrite, Fe, Cu sulfides, marcasite, and sphalerite. Three types of samples are distinguished on the basis of textures and mineral assemblages: type 1, rich in pyrrhotite, with approximately equivalent amounts of Cu, Fe sulfides, and sphalerite and minor pyrite; type 2, rich in Cu, Fe sulfides, which are cubic cubanite with exsolutions and rims of chalcopyrite; and type 3, essentially made up of sphalerite. Type 2 samples likely represent fragments of the inner chimney wall. The presence of talc intergrown with cubic cubanite/chalcopyrite in one big piece from Hole 649G is probably related to mixing of the hydrothermal fluid with seawater.

Stable oxygen and carbon isotope composition of benthic foraminifera from the western Mediterranean Sea

The influence of microhabitat, organic matter flux, and metabolism on the stable oxygen and carbon isotope composition of live (Rose Bengal stained) and dead (empty tests) deep-sea benthic foraminifera from the Gulf of Lions (western Mediterranean Sea) have been studied. The total range of observed foraminiferal isotope values exceeds 1.0 per mil for d18O and 2.2 per mil for d13C demonstrating a wide range of coexisting disequilibria relative to d18O of equilibrium calcite (d18OEQ) and d13C of bottom water dissolved inorganic carbon (d13CDIC). The mean d18O values reveal strongest disequilibria for the studied epifaunal to shallow infaunal species (Cibicidoides pachydermus, Uvigerina mediterranea, Uvigerina peregrina) while values approach equilibrium in deep infaunal species (Globobulimina affinis, Globobulimina pseudospinescens). The mean d13C values decrease with increasing average living depths of the different species, thus reflecting a dominant microhabitat (pore water) signal. At the axis of the Lacaze-Duthier Canyon a minimum d13CDIC pore water gradient of approximately -2.1 per mil is assessed for the upper 6 cm of the surface sediment. Although live individuals of U. mediterranea were found in different depth intervals their mean d13C values are consistent with calcification at an average living depth around 1 cm. The deep infaunal occurrence of U. mediterranea specimens suggests association with macrofaunal burrows creating a microenvironment with geochemical characteristics similar to the topmost centimeter. This also explains the excellent agreement between stable isotope signals of live and dead individuals. The ontogenetic enrichment in both d18O and d13C values of U. mediterranea suggests a slow-down of metabolic rates during test growth similar to that previously observed in planktic foraminifera. Enhanced organic carbon fluxes and higher proportion of resuspended terrestrial organic material at the canyon axis are reflected by d13C values of U. mediterranea on average 0.58 per mil lower than those from the open slope. These results demonstrate the general applicability of the d13C signal of this species for the reconstruction of past organic matter fluxes in the Mediterranean Sea. Further studies on live specimens are needed for a more quantitative paleoceanographic approach.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Contents of radioactive elements, main chemical composition, and sedimentation rates of bottom sediments from some stations in the Southeast Pacific

Gamma-spectrometric analysis was used for six sediment cores from the area occupied by metalliferous sediments in the Southeast Pacific. In five of these cores vertical distribution curves of 230Th enabled positions of equilibrium points to be determined and sediments to be dated. The ionium curve was normalized for one core. Vertical distribution of 230Th in metalliferous sediments resembles its distribution in normal ocean-floor sediments beyond the area of influence of active ridges. Sedimentation rates lay within the range 0.7-12.3 mm/ky.

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.

Distribution, depositional form and geochemical composition of tephra horizons in ODP Sites 186-1150 and 186-1151

Major element geochemical composition was established for 59 tephra horizons from Ocean Drilling Program Sites 1150 and 1151, located in the Japan forearc. These data, encompassing typically between 15 and 30 individual shard analyses per tephra horizon, were used to investigate the degree to which sediment reworking, postdepositional geochemical alteration, and geochemical uniqueness of individual eruptives facilitate or impede the potential for establishing a tephrostratigraphical framework for the Japan Trench, as well as usage of the tephra record to document arc evolution. Evidence was found that hydration (termed phase 1 alteration) of glass shards increases with age in the Pliocene-Pleistocene, but there is no indication that element leaching (phase 2 alteration) has occurred. Post- or syn-depositional differences in preservational style are shown to have no significant bearing on tephrogeochemical homogeneity and suitability for tephrostratigraphical analysis. Overall, therefore, the volcaniclastic record is suitable for investigating medium- to long-term changes in arc geochemistry and, provided consideration is given to the potential for nonunique geochemical signatures, is suitable for erecting tephrochronological frameworks. A limited number of Pleistocene tephra correlations are suggested in furtherance of this framework goal.

