Geochemical composition and crystallization temperatures of ODP Hole 176-735B gabbroic rocks

The transition from magmatic crystallization to high-temperature metamorphism in deep magma chambers (or lenses) beneath spreading ridges has not been fully described. High-temperature microscopic veins found in olivine gabbros, recovered from Ocean Drilling Program Hole 735B on the Southwest Indian Ridge during Leg 176, yield information on the magmatic-hydrothermal transition beneath spreading ridges. The microscopic veins are composed of high-temperature minerals, (i.e., clinopyroxene, orthopyroxene, brown amphibole, and plagioclase). An important feature of these veins is the 'along-vein variation' in mineralogy, which is correlated with the magmatic minerals that they penetrate. Within grains of magmatic plagioclase, the veins are composed of less calcic plagioclase. In grains of olivine, the veins are composed of orthopyroxene + brown amphibole + plagioclase. In clinopyroxene grains, the veins consist of plagioclase + brown amphibole and are accompanied by an intergrowth of brown amphibole + orthopyroxene. The mode of occurrence of the veins cannot be explained if these veins were crystallized from silicate melts. Consequently, these veins and nearby intergrowths were most likely formed by the reaction of magmatic minerals with fluid phases under the conditions of low fluid/rock ratios. Very similar intergrowths of brown amphibole + orthopyroxene are observed in clinopyroxene grains with 'interfingering' textures. It is believed, in general, that the penetration of seawater does not predate the ductile deformation within Layer 3 gabbros of the slow-spreading ridges. If this is the case, the fluid responsible for the veins did not originate from seawater because the formation of the veins and the interfingering textures preceded ductile deformation and, perhaps, complete solidification of the gabbroic crystal mush. It has been proposed, based on fluid inclusion data, that the exsolution of fluid from the latest-stage magma took place at temperatures >700°C in the slow-spreading Mid-Atlantic Ridge at the Kane Fracture Zone (MARK) area. No obvious mineralogical evidence, however, has been found for these magmatic fluids. The calculated temperatures for the veins and nearby intergrowths found in Hole 735B gabbros are up to 1000°C, and these veins are the most plausible candidate for the mineralogical expression of the migrating magmatic fluids.

Chemistry of gabbroic rocks of ODP Hole 118-735B

We present results of a microprobe investigation of fresh and least-deformed and metamorphosed gabbroic rocks from Leg 118, Hole 735B, drilled on the east side of the Atlantis II Fracture Zone, Southwest Indian Ridge. This rock collection comprises cumulates ranging from troctolites to olivine-gabbro and olivine-gabbronorite to ilmenite-rich ferrogabbros and ferrogabbronorites. As expected, the mineral chemistry is variable and considerably expands the usual oceanic reference spectrum. Olivine, plagioclase, and clinopyroxene are present in all the studied samples. Orthopyroxene and ilmenite, although not rare, are not ubiquitous. Olivine compositions range from Fo85 to Fo30, while plagioclase compositions vary from An70 to An27. Mg/(Mg + Fe2+) of clinopyroxene (mostly diopside to augite) varies from 0.88 to 0.54. Mg/(Mg + Fe2+) of orthopyroxene varies from 0.84 to 0.50. These minerals are not significantly zoned. All mineralogical data indicate that fractional crystallization is an important factor for the formation of cumulates. However, sharp contacts, interpreted as layering boundaries or intrusion margins, suggest polycyclic fractionation of several magma batches of limited volumes. Calculated compositions of magmas in equilibrium with the most magnesian mineral samples at the bottom of the hole represent fractionated liquids through separation of olivine, plagioclase, and clinopyroxene at moderate to low pressures (less than 9 kb). Crystallization of orthopyroxene and ilmenite occurs in the most differentiated liquids. Mixing of magmas having various compositions before entering the cumulate zone is another mechanism necessary to explain extremely differentiated iron-rich gabbros formed in this slow-spreading ridge environment.

