Evaluation of mineral precipitation potential in a spent nuclear fuel repository

In this study, the potential for mineral precipitation reactions to occur during the excavation, disposal, backfilling and closure of a deep geological repository for the final disposal of spent nuclear fuel was evaluated with the assistance of hydrogeochemical modelling. Four modelling exercises, corresponding to the main expectable geochemical scenarios in the Excavation Damaged Zone (EDZ) throughout repository evolution, were carried out and the times for sealing of the discontinuities owing to mineral precipitation in each of them were evaluated and discussed. The simulations show that mineral precipitation reactions are thermodynamically feasible in most of the studied cases. The main mineral phases potentially responsible for the hydraulic sealing of the EDZ are calcite and ferric oxyhydroxides, being the estimated volumes occupied by the precipitation of calcite between one and three orders of magnitude larger than the volume of precipitating ferric phases. The estimated times for complete sealing of the EDZ may vary between several hundreds to more than 1 million years. The shortest sealing times (less than 3,000 years) are obtained for the mixture of groundwaters from the repository depth with dilute infiltration waters.     

Geology,mineralogy, and sulfur isotope geochemistry of the Sargaz Cu–Zn volcanogenic massive sulfide deposit,Sanandaj–Sirjan Zone,Iran

The Sargaz Cu–Zn massive sulfide deposit is situated in the southeastern part of Kerman Province, in the southern Sanandaj–Sirjan Zone of Iran. The stratigraphic footwall of the Sargaz deposit is Upper Triassic to Lower Jurassic (?) pillowed basalt, whereas the stratigraphic hanging wall is andesite. Mafic volcanic rocks are overlain by andesitic volcaniclastics and volcanic breccias and locally by heterogeneous debris flows. Rhyodacitic flows and volcaniclastics overlie the sequence of basaltic and andesitic rocks. Based on the bimodal nature of volcanism, the regional geologic setting and petrochemistry of the volcanic rocks, we suggest massive sulfide mineralization in the Sargaz formed in a nascent ensialic back-arc basin. The current reserves (after ancient mining) of the Sargaz deposit are 3 Mt at 1.34% Cu, 0.38% Zn, 0.08%Pb, 0.24 g/t Au, and 7 g/t Ag. The structurally dismembered massive sulfide lens is zoned from a pyrite-rich base, to a pyrite?±?chalcopyrite-rich central part, and a sphalerite–chalcopyrite-rich upper part, with a sphalerite-rich zone lateral to the upper part. The main sulfide mineral is pyrite, with lesser chalcopyrite and sphalerite. The feeder zone, comprised of a vein stockwork consists of quartz–sulfide–sericite pesudobreccia and, in the deepest part, chlorite–quartz–pyrite pesudobreccia. Footwall hydrothermal alteration extends at least 70–80 m below the massive sulfide lens and more than a hundred meters along strike from the massive sulfide lens. Jasper and Fe–Mn bearing chert horizons lateral to the sulfide deposit represent low-temperature hydrothermal precipitates of the evolving hydrothermal system. Based on mineral textures and paragenetic relationships, the growth history of the Sargaz deposit is complex and includes: (1) early precipitation of sulfides (protore) on the seafloor as precipitation of fine-grained anhedral pyrite, sphalerite, quartz, and barite; (2) anhydrite precipitation in open spaces and mineral interstices within the sulfide mound followed by its subsequent dissolution, formation of breccia textures, and mound clasts and precipitation of coarse-grained pyrite, sphalerite, tetrahedrite–tennantite, galena and barite; (3) replacement of pre-existing sulfides by chalcopyrite precipitated at higher temperatures (zone refining); (4) continued “refining” led to the dissolution of stage 3 chalcopyrite and formation of a base-metal-depleted pyrite body in the lowermost part of the massive sulfide lens; (5) carbonate veins were emplaced into the sulfide lens, replacing stage 2 barite. The δ³⁴S composition of the sulfides ranges from +2.8‰ to +8.5‰ (average, +5.6‰) with a general increase of δ³⁴S ratios with depth within the massive sulfide lens and underlying stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones.     

