Synthesis, structure, and stability of metal-organic frameworks

Metal-organic frameworks (MOFs) obtained much attention because of their unusual structures and properties as well as their potential applications. This dissertation research was focused on (1) the effects of synthesis conditions on the structures of MOFs, (2) the thermal stability of MOFs, (3) pressure-induced amorphization, and (4) the effect of high-valent ions on the structure of a MOF. This research demonstrated that the crystal structure of MOF-5 could be controlled by drying solvents. If the vacuum solvent is dimethylformamide (DMF), the crystal structure of MOF-5 is tetragonal. In contrast, if the DMF is displaced by CH2Cl2 before the vacuum, the obtained MOF-5 occupies a cubic structure. Furthermore, it was found that the tetragonal MOF-5 exhibited a mediate surface area (300-1000 m2/g). The surface area of tetragonal MOF-5 is also dependent on Zn(NO3)2/H2BDC (H2BDC: terephthalic acid) molar ratios used for its synthesis. The optimum ratio is 1.38, at which synthesized tetragonal MOF-5 exhibits the highest crystallinity and surface area (1297 m2/g). The thermal stability and decomposition of MOF-5 were systematically investigated. The thermal decomposition of cubic and tetragonal MOF-5s resulted in the same products: CO2, benzene, amorphous carbon, and crystal ZnO. The thermal decomposition is due to breaking carboxylic bridges between benzene rings and Zn4O clusters. Identifying structural relationships between crystalline and noncrystalline states is of fundamental interest in materials research. Currently, amorphization of solid materials at ambient temperature requires an ultra-high pressure (several GPa). However, this research demonstrated that MOF-5 and IRMOF-8 can be irreversibly amorphized at ambient temperature by employing a low compressing pressure of 3.5 MPa, which is 100 times lower than that required for amorphization of other solids. Furthermore, the pressure-induced amorphization (PIA) of MOFs is strongly dependent on the changeability of bond angles. If the geometric structure of a MOF can allow bond angles to be changed without breaking bonds, it can easily be amorphized by compression. This can explain why MOF-5 and IRMOF-8 can easily be amorphized via compression than Cu-BTC. It is generally recognized that zeolitic imidazolate frameworks (ZIFs) occupy much higher stability than other types of MOFs. The representative of ZIFs is Zn(2-methylimidazole)2 (ZIF-8) exhibiting high-decomposition temperature and high chemical resistance to various solvents. However, so far, it is still unknown whether the high stability of ZIF-8 can be challenged by ions, which is important for its modification by doping ions. In this research, we performed aqueous salt solution treatment on ZIF-8, and the results showed that anions (Cl¯ and NO3¯) in a solution exhibited no effect on the crystal structure of ZIF-8. However, the effect of cations (in a solution) on structure of ZIF-8 strongly depends on the cation valences. The univalent metal cations showed no effect on the structure of ZIF-8, whereas the bivalent or higher-valent metal cations caused the collapse of ZIF-8 crystal structure. Therefore, structure stability of ZIF-8 is considered when it is subjected to the application, in which high-valent metal cations are involved.

Boron nitride nanotubes : synthesis, characterization, functionalization, and potential applications

