Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

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.

Seafloor hydrothermal activity in sediment core MV0502-15JC

A large diameter piston core containing 8.35 m of metalliferous sediment has been recovered from a small abyssal valley in the remote Southwest Pacific Basin (31°42.194'S, 143°30.331'W; 5082 m water depth), providing unique insight into hydrothermal activity and eolian sedimentation there since the early Oligocene. A combination of fish-teeth Sr-isotope stratigraphy and INAA geochemical data reveals an exponentially decreasing hydrothermal flux 31 Ma to the present. Although hydrothermal sedimentation related to seafloor spreading explains this trend, a complex history of late Eocene/early Oligocene ridge jumps, propagating rifts and plate tectonic reorganization of South Pacific seafloor could have also played a role. A possible hiatus in deposition, as recorded by changes in core composition just below 2 m depth, is beyond the resolution of the fish teeth Sr isotope dating method employed here; however, the timing of this interval may be coincident with extinction of the Pacific-Farallon Ridge at ~20 Ma. A low flux eolian component accumulating at this site shows an increase relative to the hydrothermal component above 2 m depth, consistent with dust-generating continental sources far to the west (Australia/New Zealand). This is the first long-term paleoceanographic record obtained from within the South Pacific "bare zone" (Rea et al., 2006), an anomalous region where Pacific seafloor has largely escaped sediment accumulation since the Late Cretaceous.

Geochemistry of DSDP Leg 91 basalts

Basalts recovered from Sites 595 and 596 on Mesozoic crust in the southwest Pacific range from olivine-bearing tholeiites to ferrobasalts. Despite having undergone extensive low-grade alteration, which has raised K and Rb abundances, the basalts have consistent interelement ratios of Ti, Zr, Hf, rare-earth elements, Y, Th, Ik, and Nb. La/Ta (-18), Lan/Ybn (0.6), Ti/Zr (115), Zr/Nb (20), and Th/Hf (0.08) ratios all fall within the range of N-type mid-ocean-ridge basalt. The basalts from Sites 595 and 596 indicate that the Mesozoic Pacific crust was derived from a mantle source by processes similar to those operating at the present-day East Pacific Rise.

Chemical and isotopic compositions of rocks and minerals from the Ashadze and Logachev hydrothermal fields, Mid-Atlantic Ridge

This study was aimed at reconstructing a sequence of events in the magmatic and metamorphic evolution of peridotites, gabbroids, and trondhjemites from internal oceanic complexes of the Ashadze and Logachev hydrothermal vent fields. Collections of plutonic rocks from Cruises 22 and 26 of R/V "Professor Logachev", Cruise 41 of R/V "Akademik Mstislav Keldysh", and from the Serpentine Russian-French expedition aboard R/V "Pourquoi pas?" were objects of this study. Data reported here suggest that the internal oceanic complexes of the Ashadze and Logachev fields formed via the same scenario in these two regions of the Mid-Atlantic Ridge. On the other hand, an analysis of petrological and geochemical characteristics of the rocks indicated that the internal oceanic complexes of the MAR axial zone between 12°58'N and 14°45'N show pronounced petrological and geochemical heterogeneity manifested in variations in degree of depletion of mantle residues and in Nd isotopic compositions of rocks from the gabbro-peridotite association. Trondhjemites from the Ashadze hydrothermal field can be considered as partial melting products of gabbroids under influence of hydrothermal fluids. It was supposed that presence of trondhjemites in internal oceanic complexes of MAR can be used as a marker for the highest temperature deep-rooted hydrothermal systems. Perhaps, the region of the MAR axial zone, in which petrologically and geochemically contrasting internal oceanic complexes are spatially superimposed, serves as an area for development of large hydrothermal clusters with considerable ore-forming potential.

