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Synthesis and stability of hetaerolite, ZnMn2O4, at 25°C

A precipitate of nearly pure hetaerolite, ZnMn 2 O 4 , a spinel-structured analog of hausmannite, Mn 3 O 4 , was prepared by an irreversible wprecipitation of zinc with manganese at 25°C. The synthesis technique entailed constant slow addition of a dilute solution of Mn 2+ and Zn 2+ chlorides having a Mn/Zn ratio of 2:1 to a reaction vessel that initially contained distilled deionized water, maintained at a pH of 8.50 by addition of dilute NaOH by an automated pH stat, with continuous bubbling of CO 2 -free air. The solid was identified by means of X-ray diffraction and transmission electron microscopy and consisted of bipyramidal crystals generally less than 0.10 μm in diameter. Zn 2+ ions are able to substitute extensively for Mn 2+ ions that occupy tetrahedral sites in the hausmannite structure. Hetaerolite appears to be more stable than hausmannite with respect to spontaneous conversion to γMnOOH. The value of the standard free energy of formation of hetaerolite was estimated from the experimental data to be −289.4 ± 0.8 kcal per mole. Solids intermediate in composition between hetaerolite and hausmannite can be prepared by altering the Mn/Zn ratio in the feed solution.

Geochimica et Cosmochimica Acta↗

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

Geochimica et Cosmochimica Acta↗

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

The abundance, P - T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600°C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high- T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of “average” island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H 2 O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. “Exotic” LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by “subduction-zone metasomatism,” although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments.

Geochimica et Cosmochimica Acta↗

Organic geochemistry and brine composition in Great Salt, Mono, and Walker Lakes

Samples of Recent sediments, representing up to 1000 years of accumulation, were collected from three closed basin lakes (Mono Lake, CA, Walker Lake, NV, and Great Salt Lake, UT) to assess the effects of brine composition on the accumulation of total organic carbon, the concentration of dissolved organic carbon, humic acid structure and diagenesis, and trace metal complexation. The Great Salt Lake water column is a stratified Na-Mg-Cl-SO 4 brine with low alkalinity. Algal debris is entrained in the high density (1.132–1.190 g/cc) bottom brines, and in this region maximum organic matter decomposition occurs by anaerobic processes, with sulfate ion as the terminal electron acceptor. Organic matter, below 5 cm of the sediment-water interface, degrades at a very slow rate in spite of very high pore-fluid sulfate levels. The organic carbon concentration stabilizes at 1.1 wt%. Mono Lake is an alkaline (Na-CO 3 -Cl-SO 4 ) system. The water column is stratified, but the bottom brines are of lower density relative to the Great Salt Lake, and sedimentation of algal debris is rapid. Depletion of pore-fluid sulfate, near l m of core, results in a much higher accumulation of organic carbon, approximately 6 wt%. Walker Lake is also an alkaline system. The water column is not stratified, and decomposition of organic matter occurs by aerobic processes at the sediment-water interface and by anaerobic processes below. Total organic carbon and dissolved organic carbon concentrations in Walker Lake sediments vary with location and depth due to changes in input and pore-fluid sulfate concentrations. Nuclear magnetic resonance studies ( 13 C) of humic substances and dissolved organic carbon provide information on the source of the Recent sedimentary organic carbon (aquatic vs. terrestrial), its relative state of decomposition, and its chemical structure. The spectra suggest an algal origin with little terrestrial signature at all three lakes. This is indicated by the ratio of aliphatic to aromatic carbon and the absence of chemical structures indicative of the lignin of vascular plants. The dissolved organic carbon of the Mono Lake pore fluids is structurally related to humic acid and is also related to carbohydrate metabolism. The alkaline pore fluids, due to high pH, solubilize high molecular weight organic matter from the sediments. This hydrophilic material is a metal complexing agent. Despite very high algal productivities, organic carbon accumulation can be low in stratified lakes if the anoxic bottom waters are hypersaline with high concentrations of sulfate ion. Labile organic matter is recycled to the water column and the sedimentary organic matter is relatively nonsusceptible to bacterial metabolism. As a result, pore-fluid dissolved organic carbon and metal-organic complexation are low.