Geochemistry at DSDP Leg 82 Holes

DSDP Leg 82 drilled nine sites to the southwest of the Azores Islands on the west flank of the Mid-Atlantic Ridge (MAR) in an attempt to determine the temporal and spatial evolution of the Azores "hot-spot" activity. The chemistry of the basalts recovered during Leg 82 is extremely varied: in Holes 558 and 561, both enriched (E-type: CeN/YbN = 1.5 to 2.7; Zr/Nb = 4.5 to 9.6) and depleted (or normal-N-type: CeN/YbN = 0.6 to 0.8; Zr/Nb > 20) mid-ocean ridge basalts (MORB) occur as intercalated lava flows. To the north of the Hayes Fracture Zone, there is little apparent systematic relationship between basalt chemistry and geographic position. However, to the south of the Hayes Fracture Zone, the chemical character of the basalts (N-type MORB) is more uniform. The coexistence of both E-type and N-type MORB in one hole may be explicable in terms of either complex melting/ fractionation processes during basalt genesis or chemically heterogeneous mantle sources. Significant variation in the ratios of strongly incompatible trace elements (e.g., La/Ta; Th/Ta) in the basalts of Holes 558 and 561 are not easily explicable by processes such as dynamic partial melting or open system crystal fractionation. Rather, the trace element data require that the basalts are ultimately derived from at least two chemically distinct mantle sources. The results from Leg 82 are equivocal in terms of the evolution of the Azores "hot spot," but would appear not to be compatible with a simple model of E-type MORB magmatism associated with upwelling mantle "blobs." Models that invoke a locally chemically heterogeneous mantle are best able to account for the small-scale variation in basalt chemistry.

Sulfur contents and S, C and O isotopic compositions in serpentinized peridotites at ODP Site 153-920

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated d34S_sulfide (3.7 to 12.7?). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high d34S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (~400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ~300°C. Serpentinization produces highly reducing conditions and significant amounts of H2 and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in 13C (up to 4.5?) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 mln ton seawater S per year. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.

Mineral composition and major element oxides of gabbros from ODP Hole 179-1105A, southwest Indian Ridge

Hole 1105A penetrated 158 m of gabbros at a site offset 1.3 km east-northeast from Hole 735B on the Atlantis Bank near the Atlantis II Fracture Zone. A total of 118 m of dominantly medium- to coarse-grained intercalated Fe-Ti oxide gabbro and olivine gabbro was recovered from Hole 1105A that shows many petrographic features similar to those recovered from the upper part of Hole 735B. The main rock types are distinguished based on the constituent cumulus phases, with the most primitive gabbros consisting of olivine, plagioclase, and clinopyroxene. The inferred crystallization order is subsequently Fe-Ti oxides (ilmenite and titanomagnetite), followed by orthopyroxene, then apatite, and finally biotite. Orthopyroxene appears to replace olivine in a narrow middle interval. The magmatic evolution is likewise reflected in the mineral compositions. Plagioclase varies from An66 to An28. Olivine varies from Fo78 to Fo35. The gap in olivine crystallization occurs between Fo46 and Fo40 and coincides approximately with the appearance of orthopyroxene (~En50). The clinopyroxenes show large compositional variation in Mg/(Mg + Fe total) from 0.84 to 0.51. The nonquadrilateral cations of clinopyroxene similarly show large variations with Ti increasing for the olivine gabbros and decreasing for the Fe-Ti oxide gabbros with the decrease in Mg/(Mg + Fe total). The apatites are mainly flourapatites. The compositional variation in the gabbros is interpreted as a comagmatic suite resulting from fractional crystallization. Pyroxene geothermometry suggests equilibration temperatures from 1100°C and below. The coexisting Fe-Ti oxide minerals indicate subsolidus equilibration temperatures from 900°C for olivine gabbros to 700°C for the most evolved apatite-bearing gabbros. The cryptic variation in the olivine gabbros defines two or three lenses, 40 to 60 m thick, each characterized by a distinct convex zoning with a lower segment indicating upward reverse fractionation, a central maximum, and an upper segment showing normal fractionation. The Fe-Ti oxide gabbros show cryptic variations independent of the host olivine gabbros and reveal a systematic upward normal fractionation trend transgressing host olivine gabbro boundaries. Forward fractional crystallization modeling, using a likely parental magma composition from the Atlantis II Fracture Zone (MgO = 7.2 wt%; Mg/[Mg + Fe2+] = 0.62), closely matches the compositions of coexisting olivine, plagioclase, and clinopyroxene. This modeling suggests cosaturation of olivine, plagioclase, and clinopyroxene from 1155°C and the addition of Fe-Ti oxides from 1100°C. The liquid line of descent initially shows increasing FeO with moderately increasing SiO2. After saturation of Fe-Ti oxides, the liquid strongly decreases in FeO and TiO2 and increases in SiO2, reaching dacitic compositions at ~10% liquid remaining. The calculations indicate that formation of olivine gabbros can be accounted for by <65% fractionation and that only the residual 35% liquid was saturated in Fe-Ti oxides. The modeling of the solid fractionation products shows that both the olivine gabbro and the Fe-Ti oxide gabbros contain very small amounts of trapped liquid (<5%). The implications are that the gabbros represent crystal mush that originated in a recharging and tapping subaxial chamber. Compaction and upward melt migration in the crystal mush appear to have been terminated with relatively large amounts of interstitial liquid remaining in the upper parts of the cumulate mush. This termination may have been caused by tectonic disturbances, uplift, and associated withdrawal of magma into the subaxial dike and sill system. Prolonged compaction and cooling of the trapped melt in the mush formed small differentiated bodies and lenses by pressure release migration and crystallization along syntectonic channels. This resulted in differentiation products along lateral and vertical channelways in the host gabbro that vary from olivine gabbro, to Fe-Ti oxide gabbro, gabbronorite, and apatite gabbros and show large compositional variations independent of the host olivine gabbros.

