Magnitude and frequency relations: are there geological constraints to the rockfall size?

There exists a transition between rockfalls, large rock mass failures, and rock avalanches. The magnitude and frequency relations (M/F) of the slope failure are increasingly used to assess the hazard level. The management of the rockfall risk requires the knowledge of the frequency of the events but also defining the worst case scenario, which is the one associated to the maximum expected (credible) rockfall event. The analysis of the volume distribution of the historical rockfall events in the slopes of the Solà d’Andorra during the last 50 years shows that they can be fitted to a power law. We argue that the extrapolation of the F-M relations far beyond the historical data is not appropriate in this case. Neither geomorphological evidences of past events nor the size of the potentially unstable rock masses identified in the slope support the occurrence of the large rockfall/rock avalanche volumes predicted by the power law. We have observed that the stability of the slope at the Solà is controlled by the presence of two sets of unfavorably dipping joints (F3, F5) that act as basal sliding planes of the detachable rock masses. The area of the basal sliding planes outcropping at the rockfall scars was measured with a terrestrial laser scanner. The distribution of the areas of the basal planes may be also fitted to a power law that shows a truncation for values bigger than 50 m² and a maximum exposed surface of 200 m². The analysis of the geological structure of the rock mass at the Solà d’Andorra makes us conclude that the size of the failures is controlled by the fracture pattern and that the maximum size of the failure is constrained. Two sets of steeply dipping faults (F1 and F7) interrupt the other joint sets and prevent the formation of continuous failure surfaces (F3 and F5). We conclude that due to the structural control, large slope failures in Andorra are not randomly distributed thus confirming the findings in other mountain ranges.     

Use of geochemical modeling to evaluate the hydraulic connection of aquifers: a case study from Chianan Plain, Taiwan

Aquifers are generally composed of highly permeable layers that can conduct a considerable amount of groundwater. Traditionally, aquifer units are correlated through the concept of lithostratigraphy. For low-permeable aquifers, it is difficult to define the spatial distribution of hydrogeological units, and this study attempts to use geochemical modeling to identify the groundwater flow paths in an area of Taiwan. Multiple geochemical analyses, including groundwater chemistry; stable isotopic compositions of hydrogen, oxygen and carbon; and radiocarbon contents were performed. Using these parameters as the constraints of geochemical models, the hydraulic connection was examined between pairs of possibly interlinked wells along four selected cross sections, and the conceptual groundwater model was accordingly established. The resultant model suggests that the hydraulic connection between aquifers should be correlated with the concept of chronological stratigraphy, especially for low-permeable, unconsolidated aquifers. Using Darcy’s law, the hydraulic conductivities of the fine-sand aquifers were estimated to be between 3.14 × 10⁻⁵ and 1.80 × 10⁻⁴ m/s, which are roughly one order of magnitude higher than those derived by in situ pumping tests. The substantial extraction of groundwater over a long period in the studied area could accelerate groundwater flow, leading to an overestimation of the aquifer permeability.

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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Résumé En règle générale, les aquifères sont constitués de couches très perméables capables de conduire des quantités d’eau considérables. Les unités aquifères sont traditionnellement corrélées d’un point de vue lithostratigraphique. Dans le cas des aquifères à faible perméabilité, il s’avère difficile de définir une distribution spatiale des unités hydrogéologiques, et cette étude tente d’utiliser la modélisation géochimique pour identifier les cheminements des eaux souterraines dans un secteur de Taiwan. Plusieurs analyses géochimiques ont été réalisées ; elles incluent la chimie des eaux souterraines, les isotopes stables de l’hydrogène, de l’oxygène et du carbone et l’abondance en carbone 14. En utilisant ces paramètres comme contraintes pour les modèles géochimiques, les liaisons hydrauliques entre les puits potentiellement interconnectés ont été étudiées deux par deux, le long de quatre coupes présélectionnées, et le modèle conceptuel a été établi en conséquence. Ce modèle résultant suggère que les connexions hydrauliques inter-aquifères devraient être corrélées avec les concepts stratigraphiques, surtout pour les aquifères non consolidés à faible perméabilité. Les perméabilités dans les aquifères de sables fins ont été estimées par la loi de Darcy entre 3.14 × 10⁻⁵ et 1.80 × 10⁻⁴ m/s, soit environ un ordre de grandeur au-dessus de celles issues des tests de pompage sur site. L’exploitation substantielle des eaux souterraines sur une longue période dans la zone d’étude peut accélérer les écoulements souterrains, menant à une surestimation de la perméabilité de l’aquifère.

