The Use of Stable Sulfur, Oxygen and Hydrogen Isotope Ratios as Geochemical Tracers of Sulfates in the Podwiśniówka Acid Drainage Area (South-Central Poland)

The paper presents the results of determinations of stable S and O isotopes of dissolved sulfates and O and H stable isotopes of waters from three ponds, that is, Marczakowe Do?y acid pond, Marczakowe Do?y fish pond and Podwi?niówka acid pit pond, located in the Holy Cross Mountains (south-central Poland). The δ³⁴S_V-CDT and δ¹⁸O_V-SMOW of SO₄ ^2? in waters of three ponds (n = 14) varied from ?16.2 to ?9.5 ‰ (mean of ?13.6 ‰) and from ?8.1 to ?3.2 ‰ (mean of ?4.8 ‰), respectively. The mean δ³⁴S–SO₄ ^2? values were closer to those of pyrite (mean of ?25.4 ‰) and efflorescent sulfate salts (mean of ?25.6 ‰), recorded previously in the Podwi?niówka quarry, than to sulfates derived from other anthropogenic or soil and bedrock sources. The SO₄ ^2? ions formed by bacterially induced pyrite oxidation combined with bacterial (dissimilatory) dissolved sulfate reduction, and presumably with subordinate mineralization of carbon-bonded sulfur compounds, especially in both Marczakowe Do?y ponds. In addition, the comparison of δ¹⁸O–SO₄ ^2? and δ¹⁸O–H₂O values indicated that 75–100 % of sulfate oxygen was derived from water. Due to the largest size, the Podwi?niówka acid pit pond revealed distinct seasonal variations in both δ¹⁸O–H₂O (?9.2 to ?1.6) and δD–H₂O (?29.7 to ?71.3) values. The strong correlation coefficient (r ² = 0.99) was noted between δ¹⁸O–H₂O and δD–H₂O values, which points to atmospheric precipitation as the only source of water. The sediments of both acid ponds display different mineral inventory: the Marczakowe Do?y acid pond sediment consists of schwertmannite and goethite, whereas Podwi?niówka acid pit pond sediment is composed of quartz, illite, chlorite and kaolinite with some admixture of jarosite reflecting a more acidic environment. Geochemical modeling of two acid ponds indicated that the saturation indices of schwertmannite and nanosized ε-Fe₂O₃ (Fe³⁺ oxide polymorph) were closest to thermodynamic equilibrium state with water, varying from ?1.44 to 3.05 and from ?3.42 to 6.04, respectively. This evidence matches well with the obtained mineralogical results.     

Small angle X-ray scattering mapping and kinetics study of sub-critical CO2 sorption by two Australian coals

Time- and position-resolved synchrotron small angle X-ray scattering data were acquired from samples of two Australian coal seams: Bulli seam (Bulli 4, R_o = 1.42%, Sydney Basin), which naturally contains CO₂ and Baralaba seam (R_o = 0.67%, Bowen Basin), a potential candidate for sequestering CO₂. This experimental approach has provided unique, pore-size-specific insights into the kinetics of CO₂ sorption in the micro- and small mesopores (diameter 5 to 175 Å) and the density of the sorbed CO₂ at reservoir-like conditions of temperature and hydrostatic pressure.For both samples, at pressures above 5 bar, the density of CO₂ confined in pores was found to be uniform, with no densification in near-wall regions. In the Bulli 4 sample, CO₂ first flooded the slit pores between polyaromatic sheets. In the pore-size range analysed, the confined CO₂ density was close to that of the free CO₂. The kinetics data are too noisy for reliable quantitative analysis, but qualitatively indicate faster kinetics in mineral-matter-rich regions.In the Baralaba sample, CO₂ preferentially invaded the smallest micropores and the confined CO₂ density was up to five times that of the free CO₂. Faster CO₂ sorption kinetics was found to be correlated with higher mineral matter content but, the mineral-matter-rich regions had lower-density CO₂ confined in their pores. Remarkably, the kinetics was pore-size dependent, being faster for smaller pores.These results suggest that injection into the permeable section of an interbedded coal-clastic sequence could provide a viable combination of reasonable injectivity and high sorption capacity.     

Sediment dispersal and provenance in the Silesian,Dukla and Magura flysch nappes (Outer Carpathians,Poland)

The Polish Outer Carpathians consist of several flysch series of unknown original basement. They were deposited from Late Jurassic to Miocene in a large basin dissected by tectonically uplifted ridges (cordillieras) which acted as source terrains. The actual nappe pile is correlated with palaeogeographic basin realms. From N to S the Skole, Silesian, Dukla and Magura basins are distinguished. Our paper presents a first compilation of heavy mineral data and pebble analysis in the various turbiditic fan systems. It is assumed that the heavy minerals primarily reflect the nature of basement rocks exposed in the source terrains.The individual flysch basins were supplied generally from unmetamorphosed granitic to highgrade metamorphic continental basement series. But staurolite-bearing high-grade metamorphics appear to have been present only in the northernmost provenance area (Silesian and Subsilesian ridges). A few reworked chromian spinel mineral grains in the northern parts of the basin were derived from small Caledonian/Variscan ultrabasic sutures present in the source ridges. Increased chromian spinel contents are revealed in the southern part of the basin (Maastrichtian-Eocene Magura series) and in Cretaceous Pieniny Klippen belt flysch formations. The chromian spinel in the Magura series was derived, either directly from Alpine oceanic crust obducted in the southern part of the Pieniny realm, or from re-eroded Pieniny flysch series. Hence, our heavy mineral data indicate that in the Outer Carpathian basin during Cretaceous convergence no Alpine ophiolitic crust was obducted. Therefore, an ophiolitic basement to the individual basins appears inprobable. The Outer Carpathians presumably occupied, with respect to the internal suture zone, the position of a deep continental basement floored foreland basin.