Minerals and geochemistry at DSDP Hole 62-466

Alkali-basalt clasts in Upper Cretaceous sediments from Site 466 on southern Hess Rise suggest that parts of Hess Rise were constructed by off-ridge volcanic activity. Apparently, tectonic adjustments at Hess Rise occurred during the Late Cretaceous (Campanian-Maastrichtian), when parts of the original volcanic pedestal were uplifted and provided source rocks for the clasts. Synchronous volcanism may have occurred. Causes for the Late Cretaceous tectonic adjustments (and volcanism?) are not known, but they may be related to intraplate movement along the Mendocino Fracture Zone.

Chemistry of minerals of ODP Hole 103-637A peridotites

The Galicia margin lies northwest of the Iberian Peninsula and is a passive ocean margin with thin sedimentary cover. Altered peridotite was recovered from ODP Site 637, on the north-trending ridge at the western edge of the margin, near the oceanic/continental crust boundary. The altered ultramafics were originally clinopyroxene-rich upper mantle harzburgites and are now extensively serpentinized (>85%) and cut by very late-stage carbonate veins. Despite pervasive late, low-temperature alteration, evidence of early, high-temperature alteration remains. Alteration is apparent as (1) amphibole rims on clinopyroxene (>800°C), (2) hornblende + tremolite (450° to 800°C), (3) breakdown of hornblende to form tremolite + chlorite (<450°C), (4) zoned Cr-spinels, (5) hydration of orthopyroxene and olivine to serpentine, (6) serpentine veins, (7) replacement of pyroxene and olivine by calcite, and (8) calcite veins and vugs. Both the relict igneous and the high-temperature alteration minerals (amphiboles) show evidence of brittle deformation. Subsequent low-temperature alteration veins and minerals are deformed only in faulted and brecciated zones. This textural evidence suggests that the low-temperature alteration occurred after emplacement of the ultramafics at the surface. Serpentine fills tension fractures in orthopyroxene, and both serpentine and calcite fill tension cracks in olivine. The high-temperature alterations in these samples are similar to those found in oceanic fracture zone and ophiolite ultramafics. This widespread occurrence of high-temperature alteration suggests that hot fluids were pervasive in these ultramafic blocks. Localization of high-temperature alteration close to large carbonate veins suggests channelization of the late, low-temperature fluids. Earlier hydrations (e.g., high-temperature alterations and serpentinization) were pervasive.

