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).

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 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.

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.

Geochemistry of basement carbonates from ODP Site 801 in the western Pacific Ocean

Many studies argue, based partly on Pb isotopic evidence, that recycled, subducted slabs reside in the mantle source of ocean island basalts (OIB) (Hofmann and White, 1982, doi:10.1016/0012-821X(82)90161-3; Weaver, 1991 doi:10.1016/0012-821X(91)90217-6; Lassiter, and Hauri, 1998, doi:10.1016/S0012-821X(98)00240-4). Such models, however, have remained largely untested against actual subduction zone inputs, due to the scarcity of comprehensive measurements of both radioactive parents (Th and U) and radiogenic daughter (Pb) in altered oceanic crust (AOC). Here, we discuss new, comprehensive measurements of U, Th, and Pb concentrations in the oldest AOC, ODP Site 801, and consider the effect of subducting this crust on the long-term Pb isotope evolution of the mantle. The upper 500 m of AOC at Site 801 shows >4-fold enrichment in U over pristine glass during seafloor alteration, but no net change to Pb or Th. Without subduction zone processing, ancient AOC would evolve to low 208Pb/206Pb compositions unobserved in the modern mantle (Hart and Staudigel, 1989 [Isotopic characterization and identification of recycled components, in: Crust/Mantle Recycling at Convergence Zones, Eds. S.R. Hart, L. Gqlen, NATO ASI Series. Series C: Mathematical and Physical Sciences 258, pp. 15-28, D. Reidel Publishing Company, Dordrecht-Boston, 1989]). Subduction, however, drives U-Th-Pb fractionation as AOC dehydrates in the earth's interior. Pacific arcs define mixing trends requiring 8-fold enrichment in Pb over U in AOC-derived fluid. A mass balance across the Mariana subduction zone shows that 44-75% of Pb but <10% of U is lost from AOC to the arc, and a further 10-23% of Pb and 19-40% of U is lost to the back-arc. Pb is lost shallow and U deep from subducted AOC, which may be a consequence of the stability of phases binding these elements during seafloor alteration: U in carbonate and Pb in sulfides. The upper end of these recycling estimates, which reflect maximum arc and back-arc growth rates, remove enough Pb and U from the slab to enable it to evolve rapidly (<<0.5 Ga) to sources suitable to explain the 208Pb/206Pb isotopic array of OIB, although these conditions fail to simultaneously satisfy the 207Pb/206Pb system. Lower growth rates would require additional U loss (29%) at depths beyond the zones of arc and back-arc magmagenesis, which would decrease upper mantle kappa (232Th/238U) over time, consistent with one solution to the "kappa conundrum" (Elliott et al., 1999, doi:10.1016/S0012-821X(99)00077-1). The net effects of alteration (doubling of l [238U/204Pb]) and subduction (doubling of omega [232Th/204Pb]) are sufficient to create the Pb isotopic signatures of oceanic basalts.

Chemical composition of DSDP and ODP cherts

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~11% NASC, Atlantic chert ~17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for sum REE, approximations of excessive La (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest excessive La (85% of total La) and SHL chert the least (38% of total La). As shown by interelement associations, this excessive La is most likely an adsorbed component onto aluminosilicate and phosphatic phases. Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert Ce/Ce* <<1 and normative La/Yb ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., normative La/Yb ~0.4), which increases the normative La/Yb ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and normative La/Yb ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce* ~1 and inherited normative La/Yb values of ~1.2-1.4. Ce/Ce* does not vary with age, either throughout the entire data base or within a particular basin. Overall, Ce/Ce* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.

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.

