Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

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.

Mineralogy and geochemistry at DSDP Leg 64 Holes

At DSDP Site 477, late Quaternary diatomaceous muds and delta-derived silty-sand turbidites at 2000 meters water depth have been extensively and progressively altered by a deep-seated heat source beneath a sill. Bulk petrologic and microprobe analyses have identified a crudely zoned paragenesis within 260 meters sub-bottom which ranges from unaltered to slightly altered oozes (0-50 m), anhydrite-dolomite claystones (105-125 m), illite-chlorite-pyrite claystones (125-140 m), chlorite-pyrite-calcite-carbonaceous claystones with traces of K-feldspar, albite, epidote (140-190 m), and chlorite-epidote-quartz-albite-pyrrhotite-sphene sandstone (190-260 m). Several petrologic features suggest rapid processes of ocean floor metamorphism: (1) friable and porous textures, (2) abundant relict grains with overgrowths, (3) idiomorphic habits on epidotes, feldspars, and quartz, and (4) a steep gradient in levels of alteration. Many aspects of this hydrothermal assemblage are similar to hydrothermally metamorphosed sandstones of the Cerro Prieto, Mexico, geothermal area.

Geochemistry of tephra from the Taupo Volcanic Zone

The Taupo Volcanic Zone (TVZ), central North Island, New Zealand, is the most frequently active Quaternary rhyolitic system in the world. Silicic tephras recovered from Ocean Drilling Programme Site 1123 (41°47.16'S, 171°29.94'W; 3290 m water depth) in the southwest Pacific Ocean provide a well-dated record of explosive TVZ volcanism since ~1.65 Ma. We present major, minor and trace element data for 70 Quaternary tephra layers from Site 1123 determined by electron probe microanalysis (1314 analyses) and laser ablation inductively coupled plasma mass spectrometry (654 analyses). Trace element data allow for the discrimination of different tephras with similar major element chemistries and the establishment of isochronous tie-lines between three sediment cores (1123A, 1123B and 1123C) recovered from Site 1123. These tephra tie-lines are used to evaluate the stratigraphy and orbitally tuned stable isotope age model of the Site 1123 composite record. Trace element fingerprinting of tephras identifies ~4.5 m and ~7.9 m thick sections of repeated sediments in 1123A (49.0-53.5 mbsf [metres below seafloor]) and 1123C (48.1-56.0 mbsf), respectively. These previously unrecognised repeated sections have resulted in significant errors in the Site 1123 composite stratigraphy and age model for the interval 1.15-1.38 Ma and can explain the poor correspondence between d18O profiles for Site 1123 and Site 849 (equatorial Pacific) during this interval. The revised composite stratigraphy for Site 1123 shows that the 70 tephra layers, when correlated between cores, correspond to ~37-38 individual eruptive events (tephras), 7 of which can be correlated to onshore TVZ deposits. The frequency of large-volume TVZ-derived silicic eruptions, as recorded by the deposition of tephras at Site 1123, has not been uniform through time. Rather it has been typified by short periods (25-50 ka) of intense activity bracketed by longer periods (100-130 ka) of quiescence. The most active period (at least 1 event per 7 ka) occurred between ~1.53 and 1.66 Ma, corresponding to the first ~130 ka of TVZ rhyolitic magmatism. Since 1.2 Ma, ~80% of tephras preserved at Site 1123 and the more proximal Site 1124 were erupted and deposited during glacial periods. This feature may reflect either enhanced atmospheric transport of volcanic ash to these sites (up to 1000 km from source) during glacial conditions or, more speculatively, that these events are triggered by changes in crustal stress accumulation associated with large amplitude sea-level changes. Only 8 of the ~37-38 Site 1123 tephra units (~20%) can be found in all three cores, and 22 tephra units (~60%) are only present in one of the three cores. Whether a tephra is preserved in all three cores does not have any direct relationship to eruptive volume. Instead it is postulated that tephra preservation at Site 1123 is 'patchy' and influenced by the vigorous nature of their deposition to the deep ocean floor as vertical density currents. At this site, at least 5 cores would need to have been drilled within a proximity of 10's to 100's of metres of each other to yield a >99% chance of recovering all the silicic tephras deposited on the ocean surface above it in the past 1.65 Ma.

