Characterizing heterogeneous permeable media with spatial statistics and tracer data using sequential simulated annealing

Characterizing heterogeneous permeable media using flow and transport data typically requires solution of an inverse problem. Such inverse problems are intensive computationally and may involve iterative procedures requiring many forward simulations of the flow and transport problem. Previous attempts have been limited mostly to flow data such as pressure transient (interference) tests using multiple observation wells. This paper discusses an approach to generating stochastic permeability fields conditioned to geologic data in the form of a vertical variogram derived from cores and logs as well as fluid flow and transport data, such as tracer concentration history, by sequential application of simulated annealing (SA). Thus, the method incorporates elements of geostatistics within the framework of inverse modeling. For tracer-transport calculations, we have used a semianalytic transit-time algorithm which is fast, accurate, and free of numerical dispersion. For steady velocity fields, we introduce a transit-time function which demonstrates the relative importance of data from different sources. The approach is illustrated by application to a set of spatial permeability measurements and tracer data from an experiment in the Antolini Sandstone, an eolian outcrop from northern Arizona. The results clearly reveal the importance of tracer data in reproducing the correlated features (channels) of the permeability field and the scale effects of heterogeneity.     

Geochemical and structural evolution of micas in the Rožná and Dobrá Voda pegmatites,Czech Republic

Summary The chemistry, structural parameters, polytypism, optical properties and Rb-Sr isotopes were examined in 11 to 60 samples of biotite, muscovite and lepidolite from the pegmatites at Roná (the type locality of lepidolite; 323 ± 4Ma) and Dobrá Voda (306 ± 9Ma) in western Moravia. At both localities, early endocontact biotite is followed inwards by muscovite and lepidolite, which is concentrated in and around the core. At Roná, a 1M lepidolite follows after 2M₁ muscovite but all later generations of lepidolite are 2M₂, close to Tri₅₀ Ply₅₀ and in part associated with muscovite 2M₁. At Dobrá Voda, all lepidolite types are 1M and free of muscovite, and the late varieties approximate Tri₃₀ Ply₇₀. At both localities, a trend of increasing HF is indicated during the progress of mica crystallization, culminating in precipitation of topaz. Polytypism of lepidolite is not correlatable with any compositional or growth feature, or their combination. Throughout the mica crystallization, Rb/Cs decreases but K/Rb becomes reversed after an initial decrease. Boron is partitioned preferentially into muscovite (up to 1.10 wt.% B₂O₃) but Be, Zn, Mn and Sc are enhanced in lepidolite. A slight increase in Fe, Ba and Cl in the last generation of lepidolite might be possibly due to mixing of residual pegmatite fluids with metamorphic pore solutions.

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Geochemische und strukturelle Entwicklung der Glimmer in den Pegmatiten von Roná und Dobrá Voda, Tschechische Republik

Zusammenfassung In 11 bis 60 Proben von Biotit, Muskovit und Lepidolith aus den Pegmatiten von Roná (Typlokalität des Lepidoliths; 323 ± 9 Ma) in Westmähren wurden Chemie, Struktur-parameter, Polytypie, optische Eigenschaften und Rb-Sr-Isotopie untersucht. An beiden Lokalitäten wird früher Biotit an Endokontakten nach Innen von Muskovit und Lepidolith gefolgt, letzterer ist in und um den Kern konzentriert. In Roná folgt 1M-Lepidolith auf 2M₁-Muskovit, aber alle späteren Lepidolithgenerationen sind 2M₂, nahe Tri₅₀Ply₅₀ und zum Teil mit 2M₁-Muskovit vergesellschaftet. In Dobrá Voda sind alle Lepidolithe vom Typ 1M und frei von Muskovit, die späten Varietäten kommen Tri₅₀Ply₅₀ nahe. An beiden Lokalitäten ist während des Fortschreitens der Glimmerkristallisation eine Tendenz von steigendem HF angezeigt, die in der Ausfällung von Topas ihren Höhepunkt findet. Die Polytypie des Lepidoliths kann nicht mit irgendeiner Eigenheit der Zusammensetzung oder des Wachstums korreliert worden, auch nicht mit einer Kombination von diesen. Während der ganzen Glimmerkristallisation nimmt Rb/Cs ab, aber die Tendenz von K/Rb ändert sich nach anfänglichem Abfall. Das Bor verteilt sich bevorzugt auf den Muskovit (bis zu 1.10 Gew. -% B₂O₃), aber die Be-, Zn-, Mn- und Sc-Gehalte sind im Lepidolith erhöht. Ein leichter Ansteig von Fe, Ba und Cl in der letzten Lepidolithgeneration könnte vielleicht durch eine Mischung von pegmatitischen Restlösungen mit metamorphen Porenlösungen verursacht sein.