Cloud cover analysis associated to cut-off low-pressure systems over Europe using Meteosat Imagery

Summary This paper reports a cloud cover analysis of cut-off low pressure systems (COL) using a pattern recognition method applied to IR and VIS bispectral histograms. 35 COL occurrences were studied over five years (1994–1998). Five cloud types were identified in COLs, of which high clouds (HCC) and deep convective clouds (DCC) were found to be the most relevant to characterize COL systems, though not the most numerous. Cloud cover in a COL is highly dependent on its stage of development, but a higher percentage of cloud cover is always present in the frontal zone, attributable due to higher amounts of high and deep convective clouds. These general characteristics are most marked during the first stage (when the amplitude of the geopotencial wave increases) and second stage (characterized by the development of a cold upper level low), closed cyclonic circulation minimizing differences between rearward and frontal zones during the third stage. The probability of heavy rains during this stage decreases considerably. The centres of mass of high and deep convective clouds move towards the COL-axis centre during COL evolution.     

Temperature predictability in the Great Mediterranean Area

Summary ¶Long range forecasting of annual and seasonal average temperatures has been considered from two different approaches in an area centered over the Mediterranean Sea. They both are statistical approaches trying to forecast annual or seasonal mean temperature values several months in advance. The methods are Optimate Climate Normals and an extension of this called Climate Normal Functions. Both methods try to forecast temperature from the past behavior of the series. Their performances are examined and compared. The best results are obtained for Southern Europe, while Eastern Europe exhibits the poorest predictability. The results suggest that the North Atlantic Oscillation can be a major factor ruling predictability in some areas of the region considered.Received January 28, 2003; revised October 24, 2002; accepted December 7, 2002 Published online June 2, 2003     

Potentiometrically measured Eh in groundwaters from the Scandinavian Shield

Measurement and interpretation of electrochemical Eh values in natural reducing groundwaters is a complex task. SKB, the company in charge of disposal of nuclear fuel wastes in Sweden, has developed a refined methodology for the determination of this parameter in packered sections in boreholes. The methodology consists of the simultaneous use of three different electrodes (Pt, Au and C) both at depth and at the surface, and maintaining continuous logging over a long period of time. Apart from Eh, the logging also includes other parameters such as pH, dissolved O₂, conductivity and temperature. This methodology has been used since the 80s in the framework of the hydrogeochemical characterisation programs supported by SKB at different sites in the Scandinavian Shield. All the existing databases have been revisited in this work using a uniform set of criteria to select Eh values of the Swedish groundwaters as a function of depth.     

Sensitivity and uncertainty analysis of mixing and mass balance calculations with standard and PCA-based geochemical codes

One of the most important observations that can be obtained from the study of an aquifer system dominated by mixing is the contribution of each end-member water to the chemical composition of every water parcel in the aquifer. Once the first-order effect of mixing has been taken into account via the mixing proportions, water–rock interaction can be used to explain the remaining variability. There are many sources of uncertainty that can prevent the accurate calculation of the mixing proportions of a mixing-dominated system, but the type and intensity of the chemical reactions that have taken place as a consequence of mixing is one of the most critical. Here the uncertainty in the computed mixing proportions of samples from a “synthetic” aquifer system derived from the actuation of different chemical reactions are assessed (always remembering that the chemical reactions are a second-order effect). These uncertainties are explored using two different geochemical codes in order to infer the limits of both methodological approaches: PHREEQC, as an example of a standard geochemical code; and M3, as an example of a Principal Component-based geochemical code. Several synthetic water samples are created with the direct approach of PHREEQC, both by pure mixing and including different types of chemical reactions. Together with the chemical information of the end-member waters, these samples are then fed into PHREEQC (inverse modelling) and M3 and the mixing proportions and mineral mass transfers are computed. PHREEQC calculations give a reasonable estimate of the real mixing proportions and the chemistry of the groundwaters. However, similar mixing proportions and mass transfers can be obtained using different sets of reactions, indicating a source of uncertainty that should be overcome with additional chemical information. For M3, where synthetic samples have been included in a real data set of groundwater samples from the Scandinavian Shield, mixing proportions are only mildly affected either by the number of compositional variables or the number of samples used for the Principal Component Analysis (PCA). However, the robustness of the output is quite sensitive to whether only conservative compositional variables are used or both conservative and non-conservative compositional variables. Mass balance calculations in M3 are much more sensitive to non-conservative compositional variables and the recommendation here is not to use non-conservative variables with PCA-based codes if any information about reactions is to be obtained.     

