Geochemistry of pore fluids and bulk solids of ODP Site 195-1200, South Chamorro Seamount

At the South Chamorro Seamount in the Mariana subduction zone, geochemical data of pore fluids recovered from Ocean Drilling Program Leg 195 Site 1200 indicate that these fluids evolved from dehydration of the underthrusting Pacific plate and upwelling of fluids to the surface through serpentinite mud volcanoes as cold springs at their summits. Physical conditions of the fluid source at 27 km were inferred to be at 100°-250°C and 0.8 GPa. The upwelling of fluid is more active near the spring in Holes 1200E and 1200A and becomes less so with increasing distance toward Hole 1200D. These pore fluids are depleted in Cl and Br, enriched in F (except in Hole 1200D) and B (up to 3500 µM), have low 11B (16-21), and have lower than seawater Br/Cl ratios. The mixing ratios between seawater and pore fluids is calculated to be ~2:1 at shallow depth. The F, Cl, and Br concentrations, together with B concentrations and B isotope ratios in the serpentinized igneous rocks and serpentine muds that include ultramafic clasts from Holes 1200A, 1200B, 1200D, 1200E, and 1200F, support the conclusion that the fluids involved in serpentinization originated from great depths; the dehydration of sediments and altered basalt at the top of the subducting Pacific plate released Cl, H2O, and B with enriched 10B. Calculation from B concentrations and upwelling rates indicate that B is efficiently recycled through this nonaccretionary subduction zone, as through others, and may contribute the critical missing B of the oceanic cycle.

Hydrocarbons in hydrothermal sulfides from the Rainbow Hydrothermal Field

The Rainbow Hydrothermal Field (36°N, Mid-Atlantic Ridge) is one of three presently known fields related to serpentinization of ultramafic rocks accompanied by formation of hydrogen- and methane rich solutions. Gas chromatographic and molecular gas chromatographic - mass spectrometric investigations of sulfide ores and sediments from this field confirmed predominantly biological nature of bitumoids related to high-temperature transformation of biomass of the hydrothermal biological community. At the same time ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests possibility of abiogenic synthesis of methane and even complex hydrocarbons during serpentinization of ultramafic rocks.

Chlorine concentration and isotopic data for sediments and serpentine seamount material from ODP Legs 125, 129, 185, and 195

Chlorine isotope ratios were determined for volcanic gas, geothermal well, ash, and lava samples along the Izu-Bonin-Mariana volcanic front, serpentinite clasts and muds from serpentine seamounts (Conical, South Chamorro, Torishima), basalts from the Guguan cross-chain, and sediments from Ocean Drilling Program (ODP) Sites 800, 801, 802, and 1149. There is no systematic variation in d37Cl values along the volcanic front in either gas or ash samples. In contrast, distinct variations occur across the arc, implying variations in the fluid source at different depths within the subduction zone. Serpentinite clasts and serpentine muds from the seamounts tap a source of ~30 km depth and have d37Cl values of structurally bound chloride of +0.4 per mil +/- 0.4 per mil (n = 24), identical to most seafloor serpentinites, suggesting a serpentinite (chrysotile and/or lizardite to antigorite transition) fluid source. Tapping deeper levels of the subduction zone (~115-130 km depth), volcanic gases and ashes have d37Cl values averaging -1.1 per mil +/- 1.0 per mil (n = 29), precisely overlapping the range measured in sediments from ODP cores (-1.1 per mil +/- +0.7 per mil, n = 11) and limited altered oceanic crust (AOC). Both sediments and AOC are possible Cl sources in the volcanic front. The Guguan cross-chain basalts come from the greatest depths and have an average d37Cl value of +0.2 per mil +/- 0.2 per mil (n = 3), suggesting a second serpentine-derived source, in this case from antigorite breakdown at ~200 km depth.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Rock magnetic properties of ODP Hole 109-670A