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With 9 Figures     

Probabilistic seismic hazard zonation of Syria

Earthquake hazard maps for Syria are presented in this paper. The Peak Ground Acceleration (PGA) and the Modified Mercalli Intensity (MMI) on bedrock, both with 90% probability of not being exceeded during a life time of 50, 100 and 200 years, respectively are developed. The probabilistic PGA and MMI values are evaluated assuming linear sources (faults) as potential sources of future earthquakes. A new attenuation relationship for this region is developed. Ten distinctive faults of potential earthquakes are identified in and around Syria. The pertinent parameters of each fault, such as theb-parameter in the Gutenberg-Richter formula, the annual rate ₄ and the upper bound magnitudem ₁ are determined from two sets of seismic data: the historical earthquakes and the instrumentally recorded earthquake data (AD 1900–1992). The seismic hazard maps developed are intended for preliminary analysis of new designs and seismic check of existing civil engineering structures.     

Crystallization processes in an artificial magma: variations in crystal shape,growth rate and composition with melt cooling history

A large (4.8 m³, 1.3x10⁷ g) artificial mafic melt with a bulk composition similar to that of a basalt (but with a high CaO content of 17 wt%) was generated during a demonstration of in situ vitrification and was allowed to cool naturally. During the melting process, convection was vigorous, resulting in a chemically and thermally homogeneous melt body. Once heating was complete, the cooling rate was rapid with the temperature dropping from 1500°C to 500°C in 6 days within the interior of the 3 m diameter, 1.5 m thick body. A 20 h period of constant temperature (1140°C) observed during colling was the result of latent heat released by widespread crystallization. The final crystalline assemblage consists of diopsidic to hedenbergitic pyroxene and anorthitic feldspar, with a subordinate amount of potassic feldspar, plus a small amount of evolved glass. The compositions and proportions of phases agree well with those predicted by the MELTS thermodynamic model. Thermal and textural evidence suggest that convection within the melt ceased coincident with formation of the first crystals. Textural investigation of core samples reveals large (up to 1 cm in length) acicular diopsidic pyroxenes in a matrix of smaller feldspar and zoned pyroxene crystals (500 m in length). Crystal shape and pyroxene composition vary as a function of position within the solidified body, as a function of cooling rate. Both crystal size and degree of crystallinity are highest in the central, most slowly-cooled parts of the rock. Crystal shape is characterized by tabular, equilibrium-growth forms in the slowly-cooled areas, grading to highly skeletal, dendritic forms at the rapidly-cooled edges of the body. The pyroxene crystals are dominantly homogeneous diopside, but crystals are characterized by thin Fe-rich hedenbergitic rims. These rims were deposited when Mg in the melt was depleted by diopside growth, and melt temperature had cooled sufficiently to allow Fe-rich pyroxene growth. Crystal growth rates can be calculated based on thermal behavior of the melt, reinforced by thermodynamic modelling, and are determined to be between 10^-7 and 10^-8 cm/s in the central part of the melt. These estimates agree well with growth rates in natural systems with similar cooling rates. Pyroxene crystals that formed at a higher cooling rates are characterized by higher Al and lower Mg contents relative to tabular equilibrium crystalline forms, presumably as a result of disequilibrium melt compositions at the crystal-melt interface.New Mexico Bureau of Mines and Mineral Resources, New Mexico Institute of Mining and Technology, Socorro, NM 87801, USA     

Metamorphism, Fluid Flow and Partial Melting in Pelitic Rocks from the Onawa Contact Aureole, Central Maine, USA