Investigations on seven sediment cores from the New Ireland Basin, east of Papua New Guinea

Sediment cores were recovered from the New Ireland Basin, east of Papua New Guinea, in order to investigate the late Quaternary eruptive history of the Tabar-Lihir-Tanga-Feni (TLTF) volcanic chain. Foraminifera d18O profiles were matched to the low-latitude oxygen isotope record to date the cores, which extend back to the early part of d18O Stage 9 (333 ka). Sedimentation rates decrease from >10 cm/1000 yr in cores near New Ireland to ~2 cm/1000 yr further offshore. The cores contain 36 discrete ash beds, mostly 1-8 cm thick and interpreted as either fallout or distal turbidite deposits. Most beds have compositionally homogeneous glass shard populations, indicating that they represent single volcanic events. Shards from all ash beds have the subduction-related pattern of strong enrichment in the large-ion lithophile elements relative to MORB, but three distinct compositional groups are apparent: Group A beds are shoshonitic and characterised by >1300 ppm Sr, high Ce/Yb and high Nb/Yb relative to MORB, Group B beds form a high-K series with MORB-like Nb/Yb but high Ce/Yb and well-developed negative Eu anomalies, whereas Group C beds are transitional between the low-K and medium-K series and characterised by flat chondrite-normalised REE patterns with low Nb/Yb relative to MORB. A comparison with published data from the TLTF chain, the New Britain volcanic arc and backarc including Rabaul, and Bagana on Bougainville demonstrates that only Group A beds share the distinctive phenocryst assemblage and shoshonitic geochemistry of the TLTF lavas. The crystal- and lithic-rich character of the Group A beds point to a nearby source, and their high Sr, Ce/Yb and Nb/Yb match those of Tanga and Feni lavas. A youthful stratocone on the eastern side of Babase Island in the Feni group is the most probable source. Group A beds younger than 20 ka are more fractionated than the older Group A beds, and record the progressive development of a shallow level magma chamber beneath the cone. In contrast, Group B beds represent glass-rich fallout from voluminous eruptions at Rabaul, whereas Group C beds represent distal glass-rich fallout from elsewhere along the volcanic front of the New Britain arc.

The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ(82/78)Se value for the bulk solar system. The δ(82/78)Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of −0.20±0.26‰ (2 s.d., n=14n=14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope fractionation. The results further suggest that the processes causing the high variability of Se concentrations and depletions in ordinary and enstatite chondrites did not involve any measurable isotope fractionation. Different degrees of element depletions and isotope fractionations of the moderately-volatile elements Zn, S, and Se in ordinary and enstatite chondrites indicate that their volatility is controlled by the thermal stabilities of their host phases and not by the condensation temperature under canonical nebular conditions.

Rare earth and trace elements in igneous and metamorphic minerals of oceanic gabbros from the Mid-Atlantic Ridge

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921-924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge-transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P = 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P = 0.2 GPa); (3) brittle regime (350 < T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show Cl-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxerie re-equilibrated in amphibolebearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196-22844 ppm), LREE depleted patterns and LaN/SmN = 0.10-0.33, LaN/YbN = 0.10-0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for TiN and negative anomalies for SrN and ZrN. Volatiles in amphibole are low, with Cl/F < 1; H2O% is significantly lower than the stoichiometric ratio (1.33-1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process.

Geochemistry of basalts at DSDP Site 89-462

At Site 462 in the Nauru Basin, western Pacific Ocean, 56 lithologic units have been recovered from an extensive flood basalt province. Fossil evidence suggests that the lavas were emplaced during the interval 100-115 Ma, some 30 m.y. after formation of the underlying Jurassic ocean crust. The lithologic units can be broadly divided into three chemical units, the lowermost two of which are chemically monotonous, suggesting rapid eruption of basalt from a compositionally homogeneous magma chamber. All the basalts are hypersthene- (hy-) rich tholeiites, with approximately chondritic La/Sm, La/Yb, Zr/Nb, La/Ta, and Th/Hf ratios. Chemically they resemble, in part, "transitional" mid-ocean ridge basalts (MORB) from areas such as the Reykjanes Ridge, although Rb, Ba, and K contents are very low and similar to those of "normal" MORB. Their 87Sr/86Sr ratios are higher than in N-type MORB (Fujii et al., 1981). The chemistry of the Nauru basalts differs from that of continental flood basalts, which tend to be strongly enriched in large-ion lithophile (LIL) elements, although the extent to which the differences result from sialic contamination or source variability is not clear.

