(Table 3) Contents of P2O5 and total REE in phosphorites from Pacific seamonts

Changes in concentration levels and speciation of heavy metals during sedimentation on example of a typical semi-closed bay, where bottom sediments have formed due to river run-off, are under consideration. It is shown that due to desorption of mobile manganese, zinc and copper entered the bay with river suspended matter, their total contents in bottom sediments decrease and percentages of lithogenic forms increase. Contents and speciation of iron in bottom sediments are determined by its participation in coagulation of river colloids in the mixing zone and by mechanical differentiation of sedimentary material.

Contents of P2O5 and REE in phosphorites from shelves and Pacific seamounts

Recent phosphorites from the Namibian shelf are characterized by low REE contents, depletion in REE compared to host sediments and sharp deficiency of lanthanum and europium. In Late Quaternary and Pre-Quaternary phosphorites from ocean shelves REE contents and patterns in general are the same as in host sediments. Phosphorites from seamounts are enriched in REE compared to shelf phosphorites and their patterns are close to one of seawater. Behavior of REE in shelf phosphorites is determined by the fact that in early stages of phosphorite formation REE are associated not primarily with phosphate, but with organic matter and terrigenous impurities. Only in the later stages of diagenesis phosphate begins to play a leading role in concentration of REE. In metasomatic phosphorites on seamounts concentration of REE depends on age and depth of these rocks, i.e. it is determined by duration and conditions of contact with sea water.

Rare earth element contents in deposits and minerals of the ocean floor

Current understanding of rare earth element (REE) geochemistry in the ocean is given in the book. Chemical properties determining REE migration ability in natural processes, sources of REE in the ocean, behavior of REE in river-sea mixing zones, fractionation of dissolved and particulate REE in ocean waters under aerobic and anaerobic conditions, distribution of REE in terrigenous, authigenic, hydrothermal and biogenic sediment components (clay, bone detritus, barite, phillipsite, Fe- and Mn-oxyhydroxides, Fe-Ca hydroxophosphate, diatoms and foraminiferas) are under consideration.

Major and trace element content of the 17 lithostratigraphic units recovered during DSDP Leg 49 (Table 1)

IPOD Leg 49 recovered basalts from 9 holes at 7 sites along 3 transects across the Mid-Atlantic Ridge: 63°N (Reykjanes), 45°N and 36°N (FAMOUS area). This has provided further information on the nature of mantle heterogeneity in the North Atlantic by enabling studies to be made of the variation of basalt composition with depth and with time near critical areas (Iceland and the Azores) where deep mantle plumes are thought to exist. Over 150 samples have been analysed for up to 40 major and trace elements and the results used to place constraints on the petrogenesis of the erupted basalts and hence on the geochemical nature of their source regions. It is apparent that few of the recovered basalts have the geochemical characteristics of typical "depleted" midocean ridge basalts (MORB). An unusually wide range of basalt compositions may be erupted at a single site: the range of rare earth patterns within the short section cored at Site 413, for instance, encompasses the total variation of REE patterns previously reported from the FAMOUS area. Nevertheless it is possible to account for most of the compositional variation at a single site by partial melting processes (including dynamic melting) and fractional crystallization. Partial melting mechanisms seem to be the dominant processes relating basalt compositions, particularly at 36°N and 45°N, suggesting that long-lived sub-axial magma chambers may not be a consistent feature of the slow-spreading Mid-Atlantic Ridge. Comparisons of basalts erupted at the same ridge segment for periods of the order of 35 m.y. (now lying along the same mantle flow line) do show some significant inter-site differences in Rb/Sr, Ce/Yb, 87Sr/86Sr, etc., which cannot be accounted for by fractionation mechanisms and which must reflect heterogeneities in the mantle source. However when hygromagmatophile (HYG) trace element levels and ratios are considered, it is the constancy or consistency of these HYG ratios which is the more remarkable, implying that the mantle source feeding a particular ridge segment was uniform with respect to these elements for periods of the order of 35 m.y. and probably since the opening of the Atlantic. Yet these HYG element ratios at 63°N are very different from those at 45°N and 36°N and significantly different from the values at 22°N and in "MORB". The observed variations are difficult to reconcile with current concepts of mantle plumes and binary mixing models. The mantle is certainly heterogeneous, but there is not simply an "enriched" and a "depleted" source, but rather a range of sources heterogeneous on different scales for different elements - to an extent and volume depending on previous depletion/enrichment events. HYG element ratios offer the best method of defining compositionally different mantle segments since they are little modified by the fractionation processes associated with basalt generation.

(Table 4) Contents of P2O5 and REE in phosphorites from Pacific seamounts

Changes in concentration levels and speciation of heavy metals during sedimentation on example of a typical semi-closed bay, where bottom sediments have formed due to river run-off, are under consideration. It is shown that due to desorption of mobile manganese, zinc and copper entered the bay with river suspended matter, their total contents in bottom sediments decrease and percentages of lithogenic forms increase. Contents and speciation of iron in bottom sediments are determined by its participation in coagulation of river colloids in the mixing zone and by mechanical differentiation of sedimentary material.

Calcium isotope fractionation in cultured, modern and fossil scleractinian coral skeleton

The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (d44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the d44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of d44/40Ca ranges from 0.6 to 0.1 per mil, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and d44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by d18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's d44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean.