Geochemistry of basalts from ODP Hole 109-648B

Legs 106-109 achieved the first basaltic bare-rock drill hole, on a small volcano (Serocki volcano) located on the flanks of the rift valley in the MAR about 70 km south of the Kane fracture zone. Because of severe technical difficulties only 50.5 m of basalt below seafloor was recovered. Geochemical analysis shows that the recovered basalts display typical N-MORB characteristics as expected in this segment of the Mid-Atlantic ridge. The lava flows display rather equivalent geochemical characteristics all over the drilled section and show the imprint of a previous magmatic differentiation suffered by the magmas before their emission, indicative of a fractional crystallization of plagioclase-bearing cumulates. The incompatible and alkali element content of these 648B magmas is very low, a feature which resembles those of other N-MORB. The geochemical characteristics of these basalts look closely similar to those of basalts from the same flow line emitted respectively 10 m.y. (Hole 395, Legs 45-46), and 110 m.y. (Hole 417A, Legs 51-53) ago, supporting the persistence in this ridge segment of a mantle source with depleted characteristics over the last 110 m.y., but with some variations in the degree of depletion of the source along this period. Although these rocks appear fresh, the imprint of an incipient low temperature alteration can be noticed in a few samples, as evidenced by slight increases of alkali, U elements, and 87Sr/86Sr isotopic compositions.

Volcanic rocks from the submarine Vityaz Ridge: their age, chemical and isotopic compositions

Results of geological studies at the submarine Vityaz Ridge carried out during cruises 37 and 41 of R/V Akademik Lavrent'ev in 2005 and 2006 are reported. The studied area is located at an near-island trench of the slope in the central part of the Kuril Island arc. Morphologically it consists of two parts: an inner volcanic arc represented by the Great Kuril Range and an outer arc corresponding to the submarine Vityaz Ridge. Diverse rocks composing the basement and the sedimentary cover of the ridge were recovered by dredging. Based on K-Ar dating and geochemistry, volcanics were divided into Paleocene, Eocene, late Oligocene, and Pliocene-Pleistocene complexes. Each of the complexes reflects a tectonomagmatic stage in the ridge evolution. Geochemical and isotope data on the volcanics indicate contribution of ancient crustal material in the magma source and, correspondingly, formation of this structure on the continental basement. Two-stage model ages (TDM2) vary in a wide range from zero values in mafic rocks to 0.77 Ga in felsic varieties, pointing to presence of Precambrian protolith in the source of the felsic rocks of the Vityaz Ridge. The Pliocene-Pleistocene volcanics are classed with tholeiitic, calc-alkaline, and subalkaline series, which differ in alkali contents and REE fractionation. Values of (La/Sm)_n and (La/Yb)_n ratios vary from 0.74 and 0.84 in the tholeiitic varieties to 1.19 and 1.44 in the calc-alkaline and 2.32 and 3.73 in the subalkaline rocks. All three varieties occur within the same volcanic edifices and formed during differentiation of magmatic melts that were channeled along fault zones from the mantle source slightly enriched in crustal component.

Grain size and chemical compositions of bottom sediments from the Amur Bay

Composition of clay minerals in the <0.001 mm size fraction from the uppermost layer of bottom sediments in the northern Amur Bay was determined by X-ray powder diffraction analysis, and enrichment of 33 elements in the <0.001 mm and <0.01 mm size fractions of surface sediments from a number of sites at the marginal filter of the Razdol'naya River were studied by ICP-MS. Fe, U, and chalcophile elements occur in the highest concentrations in sediments from all sampling sites within the filter. The bottom sediments are not enriched in trace, alkali, and alkaline earth elements. Maximum concentrations of chemical elements were found in deposits from the brackish part of the marginal filter, perhaps, because of formation of Fe and Mn (Al) hydroxides. Bottom sediments at the boundary between the brackish and marine parts of the filter contain the lowest concentrations of the examined elements.

Barium in sediments and pore waters of several ODP Leg 170 and Leg 205 sites

Barium concentrations were measured on 17 pore fluid and 13 sediment samples from Sites 1253 and 1254 drilled offshore Costa Rica during Ocean Drilling Program (ODP) Leg 205. An additional 83 pore fluid and 29 sediment samples were analyzed for Ba concentrations from Sites 1039 and 1040 drilled during ODP Leg 170 offshore Costa Rica. Sites 1039/1253 and 1040/1254 are part of a transect across the Middle America Trench offshore Nicoya Peninsula. The entire incoming sediment section is being underthrust beneath the margin, providing an ideal setting to examine Ba cycling in the shallow levels of the subduction zone. Results from these analyses indicate that a significant amount of Ba is liberated from the mineral barite (BaSO4) in the uppermost hemipelagic sediments arcward of the trench. The shallow distillation of Ba may impact the amount of sedimentary Ba reaching the deeper subduction zone.