Geochimica et Cosmochimica Acta↗

Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn 2+ and Cd 2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd 2 Mn 3 4+ O 8 , Mn 2+ 2 Mn 4+ 3 O 8 , MnO 2 (ramsdellite), and CdCO 3 . Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn 2+ Mn 2 3+ O 4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35°C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn 4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn 4+ oxide formation in the presence of Cd 2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn 2 O 4 Int , an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd 2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn 3+ ions. The Mn 2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn 2+ to Mn 4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd 2 Mn 3 O 8 and MnO 2 increased at the expense of other precipitate components.

Geochimica et Cosmochimica Acta↗

An aem-tem study of weathering and diagenesis, Abert Lake, Oregon: I. Weathering reactions in the volcanics

Abert Lake in south-central Oregon provides a site suitable for the study of sequential weathering and diagenetic events. In this first of two papers, transmission electron microscopy was used to characterize the igneous mineralogy, subsolidus alteration assemblage, and the structural and chemical aspects of silicate weathering reactions that occur in the volcanic rocks (basalts, basaltic andesites, and dacitic/ rhyolitic extrusive and pyroclastics) that outcrop around the lake. Olivine and pyroxene replacement occurred topotactically, whereas feldspar and glass alteration produced randomly oriented smectite in channels and cavities. The tetrahedral, octahedral, and interlayer compositions of the weathering products, largely dioctahedral smectites, varied with primary mineral composition, rock type, and as the result of addition of elements released from adjacent reaction sites. Weathering of the highly evolved, Fe-rich Jug Mountain complex at the north end of the lake produced a homogeneous smectite assemblage that contrasts with the heterogeneous smectite assemblage replacing the volcanics along the eastern margin of the lake. The variability within and between the smectite assemblages highlights the microenvironmental diversity, fluctuating redox conditions, and variable solution chemistry associated with mineral weathering reactions in the surficial environment. Late-stage exhalative and aqueous alteration of the volcanics redistributed many components and formed a variety of alkali and alkali-earth carbonate, chloride, sulfate, and fluoride minerals in vugs and cracks. Overall, substantial Mg, Si, Na, Ca, and K are released by weathering reactions that include the almost complete destruction of the Mg-smectite that initially replaced olivine. The leaching of these elements from the volcanics provides an important source of these constituents in the lake water. The nature of subsequent diagenetic reactions resulting from the interaction between the materials transported to the lake and the solution will be described in part II ( Banfield et al., 1991).

Geochimica et Cosmochimica Acta↗

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon: II. Diagenetic modification of the sedimentary assemblage

This paper compares the mineralogy and chemistry of clay minerals in sediments from various depths and positions in Abert Lake and surrounding playa with those of the weathered materials entering the lake in order to reveal the nature and extent of post-depositional mineralogical modification. Analytical electron microscope (AEM) data from individual clay particles reveal that each sample is comprised of a highly inhomogeneous smectite assemblage. The thin clay flakes (commonly less than 10 nm wide) display a complete range in octahedral sheet compositions from nearly dioctahedral to nearly trioctahedral. The very abundant Mg-rich lake smectites with an estimated composition K 0.29 (Al 0.23 -Mg 2.16 Fe 0.30 )Si 3.80 Al 0.20 O 10 (OH) 2 are not formed by weathering. This confirms the importance of diagenetic Mg uptake. Lattice-fringe imaging failed to reveal distinct brucite-like or vermiculite-like layers, suggesting that interstratifications of this type are rare or absent. Siliceous coatings on clay particles (identified by silica excess in smectite analyses) seem to favor topotactic overgrowth of stevensite rather than addition of brucite-like layers to the dioctahedral nuclei. The growth of K-stevensite dilutes the Al content of the crystal, and thus the increasing diagenetic modification reduces rather than supplements its illite component. Smectite compositions within individual samples were highly variable, yet source-related characteristics such as the abundance of Fe-rich smectite were apparent. Little evidence for systematic K or Mg enrichment with depth was identified in samples from depths of down to 16 feet below the sediment-water interface. The most magnesian assemblages are associated both with weathering sources of Mg-rich smectite and playa environments subjected to repeated wetting and drying cycles. Thus, the observations suggest that clay compositions primarily reflect changes in lake levels, brine composition, and source characteristics, rather than time and depth/compaction effects. Other diagenetic reactions in the sediment include recrystallization of Na-rich silica gel and diatom fragments. Abundant, submicron-sized, untwinned, euhedral crystals of K-feldspar are interpreted to be authigenic in origin.