The magnetic properties of 11 samples from Site 670 of Leg 109, 3 harzburgites and 8 highly serpentinized peridotites, have been studied. Reflected light microscopy and Curie temperatures confirm that magnetite is the dominant magnetic mineral in all samples. However, both rock types show different magnetic behavior. Susceptibility, saturation magnetization, and NRM are higher for the serpentinites, because of the higher magnetite content. The hysteresis parameters indicate magnetite particles with pseudosingle domain structure for both rock types. For the remarkable anisotropy of the magnetic susceptibility no definite explanation could be found, because of the complex texture of the samples. In both rock types the presence of maghemite, a product of low temperature oxidation of magnetite, has been indicated by reflected light microscopy and by thermomagnetic analysis. As the maghemite converts to hematite at temperatures above 350°C, the temperature during the serpentinization was below this value assuming that the maghemitization took place at the same time.

(Figures S2a-c) Phase diagrams of the upper crust, the lower crust and the upper mantle based on averaged compositions of the oceanic crust and mantle

The age of the subducting Nazca Plate off Chile increases northwards from 0 Ma at the Chile Triple Junction (46°S) to 37 Ma at the latitude of Valparaíso (32°S). Age-related variations in the thermal state of the subducting plate impact on (a) the water influx to the subduction zone, as well as on (b) the volumes of water that are released under the continental forearc or, alternatively, carried beyond the arc. Southern Central Chile is an ideal setting to study this effect, because other factors for the subduction zone water budget appear constant. We determine the water influx by calculating the crustal water uptake and by modeling the upper mantle serpentinization at the outer rise of the Chile Trench. The water release under forearc and arc is determined by coupling FEM thermal models of the subducting plate with stability fields of water-releasing mineral reactions for upper and lower crust and hydrated mantle. Results show that both the influx of water stored in, and the outflux of water released from upper crust, lower crust and mantle vary drastically over segment boundaries. In particular, the oldest and coldest segments carry roughly twice as much water into the subduction zone as the youngest and hottest segments, but their release flux to the forearc is only about one fourth of the latter. This high variability over a subduction zone of < 1500 km length shows that it is insufficient to consider subduction zones as uniform entities in global estimates of subduction zone fluxes. This article is protected by copyright. All rights reserved.

Rock magnetic of serpentinite seamounts in the Mariana and Izu-Bonin regions

During Leg 125, scientists drilled two serpentinite seamounts: Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. Grain densities of the serpentinized peridotites range from 2.44 to 3.02 g/cm**3. The NRM intensity of the serpentinized peridotites ranges from 0.01 to 0.59 A/m and that of serpentine sediments ranges from 0.01 to 0.43 A/m. Volume susceptibilities of serpentinized peridotites range from 0.05 * 10**-3 SI to 9.78 * 10**-3 SI and from 0.12 * 10**-3 to 4.34 * 10**-3 SI in the sediments. Koenigsberger ratios, a measure of the relative contributions of remanent vs. induced magnetization to the magnetic anomaly, vary from 0.09 to 80.93 in the serpentinites and from 0.06 to 4.74 in the sediments. The AF demagnetization behavior of the serpentinized peridotites shows that a single component of remanence (probably a chemical remanence carried by secondary magnetite) can be isolated in many samples that have a median destructive field less than 9.5 mT. Multiple remanence components are observed in other samples. Serpentine sediments exhibit similar behavior. Comparison of the AF demagnetization of saturation isothermal remanence and NRM suggests that the serpentinized peridotites contain both single-domain and multidomain magnetite particles. The variability of the magnetic properties of serpentinized peridotites reflects the complexity of magnetization acquired during serpentinization. Serpentinized peridotites may contribute to magnetic anomalies in forearc regions.

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.

Carbon geochemistry in serpentinites from and beneath the Lost City Hydrothermal Field

The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and 17863_TC values ranging from -28.7? to +2.3?. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (d13C_TOC: -28.9? to -21.5?) and variations in d13CTC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C15 to C30. Longer-chain hydrocarbons (up to C40) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C16 to n-C20 alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central dome implies fracture-controlled seawater circulation deep into the gabbroic core of the massif. Thus, our study indicates that hydrocarbons account for an important proportion of the total carbon stored in the Atlantis Massif basement and suggests that serpentinites may represent an important (as yet unidentified) reservoir for dissolved organic carbon (DOC) from seawater.

