Geochemical composition and crystallization conditions of melts from the Mid Atlantic Ridge near Ascension Island (7-11°S)

Phase equilibria simulations were performed on naturally quenched basaltic glasses to determine crystallization conditions prior to eruption of magmas at the Mid-Atlantic Ridge (MAR) east of Ascension Island (7°11°S).The results indicate that midocean ridge basalt (MORB) magmas beneath different segments of the MAR have crystallized over a wide range of pressures (100-900MPa). However, each segment seems to have a specific crystallization history. Nearly isobaric crystallization conditions (100-300MPa) were obtained for the geochemically enriched MORB magmas of the central segments, whereas normal (N)-MORB magmas of the bounding segments are characterized by polybaric crystallization conditions (200-900MPa). In addition, our results demonstrate close to anhydrous crystallization conditions of N-MORBs, whereas geochemically enriched MORBs were successfully modeled in the presence of 0.4-1wt% H2O in the parental melts.These estimates are in agreement with direct (Fourier transform IR) measurements of H2O abundances in basaltic glasses and melt inclusions for selected samples. Water contents determined in the parental melts are in the range 0.04-0.09 and 0.30-0.55 wt% H2O for depleted and enriched MORBs, respectively. Our results are in general agreement (within ±200MPa) with previous approaches used to evaluate pressure estimates in MORB. However, the determination of pre-eruptive conditions of MORBs, including temperature and water content in addition to pressure, requires the improvement of magma crystallization models to simulate liquid lines of descent in the presence of small amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation

Petrology and origin of basalts at DSDP Hole 66-487

The volcanism of Central America, according to current theory (Pichler and Weyl, 1973; Stoiber and Carr, 1974; Hey, 1977), is related to the subduction of the Cocos Plate under the North American lithospheric plate and the melting of ocean crust material in the subduction zone (Green and Ringwood, 1968; Dickinson, 1970, Fitton, 1971). Since Cocos Plate subduction occurs at the rate of more than 7 cm/y. (Hey et al., 1977), basalts underlying upper Miocene sediments of the Middle America Trench outer slope, penetrated in Hole 487 (Fig. 1) during Leg 66 (Moore et al., 1979), should have formed far from their present position if current theory is accurate. Present manifestations of basaltic magmatism in adjacent areas of the Pacific derive from the axial part of the East Pacific Rise, the Galapagos spreading center, and transform fracture zones. The question arises: Are there analogs of the Middle America Trench basalts among magmatic cock associated with these modern features, or do the trench basalts have some other origin?

Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

Chemistry of peridotites of ODP Hole 103-637A

A ridge of peridotite was drilled off of the Galicia margin (Hole 637A) during ODP Leg 103. The ridge is located at the approximate boundary between oceanic and continental crust. This setting is of interest because the peridotite may be representative of upwelling upper mantle beneath an incipient ocean basin. The composition of the Galicia margin peridotite is compared with those of other North Atlantic peridotites. Hole 637A ultramafic lithologies include clinopyroxene-rich spinel harzburgite and lherzolite, as well as plagioclase-bearing peridotites. Variations in mineral modal abundances and mineral compositions are observed but are not systematic. The peridotites are broadly similar in composition to other peridotites recovered from ocean basins, but the mineral compositions and abundances suggest that they are less depleted in basaltic components than other North Atlantic peridotites by about 10%. In particular, the peridotites are enriched in the magmaphilic elements Na, Al, and Ti, as compared with other abyssal peridotites. The high abundances of these elements suggest that the Hole 637A peridotites had experienced, at most, very small amounts of partial melting prior to their emplacement. The presence of plagioclase rimming spinel in some samples suggests that the peridotite last equilibrated at about 9 kbar, near the transition between plagioclase- and spinel-peridotite stability fields. Temperatures of equilibration of the peridotite are calculated as 900°-1100°C. The relatively undepleted composition of the peridotite indicates that it was emplaced at a shallow mantle level under a relatively cool thermal regime and cooled below solidus temperatures without having participated in any significant partial melting and basalt production. This is consistent with the emplacement of the peridotite during incipient rifting of the ocean basin, before a true spreading center was established.

