Geochemistry of rare earth elements in basalts from Walvis Ridge

Selected basalts from a suite of dredged and drilled samples (IPOD sites 525, 527, 528 and 530) from the Walvis Ridge have been analysed to determine their rare earth element (REE) contents in order to investigate the origin and evolution of this major structural feature in the South Atlantic Ocean. All of the samples show a high degree of light rare earth element (LREE) enrichment, quite unlike the flat or depleted patterns normally observed for normal mid-ocean ridge basalts (MORBs). Basalts from Sites 527, 528 and 530 show REE patterns characterised by an arcuate shape and relatively low (Ce/Yb)N ratios (1.46-5.22), and the ratios show a positive linear relationship to Nb content. A different trend is exhibited by the dredged basalts and the basalts from Site 525, and their REE patterns have a fairly constant slope, and higher (Ce/Yb)N ratios (4.31-8.50). These differences are further reflected in the ratios of incompatible trace elements, which also indicate considerable variations within the groups. Mixing hyperbolae for these ratios suggest that simple magma mixing between a 'hot spot' type of magma, similar to present-day volcanics of Tristan da Cunha, and a depleted source, possibly similar to that for magmas being erupted at the Mid-Atlantic Ridge, was an important process in the origin of parts of the Walvis Ridge, as exemplified by Sites 527, 528 and 530. Site 525 and dredged basalts cannot be explained by this mixing process, and their incompatible element ratios suggest either a mantle source of a different composition or some complexity to the mixing process. In addition, the occurrence of different types of basalt at the same location suggests there is vertical zonation within the volcanic pile, with the later erupted basalts becoming more alkaline arid more enriched in incompatible elements. The model proposed for the origin and evolution of the Walvis Ridge involves an initial stage of eruption in which the magma was essentially a mixture of enriched and depleted end-member sources, with the N-MORB component being small. The dredged basalts and Site 525, which represent either later-stage eruptives or those close to the hot spot plume, probably result from mixing of the enriched mantle source with variable amounts and variable low degrees of partial melting of the depleted mantle source. As the volcano leaves the hot spot, these late-stage eruptives continue for some time. The change from tholeiitic to alkalic volcanism is probably related either to evolution in the plumbing system and magma chamber of the individual volcano, or to changes in the depth of origin of the enriched mantle source melt, similar to processes in Hawaiian volcanoes.

Geochemistry at DSDP Leg 92 Holes

The major-element and most of the trace-element data from the different laboratories that contributed to the study of samples recovered during Leg 82 are presented in the following tables. The different basalt groups, identified on the basis of their chemical properties (major and trace elements), were defined from the data available on board the Glomar Challenger as the cruise progressed (see site chapters, all sites, this volume). Most of the data obtained since the end of the cruise and presented in these tables confirm the classification that was proposed by the shipboard party (see site chapters, all sites, this volume). Nevertheless, special mention should be made about Site 564. The shipboard party proposed a single chemical group at this site but noticed significant variations down the hole, mainly in trace-element data. However, the range of variation was small compared to the precision of the measurements. These variations were confirmed by the onshore studies (see papers in Part IV of this volume, especially Brannon's paper, partly devoted to this topic).

Mineralogy and geochemistry of altered ash, pelagic clay, and a clay vein in basalt from DSDP Leg 62 Holes

Volcanic ash was recovered from lower Aptian to Albian deposits from DSDP Sites 463, 465, and 466; pelagic clay of the upper Pleistocene to Upper Cretaceous was recovered mainly from Site 464, with minor amounts at Sites 465 and 466. We present X-ray-mineralogy data on pelagic clay and altered volcanic ash recovered from the four Leg 62 sites. In addition, two ash samples from Sites 463 and 465, a pelagic clay from Site 464, and a clay vein from the basaltic basement at Site 464 each were analyzed for major, minor, and trace elements. Our purpose is to describe the mineralogy and chemistry of altered ash and pelagic clays, to determine the sources of their parent material, and to delineate the diagenetic history of these clay-rich deposits. Correlation of chemistry and mineralogy of ash and pelagic clay with volcanic rocks suspected to be their parent material is not always straightforward, because weathering and diagenetic alteration caused depletion or enrichment of many elements.

Description, geochemistry, mineralogy and isotopes of sulfides from ODP Site 193-1189, PACMANUS field

Chemical and isotopic data for rare massive and semimassive sulfide samples cored at Site 1189 (Roman Ruins, PACMANUS) suggest their genetic relationship with sulfide chimneys at the seafloor. Sand collected from the hammer drill after commencement of Hole 1189B indicates that at least the lower section of the cased interval was occupied by material similar to the stockwork zone cored from 31 to ~100 meters below seafloor (mbsf) in this hole, but with increased content of barite, sphalerite, and lead-bearing minerals. Fractional crystallization of ascending hydrothermal fluid involving early precipitation of pyrite may explain vertical mineralogical and chemical zoning within the stockwork conduit and the high base and precious metal contents of Roman Ruins chimneys. A mineralized volcaniclastic unit cored deep in Hole 1189A possibly represents the lateral fringe of the conduit system. Lead isotope ratios in the sulfides differ slightly but significantly from those of fresh lavas from Pual Ridge, implying that at least some of the Pb within the Roman Ruins hydrothermal system derived from a deeper, more radiogenic source than the enclosing altered volcanic rocks.