Mesoscale Convective Complexes over the Western Mediterranean area during 1990–1994

Summary Mesoscale Convective Systems (MCSs) data registers from June to December during 1990–94 were obtained from the Spanish National Meteorological Institute (INM). Fifteen Mesoscale Convective Complexes (MCCs) were identified through this database. Most of the MCCs developed during the last week of September. The dominant synoptic patterns related to the mesoscale systems were cold fronts at the surface with warm and moist low-level cores, and cut-off low or deep trough throughout the middle and upper levels. These synoptic patterns were found in all the fifteen cases studied.The hourly centroid location of each MCC was used to trace their tracks, which followed a general direction towards the E or NE in almost all cases. These trajectories are clearly related to the synoptic patterns found. Finally, two MCCs chosen as representative of their evolution are described and the related physical processes are discussed.With 14 Figures     

The Mantos Blancos copper deposit: an upper Jurassic breccia-style hydrothermal system in the Coastal Range of Northern Chile

The Upper Jurassic Mantos Blancos copper deposit (500 Mt at 1.0% Cu), located in the Coastal Range of northern Chile, displays two superimposed hydrothermal events. An older phyllic alteration probably related to felsic magmatic–hydrothermal brecciation at ∼155 Ma, and younger (141–142 Ma) potassic, propylitic, and sodic alterations, coeval with dioritic and granodioritic stocks and sills, and dioritic dikes. Main ore formation is genetically related to the second hydrothermal event, and consists of hydrothermal breccias, disseminations and stockwork-style mineralization, associated with sodic alteration. Hypogene sulfide assemblages show distinctive vertical and lateral zoning, centered on magmatic and hydrothermal breccia bodies, which constitute the feeders to mineralization. A barren pyrite root zone is overlain by pyrite-chalcopyrite, and followed upwards and laterally by chalcopyrite-digenite or chalcopyrite-bornite. The assemblage digenite–supergene chalcocite characterizes the central portions of high-grade mineralization in the breccia bodies. Fluid inclusions show evidence of boiling during the potassic and sodic alteration events, which occurred at temperatures around 450–460°C and 350–410°C, and salinities between 3–53 and 13–45 wt% NaCl eq., respectively. The hydrothermal events occurred during episodic decompression due to fluid overpressuring, hydrofracturing, and sharp changes from lithostatic to hydrostatic conditions. Sulfur isotope results of hypogene sulfide minerals fall in a narrow range around 0 per mil, suggesting a dominance of magmatic sulfur. Carbon and oxygen isotopic data of calcites from propylitic alteration suggest a mantle-derived carbon and oxygen isotope fractionation due to low-temperature alteration.     

The “Pomici di mercato” Plinian eruption of Somma-Vesuvius: magma chamber processes and eruption dynamics

The Pomici di Mercato (PdM, 8,010 ± 40 a), also known in the literature as Pomici Gemelle or Pomici di Ottaviano, is one of the oldest Plinian eruptions of Somma-Vesuvius. This eruption occurred after the longest (7 ka) quiescence period of the volcano and was followed by more than 4 ka of repose. The erupted magma is phonolitic in composition. All the products have very low phenocrysts content (less than 3%) and show evidence of mineralogical disequilibria. They contain K-feldspar ± clinopyroxene (salite and diopside) ± plagioclase ± garnet ± biotite ± amphibole ± apatite ± Fe-Ti oxides. Pumice fragments collected at different stratigraphic heights are slightly less evolved and more enriched in radiogenic Sr composition upsection. The glass composition is fairly homogeneous in single pumice fragment and among pumice fragments from different layers. Glass separated from pumice fragments collected at different stratigraphic heights is homogeneous in the Sr-isotope composition (around a value of 0.70717). Glass is in isotopic equilibrium with salite throughout the entire sequence and with diopside at the base of the sequence. Diopside becomes more radiogenic upsection, reaching a value of 0.707458 ± 7, whereas feldspar is consistently slightly less radiogenic than glass. Nd-isotope composition is fairly uniform (ca. 0.51247) through the whole sequence. The isotopic disequilibria among glass, feldspar and diopside, together with the homogeneous isotopic composition of pumice glass in equilibrium with salite, and the mineralogical disequilibria between plagioclase and K-feldspar, imply that most of the diopside and plagioclase crystals are xenocrysts incorporated into the phonolitic magma during residence in a magma chamber and/or during ascent towards the surface. The PdM Tephra are compositionally and isotopically similar to the phonolitic, first-erupted products of the subsequent Pomici di Avellino Plinian eruption. On the basis of this similarity, we suggest that the magma feeding both eruptions resulted from the tapping of a unique magma chamber. Prior to the PdM eruption, this chamber was formed by a large and homogeneous phonolitic magma body. After the PdM eruption, as a consequence of new arrivals of more radiogenic in Sr, less-differentiated magma batches, the magma chamber progressively developed a slightly stratified phonolitic uppermost portion, capping a tephriphonolitic layer, both emitted during the subsequent Pomici di Avellino eruption.