Nd and Sr isotope compositions, REE concentrations and Al/Ca ratios of different phases of surface sediments in the South Pacific

The radiogenic isotope composition of neodymium (Nd) and strontium (Sr) are useful tools to investigate present and past oceanic circulation or input of terrigenous material. We present Nd and Sr isotope compositions extracted from different sedimentary phases, including early diagenetic Fe-Mn coatings, "unclean" foraminiferal shells, fossil fish teeth, and detritus of marine surface sediments (core-tops) covering the entire midlatitude South Pacific. Comparison of detrital Nd isotope compositions to deep water values from the same locations suggests that "boundary exchange" has little influence on the Nd isotope composition of western South Pacific seawater. Concentrations of Rare Earth Elements (REE) and Al/Ca ratios of "unclean" planktonic foraminifera suggest that this phase is a reliable recorder of seawater Nd isotope composition. The signatures obtained from fish teeth and "nondecarbonated" leachates of bulk sediment Fe-Mn oxyhydroxide coatings also agree with "unclean" foraminifera. Direct comparison of Nd isotope compositions extracted using these methods with seawater Nd isotope compositions is complicated by the low accumulation rates yielding radiocarbon ages of up to 24 kyr, thus mixing the signal of different ocean circulation modes. This suggests that different past seawater Nd isotope compositions have been integrated in authigenic sediments from regions with low sedimentation rates. Combined detrital Nd and Sr isotope signatures indicate a dominant role of the Westerly winds transporting lithogenic material from South New Zealand and Southeastern Australia to the open South Pacific. The proportion of this material decreases toward the east, where supply from the Andes increases and contributions from Antarctica cannot be ruled out.

Geochemistry of basalts at DSDP Leg 73 Holes

During Deep Sea Drilling Project Leg 73 (South Atlantic), basaltic pillow lava, flows, and sills were encountered in Holes 519A, 520, 522B, and 524. Paleomagnetic data indicate that the basalts from Holes 519A (magnetic Anomaly 51) and 522B (Anomaly 16) have ages of about 12 m.y. and about 38 m.y., respectively. The major- and trace- (including rare-earth-) element characteristics of the Hole 519A basalts (a total of 27 m) demonstrate that these basalts are typical normal-type mid-ocean-ridge basalts (N-type MORB). In composition the basalts overlap olivine tholeiites from other normal Mid-Atlantic Ridge segments. Both the spectra of incompatible, or less-hygromagmatophile elements (such as Ti, V, Y, and Zr) and REE abundances indicate that these basalts are the result of a low-pressure fractionation of olivine, spinel, and Plagioclase prior to eruption. In Hole 520 only 1.7 m of basalt were recovered from a total drilling depth of 10.5 m. These pillow basalts crystallized from fairly evolved (N-type MORB) tholeiitic melts. In total, 19 m of basaltic pillow lavas and flows were penetrated in Hole 522B. Thirteen cooling units were distinguished on the basis of glassy margins and fine quench textures. In contrast to Holes 519A and 520, the basalts of the Hole 522B ridge section can be divided into two major groups of tholeiites: (1) Cooling Units 1 through 12 and (2) Cooling Unit 13. The basalts in this ridge section are also N-type MORBs but are generally more differentiated than those of Holes 519A and 520. The lowermost basalts (Cooling Unit 13) have the most primitive composition and make up a compositional group distinct from the more evolved basalts in the twelve units above it. Hole 524 was drilled on the south flank of the Walvis Ridge and thus provided samples from a more complex part of the South Atlantic seafloor. Three different basaltic rock suites, interlayered with volcanic detrital sediments, were encountered. The rock suites are, from top to bottom, an alkali basaltic pillow lava; a 16-m-thick alkaline diabase sill with an age of about 65 m.y. (according to K-Ar dating and planktonic foraminifers); and a second sill that is approximately 9 m thick, about 74 m.y. in age, and tholeiitic in composition, thus contrasting strongly with the overlying alkaline rocks. The alkali basalts of Hole 524 show chemical characteristics that are very similar to the basaltic lavas of the Tristan da Cunha group volcanoes, which are located approximately 400 km east of the Mid-Atlantic Ridge crest. Thus, the Walvis Ridge may plausibly be interpreted as a line of hot-spot alkaline volcanoes.

Chemical and mineral compositions of basalts and volcanic glasses from DSDP Sites 65-483 and 65-485

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO2 content (0.88%), FeO*/MgO ratio (0.95 with total Fe as FeO), and Mg# (100 Mg/Mg + Fe" = 70), sample 483-17-2-(78-83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a La/Sm_cn (chondrite-normalized) = 0.36, and Eu/Sm_cn = 1.05. Because other samples analyzed have higher SiO2, lower Mg#, and a negative Eu anomaly (Eu/Sm_cn as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An88), 6.7% olivine (Fo86), and 4.7% clinopyroxene (Wo41En49Fs10) from 483-17-2-(78-83) to form the least differentiated sample with Mg# = 63. The La/Sm_cn of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher La/Sm_cn (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO2 and P2O5 are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower La/Sm_cn and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78-83) is required.