Rare earth element data for sediments from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Chemical composition and accumulation rates of chemical elements in metalliferous sediments from axial zones of the East Pacific Rise and the Mid-Atlantic Ridge

In the monograph metalliferous sediments of the East Pacific Rise near 21°S are under consideration. Distribution trends of chemical, mineral and grain size compositions of metalliferous sediments accumulated near the axis of this ultrafast spreading segment of the EPR are shown. On the basis of lithological and geochemical investigations spatial and temporal variations of hydrothermal activity are estimated. Migration rates of hydrothermal fields along the spreading axis are calculated. The model of cyclic hydrothermal process is suggested as a result of tectono-magmatic development of the spreding centre.

Geochemistry at DSDP Leg 82 Holes

The nine holes (556-564) drilled during DSDP Leg 82 in a region west and southwest of the Azores Platform (Fig. 1) exhibit a wide variety of chemical compositions that indicate a complex petrogenetic history involving crystal fractionation, magma mixing, complex melting, and mantle heterogeneity. The major element chemistry of each hole except Hole 557 is typical of mid-ocean ridge basalts (MORBs), whereas the trace element and rare earth element (REE) abundances and ratios are more variable, and show that both depleted Type I and enriched Type II basalts have been erupted in the region. Hole 556 (30-34 Ma), located near a flow line through the Azores Triple Junction, contains typically depleted basalts, whereas Hole 557 (18 Ma), located near the same flow line but closer to the Azores Platform, is a highly enriched FeTi basalt, indicating that the Azores hot-spot anomaly has existed in its present configuration for at least 18 Ma, but less than 30-34 Ma. Hole 558 (34-37 Ma), located near a flow line through the FAMOUS and Leg 37 sites, includes both Type I and II basalts. Although the differences in Zr/Nb and light REE/heavy REE ratios imply different mantle sources, the (La/Ce)ch (>1) and Nd isotopic ratios are almost the same, suggesting that the complex melting and pervasive, small-scale mantle heterogeneity may account for the variations in trace element and REE ratios observed in Hole 558 (and FAMOUS sites). Farther south, Hole 559 (34-37 Ma), contains enriched Type II basalts, whereas Hole 561 (14-17 Ma), located further east near the same flow line, contains Type I and II basalts. In this case, the (La/Ce)ch and Nd isotopic ratios are different, indicating two distinct mantle sources. Again, the existence along the same flow line of two holes exhibiting such different chemistry suggests that mantle heterogeneity may exist on a more pervasive and transient smaller scale. (Hole 560 was not sampled for this study because the single basalt clast recovered was used for shipboard analysis.) All of the remaining three holes (562, 563, 564), located along a flow line about 100 km south of the Hayes Fracture Zone (33°N), contain only depleted Type I basalts. The contrast in chemical compositions suggests that the Hayes Fracture Zone may act as a "domain" boundary between an area of fairly homogeneous, depleted Type I basalts to the south (Holes 562-564) and a region of complex, highly variable basalts to the north near the Azores hot-spot anomaly (Holes 556-561).

Geochemistry of basalts from ODP Hole 113-690C

Basalts from Maud Rise, Weddell Sea, are vesicular and olivine-phyric. Major, trace, and rare earth element concentrations are similar to those of alkali basalts from ocean islands and seamounts. The rocks are low in MgO, Cr, Ni, and Sc, and high in TiO2, K2O, P2O5, Zr, and LREE contents. The abundance of "primary" biotite and apatite in the matrix indicates the melting of a hydrous mantle. Prevalence of olivine and absence of plagioclase in the rocks suggests that the volatile in the melt was an H2O-CO2 mixture, where H2O was <0.5. Mantle derived xenocrysts in the basalt include corroded orthopyroxene, chromite, apatite, and olivine. Olivine (Fo90) is too magnesian to be in equilibrium with the basalts, as they contain only 5-6 wt% MgO. Based on the presence of mantle xenocrysts, the high concentration of incompatible elements, the spatial and chemical affinity with other ocean island basalts from the area, and the relative age of the basalt (overlain by late Campanian sediments), it is suggested that Maud Rise was probably generated by hot-spot activity, possible during a ridge crest jump prior to 84 Ma (anomaly 34 time). Iddingsite, a complex intergrowth of montmorillonite and goethite, is the major alteration product of second generation olivine. It is suggested that iddingsite crystallized at low temperatures (<200°C) from an oxidized fluid during deuteric alteration. Vesicles are commonly filled by zeolites which have been replaced by K-feldspars.