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Resumen Los acuíferos están generalmente compuestos de capas muy permeables que pueden conducir una cantidad considerable de agua subterránea. Tradicionalmente, se ponen en correlación las unidades acuíferas a través del concepto de litoestratigrafía. Para los acuíferos de baja-permeabilidad, es difícil de definir la distribución espacial de unidades hidrogeológicas y este estudio intenta usar modelamiento geoquímico para identificar las direcciones del flujo de agua subterránea en un área de Taiwán. Se realizó el análisis geoquímico múltiple, incluyendo la química del agua subterránea, la composición de isótopos estables de hidrógeno, oxígeno y carbono, y el contenido de radiocarbono. Usando estos parámetros como limitantes de modelos geoquímicos, la conexión hidráulica se examinó entre pares de pozos posiblemente interrelacionados, a lo largo de cuatro cortes transversales seleccionados y de acuerdo con esto se estableció el modelo conceptual del agua subterránea. El modelo resultante sugiere que la conexión hidráulica entre los acuíferos deba interrelacionarse con el concepto de estratigrafía cronológica, sobre todo para los acuíferos sin consolidar de baja permeabilidad. Usando la ley de Darcy, se estimaron las conductividades hidráulicas de los acuíferos de arena fina obteniendo valores entre 3.14 × 10⁻⁵ y 1.80 × 10⁻⁴ m/s, las cuales son aproximadamente un orden de magnitud mayor, que aquéllos obtenidos in situ por las pruebas de bombeo. La extracción considerable de agua subterránea durante un periodo largo en el área estudiada, podría acelerar el flujo de agua subterránea, llevando a una sobrestimación de la permeabilidad en los acuíferos.

     

Lake bank filtration at Nainital,India: water-quality evaluation

There are different water-supply schemes in Uttarakhand, India to tap the water from streams, rivers and lakes. At Nainital, seven tube-wells (depths 22.6–36.7 m), located at a distance of <100 m from the lake, are being used to abstract (1) lake water after passage through the soil and (2) subsurface water/groundwater flowing towards the lake. Water samples from the lake and tube-wells were analyzed in monsoon and non-monsoon periods from 1997 to 2006. Total dissolved solids, EC, alkalinity and hardness were found to be marginally greater in tube-well waters. The difference in hydrochemistry of tube-well water was mainly due to variation in flow regimes during monsoon and non-monsoon periods. Results clearly indicate that lake water as such is not potable as it contains unacceptable levels of organic matter in terms of COD (~44 mg/L), coliforms (~15.6 × 10⁴ MPN/100 mL) and nutrients. Coliform bacteria and COD have not been detected in any of the tube-well water samples over the years. Lake water, treated by sand filters did not conform to drinking water standards. These investigations have led to the closure of the treatment facility and installation of two tube-wells in addition to the existing five tube-wells.

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Résumé  Il existe divers projets d’alimentation en eau dans l’état d’Uttarakhand, Inde, afin de capter l’eau de ruisseaux, de rivières et de lacs. A Nainital, sept puits tubés (profondeur de 22.6–36.7 m), situés à une distance < à 100 m du lac, sont utilisés pour prélever (1) de l’eau du lac après transit à travers le sol et (2) de l’eau de sub-surface/eau souterraine s’écoulant vers le lac. Des échantillons d’eau du lac et des puits tubés ont été analysés en périodes de mousson et de celles sans mousson 1997 à 2006. Résidu sec, C.E., alcalinité et dureté ont été trouvés marginalement supérieurs dans l’eau des puits tubés. La différence d’hydrochimie de l’eau des puits tubés était surtout due à la variation des régimes d’écoulement pendant les périodes de mousson et de celles sans mousson. Les résultats indiquent clairement que l’eau du lac en tant que telle n’est pas potable car elle contient des teneurs inacceptables de matière organique en termes de COD (~44 mg/L), de coliformes (~15.6 × 10⁴ MPN/100 mL) et d’éléments nutritifs. Des bactéries coliformes et du COD n’ont été détectés dans aucun des échantillons d’eau de puits tubés au fil des années. L’eau du lac traitée par des filtres à sable ne se conformait pas aux normes de l’eau potable. Ces recherches ont conduit à la fermeture de l’installation de traitement et à l’implantation de deux puits tubés en plus des cinq puits existants.