Geochemistry of glass shards in the volcanic ash layers of the Izu-Bonin Arc

To examine the processes and histories of arc volcanism and of volcanism associated with backarc rifting. 130 samples containing igneous glass shards were taken from the Plioccne-Quatemai^ succession on the rift Hank (Site 788) and the Quaternary fill in the basin fill of the Sumisu Rift (Sites 790 and 791). These samples were subsequently analyzed at the University of Illinois at Chicago and Shizuoka University. The oxides determined by electron probe do not account for the total weight of the material; differences between summed oxides and 100% arise from the water contents, probably augmented by minor losses thai result from alkali vaporization during analysis. Weight losses in colorless glasses are up to 9%; those in brown glasses (dacitcs to basalts) arc no more than 4.5%; shards from the rift-flank (possibly caused by prolonged proximity to ihc scafloor) generally have higher values than those from the rift-basin fill How much of the lost water is magmatic, and how much is hydrated is uncertain; however, although the shards absorb potassium, calcium, and magnesium during hydration in the deep sea, they do so only to a minor extent that does not significantly alter their major element compositions. Therefore, the electron-probe results are useful in evaluating the magmatism recorded by the shards. Pre- and syn-rift Izu-Bonin volcanism were overwhelmingly dominated by rhyolile explosions, demonstrating that island arcs may experience significant silicic volcanism in addition to the extensive basaltic and basaltic andestic activity, documented in many arcs since the 1970s, that occurs in conjunction with the andesitic volcanism formerly thought to be dominant. Andesitic eruptions also occurred before rifting, but the andesitic component in our samples is minor. All the pre- and syn-rift rhyolites and andesites belong to the low-alkali island-arc tholeiitic suite, and contrast markedly with the alkali products of Holocene volcanism on the northernmost Mariana Arc that have been attributed to nascent rifting. The Quaternary dacites and andesites atop the rift flank and in the rift-basin fill are more potassic than those of Pliocene age, as a result of assimilation from the upper arc crust, or from variations in degrees of partial melting of the source magmas, or from metasomatic fluids. All the glass layers from the rift-flank samples belong to low-K arc-tholeiitic suites. Half of those in the Pliocene succession are exclusively rhyolitic: the others contain minor admixtures of dacite and andesite, or andesite and either basaltic andesite or basalt. In Contrast, the Quaternary (syn-rift) volcaniclastics atop the rift-flank lack basalt and basaltic andesite shards. These youngest sediments of the rift flank show close compositional affinities with five thick layers of coarse, rhyolitic pumice deposits in the basin fill, the two oldest more silicic than the younger ones. The coarse layers, and most thin ash layers that occur in hemipelagites below and intercalated between them, are low-K rhyolites and therefore probably came from sources in the arc. However, several thin rhyolitic ash beds in the hemipelagites are abnormally enriched in potassium and must have been provided by more distal sources, most likely to the west in Japan. Remarkably, the Pliocene-Pleistocene geochemistry of the volcanic front does not appear to have been influenced by the syn-rift basaltic volcanism only a few kilometers away. Rare, thin layers of basaltic ash near the bases of the rift-basin successions are not derived from the arc. They deviate strongly from trends that the arc-derived glasses display on oxide-oxide plots, and show close affinities to the basalts empted all over the Sumisu Rift during rifting. These basalts, and the basaltic ashes in the basal rift-basin fill, arc compositionally similar to those erupted from mature backarc basins elsewhere.

Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were investigated by organic geochemical methods, including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

Geochemistry of oceanic crust of the North Atlantic

87Sr/a6Sr ratios, Sr, K, Rb and Cs contents and the petrology of basalts and secondary phases recovered from deep basement drilling at DSDP Sites 332B, 417A, 417D and 418A show that the oceanic crust alters in four distinct stages characterized by formation of palagonite, smectite and calcite (Stages I, II and III, respectively). Stage IV represents the final compaction of the crust, including a dehydration of the crust without major chemical changes. Isotopic age determinations by Hart and Staudigel (1978, doi:10.1029/GL005i012p01009) and Richardson et al. (doi:10.1029/JB085iB12p07195), show that, at least for Atlantic-type crustal regimes, Stage I and II last for a maximum of 3 m.y., and Stage III lasts beyond Stage I and II, but is probably completed in significantly less than 10 m.y. Stage IV is long-lived and may still be active at 100 m.y. Stages I and II, the phase of halmyrolysis, include geochemically significant interactions between seawater and basalt for the upper 500 m of layer II and involve volumes of seawater containing a large basaltic component. Stage III solutions show evidence of less seawater-basalt interaction, at least to depths of 500 m; calcites deposited from these solutions have Sr isotopic ratios close to seawater values; but also have very low Sr/Ca ratios indicating a large basalt Ca component in the solutions. Smectite formation is the result of the interaction of seawater and basalt. The initial 87Sr/a6Sr ratios of smectites represent the Sr isotopic composition of the solution when the smectite is being formed. Thereafter, alkalies may be continuously added to interlayer positions in the smectite in order of decreasing hydration energy (Cs is more enriched than Rb, Rb more than K). The later-formed carbonates have very low alkali concentrations, and 87Sr/86Sr ratios identical to contemporaneous seawater. Therefore, since the alkali concentrations in a whole rock sample are affected by different alteration processes, the alkali concentrations alone are not reliable indicators of the degree of alteration.