Boron nitride nanotubes (BNNTs) are structurally similar to carbon nanotubes (CNTs), but exhibit completely different physical and chemical properties. Thus, BNNTs with various interesting properties may be complementary to CNTs and provide an alternative perspective to be useful in different applications. However, synthesis of high quality of BNNTs is still challenging. Hence, the major goals of this research work focus on the fundamental study of synthesis, characterizations, functionalization, and explorations of potential applications. In this work, we have established a new growth vapor trapping (GVT) approach to produce high quality and quantity BNNTs on a Si substrate, by using a conventional tube furnace. This chemical vapor deposition (CVD) approach was conducted at a growth temperature of 1200 °C. As compared to other known approaches, our GVT technique is much simpler in experimental setup and requires relatively lower growth temperatures. The as-grown BNNTs are fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Energy Filtered Mapping, Raman spectroscopy, Fourier Transform Infra Red spectroscopy (FTIR), UV-Visible (UV-vis) absorption spectroscopy, etc. Following this success, the growth of BNNTs is now as convenient as growing CNTs and ZnO nanowires. Some important parameters have been identified to produce high-quality BNNTs on Si substrates. Furthermore, we have identified a series of effective catalysts for patterned growth of BNNTs at desirable or pre-defined locations. This catalytic CVD technique is achieved based on our finding that MgO, Ni or Fe are the good catalysts for the growth of BNNTs. The success of patterned growth not only explains the role of catalysts in the formation of BNNTs, this technique will also become technologically important for future device fabrication of BNNTs. Following our success in controlled growth of BNNTs on substrates, we have discovered the superhydrophobic behavior of these partially vertically aligned BNNTs. Since BNNTs are chemically inert, resistive to oxidation up to ~1000°C, and transparent to UV-visible light, our discovery suggests that BNNTs could be useful as self-cleaning, insulating and protective coatings under rigorous chemical and thermal conditions. We have also established various approaches to functionalize BNNTs with polymeric molecules and carbon coatings. First, we showed that BNNTs can be functionalized by mPEG-DSPE (Polyethylene glycol-1,2-distearoyl-sn-glycero-3-phosphoethanolamine), a bio-compatible polymer that helps disperse and dissolve BNNTs in water solution. Furthermore, well-dispersed BNNTs in water can be cut from its original length of >10µm to(>20hrs). This success is an essential step to implement BNNTs in biomedical applications. On the other hand, we have also succeeded to functionalize BNNTs with various conjugated polymers. This success enables the dispersion of BNNTs in organic solvents instead of water. Our approaches are useful for applications of BNNTs in high-strength composites. In addition, we have also functionalized BNNTs with carbon decoration. This was performed by introducing methane (CH4) gas into the growth process of BNNT. Graphitic carbon coatings can be deposited on the side wall of BNNTs with thicknesses ranging from 2 to 5 nm. This success can modulate the conductivity of pure BNNTs from insulating to weakly electrically conductive. Finally, efforts were devoted to explore the application of the wide bandgap BNNTs in solar-blind deep UV (DUV) photo-detectors. We found that photoelectric current generated by the DUV light was dominated in the microelectrodes of our devices. The contribution of photocurrent from BNNTs is not significant if there is any. Implication from these preliminary experiments and potential future work are discussed.

A dose-controlled system for air-liquid interface cell exposure and application to zinc oxide nanoparticles

BACKGROUND: Engineered nanoparticles are becoming increasingly ubiquitous and their toxicological effects on human health, as well as on the ecosystem, have become a concern. Since initial contact with nanoparticles occurs at the epithelium in the lungs (or skin, or eyes), in vitro cell studies with nanoparticles require dose-controlled systems for delivery of nanoparticles to epithelial cells cultured at the air-liquid interface. RESULTS: A novel air-liquid interface cell exposure system (ALICE) for nanoparticles in liquids is presented and validated. The ALICE generates a dense cloud of droplets with a vibrating membrane nebulizer and utilizes combined cloud settling and single particle sedimentation for fast (~10 min; entire exposure), repeatable (<12%), low-stress and efficient delivery of nanoparticles, or dissolved substances, to cells cultured at the air-liquid interface. Validation with various types of nanoparticles (Au, ZnO and carbon black nanoparticles) and solutes (such as NaCl) showed that the ALICE provided spatially uniform deposition (<1.6% variability) and had no adverse effect on the viability of a widely used alveolar human epithelial-like cell line (A549). The cell deposited dose can be controlled with a quartz crystal microbalance (QCM) over a dynamic range of at least 0.02-200 mug/cm(2). The cell-specific deposition efficiency is currently limited to 0.072 (7.2% for two commercially available 6-er transwell plates), but a deposition efficiency of up to 0.57 (57%) is possible for better cell coverage of the exposure chamber. Dose-response measurements with ZnO nanoparticles (0.3-8.5 mug/cm(2)) showed significant differences in mRNA expression of pro-inflammatory (IL-8) and oxidative stress (HO-1) markers when comparing submerged and air-liquid interface exposures. Both exposure methods showed no cellular response below 1 mug/cm(2 )ZnO, which indicates that ZnO nanoparticles are not toxic at occupationally allowed exposure levels. CONCLUSION: The ALICE is a useful tool for dose-controlled nanoparticle (or solute) exposure of cells at the air-liquid interface. Significant differences between cellular response after ZnO nanoparticle exposure under submerged and air-liquid interface conditions suggest that pharmaceutical and toxicological studies with inhaled (nano-)particles should be performed under the more realistic air-liquid interface, rather than submerged cell conditions.