Field, petrologic and geochemical data were used to characterizefluid infiltration and partial melting during metamorphism ofpelitic rocks in the contact aureole of the Onawa pluton, centralMaine, USA. Mineral assemblages delineate five metamorphic zoneswithin the contact aureole: chlorite zone, andalusite–cordierite(a–c) zone, alkali feldspar zone, sillimanite zone andleucocratic-vein (l–v) zone. The sequence of observedmineral assemblages and mineral–fluid reactions calculatedby mass balance is similar to those observed in other contactaureoles. Pressure of contact metamorphism is 3 kbar, on thebasis of optimum geothermobarometry calculations. Metamorphictemperatures vary from 500C in the andalusite–cordieritezone to 65OC in the leucocratic-vein zone. Data from fieldobservations, mineral textures, observed reaction stoichiometry,geothermometry and major-element geochemistry suggest that theleucocratic veins of the l-v zone represent crystallized, partialmelts. Two overall calculated mineral reactions are responsiblefor vein formation: which can be modeled as combinations of two NKFMTASH meltingreactions: Progress of (M1) and (M2) was measured in eight samples, andreaction (M1) is the dominant melt-forming reaction in all samples.Partial melting (and vein formation) was therefore driven byinfiltration of the l-v zone by H²O-rich fluids. Calculatedtime-integrated fluid fluxes for l-v zone samples range from09 10⁴ to 31 10⁴ mol/cm², and flow was in the directionof increasing temperature. KEY WORDS: pelites; contact metamorphism; fluid infiltration; partial melting; Onawa Pluton; Maine; USA ^*Corresponding author. Telephone:(516) 632–8192. Fax (516)632–8240 e-mail: gsymmes{at}ccmail.sunysb.edu     

Geochemical Evidence for Subduction Fluxes, Mantle Melting and Fractional Crystallization Beneath the South Sandwich Island Arc

The volcanoes of the South Sandwich island arc follow threedistinct series: low-K tholeiitic (followed by Zavodovski, Candlemas,Vindication, Montagu and Bristol), tholeiitic (followed by Visokoi,Saunders and Bellinghausen) and calcalkaline (followed by Leskov,Freehand and part of Cook and Thule). Flux calculations indicatethat the percentage contribution of the subduction componentto the mantle source of all three series varies from undetectable(e.g. Zr) through small (e.g. Nd=20%) and moderate (e.g. La,Ce, Sr=50–80%) to dominant (e.g. Pb, K, Ba, Rb, Cs >90%)with little change along the arc. Isotope systematics (Pb, Nd,Sr) show that this subduction component obtains a greater contributionfrom altered oceanic crust than from pelagic sediment. Elementsfor which the subduction contribution is small show that themantle is already depleted relative to N-MORB mantle (equivalentto loss of an 2•5% melt fraction) before melting beneaththe arc. After addition of the subduction component, dynamicmelting of this depleted mantle then causes the variations inK that distinguish the three series. The estimated degree ofpartial melting (20%) is slightly greater than that beneathocean ridges, though geothermometry suggests that the primarymagma temperature (1225C) is similar to that of primary MORB.About half of the melting may be attributed to volatile addition,and half to decompression. Dynamic melting involving three-dimensional,two-phase flow may be needed to explain fully the inter-islandvariations. KEY WORDS: geochemistry; petrology; fluxes; melting; subduction ^*Corresponding author     

A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.     

Radiometric constraints on hydrothermal circulation in cooling granite plutons

Improved precision of radiometric dating of ore deposits can provide information about the thermal history of hydrothermal circulation in cooling plutons. In Jales a Hercynian porphyritic two-mica granite and pre-Ordovician mica schists are cut and intensely altered by the Campo gold-quartz vein. The unaltered granite must be younger than 320 ± 6 Ma, and gives mica Rb-Sr ages of 308.5 ± 2.4 (1) Ma (muscovite) and 294.5 ± 1.1 Ma (biotite). Alteration muscovites from the granite give a weighted mean Rb-Sr age of 308.1 ± 1.5 Ma, and a mean ³⁹Ar-⁴⁰Ar age of 300.7 ± 2.8 Ma. Alteration muscovites from the mica schists give similar ³⁹Ar-⁴⁰Ar ages, averaging 303.0 ± 2.8 Ma. The results suggest that circulation of the Campo mineralising fluids took place no more than 2–4 Ma after the granite cooled through the muscovite Rb-Sr closure temperature, about 500 °C, and that subsequent cooling to biotite closure at about 300 °C took place at less than 14°C/Ma. The mean cooling rate following emplacement was 15 to 25 °C/Ma. The most detailed comparable published data, for the Cornubian ore field, imply much faster cooling rates.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.