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At least 487 records · Page 27Linked to original sources
USGS2007

Biodegradation of PAHs and PCBs in soils and sludges

Results from a multi-year, pilot-scale land treatment project for PAHs and PCBs biodegradation were evaluated. A mathematical model, capable of describing sorption, sequestration, and biodegradation in soil/water systems, is applied to interpret the efficacy of a sequential active-passive biotreatment process of organic chemicals on remediation sites. To account for the recalcitrance of PAHs and PCBs in soils and sludges during long-term biotreatment, this model comprises a kinetic equation for organic chemical intraparticle sequestration process. Model responses were verified by comparison to measurements of biodegradation of PAHs and PCBs in land treatment units; a favorable match was found between them. Model simulations were performed to predict on-going biodegradation behavior of PAHs and PCBs in land treatment units. Simulation results indicate that complete biostabilization will be achieved when the concentration of reversibly sorbed chemical (S RA) reduces to undetectable levels, with a certain amount of irreversibly sequestrated residual chemical (S IA) remaining within the soil particle solid phase. The residual fraction (S IA) tends to lose its original chemical and biological activity, and hence, is much less available, toxic, and mobile than the "free" compounds. Therefore, little or no PAHs and PCBs will leach from the treatment site and constitutes no threat to human health or the environment. Biotreatment of PAHs and PCBs can be terminated accordingly. Results from the pilot-scale testing data and model calculations also suggest that a significant fraction (10-30%) of high-molecular-weight PAHs and PCBs could be sequestrated and become unavailable for biodegradation. Bioavailability (large K d , i.e., slow desorption rate) is the key factor limiting the PAHs degradation. However, both bioavailability and bioactivity (K in Monod kinetics, i.e., number of microbes, nutrients, and electron acceptor, etc.) regulate PCBs biodegradation. The sequential active-passive biotreatment can be a cost-effective approach for remediation of highly hydrophobic organic contaminants. The mathematical model proposed here would be useful in the design and operation of such organic chemical biodegradation processes on remediation sites. ?? 2007 Springer Science+Business Media B.V.

Water, Air, & Soil Pollution↗
USGS2020

Sediment record of mining legacy and water quality from a drinking-water reservoir, Aztec, New Mexico, USA

The record of mining legacy and water quality was investigated in sediments collected in 2018 from four trenches in the Aztec, New Mexico, drinking-water reservoir #1. Bulk chemical analysis of sediments with depth in the reservoir revealed variable trace-element (uranium, vanadium, arsenic, copper, sulfur, silver, lead, and zinc) concentrations, which appear to coincide with historical mining and milling operations. Cesium-137 age dating, which identified the location of the 1963 radioactive fallout maximum, combined with the known age of the bottom and top of the sediment trenches, was used to estimate a polynomial sedimentation rate (average rate = 1.7 cm/yr). The clay size fraction (< 0.004 mm) was the dominant grain-size fraction of the sediments. Abundant fine-grained phyllosilicate (clay) minerals, predominantly montmorillonite and kaolinite, may explain sorption properties of trace elements. Scanning electron microscopy evaluation of sediments from two trenches showed copper and zinc associated with sulfur, and arsenic associated with iron and aluminum oxides. Results from laboratory batch experiments indicated that uranium, vanadium, and arsenic were released when sediments were reacted with a 150 mg/L sodium bicarbonate solution whereas copper was released when sediments were reacted with 2 mMol/L acetic acid. Observed concentrations from the two leach tests were below regulatory thresholds for delivery of solids to a landfill and were below drinking-water standards. Diatom relative abundance indicates that the water quality in the reservoir was not impaired by high metal concentrations.

Colorado, New Mexico↗
USGS1972

Occurrence of chromian, hercynitic spinel ("pleonaste") in Apollo-14 samples and its petrologic implications

Many isolated grains of a reddish pleonaste-type spinel occur in fines and metabreccia samples, particularly 14 319. Electron microprobe analyses (104) of spinels and their associated phases include 58 of pleonaste which show Mg/(Mg + Fe) 0.44–0.62 and Cr/(Cr + Al) 0.017–0.134 (atomic), plus minor amounts of other ions, and differ greatly from almost all previously recorded lunar spinels; almost no spinels of intermediate composition were found. Two types of compositional zoning exist: a diffuse primary one with cores lower in Ti, and a narrow secondary one from reaction with matrix yielding rims higher in Cr, Ti, and Mn. At contacts with breccia matrix there is a narrow corona of almost pure plagioclase (An 80 -An 94 ), free of opaque minerals and pyroxene. Two types of solid inclusions found in the pleonaste are calcic plagioclase, and tiny spherical masses of nickel-rich sulfide. Similar pleonaste occurs in crystalline rock clasts, mainly with plagioclase; one clast (A) consists only of coarse olivine, plagioclase, and pleonaste, with granulated grain boundaries suggestive of deformation. From composition and texture, this clast is one possible candidate for the mafic cumulate counterpart of the “anorthositic” crust. Another clast (B), also made solely of olivine, plagioclase and pleonaste, is itself a breccia. These data suggest a two-stage brecciation process: 1) disruption (probably pre-Imbrian) of a deep-seated pleonaste-bearing source rock like A and reconsolidation to form a breccia without addition of pyroxene, ilmenite or other minerals; and 2) disruption of this breccia to yield breccia clast B which was then incorporated into the Fra Mauro formation.