Geochemistry of Miocene Alborán Basin volcanism

We present new major and trace element and O-Sr-Nd-isotope data for igneous rocks from the western Mediterranean Alborán Sea, collected during the METEOR 51/1 cruise, and for high-grade schists and gneisses from the continental Alborán basement, drilled during the Ocean Drilling Programme (ODP Leg 161, Site 976). The geochemical data allow a detailed examination of crustal and mantle processes involved in the petrogenesis of the lavas and for the first time reveal a zonation of the Miocene Alborán Sea volcanism: (1) a keel-shaped area of LREE-depleted (mainly tholeiitic series) lavas in the central Alborán Sea, generated by high degrees of partial melting of a depleted mantle source and involving hydrous fluids from subducted marine sediments, that is surrounded by (2) a horseshoe-shaped zone with LREE-enriched (mainly calc-alkaline series) lavas subparallel to the arcuate Betic-Gibraltar-Rif mountain belt. We propose that the geochemical zonation of the Miocene Alborán Basin volcanism results from eastward subduction of Tethys oceanic lithosphere coupled with increasing lithospheric thickness between the central Alborán Sea and the continental margins of Iberia and Africa.

Geochemistry of bulk sediment from the Cape Basin

A technique for onsite application of X-ray fluorescence (XRF) spectrometry to samples from sediment cores aboard a research vessel was developed and tested. The method is sufficiently simple, precise, and fast to be used routinely for high-resolution analyses of depth profiles as well as surface samples. Analyses were performed with the compact high-performance energy-dispersive polarisation X-ray fluorescence (EDPXRF) analyser Spectro Xepos. Contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, K, Sr, Ba, Rb, Cu, Ni, Zn, P, S, Cl and Br were simultaneously determined on 200-225 samples of each core within 24 h of recovery. This study presents a description of the employed shipboard preparation and analysis technique, along with some example data. We show land-based datasets that support our decisions to use powder samples and to reduce the original measuring time for onboard analyses. We demonstrate how well the results from shipboard measurements for the various elements compare with the land-based findings. The onboard geochemical data enabled us to establish an element stratigraphy already during the cruise. Correlation of iron, calcium and silicon enrichment trends with an older reference core provided an age model for the newly retrieved cores. The Spectro Xepos instrument performed without any analytical and technical difficulties which could have been caused by rougher weather conditions or continuous movement and vibration of the research vessel. By now, this XRF technique has been applied during three RV Meteor cruises to approximately 5,000 Late Quaternary sediment samples from altogether 23 gravity cores, 25 multicorer cores and two box cores from the eastern South Atlantic off South Africa/Namibia and the eastern Atlantic off NW Africa.

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.

(Table 2) Geochemistry of K-feldspars and associated plagioclase phenocrysts and rims at DSDP Legs 69, 52, 51 and 19

Basalts from some holes of the Deep Sea Drilling Project contain secondary K-feldspar which forms pseudomorphs after calcic (>76% An) Plagioclase cores, whereas Plagioclase of rims and microlites (68-74% An) remains unaltered. In basalts of Hole 504B two such grains with relics of Plagioclase in the central parts of phenocysts were recovered. The composition of the Plagioclase rims and of non-replaced phenocrysts is An79-81; the composition of relics is An83. The An and Ab contents of the K-feldspar is higher than in K-feldspar from altered basalt in Hole 418A in the Atlantic Ocean near the Bermuda Rise. Replacement of plagioclases by K-feldspar evidently is caused by oxygen-rich nearbottom sea water penetrating into basalts. The temperature interval of K-feldspathization is probably in the range 30 to 80°C, more-calcic Plagioclase being replaced by K-feldspar at higher temperatures.