Morphological ripening of fluid inclusions and coupled zone-refining in quartz crystals revealed by cathodoluminescence imaging: Implications for CL-petrography, fluid inclusion analysis and trace-element geothermometry

Cathodoluminescence (CL) studies have previously shown that some secondary fluid inclusions in luminescent quartz are surrounded by dark, non-luminescent patches, resulting from fracture-sealing by late, trace-element-poor quartz. This finding has led to the tacit generalization that all dark CL patches indicate influx of low temperature, late-stage fluids. In this study we have examined natural and synthetic hydrothermal quartz crystals using CL imaging supplemented by in-situ elemental analysis. The results lead us to propose that all natural, liquid-water-bearing inclusions in quartz, whether trapped on former crystal growth surfaces (i.e., of primary origin) or in healed fractures (i.e., of pseudosecondary or secondary origin), are surrounded by three-dimensional, non-luminescent patches. Cross-cutting relations show that the patches form after entrapment of the fluid inclusions and therefore they are not diagnostic of the timing of fluid entrapment. Instead, the dark patches reveal the mechanism by which fluid inclusions spontaneously approach morphological equilibrium and purify their host quartz over geological time. Fluid inclusions that contain solvent water perpetually dissolve and reprecipitate their walls, gradually adopting low-energy euhedral and equant shapes. Defects in the host quartz constitute solubility gradients that drive physical migration of the inclusions over distances of tens of μm (commonly) up to several mm (rarely). Inclusions thus sequester from their walls any trace elements (e.g., Li, Al, Na, Ti) present in excess of equilibrium concentrations, thereby chemically purifying their host crystals in a process analogous to industrial zone refining. Non-luminescent patches of quartz are left in their wake. Fluid inclusions that contain no liquid water as solvent (e.g., inclusions of low-density H2O vapor or other non-aqueous volatiles) do not undergo this process and therefore do not migrate, do not modify their shapes with time, and are not associated with dark-CL zone-refined patches. This new understanding has implications for the interpretation of solids within fluid inclusions (e.g., Ti- and Al-minerals) and for the elemental analysis of hydrothermal and metamorphic quartz and its fluid inclusions by microbeam methods such as LA-ICPMS and SIMS. As Ti is a common trace element in quartz, its sequestration by fluid inclusions and its depletion in zone-refined patches impacts on applications of the Ti-in-quartz geothermometer.

UHP Metamorphism Documented in Ti-chondrodite- and Ti-clinohumite-bearing Serpentinized Ultramafic Rocks from Chinese Southwestern Tianshan

The southwestern Tianshan (China) metamorphic belt records high-pressure (HP) to ultrahigh-pressure (UHP) conditions corresponding to a cold oceanic subduction-zone setting. Serpentinites enclosing retrogressed eclogite and rodingite occur as lenses within metapelites in the UHP unit, which also hosts coesite-bearing eclogites. Based on the petrology and petrography of these serpentinites, five events are recognized: (1) formation of a wehrlite–harzburgite–dunite association in the mantle; (2) retrograde metamorphism and partial hydration during exhumation of the mantle rocks close to the seafloor; (3) oceanic metamorphism leading to the first serpentinization and rodingitization; (4) UHP metamorphism during subduction; (5) retrograde metamorphism during exhumation together with a second serpentinization. The peak metamorphic mineral assemblage of the serpentinized wehrlite comprises Ti-chondrodite + olivine + antigorite + chlorite + magnetite + brucite. A computed pseudosection for this serpentinized wehrlite shows that the Al content in antigorite is mostly sensititive to temperature but can also be used to constrain pressure. The average XAl = 0·204 ± 0·026 of antigorite (XAl = Al (a.p.f.u.)/8, where Al is in atoms per formula unit for a structural formula M48T34O85(OH)62, and M and T are octahedral and tetrahedral sites, respectively) included in Ti-chondrodite and average XAl = 0·203 ± 0·019 of antigorite in the matrix result in a well-constrained peak metamorphic temperature of 510–530°C. Peak pressures are less precisely constrained at 37 ± 7 kbar. The Tianshan serpentinites thus record UHP metamorphic conditions and represent the deepest subducted serpentinites discovered so far. The retrograde evolution occurs within the stability field of brucite + antigorite + olivine + chlorite and formation of Ti-clinohumite at the expense of Ti-chondrodite has been observed, suggesting isothermal decompression. The resulting P–T path is in excellent agreement with the metamorphic evolution of country rocks, indicating that the UHP unit in Tianshan was subducted and exhumed as a coherent block. To refine the metamorphic path of the ultramafic rocks, we have investigated the stability fields of Ti-chondrodite and Ti-clinohumite using piston-cylinder experiments. A total of 11 experiments were conducted at 25–55 kbar and 600–750°C in a F-free natural system. Combined with previous experiments and information from natural rocks we constructed a petrogenetic grid for the stability of Ti-chondrodite and Ti-clinohumite in F-free peridotite compositions. The formation of Ti-chondrodite in serpentinites requires a minimum pressure of about 26 kbar, whereas in Ti-rich systems it can form at considerably lower pressures. A key finding is that at UHP conditions, F-free Ti-chondrodite or Ti-clinohumite breaks down in the presence of orthopyroxene between 700 and 750°C, at temperatures that are significantly lower than those of the terminal breakdown reactions of these humite minerals. These breakdown reactions are an additional source of fluid during prograde subduction of serpentinites.