Chemical composition of ferromanganese concretions and host bottom sediments from the Black Sea

Ferromanganese concretions spread out on the bottom of the shallow northwest part of the Black Sea are mainly represented by Fe and Mn nodules on shells and substituted worm tubes. Element composition of these formations was measured by methods of chemical, atomic absorbtion, neutron activation, and ICP-MS analyses. It was established that Fe and Mn contents and Mn/Fe ratio in the concretions varied considerably and which controlled occurrence of several associated metals and minor elements; some of them have not been studied in Black Sea concretions before.

Chemical and isotopic compositions of basaltic glasses and crusts from the Mid-Atlantic Ridge rift valley

Data presented in the paper suggest significant differences between thermodynamic conditions, under which magmatic complexes were formed in MAR at 29°-34°N and 12°-18°N. Melts occurring at 29°-34°N were derived by melting of a mantle source with homogeneous distribution of volatile components and arrived at the surface without significant fractionation, likely, due to their rapid ascent. The MAR segments between 12° and 18°N combine contrasting geodynamic environments of magmatism, which predetermined development of a large plume region with widespread mixing of melting products of geochemically distinct mantle sources. At the same time, this region is characterized by conditions favorable for origin of localized zones of anomalous plume magmatism. These sporadic magmatic sources were spatially restricted to MAR fragments with the Hess crust, whose compositional and mechanical properties were, perhaps, favorable for focusing and localization of plume magmatism. The plume source between 12° and 18°N beneath MAR may be geochemically heterogeneous.

Physical properties and geochemistry at DSDP Leg 70 Holes

Ashes occurring both as distinct layers and mixed with pelagic sediments of the hydrothermal mounds lying south of the Galapagos Rift are mainly rhyolitic and basaltic. The ashes, of rhyolitic to intermediate composition, appear to belong to a calc-alkalic series and were probably derived from Plinian eruptions in Ecuador or Colombia. Basaltic ashes are made of nonvesicular sideromelane spalling shards and are of tholeiitic composition. They probably were derived locally from fault scarps. Most rhyolitic and basaltic glass shards studied are fresh except for hydration of the rhyolitic shards. Some shards are severely altered, however. Basaltic ash may be more common in pelagic sediments deposited near accretion zones and may be a source of silica and other elements released during diagenesis

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.

Geochemistry and petrology of basalts from Celebes Sea

Major-, trace-, and rare-earth element analyses are presented from a suite of basaltic rocks from the basement of the Celebes Sea. The major elements and trace-elements were determined by X-ray fluorescence techniques, and the rare-earth elements were analyzed by instrumental neutron activation analysis. Compositionally the Celebes Sea basalts are very similar to typical normal mid-ocean ridge basalts, such as those described from the Indian Ocean triple junction. Petrogenetic modeling shows that all of the basalts analyzed can be formed by 10% to 20% partial melting of a light rare-earth element-depleted spinel lherzolite followed by fractional crystallization of mixtures of olivine, Plagioclase, and iron oxide. The Celebes Sea is interpreted as a fragment of the basement of the Jurassic Argo abyssal plain trapped during the Eocene to the north of Australia.

Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Whole-rock geochemical analyses of serpentinized harzburgites from ODP Site 209-1270

Small-scale shear zones are present in drillcore samples of abyssal peridotites from the Mid-Atlantic ridge at 15°20'N (Ocean Drilling Program Leg 209). The shear zones act as pathways for both evolved melts and hydrothermal fluids. We examined serpentinites directly adjacent to such zones to evaluate chemical changes resulting from melt-rock and fluid-rock interaction and their influence on the mineralogy. Compared to fresh harzburgite and melt-unaffected serpentinites, serpentinites adjacent to melt-bearing veins show a marked enrichment in rare earth elements (REE), strontium and high field strength elements (HFSE) zirconium and niobium. From comparison with published chemical data of variably serpentinized and melt-unaffected harzburgites, one possible interpretation is that interaction with the adjacent melt veins caused the enrichment in HFSE, whereas the REE contents might also be enriched due to hydrothermal processes. Enrichment in alumina during serpentinization is corroborated by reaction path models for interaction of seawater with harzburgite-plagiogranite mixtures. These models explain both increased amounts of alumina in the serpentinizing fluid for increasing amounts of plagiogranitic material mixed with harzburgite, and the absence of brucite from the secondary mineralogy due to elevated silica activity. By destabilizing brucite, nearby melt veins might fundamentally influence the low-temperature alteration behaviour of serpentinites. Although observations and model results are in general agreement, due to absence of any unaltered protolith a quantification of element transport during serpentinization is not straightforward.