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Resumen  En el estado de Uttarakhand, India, existen diferentes esquemas de abastecimiento de agua que explotan agua de arroyos, ríos y lagos. En Nainital, siete pozos (profundidades entre 22.6–36.7 m), ubicados a una distancia de <100 m del lago, se usan para extraer (1) agua del lago luego de su pasaje a través del suelo y (2) agua superficial y subterránea que fluye hacia el lago. En períodos de monzón y de no monzón de 1997 a 2006 se han analizado muestras de agua del lago y de las captaciones. Se halló que el agua de los pozos es ligeramente mayor en términos del total de sólidos disueltos, la conductividad eléctrica, la alcalinidad y la dureza. La diferencia en la hidroquímica del agua de las perforaciones se debe principalmente a la variación de los regímenes de flujo durante los períodos de monzón y de no monzón. Los resultados claramente indican que el agua del lago no es potable por su contenido inaceptable de materia orgánica medida como demanda de carbono orgánico/oxígeno –DCO- (~44 mg/L), coliformes (~15.6 × 10⁴ NMP/100 mL) y nutrientes. En el período, no se han detectado bacterias coliformes ni DCO en las muestras de agua de las captaciones. El agua del lago, tratada con filtros de arena, no conformó los estándares de agua para bebida. Estas investigaciones han demostrado la necesidad de clausurar las instalaciones de tratamiento y la adición de dos captaciones a las cinco ya existentes.

     

Rare-earth and trace element imprints on the origin and tectonic setting of gabbro-diorite complex in the Pan-African belt of Southeast Obudu Plateau,Nigeria

A gabbro-diorite plutonic complex from the Southeast Obudu Plateau, representing limited volumes of magma, was studied for its trace and rare-earth element characteristics, in an attempt to document its genetic and geodynamic history. Geochemical studies indicate that the gabbro samples are characterized by variable concentrations and low averages of such index elements as Cr (40×10-6–200×10-6; av. 80×10-6), Ni (40×10-6–170×10-6; 53.33×10-6) and Zr (110×10-6–240×10-6; 116.67×10-6); variable and high average...     

Chemical and Strontium Isotopic Compositions of the Hanjiang Basin Rivers in China: Anthropogenic Impacts and Chemical Weathering

The Hanjiang River, the largest tributaries of the Changjiang (Yangtze) River, is the water source area of the Middle Route of China’s South-to-North Water Transfer Project. The chemical and strontium isotopic compositions of the river waters are determined with the main purpose of understanding the contribution of chemical weathering processes and anthropogenic inputs on river solutes, as well as the associated CO₂ consumption in the carbonate-dominated basin. The major ion compositions of the Hanjiang River waters are characterized by the dominance of Ca²⁺ and HCO₃ ⁻, followed by Mg²⁺ and SO₄ ²⁻. The increase in TDS and major anions (Cl⁻, NO₃ ⁻, and SO₄ ²⁻) concentrations from upstream to downstream is ascribed to both extensive influences from agriculture and domestic activities over the Hanjiang basin. The chemical and Sr isotopic analyses indicate that three major weathering sources (dolomite, limestone, and silicates) contribute to the total dissolved loads. The contributions of the different end-members to the dissolved load are calculated with the mass balance approach. The calculated results show that the dissolved load is dominated by carbonates weathering, the contribution of which accounts for about 79.4% for the Hanjiang River. The silicate weathering and anthropogenic contributions are approximately 12.3 and 6.87%, respectively. The total TDS fluxes from chemical weathering calculated for the water source area (the upper Hanjiang basin) and the whole Hanjiang basin are approximately 3.8 × 10⁶ and 6.1 × 10⁶ ton/year, respectively. The total chemical weathering (carbonate and silicate) rate for the Hanjiang basin is approximately 38.5 ton/km²/year or 18.6 mm/k year, which is higher than global mean values. The fluxes of CO₂ consumption by carbonate and silicate weathering are estimated to be 56.4 × 10⁹ and 12.9 × 10⁹ mol/year, respectively.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

Contents of Fixed-Ammonium （ NH4^＋ ） in Lamprophyres in the Zhenyuan Gold Orefield, Yunnan Province, China： Implications for Its Characteristics of the Source Region

This paper determined the fixed-ammonium (NH₄ ⁺) contents of lamprophyres in the Zhenyuan gold orefield, Yunnan Province, China. The results show that the NH₄ ⁺ contents of minettes in the orefield range from 120 × 10⁻⁶ to 469 × 10⁻⁶ and those of kersantites from 74.3 × 10⁻⁶ to 136 × 10⁻⁶. These values are higher than those of other mantle-derived rocks (less than 50 × 10⁻⁶), but lower than those of carbonaceous wall rocks in the orefield (from 1200 × 10⁻⁶ to 1343 × 10⁻⁶). Combining with the Sr isotopic composition, this paper suggested that lamprophyres in the orefield with high NH₄ ⁺ contents relative to other mantle-derived rocks would not have resulted from the primary magma contaminated by crustal materials in the process of rising or in the magma chamber, but from mantel metasomatism. This research project was financially supported jointly by the State Key Basic Research Program of the People’s Republic of China (No. G1999043203) and the Chinese Academy of Sciences Knowledge-Innovation Program (No. KZCX3-SW-125).     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