Composition of Cretaceous basalts from DSDP Hole 16-163

Basalt underlying early Campanian chalk at Deep Sea Drilling Project (DSDP) Site 163 is divided into seven extrusive cooling units bounded by glassy margins. The margins have dips of 15° to 70°, suggestive of pillow flows rather than tabular flows. The margins are fresh sideromelane (glass) grading inward to opaque and reddish-brown globules containing microcrystalline material with radial, undulose extinction. Relative to adjacent sideromelane, the reddish-brown globules are enriched in sodium and calcium, whereas the opaque globules are depleted in these elements and enriched in iron and magnesium. It appears that basalt just inside the pillow margins has differentiated in place into globules of two distinct compositions. This globule zone grades inward to less rapidly cooled pyroxene varioles and intergrowths of plagioclase and opaque minerals. In the center of the thicker cooling units, the texture is diabasic. Alteration and calcite vein abundance are greatest at pillow margins and decrease inward; the interior of the thickest cooling unit is only slightly altered, and calcite veins are absent. Chemical analysis of whole rock by atomic absorption spectrophotometry, and of sideromelane by electron microprobe, indicates that the rock is a slightly weathered tholeiite. The atomic absorption analyses, except the one nearest the top of the basalt, are relatively uniform and similar to the sideromelane microprobe analyses, including those near the top of the basalt. This suggests that deep penetration is not necessary to get through the severely altered layer at the basalt surface, and that within this altered layer, analyses of sideromelane may be more representative of crustal composition than analyses of whole rock.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Composition of minerals at DSDP Leg 67 Holes

During the Leg 67 drilling of the Middle America Trench (Guatemala transect), basalts were reached in Hole 495, 22 km seaward from the Trench axis, in Holes 500 and 500B at the foot of the continental slope, and at four other holes not sampled for this study. Only olivine-plagioclase phyric basalts are present in Hole 495, whereas in Holes 500 and 500B these rocks are associated with plagioclase phyric high-alumina basalts. As illustrated by the content of TiO2, Al2O3, and the K2O/K2O + Na2O ratio, some of the Middle America Trench basalts do not differ essentially from oceanic tholeiites, but others have a composition transitional to island-arc tholeiitic basalts. It is suggested that basalts transitional from oceanic to island-arc tholeiites are typical manifestations of magmatism in zones of convergence of the oceanic and continental or island-arc crust.

Minerals of bulk samples and clay fraction at DSDP Leg 80 Holes

At the request of the Leg 80 scientific party, selected samples of Cretaceous age were processed by X-ray diffraction at the mineralogy laboratories at the Ecole des Mines (Albian to Late Cretaceous samples) and at the Institut de Géologie at Dijon (Barremian samples). The results were used in developing the lithostratigraphy and sedimentology discussed in this volume by Rat et al. 1985 (doi:10.2973/dsdp.proc.80.140.1985) in their study of Barremian-Albian paleoenvironment, by Graciansky and Gillot in their study of Albian and Cenomanian limestones, and by Graciansky and Bourbon in their paleoenvironmental reconstructions for the Late Cretaceous chalks.

Tab. 1: Mineralogical composition and chemical analyses of major and trace elements of Ameghino Formation rocks

As a result of a petrographical, mineralogical and geochemical characterization of the Ameghino Formation mudstones (Upper Jurassic- Lower Cretaceous, Antarctic Peninsula), "epiclastic" radiolaria-rich and mixed (radiolaria-rich + tuff) mudstone types were recognized. Contents of clastic material in the mudstones generally increase with younger paleontological age, but local exceptions to this trend have been found. The anoxic environment of the lower part of the sequence changes to more oxidizing conditions towards the top, in transition to the Hauterivian - Barrêmian conglomerates. Element to element correlations show good agreement with the normal differentiation trends of volcanic (andesite-rhyolite) rocks, suggesting that the overall sequence is mainly volcanic in origin with various grade of reworking. For example, the radiolaria-rich mudstone matrix could have been originated from very fine touffaceous suspensions deposited very slowly after the main fall of the tuffs. However, in the upper part of the sequence, some epiclastic supply is revealed by petrographic evidence and illite crystallinity index. The clay mineral association (illite, chlorite and illite-smectite mixed layers) is mainly of diagenetic origin in the stratigraphically lower sections. Low percentages of expandable layers in the illite-smectite mixed layers, as well as the general mineralogical association, suggest a late mesodiagenetic stage, and together with geological evidence, a relatively deep burial (> 1000 m - probably > 2500 m) and temperatures exceeding 100°C.