Petrology and geochemistry at DSDP Site 89-462

The 16 samples of Deep Sea Drilling Project (DSDP) Leg 89 basalts that we analyzed for whole rock major and trace elements and for mineralogic compositions are identical to some of the basalts recovered during Leg 61. Leg 89 samples are mostly olivine-plagioclase-clinopyroxene sparsely phyric basalts and exhibit a wide variety of textures. These basalts have lower TiO2 at a given Mg/(Mg+Fe2+)*100 than MORB (midocean ridge basalt). We recognize three major chemical types of basalts in the Nauru Basin. We believe that different degrees of partial melting, modified by fractional crystallization and possibly by magma mixing at shallow depths, can explain the chemical differences among the three groups. This petrogenetic model is consistent with the observed downhole chemical-chronostratigraphic relations of the samples. New 87Sr/86Sr and U3Nd/144Nd analyses of basalt samples from DSDP Site 462 indicate that the Nauru Basin igneous complex is within the Sr-Nd isotopic range of ocean island basalt. Thus the Nauru Basin igneous complex resembles MORB in many aspects of its chemistry, morphology, and secondary alteration patterns (Larson, Schlanger, et al., 1981), but not in its isotopic characteristics. If it were not for the unambiguous evidence that the Nauru Basin complex was erupted off-ridge, the complex could easily be interpreted as normal oceanic layer 2. For this reason, we speculate that the Nauru Basin igneous complex was produced in an oceanic riftlike environment when multiple, fast-propagating rifts were formed during the fast seafloor spreading episode in the Cretaceous.

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.

Petrography and geochemistry of organic matter at DSDP Holes 80-549 and 80-550B

Three lower Barremian to middle/upper Cenomanian samples from DSDP Hole 549 and three lower Cenomanian to lower Maestrichtian samples from DSDP Hole 550B were investigated by organic geochemical and organic petrographic methods. The samples came from wells drilled in the area of the Goban Spur in the northeastern Atlantic; they represent gray to greenish gray carbonaceous mud or siltstones from the deeper parts of the Cretaceous sequences penetrated and light-colored chalks from the shallower ones. The total amount of organic carbon is below 1% in all samples; it is especially low in the Cenomanian to Maestrichtian chalks. Terrigenous organic matter predominates; only the Barremian sample shows a moderate number of marine phytoclasts. As indicated by several parameters, the maturity of the organic matter is low, corresponding to about 0.4% vitrinite reflectance.

Magnetic properties and oxide petrography of ODP Hole 111-504B

Magnetic properties measurements were performed on 47 samples drilled during Leg 111 of the Ocean Drilling Program and oxide petrography was studied in 32 samples taken at depths throughout the sheeted dike complex in Hole 504B. Integration of these data with results from previous DSDP legs shows that while natural remanent magnetization is constant with depth, magnetic susceptibility increases and median demagnetizing field and the Q ratio decrease with depth in the section. These trends appear to be a result of an increase in deuteric oxidation and a decrease in hydrothermal alteration of primary titanomagnetite with depth. A distinct change in stable magnetic inclination occurs between the extrusive basalts and the sheeted dikes and may be a result of tectonic rotation of the upper extrusive basalts.

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.

Organic petrography and extractable hydrocarbons of sediments at DSDP Leg 58 Holes

The quantity, type, and maturity of organic matter of Quaternary and Tertiary sediments from the Philippine Sea (DSDP Leg 58; Sites 442-446) were determined. Hydrocarbons in lipid extracts were analyzed by capillary-column gas chromatography. Kerogen concentrates were investigated by microscopy for vitrinite reflectance values and maceral composition. In the Shikoku Basin sediments (Sites 442, 443, and 444), organic carbon values range between 0.03 and 0.44 per cent. The higher values in the younger sediments are interpreted as an indication of increasing deposition of eroded organic particles during the past 4 m.y. Microscopic analyses revealed a dominance of reworked organic matter. Primary material could not be distinguished readily; thus, no maturation trend could be established. Extract yields were low. TV-alkane distributions mostly show maxima at n-C29 and n-C31 and high odd-over-even predominances, typical of material which originated in terrigenous higher plants. The organic-carbon values of sediments of the Daito Ridge and Basin region (Sites 444 and 445) range from less than 0.01 to 0.05 per cent. TV-alkanes exhibit varying marine and terrigenous influences. Some carbonate-rich samples show a pronounced even-over-odd predominance. At least the older sediments contained less recycled organic matter than the Shikoku Basin samples. The maturity, where measurable, was low. None of the Philippine Sea samples indicates a significant hydrocarbon-generation potential.