(Table 1) Organohalogen contaminants in adipose tissue of captive sledge dogs (Canis familiaris) fed with whale blubber or pork fat

Studies on the fate of organohalogen contaminants (OHCs) in wild top predator mammals in the Arctic have often been a challenge due to important knowledge deficiencies in the life history of the sampled animals. The present study investigated the influence of age, dietary and trans-generational factors on the fate of major lipophilic chlorinated and brominated OHCs in adipose tissue of a potential surrogate captive species for the polar bear (Ursus maritimus), the sledge dog (Canis familiaris) in West Greenland. Adult female sledge dogs (P) and their sexually-mature (F1) and/or pre-weaning pups (F1-MLK) were divided into an exposed group (EXP) fed blubber from a Greenland minke whale (Balaenoptera acutorostrata) and a control group (CON) given commercially available pork fat. Large dietary treatment-related differences in summed and individual congener/compound adipose tissue concentrations of polybrominated diphenyl ethers (PBDEs), hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs) were found between the EXP and CON groups for all the sledge dog cohorts. However, among the F1-MLK, F1 and P dogs in both of the EXP and CON groups, little or no difference existed in PBDE, HCB, CHL and PCB concentrations, suggesting higher state of equilibrium in adipose tissue concentrations from a very early stage of life. In contrast, the distribution pattern (proportions to the summed concentrations) of OHC classes, and the major congeners/ compounds constituting those classes, varied on a dietary group- and/or cohort-dependent manner. The present captive sledge dog study demonstrated the importance of the confounding effects of diet composition, mother-pup association (maternal transfer), reproductive status (nursing), and to a lesser extent age in the fate of OHCs in adipose tissue of a large top carnivore mammal.

Geochemistry of basalts from the Caribbean Large Igneous Province

Oceanic flood basalts are poorly understood, short-term expressions of highly increased heat flux and mass flow within the convecting mantle. The uniqueness of the Caribbean Large Igneous Province (CLIP, 92-74 Ma) with respect to other Cretaceous oceanic plateaus is its extensive sub-aerial exposures, providing an excellent basis to investigate the temporal and compositional relationships within a starting plume head. We present major element, trace element and initial Sr-Nd-Pb isotope composition of 40 extrusive rocks from the Caribbean Plateau, including onland sections in Costa Rica, Colombia and Curaçao as well as DSDP Sites in the Central Caribbean. Even though the lavas were erupted over an area of ~3*10**6 km**2, the majority have strikingly uniform incompatible element patterns (La/Yb=0.96+/-0.16, n=64 out of 79 samples, 2sigma) and initial Nd-Pb isotopic compositions (e.g. 143Nd/144Ndin=0.51291+/-3, epsilon-Nd i=7.3+/-0.6, 206Pb/204Pbin=18.86+/-0.12, n=54 out of 66, 2sigma). Lavas with endmember compositions have only been sampled at the DSDP Sites, Gorgona Island (Colombia) and the 65-60 Ma accreted Quepos and Osa igneous complexes (Costa Rica) of the subsequent hotspot track. Despite the relatively uniform composition of most lavas, linear correlations exist between isotope ratios and between isotope and highly incompatible trace element ratios. The Sr-Nd-Pb isotope and trace element signatures of the chemically enriched lavas are compatible with derivation from recycled oceanic crust, while the depleted lavas are derived from a highly residual source. This source could represent either oceanic lithospheric mantle left after ocean crust formation or gabbros with interlayered ultramafic cumulates of the lower oceanic crust. High 3He/4He in olivines of enriched picrites at Quepos are ~12 times higher than the atmospheric ratio suggesting that the enriched component may have once resided in the lower mantle. Evaluation of the Sm-Nd and U-Pb isotope systematics on isochron diagrams suggests that the age of separation of enriched and depleted components from the depleted MORB source mantle could have been <=500 Ma before CLIP formation and interpreted to reflect the recycling time of the CLIP source. Mantle plume heads may provide a mechanism for transporting large volumes of possibly young recycled oceanic lithosphere residing in the lower mantle back into the shallow MORB source mantle.

(Table T1) Geochemical composition of coastal sediments from the Schleswig-Holstein Wadden Sea, Germany

Approximately quantitative values are presented on the mineral content of the clay and silt fractions of marine sediments from the Wadden Sea. Considering the extent of clay mineral transformation and neoformation in a marine environment, it is believed to be insignificant, because of the sea water and pore solutions of the sediments seem to represent - with the exception of a small Mg-surplus - a kind of equilibrium solution for three- and four-layer minerals, which neither favors a considerable base fixation nor base release. Therefore, illite neoformation during halmyrolysis or early diagenesis seems to be impossible, especially because of unfavourable relations of potassium to all other cations in the sea water. Obviously the neoformation of illite takes place only during later diagenetic stages. The processes of clay mineral neoformation in a marine environment are probably restricted to the formation of amorphous (Mg-)Fe-Si-particles which may be first steps in the formation of chamosites, chlorites or smectites.