Geochimica et Cosmochimica Acta↗

Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe

Fluorescence emission spectra of three samples of fluorite containing 226–867 ppm total rare earth elements (REE) were excited by visible and ultraviolet wavelength lines of an argon ion laser and recorded with a Raman microprobe spectrometer system. Narrow emission lines (< 1 nm) due to 4f-4f electron transitions in individual trivalent REE (Pr, Nd, Sm, Eu?, Tb, Dy, Ho, Er, Tm) were observed in the wavelength range of 400–900 nm. Emission from individual REE occur in bands of overlapping lines in the wavelength intervals of 470–495 nm, 535–560 nm, 565–580 nm, 585–620 nm, 640–643 nm, 671.4 nm, and 758.2 nm. A broad band at 419 nm excited by the 363.8-nm ultraviolet line of the laser is due to a 4f-5 d transition in Eu 2+ . Two bands of enigmatic origin are a narrow line at 682.8 nm present at all excitation wavelengths in only one sample and a broad band at 720 nm. We have tentatively assigned individual REE to specific lines in each emission band based on selection rules for strongly and weakly allowed 4f-4f transitions and the position of absorption and emission bands documented in the literature for REE in CaF 2 and LaF 3 host crystals. Working curves of integrated peak intensity of emission from Er 3+ and Eu 2+ vs. ppm measured by ICP-MS give linear log-log fits with R 2 > 0.9 for Eu 2+ and 0.99 for Er 3+ . Detection limits for three micrometer spots are about 0.01 ppm Eu 2+ and 0.07 ppm Er 3+ . These limits are less than chondrite abundance for Eu and Er, demonstrating the potential microprobe analytical applications of laser-excited fluorescence of REE in fluorite. However, application of this technique to common rock-forming minerals may be hampered by competition between fluorescence emission and radiationless energy transfer processes involving lattice phonons.

Geochimica et Cosmochimica Acta↗

Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12

The heat capacity of a synthetic almandine, Fe 3 Al 2 Si 3 O 12 , was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp 298 = 342.80 ± 1.4 J/mol · K and S 298 o = 342.60 J/mol · K. Mössbauer characterizations show the almandine to contain less than 2 ± 1% of the total iron as Fe 3+ . X-ray diffraction studies of this synthetic almandine yield a = 11.521 ± 0.001 Å and V 298 o = 115.11 +- 0.01 cm 3 /mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with T N = 7.5 K . Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ΔG f ,298 o = −4938.3 kJ/mol and ΔH f ,298 o = —5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T P "> TP for almandine and is metastably located at ca. 570°C at P = 1 bar, with a dP dT "> dPdT of +17 bars/°C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In ‖ O 2- T space, almandine oxidizes near QFM by the reactions almandine + O 2 = magnetite + sillimanite + quartz and almandine + 02 = hercynite + magnetite + quartz . With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks.

Geochimica et Cosmochimica Acta↗

Surface alteration and physical properties of glass from the Cretaceous-Tertiary boundary

The scalloped surface feature on Cretaceous-Tertiary boundary glass is often explained as being due to terrestrial aqueous leaching. Leaching of man-made glass results in a reduction in density of the glass. Also, Fe, because of its relative insolubility, is concentrated by the leaching process. Thus, the Haitian glass specimens which have been heavily altered should have a thin rim of less dense glass in which the Fe is concentrated compared to the core glass. The higher Fe concentration in the rim glass should cause it to have an enhanced Curie constant and a lower density compared to the unaltered glass. The magnetic Curie constant, density, and scanning electron microscopic studies were made on altered specimens of Haitian glass and also on specimens showing a minimum of alteration. The results show that the less altered samples have the highest density and the lowest Curie constant. The data substantiate the terrestrial hypothesis.