Geochemistry of silicate melt inclusions from ODP Holes 137-504B and 140-504B

Geochemical data from plagioclase-hosted silicate melt inclusions from Leg 140, Hole 504B diabase dikes are reported. Hand-picked plagioclase grains were heated to 1260°-1280°C to remelt the glass inclusions and to infer trapping temperatures. The samples were then polished to expose the inclusions, which were analyzed by electron and ion microprobes. Inclusion compositions are mainly in equilibrium with the host plagioclase and are more depleted in incompatible elements than the host rock. Simple crystal-liquid equilibrium calculations show that the melt inclusions could have been in equilibrium with depleted abyssal peridotite diopsides, whereas whole-rock basalt compositions generally could not have been. The melt inclusions are significantly more depleted than normal (N-type) mid-ocean-ridge basalt (MORB) and are consistent with being produced by 8%-16% incremental or open-system melting with 2% residual porosity in the peridotite source. These magmas were formed during pressure-release melting of the mantle over a range of depths between 30 and 15 km.

Chemical characterization of earth's most ancient clastic metasediments from the Isua Greenstone Belt, southern West Greenland

New and published major and trace element abundances of elastic metasediments (mainly garnet-biotite-plagioclase schists) from the similar to 3.8 Ga Isua Greenstone Belt (IGB), southern West Greenland, are used in an attempt to identify the compositional characteristics of the protoliths of these sediments. Compositionally, the metasediments are heterogeneous with enrichment of LREE (La/Sm-chord = 1.1-3.9) and variable enrichment and depletion of HREE (Gd/Yb-chord = 0.8-4.3). Chondrite-normalized Eu is also variable, spanning a range from relative Eu depletion to enrichment (Eu/Eu* = 0.6-1.3). A series of geochemical and geological criteria provides conclusive evidence for a sedimentary origin, in disagreement with some previous studies that questioned the presence of genuine elastic metasediments. In particular, trace element systematics of IGB metasediments show strong resemblance to other well-documented Archaean clastic sediments, and are consistent with a provenance consisting of ultramafic, malic and felsic igneous rocks. Two schists, identified as metasomatized mafic igneous rocks from petrographic and field evidence, show distinct compositional differences to the metasediments. Major element systematics document incipient-to-moderate source weathering in the majority of metasediments, while signs of secondary K-addition are rare. Detailed inspection of Eu/Eu*, Fe2O3 and CIW (chemical index of weathering) relationships reveals that elevated iron contents (when compared to averages for continental crust) and strong relative enrichment in Eu may be due to precipitation of marine Fe-oxyhydroxides during deposition or diagenesis on the seafloor. Some of the IGB metasediments have yielded anomalous Nd-142 and W-182 isotopic compositions that were respectively interpreted in terms of early mantle differentiation processes and the presence of a meteorite component. Alternatively, W and possibly Nd isotopes could have been affected by thermal neutron capture on the Hadean surface. The latter process was tested in this study by analysis of Sm isotope compositions, which serve as an effective monitor for neutron capture effects. As no anomalous variation from terrestrial values was detected, we infer that isotope systematics (including W-182 and Nd-142) of IGB metasediments were not affected by neutron capture, but reflect decay of radioactive parent isotopes. Copyright (c) 2005 Elsevier Ltd.