(Table T1) Geochemical composition of xenoliths and host rocks from ODP Hole 193-1188A and dredge haul MD-138, PACMANUS field

A number of intensely altered, dark xenoliths with palimpsest quench textures were recorded within altered dacitic host rocks at Site 1189 (Roman Ruins, PACMANUS) during Ocean Drilling Program (ODP) Leg 193. Several of these displayed puzzling marginal fringes, apparently of altered plagioclase with variolitic texture, protruding into adjacent host rocks. Despite their alteration, the xenoliths were interpreted as fragments of rapidly chilled, possibly olivine-bearing basalts incorporated into the dacitic magmas either within the crustal plumbing system or during eruption at the seafloor (figures F15, F16, F17, F42, and F43 in Shipboard Scientific Party, 2002, doi:10.2973/odp.proc.ir.193.104.2002). An additional example of formerly spinifex-textured xenolith, the first from Site 1188 (Snowcap) and the first from the upper cristobalite-bearing zone of alteration, has been revealed by postcruise studies. Furthermore, a pristine sample of the parent lithology has been found within a dredge haul (MD-138, Binatang-2000 Cruise of Franklin; 3°43.60'S, 151°40.35'E, 1688 meters below sea level) from the Satanic Mills hydrothermal field at PACMANUS, near ODP Site 1191. The purpose of this report is to document these discoveries and thereby to confirm and build on shipboard interpretations. To my knowledge, similar xenoliths have never before been found in modern island arc or backarc volcanic sequences. Spinifex textures are most common in Archean komatiites, some of which are bimodally associated with calc-alkaline felsic volcanic rocks.

(Table T1) Mineral composition of turbidite sands and sandstones from ODP Leg 190 sites

During Ocean Drilling Program Leg 190 several turbidite successions in the Nankai Trough were drilled through including Pleistocene trench fill (Sites 1173 and 1174), Pleistocene-Pliocene slope basin deposits and underlying trench fill (Sites 1175 and 1176), Miocene Shikoku Basin deposits (Site 1177), and upper Miocene trench fill (Site 1178). Sands from the Pleistocene trench-fill succession of the Nankai Trough are of mixed derivation with significant monomineralic components (quartz and feldspar) and mafic to intermediate volcanic rock fragments, in addition to sedimentary and less abundant metamorphic detritus. They have a source in the Izu collision zone in central Honshu. Sands from the slope and accreted trench fill at Sites 1175 and 1176 are dominated by quartz with less abundant feldspar, sedimentary rock fragments, and only minor volcanic and metamorphic rock fragments. In contrast to the trench turbidites of Sites 1173 and 1174, these sands are very quartzose with characteristic radiolarian chert fragments. Volcanic rock fragments are mainly of silicic composition. Potential sources of these sands are uplifted subduction complexes of southwest Japan. Sands from the accreted trench turbidites at Site 1178 have clast types similar to those at Sites 1175 and 1176. In contrast, however, framework detrital modes are distinctive, with Site 1178 sands having substantially lower total quartz contents and more abundant fine-grained sedimentary rock fragments. These sands were also probably derived from the island of Shikoku, but their composition indicates that sedimentary rocks were abundant in the source area and these may have been Miocene forearc basin successions that were largely removed by erosion. Erosional remnants of Miocene forearc basin deposits are present on the Kii Peninsula east-northeast of Shikoku. Erosion followed a phase of exhumation of the Shimanto Belt indicated by apatite fission track ages at ~10 Ma. Sand in the lower-upper Miocene turbidites of the lower Shikoku Basin section at Site 1177 is more varied in composition, with the upper part of the unit similar to Site 1178 (i.e., rich in sedimentary rock fragments) and the lower part similar to those at Sites 1175 and 1176 (i.e., rich in quartz with some silicic volcanic rock fragments). Sands from the lower part of the Miocene turbidite unit were derived from a continental source with plutonic and volcanic rocks, possibly the inner zone of southwest Japan.

Composition of bottom sediments, rocks, and ores from the Tropical Atlantic

Geological features of some areas of the Tropical Atlantic (stratigraphy, tectonic structure, lithology, distribution of ore components in bottom sediments, petrography of bedrocks, etc.) are under consideration in the book. Regularities of concentration of trace elements in iron-manganese nodules, features of these nodules in bottom sediments, distribution of phosphorite nodules and other phosphorites have been studied. Much attention is paid to rocks of the ocean crust. A wide range of mineralization represented by magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals has been found.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Oxygen and hydrogen isotopes at DSDP Leg 65 Holes

In order to provide information on the degree of alteration of the very young basaltic basement drilled on Leg 65 in the mouth of the Gulf of California, we have measured the oxygen isotopic composition of whole rocks and mineral separates. Considerable data already exist for older ocean crust, in particular for the deep holes drilled in the Atlantic Ocean on Deep Sea Drilling Project (DSDP) Legs 37, 45, 46, and 51-53. These data indicate that in all of these holes, which include crust as young as 3.5 m.y. old, a significant amount of alteration has taken place as the result of low-temperature interaction between basalt and seawater (cf. Muehlenbachs, 1977, 1980; Hoernes et al., 1978; Friedrichsen and Hoernes, 1980). It is therefore of interest to determine whether Leg 65 crust, which is only 0.5 to 1.5 m.y. old, has experienced a similar degree of alteration.

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.