Geochimica et Cosmochimica Acta↗

Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400°C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from −6.25 moles alkali m −2 s −1 at 400°C to − 11.7 moles alkali m −2 s −1 at 200°C. The variation in these rates with temperature is given by the equation log k&#x2217; = &#x2212;8.17(1000/T(K)) + 5.54 (r 2 = 0.987) "> k∗ = −8.17(1000/T(K)) + 5.54 (r 2 = 0.987) which yields an activation energy of 37.4 ± 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ± 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100°C. Computed hydrogen diffusion coefficients range from −15.7 to −17.3 cm 2 s −1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause alteration of their radiometric ages. Furthermore, the rapid rate of hydrogen diffusion observed at 100–150°C suggests that fine-grained alunites are susceptible to rapid D-H re-equilibration even at surficial conditions.

Geochimica et Cosmochimica Acta↗

Chemistry of manganese precipitation in Pinal Creek, Arizona, USA: A laboratory study

Groundwater underlying the valley of Pinal Creek downstream from Globe, Arizona, has been contaminated by low-pH metal-enriched wastewater from copper mining and ore processing at Miami, Arizona. At present, the acidity and most of the dissolved metal content, except for Mn, of the wastewater is removed by reactions with carbonate and other solids in the alluvial aquifer before the neutralized contaminated water enters the creek channel and becomes surface flow. Where flow in the creek is perennial, Mn-bearing precipitates are formed in the stream bed and in some places in the subsurface. As an aid to understanding the processes involved and explaining the mineralogy of the precipitates, closely controlled laboratory redox titration experiments were performed on samples of surface flow and groundwater taken near the head of perennial flow in the creek. The high content of dissolved Ca, Mg, Mn and COP 2 species in the neutralized contaminated groundwater caused precipitation of some of the Mn as kutnahorite, (Mn, Mg)Ca(CO 3 ) 2 , when the experimental system was held between pH 8.5 and 9.0 while CO 2 -free air was bubbled into the solution. Hausmannite and manganite also were precipitated, in somewhat lower amounts. When the concentrations of dissolved CO 2 species in the groundwater sample were decreased before the experiment was started, the Mn precipitated was predominantly in the oxides hausmannite and manganite. In some of the experimental titrations clinoenstatite, (MgSiO 3 ), was precipitated. After titrations were stopped the solutions and precipitates were allowed to stand, with limited access to the atmosphere, for several months. During this aging period the degree of oxidation of the precipitated Mn increased and in one precipitate from an experimental solution the Ca + Mn 4+ oxides todorokite and takanelite were identified. These oxides also have been identified in streambed precipitates. Some of these precipitates also gave X-ray diffraction reflections for kutnahorite. Thermodynamic feasibilities of eight potential chemical reactions forming solid phases of interest were evaluated by calculating their respective reaction affinities attained during titration and aging. The results are in general agreement with the indications for the presence of these species given by X-ray and electron diffraction. The presence of carbonates in precipitated encrustations formed from groundwater below the land surface and their occurrence in manganese oxide crusts that precipitate from the creek water, also are predicted by these results.

Geochimica et Cosmochimica Acta↗

Imaging experiment: The Viking Mars orbiter

The general objectives of the Imaging Experiment on the Viking Orbiter are to aid the selection of Viking Lander sites, to map and monitor the chosen sites during lander operations, to aid in the selection of future landing sites, and to extend our knowledge of the planet. The imaging system consists of two identical vidicon cameras each attached to a 1026 mm T/8 telescope giving approximately 1° square field of view. From an altitude of 1500 km the picture elements will be approximately 24m apart. The vidicon is coupled with an image intensifier which provides increased sensitivity and permits electronic shuttering and image motion compensation. A vidicon readout time of 2.24 sec enables pictures to be taken in rapid sequence for contiguous coverage at high resolution. The camera differs from those previously flown to Mars by providing contiguous coverage at high resolution on a single orbital pass, by having sufficient sensitivity to use narrow band color filters at maximum resolution, and by having response in the ultraviolet. These capabilities will be utelized to supplement lander observations and to extend our knowledge particularly of volcanic, erosional, and atmospheric phenomena on Mars.