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Zusammenfassung Die Äußeren Karpathen in Polen bestehen aus mehreren von ihrem Untergrund abgescherten Flysch-Serien, die von oberem Jura bis Miozän in einem Großbecken abgelagert wurden, das durch mehrere tektonisch hochgehobene Rücken (Cordillieren oder Liefergebiete) in Teilbecken gegliedert war. Das ursprüngliche Substrat der verschiedenen Becken ist unbekannt und die heutige Deckenstruktur wird mit der ursprünglichen Beckenanordnung korreliert. Von N nach S werden die Skole-, Silesien-, Duklaund Magura-Becken unterschieden. Die vorliegende Arbeit präsentiert eine erste Zusammenfassung von Schwermineraldaten und Geröllanalysen in den verschiedenen turbiditischen Schüttungssystemen. Dabei wird davon ausgegangen, daß die Schwermineralgehalte der Sandsteine primär die Zusammensetzung des kristallinen Grundgebirges in den Liefergebieten widergeben.Die einzelnen Flyschbecken wurden zumeist von unmetamorphem granitischem bis hochgradig metamorphem kontinentalem Grundgebirge beliefert. Staurolith-führende hochgradige Metamorphite waren jedoch nur in den nördlichst gelegenen Liefergebietsprovinzen (Silesischer und Subsilesischer Rücken) anstehend. Geringe Vorkommen von Chromspinell in den nördlichen Beckenteilen stammen von kleineren caledonisch/variszischen ultrabasischen Einschlüssen (Suturen) in den Cordillieren. Erhöhte Chromspinellgehalte werden nur im südlichen Becken (Maastricht bis Tertiär des Magura-Beckens) und in kretazischen Flyschen der Pieniny-Klippen festgestellt. Der Chromspinell in den Magura-Serien stammt von alpiner ozeanischer Kruste, die während der Kreide im südlichen Pieniny-Raume obduziert wurde oder von neuerlich erodierten Flyschen aus den Pieniny-Becken. Unsere Schwermineraldaten weisen folglich darauf hin, daß während der kretazischen tektonischen Konvergenz im Bereich der Äußeren Karpathen keine alpin gebildete ophiolithische Kruste aufgeschuppt wurde. Die Anwesenheit eines ozeanischen Untergrundes der einzelnen Teilbecken erscheint deshalb unwahrscheinlich. Die Äußeren Karpathen nahmen deshalb vermutlich gegenüber der internen Suturzone die Stellung eines tiefen Foreland-Beckens über kontinentaler Kruste ein.

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Résumé Les Carpathes externes, en Pologne, sont composées de plusieurs séries de flysch d'âge jurassique à miocène déposées dans un grand bassin alimenté par l'érosion de rides tectoniques internes et externes (cordillères). Ces séries de flysch sont préservées en nappes, classiquement corrélées avec différents domaines paléogéographiques du bassin. Le substratum originel de ces bassins individuels n'est pas connu et reste discuté. On distingue, du nord au sud, les bassins de Skole, de Silésie, de Dukla et de Magura. Nous présentons ici les premiers résultats de l'analyse des minéraux lourds et des lithoclastes reconnus dans les principaux éventails turbiditiques sous-marins. Nous partons de l'hypothèse que le contenu des grès en minéraux lourds reflète la nature du socle cristallin qui était à l'affleurement dans les diverses régions-source.D'une manière générale, les bassins de flysch ont été alimentés par des terrains granitiques non métamorphiques et par des formations métamorphiques de moyenne et haute température. Il semble cependant que les terrains métamorphiques de haut degré à staurotide étaient présents seulement dans les sources les plus septentrionales (rides silésienne et subsilésienne). Le spinelle chromifère présent en petite quantité dans la partie nord du bassin peut être expliqué par la présence d'inclusions ultramafiques calédoniennes ou varisques (zones de sutures) dans les cordillères. Une proportion élevée de grains de spinelle chromifère ne s'observe que dans la partie méridionale du bassin des Carpathes externes (séries maastrichtiennes et tertiaires du bassin de Magura) et dans les flyschs crétacés des clippes de Pieniny. Il est suggéré que le spinelle chromifère du bassin de Magura a été fourni par la croûte océanique alpine, obductée au cours du Crétacé dans la partie interne du domaine des clippes de Pieniny, ou par l'érosion secondaire des flyschs de Pieniny.La rareté et l'origine probablement ancienne des spinelles chromifères dans la partie septentrionale indique que lors des mouvements convergents crétacés aucune roche ophiolitique alpine n'était exposée à l'érosion. Par conséquent, la présence de fonds océaniques dans ces bassins individuels semble peu probable. Les Carpathes externes représentent probablement un bassin profond, de type «foreland» par rapport à une zone de suture ophiolitique plus interne.