Chemistry of peridotites from ODP 109-670A

During Leg 109 of the Ocean Drilling Program, about 100 m of serpentinized peridotites were drilled on the western wall of the M.A.R. axial rift valley, 45 km south of the Kane Fracture Zone. The present study reports petrological and mineralogical data obtained from 29 small pieces of these ultramafic rocks, including about 60% serpentinized harzburgites, 26% serpentinized lherzolites, 14% serpentinized dunites, and one sample of olivine websterite. Modal analyses show that all these rocks are plagioclase-free four-phase peridotites equilibrated in the spinel lherzolite facies. The estimated average modal composition of the sample set is about 80% olivine, 14% opx, 5% cpx, and 1% spinel, that is, a cpx-poor lherzolite. The well developed porphyroclastic structures and mineralogical characteristics of these rocks indicate their affinity with the group of residual mantle tectonites, among the abyssal peridotites. Features typical of magmatic cumulates are lacking. The high contents in Al2O3 of the cpx (average 5.4%) and of the opx (average 4.3%) porphyroclasts, the low Cr# of the spinels (average 22.9%), and the rather high content in modal cpx (about 5%), indicate a moderate percentage of melting, of the order of 10%-15%. Site 670 peridotites plot close to the least depleted mantle rocks collected in the oceans in most diagrams used to define the average trend of the ocean-floor peridotites. Microprobe traverses across the cores of the exsolved opx and cpx porphyroclasts permitted the recalculation of the magmatic compositions of these pyroxenes: the 'primitive' opx were equilibrated at about 1300°C, probably at the end of the main melting episodes, whereas the 'primitive' cpx show lower equilibration temperatures, at about 1200°C, reflecting a more complex thermal history. The subsolidus evolution is well recorded, from 1200°C to about 950CC, by the exsolved pyroxenes and the olivine and spinel phases. Unusually high blocking temperatures, close to 1000°C, indicate that the peridotite body was cooled very rapidly between 1000°C and the beginning of serpentinization. Oxygen fugacities, calculated for 10 kb and at the blocking temperatures indicated by the olivine/spinel geothermometer, are close to the usual fugacities calculated in oceanic peridotites and basalts (of the order of 10**-10 to 10**-11, on the QFM buffer). Site 670 peridotites have compositions close to those of the peridotites collected in the Kane Fracture Zone area, and obviously belong to the moderately depleted mantle peridotites which characterize abyssal peridotites collected away from mantle plumes and oceanic islands. In particular, they differ from the highly residual harzburgites collected along the M.A.R. over the Azores bulge.

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.

Oxygen and sulfur isotopes of peridotite and gabbro from the Mid-Atlantic Ridge

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20'N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (~250-350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6-4.4 per mil), elevated sulfide-S, and high delta34S (up to ~2 wt% and 4.4-10.8 per mil). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated delta18O (up to 8.1 per mil), high sulfide-S (up to ~3000 ppm), and negative delta34S (to -32.1 per mil) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low delta34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-delta34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids +/- heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Magnetic properties of plutonic rocks at DSDP Leg 82 holes

Ten samples of gabbro and peridotite, with varying degrees of serpentinization, were studied by magnetic techniques and reflected light microscopy. Evidence from these methods suggests that the natural remanent magnetization is primarily of chemical origin. It is generally weak for the gabbros and much stronger for the peridotites. This difference is offset by the fact that the peridotites have generally lower magnetic stability and Koenigsberger ratios. There is a considerable variation in both magnetic parameters and petrology even among closely spaced samples, which suggests that some combination of source heterogeneity and tectonic mixing was involved in the production of these rocks. However, the small number of samples makes this conclusion tentative. There may also have been significant postemplacement alteration involved. All samples show a significant anisotropy of weak field susceptibility that appears to be related to deformation. This anisotropy may be useful in defining petrofabrics.