Icarus↗

Naturally occurring vapor-liquid-solid (VLS) Whisker growth of germanium sulfide

The first naturally occurring terrestrial example of vapor-liquid-solid (VLS) growth has been observed in condensates from gases released by burning coal in culm banks. Scanning electron microscopy, X-ray diffraction, and energy dispersive analysis indicate that the crystals consist of elongated rods (≈ 100 μm) of germanium sulfide capped by bulbs depleted in germanium.

Journal of Crystal Growth↗

Can otolith microchemistry chart patterns of migration and habitat utilization in anadromous fishes?

Seasonal and ontogenetic patterns in estuarine and coastal migrations of anadromous fish species have important consequences to their survival, growth, recruitment, and reproduction. We tested the hypothesis that otolith (sagitta) microchemistry can document the environmental history of individual fish across an estuarine salinity gradient. Juvenile striped bass, Morone saxatilis (Walbaum), (80 days posthatch) were reared for 3 wk in aquaria at two temperatures and six salinities. The ratio of strontium/calcium ( Sr Ca "> SrCa ) deposited in the sagittal otoliths of reared juveniles was positively related to salinity. Temperature and growth rate had relatively minor, but significant effects on the Sr Ca "> SrCa ratio. In a second experiment, juveniles (80 days posthatch) were exposed to increasing salinity (0 ppt to 25 ppt) and then decreasing salinity (25 ppt to 0 ppt) over a 20-wk period. Electron microprobe examination of the otoliths from these juveniles showed a gradual rise and decline in Sr Ca "> SrCa during the experimental period which corresponded directly with experimental changes in salinity. Field data on subadult and adult striped bass corroborated the laboratory analyses and indicated a logistic relationship between ambient salinity and otolith Sr Ca "> SrCa ratio. Verification studies support the use of otolith microchemistry to measure migratory schedules and habitat utilization patterns in anadromous striped bass populations.

Journal of Experimental Marine Biology and Ecology↗

Phase relations in the CuVS system

Phase relations in the system Cu-V-S were studied by using a sealedcapsule technique, reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis. In the temperature range between 300 and 900 ??C, six vanadium sulfides exist in the V-S system. These are VS, V7S8, V3S4, V5S8, V3S5 and VS4. In the Cu-V-S system, three Cu-V sulfides are stable. Both Cu3VS4 (sulvanite) and CuV2S4 are cubic with a = 5.391 ?? 0.005 A ?? and a = 9.789 ?? 0.005 A ?? respectively, and the third has a composition Cu0.8V1.1S2. CuV2S4 forms equilibrium assemblages with all vanadium sulfides, which restricts their effects on the phase relations in the system to a small region. ?? 1986.

Journal of the Less-Common Metals↗

Phase relations in the system CuMoS

Phase relations in the system CuMoS were studied in the temperature range 500-1000 ??C by using the conventional sealed, evacuated glass capsule technique. Reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis were used for phase characterization. The chevrel-type phase, CuxMo3S4, is stable above 600??C, and forms equilibrium assemblages with the cubic Cu2S solid solution, copper, molybdenum, Mo2S3 and MoS2. Its solid solution ranges from Cu1.50-2.00Mo3S4 at 700??C to Cu1.22-2.00Mo3S4 at 1000 ??C. ?? 1990.

Journal of the Less-Common Metals↗

Coexisting cummingtonite and aluminous hornblende from garnet amphibolite, Boehls Butte area, Idaho, USA

Electron microprobe analyses of green hornblende and coexisting cummingtonite from garnet amphibolite show identical Fe/Mg ratios ( = 0.9). Cummingtonite is iron-magnesium silicate with very little calcium and aluminum and practically no alkalies. In contrast, the hornblende has 1.5 tetrahedral Al, 0.9 octahedral Al and a considerable amount of Ca and alkalies. Comparison with the hornblendes from the Sierra Nevada shows a higher relative amount of tschemakite molecule in the hornblendes from Idaho where pressures during the recrystallization were higher.

Idaho↗