Position de la limite Cénomanien-Turonien dans la Formation Bahloul de Tunisie centrale: apports intégrés des ammonites et des isotopes du carbone (δ13C)

Resume. Deux coupes de la Formation Bahloul en Tunisie centrale ont livré plus de 250 ammonites qui fondent une zonation en quatre termes allant du Cénomanien terminal (Zones à Metoicoceras geslinianum et à Pseudaspidoceras pseudonodosoides) au Turonien basal (Zones à Watinoceras spp et à Pseudaspidoceras flexuosum). La position de la limite Cénomanien-Turonien (C-T) étant définie par l’apparition de Watinoceras spp, cette limite est placée à 0,60m près dans la localité-type de la Formation à l’Oued Bahloul. Sur les deux coupes étudiées des mesures du carbone isotopique ont mis en évidence quatre événements – ou pics en δ¹³C – formant des lignes temporelles considérées comme synchrones dans la région considérée. L’événement δ¹³C indexé III, d’age encore cénomanien, est le plus proche de la limite C-T. Un événement biologique relatif à l’apparition de ?filaments? – ou microlamellibranches pélagiques – toujours cénomanien, est encore plus proche de la limite C-T. Enfin, une comparaison est tentée avec les Marnes à Plenus d’Eastbourne (UK) et avec le stratotype de la limite C-T à Pueblo (USA). Manuscrit re?u le 15 octobre, 2004 Révision acceptée le 2 février, 2005     

Geoelectric section of the lithosphere of the Amur-Zeya sedimentary basin deduced from magnetotelluric sounding along the Blagoveshchensk-Birakan profile

The results of magnetotelluric sounding along the 350-km long Blagoveshchensk-Birakan profile are discussed. The profile begins in the Longjiang-Selemdzha orogenic belt and ends in the Jiamusi-Bureya massif, thus intersecting the southern Amur-Zeya sedimentary basin from the northwest to the southeast. Twelve soundings have been performed in the broad range from 1 × 10⁴ to 2 × 10⁻⁴ Hz. Geoelectric sections have been constructed for the depths of 2 and 150 km with the determination of the geoelectric parameters of the sedimentary cover within the basin and the identification of the zones of anomalous conductivity in the Earth’s crust and upper mantle.     

Thermochemical behaviour of Pt, Ir, Rh and Ru vs fO2 and fS2 in a basaltic melt. Implications for the differentiation and precipitation of these elements

Summary ?This paper describes an experiment conducted at 1430°C to study the behaviour of Pt, Ir, Rh and Ru in a silicate melt of basaltic composition in relation to fO₂ and fS₂. Previous results showing the existence of a passivation layer on the metals are confirmed and demonstrated by an electrochemical technique. The presence in the silicate melt of platinum and iridium at zero valency is used to explain the observed behaviour for these elements. On the other hand, the presence of Rh³⁺ and Ru³⁺ ions likely to enter the spinel lattice helps to explain the mineralogical observations made on the samples of a Tropoja chromite (Albania), formed in a sulphur-depleted system. While the variation in oxygen fugacity can explain the premature precipitation of IPGEs (Ir, Ru, Os), it is the variation in sulphur fugacity which explains the similar precipitation of PPGEs (Rh, Pt, Pd). Complex Pt (or Rh) compounds in the silicate melt are highlighted for a sulphur fugacity greater than 1.5 × 10⁻² atm. The PPGEs precipitate only when the base metal sulphides (BMS) precipitate. This occurs after precipitation of a large amount of iron and calcium, i.e., after a significant reduction in the sulphur capacity of the magmatic liquid and a concomitant increase in fS₂. The temperature and oxygen fugacity of a dunitic assemblage are determined from intrinsic oxygen fugacity measurements performed by means of a solid electrolyte cell with chromites and olivines from the Krasta (Albania) differentiated series. This enabled the validity of the thermochemical results to be checked. Finally, a PGE differentiation and precipitation scheme is proposed as a function of oxygen and sulphur fugacities and in the presence of a fluid phase.