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The kinematic inverse problem for weakly laterally inhomogeneous anisotropic media

We derive a dynamic ray tracing system for seismic waves in an anisotropic medium. It consists of ten equations and can be solved numerically. For isotropic media it does not reduce to the DRT systems derived by other authors.     

Liapunov instability of the hypoplastic model for soils

The hypoplastic constitutive model is known for its numerous application to the problems of soil mechanics and also for its excessive ratcheting. The paper shows that this deficiency can be interpreted as Liapunov instability in dynamic case. This is demonstrated with a simple one-dimensional swinger. Infinitesimally small as well as finite oscillations are analytically examined and the variability of stiffness upon a single cycle is considered. Several methods to circumvent the problem of ratcheting are discussed: implementation of ‘elastic’ range by means of so-called intergranular strain, usage of overlay modelling with parallel coupling of hypoplastic materials as originally proposed by Valanis in his endochronic theory and a special coupling of hypoplastic models based on comparison of partial stiffnesses.     

Non-Integrability of the Generalized Two Fixed Centres Problem

We consider two fixed centres attracting a third body. Each centre is the source of a force field with potential V=−ar ⁻²ⁿ , where n is a real number. We prove that this generalization of the classical two fixed centres problem is non-integrable except when n= 0, 1/2, −1 and −2. This revised version was published online in July 2006 with corrections to the Cover Date.     

Maximum likelihood estimation of Gutenberg-Richterb parameter for uncertain magnitude values

The maximum likelihood estimation of theb parameter in the Gutenberg-Richter relation is extended to the case of uncertain magnitude. An interval which contains the real unknown magnitude is used rather than the uncertain magnitude itself. The proposed approach is very flexible, it allows for the combination of the parts of a catalog of different quality into a single minimally biased set of recurrence parameters.On leave from the Institute of Geophysics, Polish Academy of Sciences, 00-973 Warsaw, Pasteura 3, Poland     

Numerical modeling and neural networks to identify model parameters from piezocone tests: II. Multi‐parameter identification from piezocone data

This paper completes the study presented in the accompanying paper, and demonstrates a numerical algorithm for parameter prediction from the piezocone test (CPTU) data. This part deals with a development of neural network (NN) models which are able to map multi‐variable input data onto typical geotechnical characteristics and constitutive parameters of the modified Cam clay model, which has been applied in this study. The identification procedure is designed for the coupled hydro‐mechanical boundary value problem in normally‐and lightly overconsolidated clayey soils including partially drained conditions that may appear during cone penetration. The NN models are trained with pseudo‐experimental measurements derived with the aid of the numerical model of the piezocone test, presented in the accompanying paper. Different input configurations containing CPTU measurements and some complementary data are studied with respect to the accuracy of predicted parameter values. Finally, the performance of the developed NN predictors is tested with field CPTU data which are derived from three well‐documented characterization sites, and the obtained predictions are compared with benchmark laboratory results. Copyright © 2011 John Wiley & Sons, Ltd.     

Short ingestion tests as alternative proposal for conventional range finding assays with Thamnocephalus platyurus and Brachionus calyciflorus

The goal of this study was to evaluate whether short 1 h sublethal assays may predict the results of 24 h lethality assays with rotifers Brachionus calyciflorus and anostracan crustaceans Thamnocephalus platyurus. The test bionts were hatched from cysts. Inhibition of ingestion was observed after 15 min of incubation of rotifers and crustaceans with the suspension of carmine and latex beads, respectively. Nine compounds with different modes of action were used as toxicants zinc ions, sodium dodecyl sulphate, p-nitrophenol, 3, 5-dichlorophenol and pharmaceuticals propranolol, fluoxetine, abamectin, doramectin and ivermectin. The toxicity values observed in the ingestion tests were very close to the mortality values over a wide range of toxicity from a low toxic surfactant to very toxic avermectins. The ratio between the 1 h EC₅₀’s in the ingestion test and the 24 h LC₅₀’s in the lethality test was below 2 in all cases for rotifers, and 7 in 9 cases for crustaceans. The toxicity of zinc and 3,5-dichlorophenol in the Thamnotoxkit F? was 15-fold higher and 10 fold lower than in the ingestion test, respectively. The 24 h LC₅₀ values are within the range of 25–400 % of the 1 h EC₅₀ values for almost all toxicants tested with the exception of p-nitrophenol for B. calyciflorus and zinc and 3, 5-dichlorophenol for T. platyurus. Short, 1 h ingestion assays Rotoxrapid and Rapidtoxkit are good predictors of the mortality over the next 24 h and can be used as a range finding tests for representatives of pharmaceuticals and surfactants.