Geochemistry of ODP Sites 128-798 and 128-799 sediments

Nineteen trace elements, including seven rare earth elements (REE's), and 10 major and minor elements in 76 sediment samples from Sites 798 (Oki Ridge) and 799 (Yamato Trough) were determined by means of instrumental neutron activation analysis and X-ray fluorescence spectrometry. Most REE patterns (chondrite-normalized) of the sediments from both sites were nearly identical to the patterns of terrigenous materials. The cerium anomaly (slightly positive) frequently appeared in REE patterns of the sediments (200-750 mbsf) from Site 799. Cerium may be selectively incorporated into the sediments with hydrogenous manganese precipitation. However, the degree of the anomaly was not well correlated with manganese content, suggesting that cerium may behave as a trivalent REE (like the other REE's) during diagenesis while manganese is transported in the sediment column accompanied by reduction to a lower oxidation state. The Th/Sc ratio of the sediments from Sites 798 and 799 tended to decrease with penetration depth. Such a depth profile may indicate a decrease in basic volcanism activities from the Pliocene (Site 798) and Miocene (Site 799). The La/Yb ratio and degree of europium anomaly also varied with depth, which may imply that two or more components with different REE patterns were supplied throughout sedimentation at sites in the Japan Sea.

Geochemical analysis of minerals from sediment core CRP-2 in the Ross Sea, Antarctica

Distribution patterns, petrography, whole-rock and mineral chemistry, and shape and fabric data are described for the most representative basement lithologies occurring as clasts (granule to bolder grain-size class) from the 625 m deep CRP-2/2A drillcore. A major change in the distribution pattern of the clast types occurs at c. 310 mbsf., with granitoid-dominated clasts above and mainly dolerite clasts below; moreover, compositional and modal data suggest a further division into seven main detrital assemblages or petrofacies. In spite of this variability, most granitoid pebbles consist of either pink or grey biotite±hornblende monzogranites. Other less common and ubiquitous lithologies include biotite syenogranite, biotite-hornblende granodiorite, tonalite, monzogranitic porphyries (very common below 310 mbsf), microgranite, and subordinately, monzogabbro, Ca-silicate rocks, biotite-clinozoisite schist and biotite orthogneiss (restricted to the pre-Pliocene strata). The ubiquitous occurrence of biotite±hornblende monzogranite pebbles in both the Quaternary-Pliocene and Miocene-Oligocene sections, apparently reflects the dominance of these lithologies in the onshore basement, and particularly in the Cambro-Ordovician Granite Harbour Igneous Complex which forms the most extensive outcrop in southern Victoria Land. The petrographical features of the other CRP-2/2A pebble lithologies are consistent with a supply dominantly from areas of the Transantarctic Mountains facing the CRP-2/2A site, and they thus provide further evidence of a local provenance for the supply of basement clasts to the CRP-2/2A sedimentary strata.

Chemical composition of sediments from DSDP Site 223, Indian Ocean

Detailed major- and trace-element chemistry is presented for 41 sediment samples from DSDP Site-223 borehole cores. A marked change in chemical (and mineralogical) character is shown at the end of the Early Miocene Epoch which relates to tectonic events and associated changes in sedimentary regime. Enrichment in the contents of such elements as Mg, Cr and Ni compared with average values for fine-grained sediments occurs throughout the sequence and is particularly marked in the upper group of samples. A basic-ultrabasic provenance is suggested - the Oman ophiolites. Leaching with combined acid-reducing agent indicated typical lithogenous-character ordering for the elements and emphasised the enrichment of Mg, Cr, Ni (and Li, Cu, Zn, Pb, Fe and Ti) over values for near-shore muds and terrigenous material. Factor analysis on the bulk chemical data identifies the main lithogenous and biogenous components, subdividing the latter. It separates the upper and lower group of chemically dissimilar sediments and delineates a Mn-hydroxide phase. It also shows the essentially independent roles of Na, Ba and P.