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Résumé ?Le comportement de Pt, Ir, Rh et Ru a étéétudié dans un bain silicaté fondu à 1430 °C en fonction de fO₂ et fS₂, ce qui a permis de tracer des diagrammes de prédominance. Les résultats antérieurs mettant en évidence l'existence d'une couche de passivation sur les métaux sont confirmés, et l'existence de cette couche de passivation est démontrée par une expérience de chronopotentiométrie. La présence dans le silicate fondu de platine et d'iridium à la valence zéro est utilisée pour expliquer le comportement de ces éléments. En outre, la présence dans le bain silicaté d'ions Rh³⁺ et Ru³⁺, susceptibles d'entrer dans le réseau des spinelles, est mise en évidence thermochimiquement et permet d'expliquer la présence de phases minéralogiques aux compositions inhabituelles trouvées dans des échantillons d’une chromite de Tropoja (Albanie), formés dans un syste-me pauvre en soufre. Alors que la variation de la fugacité en oxygène peut expliquer la précipitation précoce des IPGEs (Ir, Ru, Os), c’est la variation de la fugacité en soufre qui permet d’expliquer la précipitation des PPGEs (Rh, Pt, Pd). Un composé complexe de platine (et/ou de rhodium) est mis en évidence dans le bain silicaté pour une fugacité en soufre supérieure à 1.5 10⁻² atm. On explique ainsi que les PGEs précipitent seulement quand les sulfures de métaux de base (BMS) précipitent. Cette précipitation se produit après une précipitation importante de fer et/ou de calcium c’est à dire après une réduction significative de la capacité en soufre du liquide magmatique et une augmentation concomitante de fS₂. La température de cristallisation et la fugacité en oxygène d’un assemblage dunitique sont déterminées à partir de mesures de fugacités intrinsèques d’oxygène réalisées par piles àélectrolyte solide avec les chromites et les olivines d’une série différenciée cumulative de Krasta (Albanie). Ces mesures permettent de controler que les minéralisations observées se produisent effectivement pour les valeurs de fugacités en oxygène qui ont été déterminées thermochimiquement au Laboratoire et pour des températures de l’ordre de 1130 °C. Enfin un schéma de différenciation et de précipitation des PGEs est tracé, montrant l’apparition des phases minéralogiques en fonction des fugacités en oxygène et en soufre et en présence d’une phase fluide.

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Received August 7, 1998/Revised version accepted July 16, 1999     

X-ray diffraction study of magnesite at high pressure and high temperature

 P–V–T measurements on magnesite MgCO₃ have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′₀ fixed at 4, we obtain K₀=103(1) GPa, α(K⁻¹)=3.15(17)×10⁻⁵ +2.32(28)×10⁻⁸ T, (∂K_T/∂T)_P=−0.021(2) GPaK⁻¹, (dα/∂P)_T=−1.81×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V= −0.007(1) GPaK⁻¹; whereas the third-order Birch-Murnaghan equation of state with K′₀ as an adjustable parameter yields the following values: K₀=108(3) GPa, K′₀=2.33(94), α(K⁻¹)=3.08(16)×10⁻⁵+2.05(27) ×10⁻⁸ T, (∂K_T/∂T)_P=−0.017(1) GPaK⁻¹, (dα/∂P)_T= −1.41×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V=−0.008(1) GPaK⁻¹. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂K_T/∂T)_P, (∂α/∂P)_T and (∂K_T/∂T)_V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO₂ and (2) magnesite+enstatite=forsterite+CO₂ are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: Part III: Eh-pH diagrams of the Me-As-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of arsenic at the Earth’s surface and nearby at low temperatures and pressures depends mainly on the redox potential and the acidity-alkalinity of the crystallization media. These parameters determine the migration of arsenic compounds and their precipitation as various solid phases. Understanding the mechanism of arsenic’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of the components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with arsenic (a _ΣAs = 3 × 10⁻⁸, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻³, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-As-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in the underground water and for their higher contents in the oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb arsenates at the surface is discussed.     

Stable isotopic fingerprint of a hyporheic–hypolentic boundary in a reservoir

Stable isotopes of H₂O are used to define the hyporheic–hypolentic boundary in Ledbetter Creek as it discharges to Kentucky Lake, a constructed reservoir in western Kentucky, USA. High-resolution (centimeter-scale) sample collection and analysis were utilized to determine one-dimensional variations in δ²H and δ¹⁸O of H₂O and chloride (Cl⁻) across the boundary. During reservoir low stand in winter, the hyporheic–hypolentic zone contains water from Ledbetter Creek and groundwater separated by an interface at ~10 cm below the channel bottom. Following reservoir-stage increase in spring and summer, water from Kentucky Lake infiltrates into the hyporheic–hypolentic zone to a depth of at least 18 cm below the channel bottom. Reservoir-stage decline in autumn causes source-water mixing, largely obscuring the hyporheic–hypolentic boundary. Stable isotopes provide an effective complement to conventional tracers for delineation of water masses within the hyporheic–hypolentic zone.