Geochemistry of manganese nodules from a British Columbia fjord

Concretions of iron and manganese oxides and hydrous oxidesóobjects commonly called manganese nodulesóare widely distributed not only on the deep-sea floor but also in shallow marine environments1. Such concretions were not known to occur north of Cape Mendocino in the shallow water zones bordering the North-East Pacific Ocean until the summer of 1966 when they were recovered by one of us (J. W. M.) in dredge samples from Jervis Inlet, a fjord approximately 50 miles north-west of Vancouver, British Columbia.

Geochemistry and petrology of ODP Leg 121 basalts

Basement lavas from Sites 756, 757, and 758 on Ninetyeast Ridge are tholeiitic basalts. Lavas from Sites 756 and 757 appear to be subaerial eruptives, but the lowermost flows from Hole 758A are pillow lavas. In contrast to the compositional variation during the waning stages of Hawaiian volcanism, no alkalic lavas have been recovered from Ninetyeast Ridge and highly evolved lavas were recovered from only one of seven drill sites (DSDP Site 214). All lavas from Site 758 have relatively high MgO contents (8-10 wt%), and they are less evolved than lavas from Sites 756 and 757. Although abundances of alkali metals in these Ninetyeast Ridge basalts were significantly modified by postmagmatic alteration, abundances of other elements reflect magmatic processes. At Site 757 most of the lavas are Plagioclase cumulates, but lava compositions require two compositionally distinct, AhCb-rich parental magmas, perhaps segregated at relatively low mantle pressures. In addition, at both Sites 756 and 758 more than one compositionally distinct parental magma is required. The compositions of these Ninetyeast Ridge lavas, especially those from Site 758, require a source component with a depleted composition; specifically, the abundance ratios Th/Ta, Th/La, Ba/Nb, Ba/La, and La/Ce in these lavas are generally less than the ratios inferred for primitive mantle. Lavas from Ninetyeast Ridge and the Kerguelen Archipelago have very different chondrite-normalized REE patterns, with lower light REE/heavy REE (LREE/HREE) ratios in lavas from Ninetyeast Ridge. However, lavas from Sites 757 and 758 have Pb isotope ratios that overlap with the field defined by lavas from the Kerguelen Archipelago (Weis and Frey, this volume). Therefore, these Ninetyeast Ridge lavas contain more of a component that is relatively depleted in LREE and other highly incompatible elements, but have similar amounts of the component that controls radiogenic Pb isotopes. A model involving mixing between components related to a depleted source and an enriched plume source has been proposed for the oldest Kerguelen Archipelago basalts and Ninetyeast Ridge lavas. Although the incompatible element characteristics of the Ninetyeast Ridge lavas are intermediate between depleted MORB and Kerguelen Archipelago basalts, these data are not consistent with a simple two-component mixing process. A more complex model is required.

Major element oxides of minerals from a lava pond at ODP Site 206-1256

At Ocean Drilling Program Site 1256 (6°44.2'N, 91°56.1'W), during Leg 206, a thick massive unit was cored in two neighboring penetrations of the uppermost basement, Holes 1256C and 1256D. This thick massive lava flow, commonly referred to as the "Lava Pond," is identified as Unit 18 (>30 m thick) in Hole 1256C and Unit 1 (>74.2 m thick) in Hole 1256D (Wilson et al., 2003, doi:10.2973/odp.proc.ir.206.2003). In the coarse-grained basalt that comprises this lithological unit, low-temperature "background" alteration events are present. This report provides microprobe analyses of both primary and secondary minerals present in this massive lava pond. The analyses of typically magmatic minerals (titanomagnetite, plagioclase, and clinopyroxene) are given for comparison with secondary minerals.