Petrology and geochemistry of sedimentary Unit III of ODP Hole 135-840B

The sedimentary sequence recovered at Site 840, on the Tonga frontal-arc platform, is 597.3 m thick and is subdivided into three lithostratigraphic units. The lowermost, late Miocene Unit III is 336.8 m thick and consists of a sequence of volcaniclastic mass-flow deposits (predominantly turbidites) interbedded with pelagic/hemipelagic deposits. Unit III was deposited in the forearc basin of the Lau volcanic arc, probably on a slope dominated by mass flows that built eastward from the ridge front and across the forearc. Upward through the unit a thinning and fining of individual turbidites takes place, interpreted to reflect a reduced sediment supply and a change from large to smaller flows. Decreasing volcanic activity with time is inferred from a decrease in coarse-grained volcaniclastic content in the upper part of the unit. The majority of the turbidites show the typical Bouma-type divisions, although both high- and low-density turbidity currents are inferred. High-density turbidity currents were especially common in the lower part of the unit. Geochemical analyses of detrital glass lie mainly in the low-K tholeiite field with a compositional range from basalt to rhyolite. A coherent igneous trend indicates derivation from a single volcanic source. This source was probably situated on the rifted part of the Lau-Tonga Ridge, within the present Lau backarc basin. The initial opening of the Lau Basin may have been around 6.0 m.y. ago. The onset of more extensive rifting, approximately 5.6 m.y. ago, is reflected in an increase in the silica content of volcanic glass. At the boundary toward Unit II, at approximately 5.25 Ma, an influx of thicker bedded and coarser grained volcaniclastic material is interpreted to reflect increasing volcanism and tectonism during the final breakup of the Lau-Tonga Ridge.

Petrology and geochemistry at DSDP Site 59-448

This chemical and petrologic study of rocks from Site 448 on the Palau-Kyushu Ridge is designed to answer some fundamental questions concerning the volcanic origin of remnant island arcs. According to the reconstruction of the Western Pacific prior to about 45 m.y. ago (Hilde et al., 1977), the site of the Palau-Kyushu Ridge was a major transform fault. From a synthesis of existing geological and geophysical data (R. Scott et al., this volume), it appears that the ridge originated by subduction of the Pacific plate under the West Philippine Basin. Thus the Palau-Kyushu Ridge should be a prime example of both initial volcanism of an incipient arc formed by interaction of oceanic lithospheric plates and remnant-arc volcanic evolution. The Palau-Kyushu Ridge was an active island arc from about 42 to 30 m.y. ago, after which initiation of back-arc spreading formed the Parece Vela Basin (R. Scott et al., this volume; Karig, 1975a). This spreading left the western portion of the ridge as a remnant arc that separates the West Philippine Basin from the Parece Vela Basin. In spite of numerous oceanographic expeditions to the Philippine Sea, including the two previous DSDP Legs 6 and 31 (Fischer, Heezen et al., 1971; Karig, Ingle et al., 1975), and even though the origins of inter-arc basins have been linked by various hypotheses to that of remnant island arcs (Karig, 1971, 1972, 1975a, and 1975b; Gill, 1976; Uyeda and Ben-Avraham, 1972; Hilde et al., 1977), very little hard data are available on inactive remnant arcs.

Petrology and diagenesis of sandstones at DSDP Hole 58-445

The sandstone succession in the lower 240 meters of DSDP Site 445, on the Daito Ridge, provided an opportunity to evaluate the effect of burial diagenesis of sandstones in a deep hole in a tectonic environment (remnant arc) characterized by a history of high heat flow. This report provides preliminary data concerning the petrology and diagenesis of these sandstones and records diagenetic changes which have occurred with increasing depth of burial. Methods used for this study included grain-size analysis (measured from thin sections using the method of Friedman, 1958), polarizing microscopy, X-ray diffraction, and scanning electron microscopy. A JEOL scanning electron microscope fitted with an energydispersive- X-ray detector was used for obtaining qualitative chemical data on certain minerals to aid in identification.