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Resumen Se han utilizado isótopos estables del agua para definir el límite hiporreico-hipoléntico en Ledbetter Creek, que constituye una zona de descarga del lago Kentucky, una presa construida al Oeste de Kentucky, USA. Se ha llevado a cabo una recogida de muestras de alta resolución (a escala centimétrica) y se utilizaron los resultados para determinar las variaciones unidimensionales en δ²H y δ¹⁸O del H₂O y los cloruros (Cl⁻) alrededor del límite. Durante la época de niveles bajos en invierno, la zona hiporreica-hipolentica tiene agua procedente de Ledbetter Creek y de agua subterránea separada por una interfase de ~10 cm debajo del límite del canal. Siguiendo el incremento de los niveles en la presa en primavera y verano, el agua del Lago Kentucky se infiltra en la zona hiporreica-hipoléntica hasta una profundidad de, al menos, 18 cm bajo el límite hiporreico-hipoléntico. Los isótopos estables aportan un complemento efectivo a los trazadores convencionales para la delimitación de masas de agua dentro de la zona hiporreica-hipoléntica.

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Résumé L’utilisation des isotopes stables de la molécule d’eau a permis de définir l’interface hyporhéique-hypolentique dans la Ledbetter Creek, au point de déversement dans le réservoir artificiel que constitue le Kentucky Lake (Ouest du Kentucky, Etats-Unis). Une campagne de prélèvements à haute résolution (échelle centimétrique) a contribué à déterminer les variations unidimensionnelles des valeurs de δ2H et de δ18O de la molécule d’eau et de la concentration en chlorures (Cl⁻) de part et d’autre de l’interface. En hiver, lorsque le niveau du réservoir est minimal, la zone hyporhéique-hypolentique contient de l’eau de la Ledbetter Creek et de l’eau souterraine, séparées par un interface situé environ 10 cm sous le fond du chenal. Suite aux recharges printanières et estivales, l’eau du Kentucky Lake envahit la zone hyporhéique-hypolentique sur plus de 18 cm sous le fond du chenal. En automne, la baisse de niveau dans le réservoir occasionne un mélange des eaux, rendant diffus l’interface hyporhéique-hypolentique. Les isotopes stables constituent ainsi un complément efficace aux traceurs conventionnels pour la délimitation des masses d’eau dans la zone hyporhéique-hypolentique.

     

Geochemistry and environmental effect of cadmium in the super-large Jinding Pb-Zn deposit,Yunnan Province,China

The Jinding Pb-Zn deposit in Yunnan Province is the representative of a Cd-enriched area and mining activities lead to the release of Cd into the hypergenic ecosystem, resulting in Cd pollution. The concentrations of Cd vary greatly from one type to another type of rocks in the mining district. In the host rock, Cd concentrations range from 50×10^-6 to 650×10^-6 with an average of 310×10^-6. In primary ores, Cd concentrations range from 14×10^-6 to 2800×10^-6 with an average of 767×10^-6. However, in oxidized ores, Cd concentrations are highest, varying within the range of 110×10^-6 to 8200×10^-6 , averaging 1661×10^-6. It is shown that the oxidized ores are the main carder and environmental source of Cd. Leaching test showed that Pb/Zn ores are easy to oxidize and thereafter release Cd and other harmful elements. These leached elements in the leachate may be precipitated rapidly in the order of Zn〉Pb〉Cd. As for the concentration distribution of Cd in the Bijiang River, it is estimated to be 15.7 μg/L Cd in water, 49.3 mg/L in suspended substances, and 203.7 mg/L in sediments. The average value of Cd in soil from the polluted area is 83.0 mg/kg. Natural weathering of Cd-rich rocks and minerals imposes a potential environmental risk on the aquatic ecosystem of the Bijiang catchment.     

Rare-earth elements as source indicators of Pan-African granites from Obudu Plateau,Southeastern Nigeria

The rare-earth element （REE） concentrations of representative granite samples from the southeast of the Obudu Plateau, Nigeria, were analyzed with an attempt to determine the signatures of their source, evolutionary history and tectonic setting. Results indicated that the granites have high absolute REE concentrations （190×10^-6-1191×10^-6; av.=549×10^-6） with the chondrite-normalized REE patterns characterized by steep negative slopes and prominent to slight or no negative Eu anomalies. All the samples are also characterized by high and variable concentrations of the LREE （151×10^-6-1169×10^-6; av.= 466×10^-6）, while the HREE show low abundance （4×10^-6-107×10^-6; av.=28×10^-6）. These are consistent with the variable levels of REE fractionation, and differentiation of the granites. This is further supported by the range of REE contents, the chondrite-normalized patterns and the ratios of LaN/YbN （2.30-343.37）, CeN/YbN （5.94-716.87）, LaN/SmN （3.14-11.68） and TbN/YbN （0.58-1.65）. The general parallelism of the REE patterns, suggest that all the granites were comagmatic in origin, while the high Eu/Eu＊ ratios （0.085-2.807; av.=0.9398） indicate high fo2 at the source. Similarly, irregular variations in LaN/YbN, CeN/YbN and Eu/Eu＊ ratios and REE abundances among the samples suggest behaviors that are related to mantle and crustal sources.     