Petrography, microprobe analyses and isotope composition of ultramafic rock from the northern Haskard Highlands, Shackleton Range, East Antarctica

In the Shackleton Range of East Antarctica, garnet-bearing ultramafic rocks occur as lenses in supracrustal high-grade gneisses. In the presence of olivine, garnet is an unmistakable indicator of eclogite facies metamorphic conditions. The eclogite facies assemblages are only present in ultramafic rocks, particularly in pyroxenites, whereas other lithologies - including metabasites - lack such assemblages. We conclude that under high-temperature conditions, pyroxenites preserve high-pressure assemblages better than isofacial metabasites, provided the pressure is high enough to stabilize garnet-olivine assemblages (i.e. >=18-20 kbar). The Shackleton Range ultramafic rocks experienced a clockwise P-T path and peak conditions of 800-850 °C and 23-25 kbar. These conditions correspond to ~70 km depth of burial and a metamorphic gradient of 11-12 °C/km that is typical of a convergent plate-margin setting. The age of metamorphism is defined by two garnet-whole-rock Sm-Nd isochrons that give ages of 525 ± 5 and 520 ± 14 Ma corresponding to the time of the Pan-African orogeny. These results are evidence of a Pan-African suture zone within the northern Shackleton Range. This suture marks the site of a palaeo-subduction zone that likely continues to the Herbert Mountains, where ophiolitic rocks of Neoproterozoic age testify to an ocean basin that was closed during Pan-African collision. The garnet-bearing ultramafic rocks in the Shackleton Range are the first known example of eclogite facies metamorphism in Antarctica that is related to the collision of East and West Gondwana and the first example of Pan-African eclogite facies ultramafic rocks worldwide. Eclogites in the Lanterman Range of the Transantarctic Mountains formed during subduction of the palaeo-Pacific beneath the East Antarctic craton.

Magnetic mineralogy and geochemistry of ODP Holes 137-504B and 140-504B samples

Leg 140 of the Ocean Drilling Program deepened Hole 504B to a total depth of 2000.4 m below seafloor (mbsf), making it the deepest hole drilled into ocean crust. Site 504, south of the Costa Rica Rift, is considered the most important in-situ reference section for the structure of shallow ocean crust. We present the results of studies of magnetic mineralogy and magnetic properties of Hole 504B upper crustal rocks recovered during Legs 137 and 140. Results from this sample set are consistent with those discussed in Pariso et al. (this volume) from Legs 111, 137, and 140. Coercivity (Hc) ranges from 5.3 to 27.7 mT (mean 12 mT), coercivity of remanence (HCR) ranges from 13.3 to 50.6 mT (mean 26 mT), and the ratio HCR/HC ranges from 1.6 to 3.19 (mean 2.13). Saturation magnetization (JS) ranges from 0.03 to 5.94 * 10**-6 Am**2, (mean 2.52 * 10**-6 Am**2), saturation remanence (JR) ranges from 0.01 to 0.58 * 10**-6 Am2 (mean 0.37 * 10**-6 Am**2), and the ratio JR/JS ranges from 0.08 to 0.29 (mean 0.16), consistent with pseudo-single-domain behavior. Natural remanent magnetization (NRM) intensity ranges from 0.029 to 7.18 A/m (mean 2.95 A/m), whereas RM10 intensity varies only from 0.006 to 4.8 A/m and has a mean of only 1.02 A/m. Anhysteretic remanent magnetization (ARM) intensity ranges from 0.04 to 6.0 A/m, with a mean of 2.46 A/m, and isothermal remanent magnetization (IRM) intensity ranges from 0.5 to 1683 A/m, with a mean of 430.7 A/m. Volume susceptibility ranges from 0.0003 to 0.043 SI (mean 0.011 SI). In all samples examined, high-temperature oxidation of primary titanomagnetite has produced lamellae or pods of magnetite and ilmenite. Hydrothermal alteration has further altered the minerals in some samples to a mixture of magnetite, ilmenite, titanite, and a high-titanium mineral (either rutile or anatase). Electron microprobe analyses show that magnetite lamellae are enriched in the trivalent oxides Cr2O3, Al2O3, and V2O5, whereas divalent oxides (MnO and MgO) are concentrated in ilmenite lamellae.

