Yen Hong Shau

Corrensite and mixed-layer chlorite/corrensite in metabasalt from northern Taiwan: TEM/AEM, EMPA, XRD, and optical studies

Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (“expandable chlorite”) and/or have excess AlVI relative to AlIV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and “expandable chlorite”, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high AlVI/AlIV and low FeVI/(Fe+Mg)VI ratios of “chlorites” are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low AlIV/SiIV and low FeVI/(Fe+Mg)VI, while chlorite has high AlIV/SiIV and high FeVI/(Fe+Mg)VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower AlIV/SiIV and FeVI/(Fe+Mg)VI. The ratios of FeVI/(Fe+Mg)VI and AlIV/SiIV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of “chlorites” in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.

Phyllosilicates in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 — a TEM and AEM study

Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or ohvine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from< 100 Å to a few hundred Å. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystal-linity of saponite. by contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of Å thick. The Si/(Si+Al) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe+Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+Al) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite±mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.

Genesis and solvus relations of submicroscopically intergrown paragonite and phengite in a blueschist from northern California

Electron microbeam techniques have been used to examine submicroscopically intergrown paragonite, phengite and chlorite from the South Fork Mountain Schist of the Franciscan Terrane of northern California, which was subjected to blueschist facies metamorphism. The sample also contains quartz, albite, lawsonite, and rutile. The subassemblage albite-lawsonite-rutile requires metamorphic conditions on the low-temperature side of the equilibrium albite+lawsonite+rutile=paragonite+sphene+quartz+H2O (T<200° C and P<7.4 kbars based on thermodynamic data of Holland and Powell 1990). The white micas appear to be optically homogeneous, but back-scattered electron images can distinguish two different micas by their slight difference in contrast. Electron microprobe analyses (EMPA) of micas show Na/(Na+K) ranging from 0.2 to 0.8. The two micas are resolved by transmission electron microscopy (TEM) as packets of phengite and paragonite that range from 20 to several hundred nm in thickness. The compositions, determined by analytical electron microscopy (AEM), constrain the limbs of the phengite-paragonite solvus to values of Na/(Na+K)=<0.02 and 0.97, representing less mutual solid solution than ever reported by EMPA. The textural relations imply that the sheet silicates were derived from reactions between fluids and detrital clays and that they are in an intermediate stage of textural development. We caution that microprobe analyses of apparently homogeneous sheet silicates may yield erroneous data and lead to faulty conclusions using phengite barometry and paragonite-muscovite thermometry, especially in fine-grained rocks that formed at relatively low temperatures.

Formation of Magnetic Single-Domain Magnetite in Ocean Ridge Basalts with Implications for Sea-Floor Magnetism

Although magnetic data are the primary evidence for ocean floor spreading, the processes by which magnetic phases in ocean floor basalts are formed remain poorly constrained. Scanning transmission electron microscopic observations show that magnetic single-domain magnetite in sheeted dike basalts of Deep Sea Drilling Project hole 504B formed through oxidation-exsolution of ilmenite, exsolution of ulv�spinel lamellae, and recrystallization of end-member magnetite by interaction with convecting fluids. The data suggest that the sheeted dike basalts, with single-domain magnetite as an efficient and stable magnetic carrier, contribute significantly to sea-floor magnetism.

ORIGIN AND MINERALOGY OF SEPIOLITE AND PALYGORSKITE FROM THE TULUANSHAN FORMATION, EASTERN TAIWAN

The Tuluanshan Formation of the eastern Coastal Range of Taiwan overlies an andesitic core complex presumed to be the source of hydrothermal fluids responsible for the Si- and Mg-rich mineralization of sepiolite and palygorskite (attapulgite) which are found in veins within fissures and in fracture zones of the volcanic rocks of the region. This study was undertaken in order to understand these relationships better by characterizing sepiolite and palygorskite in this Formation and by examining their occurrence and distribution in the Tungho (TH) and Chunjih (CJ) areas. Samples were analyzed using X-ray diffraction (XRD), thermal analysis, Fourier-transform infrared (FTIR) spectroscopy, and petrographic, scanning (SEM), and transmission (TEM) electron microscopic methods. Sepiolite and palygorskite are blocky and earthy-type materials that display fibrous characteristics when viewed using TEM and SEM and occurred alone or with chalcedony in veins. The fibers of blocky sepiolite are commonly intercalated with smectite but the earthy type of sepiolite and palygorskite observed in this study displayed precipitation from fluid enriched in Si, Al, Mg, and minor Fe and depleted in other ions at an earlier stage of offset of the andesitic veins. Continuation of reverse faulting and high shearing stress caused the precipitation of a significant quantity of interlaminated sepiolite. Sepiolite and palygorskite were formed at an earlier stage of fluid interaction relative to smectite in the Tuluanshan Formation.