Geochemistry of basement basaltic rocks of ODP Hole 131-808C

Major- and trace-element analyses, mineral chemistry, and Sr-Nd isotopic determinations were obtained on representative igneous rocks drilled from the Nankai accretionary complex (Site 808) during Ocean Drilling Program Leg 131. For the first time, the oceanic basement of the subducting plate below an accretionary prism has been reached. The Nankai Trough basement was encountered at a depth of 1289.9 mbsf and a total of 37.1 m of igneous rocks, middle Miocene (15.6 Ma) in age, was penetrated. Two main lithological units have been distinguished from the top downward; sill-like rocks (Unit I: Cores 105, 106, 107) and pillow lavas (Unit II: Core 108). Basalts are predominantly nonvesicular, hypocrystalline, aphyric to slightly phyric with intersertal to intergranular textures. Alteration is generally slight to moderate. All the basaltic rocks are cut by ramifying veins of varying widths. Secondary mineral assemblages (including vein fillings) are typical of submarine alteration and zeolite to low greenschist facies metamorphism. The order of crystallization of primary minerals is: olivine, plagioclase, clinopyroxene. This, together with mineral chemistry, characterized by forsteritic olivine (Fo 84-85), highly anorthitic Plagioclase (up to An 90), and in particular the composition of clinopyroxene, are typical of normal mid-ocean ridge basalts (MORB). In terms of Zr/Y (2.9-3.8) and Zr/Nb (21-58), all the analyzed samples plot in the normal MORB field. The chondrite-normalized REE patterns confirm the close affinity with normal MORB type (LaN/SmN: 0.6-0.8). Note that such magmatism does not reveal any evidence of subduction-related geochemical components. The 87Sr/86Sr isotopic ratios range from 0.70339 in pillow lavas to 0.70317 in the least-altered basalts of sill units (ratios reduced to 0.70265-0.70271 by HC1 2.5 N hot leaching), whereas 143Nd/144Nd ratios are 0.51314-0.51326. These values conform with those of normal MORB. Stratigraphy, petrography, and geochemistry of the basaltic rocks recovered at Site 808 appear very similar to those from the Shikoku Basin basement (particularly Sites 442 and 443, DSDP Leg 58), analogously identified as normal MORB.

Geochemistry in the mid Atlantic Ocean ridge basalts

The main objective of Leg 82 of the Glomar Challenger was to document mantle heterogeneity in the vicinity of, and away from, a so-called hot spot: the Azores Triple Junction. One of the geochemical tools that permits, at least in part, the recognition of mantle heterogeneities uses hygromagmaphile elements, those elements that have an affinity for the liquid. This tool is presented in terms of an extended Coryell-Masuda plot, which incorporates within the rare earth elements the hygromagmaphile transition elements Th, Ta, Zr, Hf, Ti, Y, and V. The extended Coryell-Masuda plot is used to summarize our knowledge of mantle heterogeneity along the ridge axis at zero-age. It is also used by choosing those hygromagmaphile elements that can be analyzed on board by X-ray fluorescence spectrometry to give preliminary information on the enriched or depleted character of recovered samples. Shore-based results, which include analyses of most of the hygromagmaphile elements measured either by X-ray spectrometry or neutron activation analysis, confirm the shipboard data. From the point of view of comparative geochemistry, the variety of basalts recovered during Leg 82 provides a good opportunity to test and verify the classification of the hygromagmaphile elements. Analyses from Leg 82 provide new data about the relationship between extended rare earth patterns (enriched or depleted) that can be estimated either by La/Sm ratio or Nb/Zr (or Ta/Hf) ratios: samples from Hole 556 are depleted (low Nb/Zr ratio) but have a high 206Pb/ 204Pb (19.5) ratio; in Hole 558 a moderately enriched basalt unit with a La/Sm (= Nb/Zr) ratio (chondrite normalized) of 2 has a high 206Pb/204Pb (20) ratio. One of the most interesting results of Leg 82 lies in the crossing patterns of extended Coryell-Masuda plots for basalts from the same hole. This result enhances the notion of local mantle heterogeneity versus regional mantle heterogeneity and is confirmed by isotope data; it also favors a model of short-lived, discrete magma chambers. The data tend to confirm the Hayes Fracture Zone as a southern limit for the influence of Azores-type mantle. Nevertheless, north of the Hayes Fracture Zone, the influence of a plumelike mantle source is not simple and probably requires an explanation more complex than a contribution from a single fixed hot spot.