Chemical and isotopic composition of rocks and minerals at ODP Site 209-1275

This paper reports results of an investigation of a representative collection of samples recovered by deep-sea drilling from the oceanic basement 10 miles west of the rift valley axis in the crest zone of the Mid- Atlantic Ridge at 15°44'N (Sites 1275B and 1275D). Drilling operations were carried out during Leg 209 of the Drilling Vessel JOIDES Resolution within the framework of the Ocean Drilling Program (ODP). The oceanic crust was penetrated to depth of 108.7 m at Site 1275B and 209 m at Site 1275D. We reconstructed the following sequence of magmatic and metamorphic events resulting in the formation of a typical oceanic core complex of slow-spreading ridges: (1) formation of strongly fractionated (enriched in iron and titanium) tholeiitic magmatic melt parental to gabbroids under investigation in a large magma chamber located in a shallow mantle and operating for a long time under steady-state conditions; (2) transfer of the parental magmatic melt of the gabbroids to the base of the oceanic crust, its interaction with host mantle peridotites, and formation of troctolites and plagioclase peridotites; (3) intrusion of enriched trondhjemite melts as veins and dikes in the early formed plutonic complex, contact recrystallization of the gabbro, and development in the peridotite-gabbro complex of enriched geochemical signatures owing to influence of trondhjemite injections; (4) emplacement of dolerite dikes (transformed to diabases); (5) metamorphism of upper epidoteamphibolite facies with participation of marine fluids; and (6) rapid exhumation of the plutonic complex to the seafloor accompanied by greenschist-facies metamorphism. Distribution patterns of Sr and Nd isotopes and strongly incompatible elements in the rocks suggest contributions from two melt sources to the magmatic evolution of the MAR crest at 15°44'N: a depleted reservoir responsible for formation of the gabbros and diabases and an enriched reservoir, from which trondhjemites (granophyres) were derived.

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.

Analysis of the iron oxide assemblages in the ANDRILL AND-1B drill core, Ross Sea, Antarctica

The AND-1B drill core recovered a 13.57 million year Miocene through Pleistocene record from beneath the McMurdo Ice Shelf in Antarctica (77.9°S, 167.1°E). Varying sedimentary facies in the 1285 m core indicate glacial-interglacial cyclicity with the proximity of ice at the site ranging from grounding of ice in 917 m of water to ice free marine conditions. Broader interpretation of climatic conditions of the wider Ross Sea Embayment is deduced from provenance studies. Here we present an analysis of the iron oxide assemblages in the AND-1B core and interpret their variability with respect to wider paleoclimatic conditions. The core is naturally divided into an upper and lower succession by an expanded 170 m thick volcanic interval between 590 and 760 m. Above 590 m the Plio-Pleistocene glacial cycles are diatom rich and below 760 m late Miocene glacial cycles are terrigenous. Electron microscopy and rock magnetic parameters confirm the subdivision with biogenic silica diluting the terrigenous input (fine pseudo-single domain and stable single domain titanomagnetite from the McMurdo Volcanic Group with a variety of textures and compositions) above 590 m. Below 760 m, the Miocene section consists of coarse-grained ilmenite and multidomain magnetite derived from Transantarctic Mountain lithologies. This may reflect ice flow patterns and the absence of McMurdo Volcanic Group volcanic centers or indicate that volcanic centers had not yet grown to a significant size. The combined rock magnetic and electron microscopy signatures of magnetic minerals serve as provenance tracers in both ice proximal and distal sedimentary units, aiding in the study of ice sheet extent and dynamics, and the identification of ice rafted debris sources and dispersal patterns in the Ross Sea sector of Antarctica.

Chemistry on manganese nodules from the Pacific Ocean

Three manganese nodules from the Pacific Ocean have been analysed for 35 elements by using mainly spectrophotometric and spectrographic methods. Cu, Co, Ni, Zn, and Pb were found in amounts approaching 1 %, which far exceeds their average concentrations in igneous rocks. On the other hand, elements having readily hydrolysable ions, such as Ga, Sc, Zr, Y, La and Ti, are present only in amounts comparable with their concentrations in igneous rocks. Sb, Bit Be, and Cr were not detected. The hydrochloric acid-insoluble fraction of nodules is practically free of the heavy metals that are characteristic of the acid-soluble fraction; it consists principally of clay minerals, together with lesser amounts of quartz, apatite, biotite and sodium and potassium felspars.