Earth and Planetary Science Letters↗
USGS1972

Silicate melt inclusions and glasses in lunar soil fragments from the Luna 16 core sample

More than 2000 fragments were studied microscopically, and electron microprobe analyses were made of 39 selected areas, from a few square mm of polished surface, through 75- to 425-μm fragments of lunar soil from two samples of the Luna 16 core. The silicate melt inclusions and glasses differ in important details from those observed earlier in the Apollo samples. Melt inclusions in olivine contain epitaxially oriented daughter crystals, but also show a similar epitaxy around the outside of the crystals not observed in previous lunar samples. Melt inclusions in ilmenite suggest trapping at successive stages in a differentiation sequence. There is abundant evidence for late-stage silicate liquid immiscibility, with melt compositions similar but not identical to those from Apollo 11 and 12. A comparison of the alkali ratio of any given bulk rock analysis with that of its late-stage, high-silica melt shows gross differences for different rocks. This is pertinent to understanding late-stage differentiation processes. Glass fragments and spherules exhibit a wide range of crystallization textures, reflecting their wide range of compositions and cooling histories. No significant differences were found between the two portions of core examined (Zones A and D).

Earth and Planetary Science Letters↗
USGS1996

Distinguishing shocked from tectonically deformed quartz by the use of the SEM and chemical etching

Multiple sets of crystallographically-oriented planar deformation features (PDFs) are generated by high-strain-rate shock waves at pressures of > 12 GPa in naturally shocked quartz samples. On surfaces, PDFs appear as narrow (50-500 nm) lamellae filled with amorphosed quartz (diaplectic glass) which can be etched with hydrofluoric acid or with hydrothermal alkaline solutions. In contrast, slow-strain-rate tectonic deformation pressure produces wider, semi-linear and widely spaced arrays of dislocation loops that are not glass filled. Etching samples with HF before examination in a scanning electron microscope (SEM) allows for unambiguous visual distinction between glass-filled PDFs and glass-free tectonic deformation arrays in quartz. This etching also reveals the internal 'pillaring' often characteristic of shock-induced PDFs. This technique is useful for easily distinguishing between shock and tectonic deformation in quartz, but does not replace optical techniques for characterizing the shock features.

Earth and Planetary Science Letters↗
USGS1984

Distribution of trace elements in coal from the Powhatan No. 6 mine, Ohio

Size and density separates of low-temperature-ashed coal from the Powhatan No. 6 mine, Ohio, have been used to determine the mode of occurrence of 28 minor and trace elements in coal. The size distribution of the major minerals has been determined, and correlations of trace elements with major minerals have been made. The role of minor minerals in the mode of occurrence of trace elements is also discussed. Instrumental-neutron-activation analysis was used to determine elemental concentrations, and X-ray diffraction and scanning electron microscopy were used for mineral identification.

Ohio↗
USGS1980

Deep-sea spherules from Pacific clay: Mass distribution and influx rate

From 411 kg of Pacific clay, 22 mg of stony spherules and 50 mg of iron spherules larger than 150 μm were concentrated. The extraterrestrial origin of these particles was evaluated with the aid of both optical and electron microscopy as well as atomic absorption elemental analysis. The integral number ( N ) of stony particles from this sediment in the mass (M) range 20–300 μg is given by N ( > M ( g )) = 5.13 × 10 −6 × M −1.65 . The world-wide influx rate of stony particles in the mass range which survive atmospheric heating and ocean sediment storage is calculated to be 90 tons/yr. The relative contributions of ablation debris vs fused interplanetary dust to the influx of stony spherules is discussed, but as yet the question remains unanswered.

Geochimica et Cosmochimica Acta↗
USGS1983

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO 2 initially, and open to organic carbon at more distant points down gradient.

Geochimica et Cosmochimica Acta↗
USGS1985

Degradation of carbohydrates and lignins in buried woods

Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, 13 C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15–25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, 13 C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and p- hydroxyl "> p-hydroxyl lignin structural units > syringyl and lignin structural units > pectin > α-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source.

Geochimica et Cosmochimica Acta↗
USGS1987

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↗
USGS1988

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↗
USGS1989

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↗
USGS1989

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↗
USGS1991

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↗
USGS1991

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↗
USGS1994

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↗
USGS1994

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↗
USGS1972

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↗