Estimation of methane emission from whole waste landfill site using correlation between flux and ground temperature

A methodology to estimate a methane emission in a waste landfill site was developed. The methane flux at a waste landfill site in summer, autumn, and winter was within the following ranges: from −1.3×10⁻² to 16, from −6.4×10⁻² to 7.5, and from −1.6×10⁻³ to 1.5×10⁻² g-CH₄ m⁻² h⁻¹, respectively. In those seasons, the mean methane emission rate and coefficient of variation were 1.1 g-CH₄ m⁻² h⁻¹ ±290%, 0.57 g-CH₄ m⁻² h⁻¹ ±347%, and 5.4×10⁻² g-CH₄ m⁻² h⁻¹ ±370%, respectively. These results simultaneously showed that fluctuations of methane emission from the landfill surface were both of spatial and temporal variability. In each season, an exponential relationship was observed between the methane flux density and the ground temperature. Total methane emissions were estimated to be 5.7×10⁻², 7.1×10⁻³, and 1.7×10⁻³ g-CH₄ m⁻² h⁻¹ in the summer, autumn, and winter surveys, respectively, using a temperature surrogated-kriging method. The results of this study would improve upon the labor-intensive closed-chamber method, and could be a more practical way to estimate methane emissions from waste landfills.     

Upwellings in Lake Baikal

Based on shipboard and satellite observations, the characteristics of upwelling in Lake Baikal in the period of direct temperature stratification have been determined for the first time. Coastal upwellings appear annually under the effect of run-down and alongshore winds and are traced along the coast to a distance of up to 60–100 km and up to 250 km in North Baikal. Analogous to the way it occurs in seas, water rises from the depths of 100–200 m (350 m as a maximum) at the velocity of 0.1 × 10⁻²−6.5 × 10⁻² cm/s. Divergence in the field of intràbasin cyclonic macrovortices produces upwelling in the Baikal pelagic zone and downwelling in the vicinity of shores; this lasts from 7 to 88 days and covers the depth interval of 80–300 m in August and up to 400–800 m in early-mid November. The area of upwellings occupies up to 20–60% of the separate basins of the lake. Vertical circulation of water in the field of pelagic upwellings leads to intensification of coastal currents and to formation of the thermobar with a heat inert zone in the central part of the lake in November, and this thermobar is not observed in other lakes, at that.     

Helium isotopes in gases of Mineral Waters in the western Caucasus

The He isotope composition as an indicator of mantle-derived component was studied in gases from mineral springs, stratal waters, and mud volcanoes developed west of the Teberda River valley (10 objects) and two springs in the central segment of the Greater Caucasus orogen between the active El’brus and Kazbek volcanoes. In the western segment of the orogen, the values of ³He/⁴He = R_corr vary in the range of (46–114) × 10⁻⁸ = (0.33–0.81)R_atm, where R_atm =1.4 × 10⁻⁶ is the atmospheric ratio. They are substantially lower as compared with values in the vicinity of El’brus and Kazbek and close to those in samples from the central segment equal to (70–134) × 10⁻⁸ = (0.50–0.96)R_atm, as well as to the values previously recorded in the Caucasian Mineral Waters (CMW) area. Moreover, the content of ³He in them is notably higher as compared with its crustal radiogenic level characteristic of mud volcanoes in the Taman Peninsula, where R = (1.4–2.8) × 10⁻⁸ = (0.01–0.02)R_atm. Nitrogen-methane gas from northern piedmonts of the western Caucasus also contain nonatmogenic components, including the radiogenic ⁴⁰Ar (⁴⁰Ar/³⁶Ar = 900), “excess” nitrogen (∼87% of the total N₂ concentration in sample) and the mantle He. These data specify the distribution of mantle derivates along the orogen strike and age of intrusive magmatic activity in its different segments.     

Mineralogy and geochemistry of Late Ordovician phosphate-bearing oolitic ironstones from NW Sardinia, Italy