Geochemistry of serpentinized peridotites from ODP Holes 207-1272A and 207-1274A

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.

Composition and alteration of volcanic rocks of ODP Hole 119-738C

During ODP Leg 119 one basement hole was drilled at Site 738, on the Southern Kerguelen Plateau. The 38.2 m of basement rocks drilled comprises three basaltic aa-lava flows with basal and top breccias, overlain by Turanian marine carbonates. Site 738 basalts probably erupted near a fracture zone, and were emplaced during the plateau-forming stage of Kerguelen Plateau evolution under quiet, subaerial to shallow water conditions. The basalts are T-MORB, chemically resembling Mesozoic continental flood basalts of the southern hemisphere. Two slightly different magma batches are distinguished by Fe, Ti, Al, Zr, and REE concentrations. Prior to eruption, the magmas had undergone significant olivine and some clinopyroxene fractionation. Incompatible and immobile trace element concentrations and ratios point to a veined upper mantle source, where a refractory mineral assemblage retains Nb, Ta, and the HREE. The basaltic melts derived from this regionally veined, enriched upper mantle have high LREE, and especially Ba and Th concentrations and bear the DUPAL isotopic signature gained from deep- seated, recycled, old oceanic(?) crust. A saponite-celadonite secondary mineral assemblage confines the alteration temperature to <170°C. Alteration is accompanied by net gains of H2O, CO2, K2O, and Rb, higher oxidation, minor Na2O, SiO2 gains, and losses of V and CaO. Released Ca, together with Ca from seawater, precipitated as calcite in veins and vesicles, plumbed the circulation system and terminated the rock/open seawater interaction.

Geochemistry at DSDP Leg 82 Holes

The nine holes (556-564) drilled during DSDP Leg 82 in a region west and southwest of the Azores Platform (Fig. 1) exhibit a wide variety of chemical compositions that indicate a complex petrogenetic history involving crystal fractionation, magma mixing, complex melting, and mantle heterogeneity. The major element chemistry of each hole except Hole 557 is typical of mid-ocean ridge basalts (MORBs), whereas the trace element and rare earth element (REE) abundances and ratios are more variable, and show that both depleted Type I and enriched Type II basalts have been erupted in the region. Hole 556 (30-34 Ma), located near a flow line through the Azores Triple Junction, contains typically depleted basalts, whereas Hole 557 (18 Ma), located near the same flow line but closer to the Azores Platform, is a highly enriched FeTi basalt, indicating that the Azores hot-spot anomaly has existed in its present configuration for at least 18 Ma, but less than 30-34 Ma. Hole 558 (34-37 Ma), located near a flow line through the FAMOUS and Leg 37 sites, includes both Type I and II basalts. Although the differences in Zr/Nb and light REE/heavy REE ratios imply different mantle sources, the (La/Ce)ch (>1) and Nd isotopic ratios are almost the same, suggesting that the complex melting and pervasive, small-scale mantle heterogeneity may account for the variations in trace element and REE ratios observed in Hole 558 (and FAMOUS sites). Farther south, Hole 559 (34-37 Ma), contains enriched Type II basalts, whereas Hole 561 (14-17 Ma), located further east near the same flow line, contains Type I and II basalts. In this case, the (La/Ce)ch and Nd isotopic ratios are different, indicating two distinct mantle sources. Again, the existence along the same flow line of two holes exhibiting such different chemistry suggests that mantle heterogeneity may exist on a more pervasive and transient smaller scale. (Hole 560 was not sampled for this study because the single basalt clast recovered was used for shipboard analysis.) All of the remaining three holes (562, 563, 564), located along a flow line about 100 km south of the Hayes Fracture Zone (33°N), contain only depleted Type I basalts. The contrast in chemical compositions suggests that the Hayes Fracture Zone may act as a "domain" boundary between an area of fairly homogeneous, depleted Type I basalts to the south (Holes 562-564) and a region of complex, highly variable basalts to the north near the Azores hot-spot anomaly (Holes 556-561).