Chemical composition of minerals and rocks from the Sierra Leone segment of the Mid-Atlantic Ridge and from the Markov depression, Central Atlantic

Silicic Fe-Ti-oxide magmatic series was the first recognized in the Sierra Leone axial segment of the Mid-Atlantic Ridge near 6°N. The series consists of intrusive rocks (harzburgites, lherzolites, bronzitites, norites, gabbronorites, hornblende Fe-Ti-oxide gabbronorites and gabbronorite-diorites, quartz diorites, and trondhjemites) and their subvolcanic (ilmenite-hornblende dolerites) and, possibly, volcanic analogues (ilmenite-bearing basalts). Deficit of most incompatible elements in the rocks of the series suggests that parental melts derived from a source that had already been melted. Correspondingly, these melts could not be MORB derivatives. Origin of the series is thought to be related to melting of the hydrated oceanic lithosphere during emplacement of an asthenospheric plume (protuberance on the surface of large asthenospheric lens beneath MAR). Genesis of different melts was supposedly controlled by ascent of a chamber of hot mantle magmas thought this lithosphere in compliance with the zone melting mechanism. Melt acquired fluid components from heated rocks at peripheries of the plume and became enriched in Fe, Ti, Pb, Cu, Zn, and other components mobile in fluids.

Geochemistry of ODP Leg 135 basalts

Cr-spinels in cores drilled during Ocean Drilling Program Leg 135 exhibit wide variations in composition and morphology that reflect complex petrogenetic histories. These Cr-spinels are found within basaltic lava flows that erupted in north-trending sub-basins within the Lau Basin backarc. Cr-spinels from Sites 834 and 836 occur as euhedral groundmass grains and inclusions in plagioclase, and range up to 300 ?m in size. These Cr-spinels are similar in composition, morphology, and mode of occurrence to Cr-spinels found within depleted, N-type mid-ocean-ridge basalts (N-MORB), reflecting similar crystallization conditions and host lava composition to N-MORB. Their compositional range is relatively narrow, with Cr/(Cr + Al + Fe3+) (Cr#) and Mg/(Mg + Fe2+) (Mg#) varying from 0.38 to 0.48 and 0.56 to 0.72, respectively; like Cr-spinels from N-MORB, they contain low amounts of TiO2 (0.37%-1.05%) and Fe3+/(Cr + Al + Fe3+) (Fe3+#; <0.11). In contrast, Cr-spinels from Site 839 have much higher Cr# at a given Mg#, with Cr# varying from 0.52 to 0.76 and Mg# varying from 0.27 to 0.75. These Cr-spinels are similar in composition to those from primitive, boninitic or low-Al2O3 arc basalts, sharing their low TiO2 and Fe3+# (typically below 0.35% and 0.1, respectively for spinel grain interiors). Site 839 Cr-spinels occur as small (to 50 µm) euhedra within strongly zoned olivine or as unusually large (to 3 mm), euhedral to subhedral megacrysts. These megacrysts are strongly zoned in Mg#, but they display little zoning in Cr#, providing evidence of strong compositional disequilibria with the host melt. The magnesian cores of the megacrysts crystallized from primitive, near-primary melts derived from harzburgitic or highly depleted lherzolitic sources, and they provide evidence that the Site 839 spinel-bearing lavas were derived by the mixing of melt with a Mg# of 0.75-0.80 and evolved, Cr-spinel barren melt with a Mg# < 0.6 shortly before eruption.

Chemical and mineral composition of rocks and sediments from the Amirante Arc

New geological and geophysical data on the Amirante Arc, which locates to the south of the Seychelles Islands, are presented. These data were obtained by Pacific Oceanological Institute during the 33-rd cruise of R/V Professor Bogorov in 1990. The Amirante Arc represents a seamount chain, which has submeridional strike and total length about 400 km. To the west of the Amirante Arc there are a deep sea trench and a back-arc basin, i.e. this area is characterized by structural elements associated with the subduction zone of Western Pacific type. According to our data the Amirante Arc is composed by tholeiites of ocean plateau type. This facts are evidences that the Amirante Arc differs from typical Pacific island arcs. This gives an opportunity to distinguish a special type of oceanic structures, i.e. non-volcanic (amagmatic) ridges. The Amirante Ridge has been probably formed as a result of oceanic crust heaping due to horizontal displacements of its blocks in the process of spreding ridge formation in the Indian Ocean during Cretaceous-Paleogene.