Summary. ?In the Nurra region, NW Sardinia, oolitic ironstones are interlayered within coarsening upward metasedimentary sequences of siltstone, sandstone, breccia, and conglomerate. A Caradoc-Early Ashgill age is suggested by the analogies with metasediments of Central-Southern Sardinia following the Sardinian tectonic phase. The sequences including oolitic ironstones are overlain by black metapelite of inferred Hirnantian to early Silurian age. The ooids consist of chamosite, siderite or magnetite or, rarely, stilpnomelane. Chamosite ooids consist of up to 30 lamellae and sporadically show clustering of magnetite grains in core and rim, and widespread late replacement by siderite. The alternation of chamosite and Fe-oxide observed in a few samples points to an ooid transport over the crests and hollows of megaripples in a continental shelf at 0–60 m depth, and/or a random displacement of the littoral environments in a rapidly evolving continent-sea transition zone producing an alternation of oxidizing and reducing conditions. Black phosphate clasts, including older Fe-ooids, frequently occur. The oolitic ironstones of Nurra are variable mixtures of an Al-Si-Ti rich- detrital component and a Fe-rich chemical component. The abundance of chamosite and siderite explains the high values of LOI and the high Fe_tot, Fe²⁺ and Al contents and the low Si amounts in comparison with other Phanerozoic oolitic ironstones. The detrital elements are Al, Si, Ti, Mg, Zr, Th. Chemical precipitation processes supplied Fe, Ca, P, Sr, HREE. The chondrite-normalized pattern shows a slight LREE enrichment, a clear negative Eu anomaly, and a flat HREE trend typical of many Ordovician oolitic ironstones. The NASC-normalized pattern has a convex shape, with peaks for Sm, Gd, like in all the pre-Devonian phosphate deposits. The numerous phosphate clasts, pyrite pockets, diffuse organic matter, and lack of glauconite suggest an upward extension of the oxygen minimum layer in a stratified basin, up to a depth of 60 m, and allow the estimation of log fO₂ = − 72 to − 80 and pH = 9.0–9.5. for the underlying pyrite zone (depth > 60 m). Here the pore waters leached Eu²⁺ from the bottom sediments giving the observed negative anomaly of the chondrite-normalized REE pattern.

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Résumé ?Dans la région de la Nurra, Sardaigne nord-ouest, des niveaux ferrugineux oolithiques sont intercalés dans des séquences métasédimentaires composées de silts, grès, brèches et conglomerats. Un age Caradoc-Ashgill inférieur est suggéré par les analogies avec les métasédiments de la Sardaigne centrale-méridionale postérieurs à la phase tectonique Sarde. Les séquences qui contiennent les niveaux ferrugineux oolithiques sont surmontées par des métapélites noires pour lesquelles on suppose un age Hirnantien à Siliurien inférier. Les oolithes sont constituées de chamosite, siderite ou magnétite ou rarement, stilpnomelane. Les oolithes de chamosite peuvent avoir jusq’à 30 enveloppes dans le cortex et sporadiquement elles montrent une concentration de grains de magnétite au centre et sur le bord et un vaste replacement tardif par de la sidérite. L’alternation de enveloppes à chamosite et à oxydes de fer observée dans quelques échantillons indique un transport des oolithes sur la crête et dans la dépression de rides géantes sur une plateforme continentale à 0–60 m de profondeur et/ou bien un déplacement casuel des milieux c?tiers dans une zone de transition entre mer et continent en rapide évolution, ce qui produisait une alternation de conditions oxydantes et réduisantes. On trouve fréquemment des intraclastes noirs de phosphate qui contiennent des oolithes ferrugineuses plus anciennes. Les niveaux oolithiques ferrugineux de la Nurra sont le résultat d’un mélange en proportions variables entre une composante détritique riche en Al, Si,Ti et une composante chimique riche en fer. L’abondance de chamosite et sidérite explique les hautes valeurs de perte au feu et la haute teneur en Fe_tot, Fe²⁺ et Al et la basse teneur en Si en comparaison avec d’autres formations oolithiques ferrugineuses Phanérozo?ques. Les éléments détritiques sont Al, Si, Ti, Mg, Zr, Th. Les processus de précipitation chimique ont fourni Fe, Ca., P, Sr, HREE. Les teneurs de terres rares normalisées aux chondrites montrent un léger enrichissement en LREE, une évidente anomalie négative de Eu, et une disposition en plateau des HREE, qui est tipique de beaucoup de formations oolithiques ferrugineuses Ordoviciennes. Les teneurs normalisées aux NASC forment une courbe convexe avec deux maxima pour Sm et Gd, comme dans tout les dép?ts phosphatés pré-Dévoniens. Les nombreux intraclastes de phosphate, les cavités pleines de pyrite, l’abondance de matière organique et l’absence de glacounie suggèrent une extension vers plus faible profondeurs ( jusq’à 60 m) de la couche d’eau marine ayant la moindre teneur en oxygène dans un bassin stratifié. Pour la zone à pyrite qui est en dessous de la zone oolithique (profondeur > 60 m) on estime les conditions suivantes: log fO₂ = − 72 à− 80 et pH = 9.0–9.5. Les eaux intergranulaires solubilisent et emportent le Eu²⁺ des sediments du fond et donnent l’anomalie négative de Eu pour les teneurs de terres rares normalisées aux chondrites.

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Received February 10, 1999;/revised version accepted June 30, 1999