Distribution and hosts of arsenic in a sediment core from the Chianan Plain in SW Taiwan: Implications on arsenic primary source and release mechanisms

High arsenic abundance of 50-700μg/L in the groundwater from the Chianan Plain in southwestern Taiwan is a well-known environmental hazard. The groundwater-associated sediments, however, have not been geochemically characterized, thus hindering a comprehensive understanding of arsenic cycling in this region. In this study, samples collected from a 250m sediment core at the centre of the Chianan Plain were analyzed for arsenic and TOC concentrations (N=158), constituent minerals (N=25), major element abundances (N=105), and sequential arsenic extraction (N=23). The arsenic data show a prevalence of >10mg/kg with higher concentrations of 20-50mg/kg concentrated at 60-80 and 195-210m. Arsenic was extracted mainly as an adsorbate on clay minerals, as a co-precipitate in amorphous iron oxyhydroxide, and as a structural component in clay minerals. Since the sediments consist mainly of quartz, chlorite, and illite, the correlations between arsenic concentration and abundances of K2O and MgO pinpoint illite and chlorite as the major arsenic hosts. The arsenic-total iron correlation reflects the role of chlorite along with the contribution from amorphous iron oxyhydroxide as indicated by arsenic extraction data. Organic matter is not the dominant arsenic host for low TOC content, low arsenic abundance extracted from it, and a relatively low R(2) of the arsenic-TOC correlation. The major constituent minerals in the sediments are the same as those of the upriver metapelites, establishing a sink-source relationship. Composition data from two deep groundwater samples near the sediment core show Eh values and As(V)/As(III) ratios of reducing environments and high arsenic, K, Mg, and Fe contents necessary for deriving arsenic from sediments by desorption from clay and dissolution of iron oxyhydroxide. Therefore, groundwater arsenic was mainly derived from groundwater-associated sediments with limited contributions from other sources, such as mud volcanoes.

CO2 sequestration utilizing basic-oxygen furnace slag: Controlling factors, reaction mechanisms and V-Cr concerns

Basic-oxygen furnace slag (BOF-slag) contains >35% CaO, a potential component for CO2 sequestration. In this study, slag-water-CO2 reaction experiments were conducted with the longest reaction duration extending to 96hr under high CO2 pressures of 100-300kg/cm(2) to optimize BOF-slag carbonation conditions, to address carbonation mechanisms, and to evaluate the extents of V and Cr release from slag carbonation. The slag carbonation degree generally reached the maximum values after 24hr slag-water-CO2 reaction and was controlled by slag particle size and reaction temperature. The maximum carbonation degree of 71% was produced from the experiment using fine slag of ≤0.5mm under 100°C and a CO2 pressure of 250kg/cm(2) with a water/slag ratio of 5. Vanadium release from the slag to water was significantly enhanced (generally >2 orders) by slag carbonation. In contrast, slag carbonation did not promote chromium release until the reaction duration exceeded 24hr. However, the water chromium content was generally at least an order lower than the vanadium concentration, which decreased when the reaction duration exceeded 24hr. Therefore, long reaction durations of 48-96hr are proposed to reduce environmental impacts while keeping high carbonation degrees. Mineral textures and water compositions indicated that Mg-wüstite, in addition to CaO-containing minerals, can also be carbonated. Consequently, the conventional expression that only considered carbonation of the CaO-containing minerals undervalued the CO2 sequestration capability of the BOF-slag by ~20%. Therefore, the BOF-slag is a better CO2 storage medium than that previously recognized.