Trace-element geochemistry of tholeiitic basalts from DSDP Hole 55-433C

Hole 433C, a multiple re-entry hole drilled in 1862 meters of water on Suiko Seamount in the central Emperor Seamounts, penetrated 387.5 meters of lava flows overlain by 163.0 meters of sediments. The recovered volcanic rocks consist of three flow units (1-3) of alkalic basalt underlain by more than 105 flows or flow lobes (Flow Units 4-67) of tholeiitic basalt. This study reports trace-element, including rare-earth element (REE), data for 25 samples from 24 of the least altered tholeiitic flows. These data are used to evaluate the origin and evolution of tholeiitic basalts from Suiko Seamount and to evaluate changes in the mantle source between the time when Suiko Seamount formed, 64.7 ± 1.1 m.y. ago (see Dalrymple et al., 1980), and the present day. Stearns (1946), Macdonald and Katsura (1964) and Macdonald (1968) have established that chemically distinct lavas erupt during four eruptive stages of development of a Hawaiian volcano. These stages, from initial to final, are shield-building, caldera-filling, post-caldera, and post-erosional. The lavas of the shield-building stage are tholeiitic basalts, which erupt rapidly and in great volume. The shield-building stage is quickly followed by caldera collapse and by the caldera-filling stage, during which the caldera is filled by tholeiitic and alkalic lavas. During the post-caldera stage, a relatively thin veneer of alkalic basalts and associated differentiated lavas are erupted, sometimes accompanied by minor eruptions of tholeiitic lava. After a period of volcanic quiescence and erosion, lavas of the nephelinitic suite, which include both alkalic basalts and strongly SiO2-undersaturated nephelinitic basalts, may erupt from satellite vents during the post-erosional stage. Many Hawaiian volcanoes develop through all four stages; but individual volcanoes have become extinct before the cycle is complete. We interpret the tholeiitic lavas drilled on Suiko Seamount to have erupted during either the shield-building or the caldera-filling stage, and the overlying alkalic flows to have erupted during either the caldera-filling or the post-caldera stage (see Kirkpatrick et al., 1980).

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

(Table 1) Chemical composition of volcanic rocks from the Mariisky sequence and extrusive vent rocks of the Mary Cape, Schmidt Peninsula (North Sakhalin)

Early Cretaceous volcanic rocks of the Mariisky sequence and Early Cenozoic extrusive-vent rocks of the Mary Cape are exposed at the most northwest of the Schmidt Peninsula, North Sakhalin. In chemical composition, all the rocks are subdivided into four groups. Three groups include volcanic rocks of the Mariisky sequence, which consists, from bottom to top, of calc-alkaline rocks, transitional calc-alkaline-tholeiite rocks, and incompatible element-depleted tholeiites. These rocks show subduction geochemical signatures and are considered as a fragment of the Moneron-Samarga island arc system. Trace-element modeling indicates their derivation through successive melting of a garnet-bearing mantle and garnet-free shallower mantle sources containing amphibole; pyroxene; and, possibly, spinel. The mixed subduction and intra-plate characteristics of the extrusive vent rocks of the Mary Cape attest to their formation in a transform continental margin setting.

Chemistry on manganese nodules from the Pacific Ocean

Three manganese nodules from the Pacific Ocean have been analysed for 35 elements by using mainly spectrophotometric and spectrographic methods. Cu, Co, Ni, Zn, and Pb were found in amounts approaching 1 %, which far exceeds their average concentrations in igneous rocks. On the other hand, elements having readily hydrolysable ions, such as Ga, Sc, Zr, Y, La and Ti, are present only in amounts comparable with their concentrations in igneous rocks. Sb, Bit Be, and Cr were not detected. The hydrochloric acid-insoluble fraction of nodules is practically free of the heavy metals that are characteristic of the acid-soluble fraction; it consists principally of clay minerals, together with lesser amounts of quartz, apatite, biotite and sodium and potassium felspars.

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.