The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Diagenetic processes on metals in hypersaline mudflat sediments from a subtropical saltmarsh (SE Gulf of California): Postdepositional mobility and geochemical fractions

To understand the biogeochemical cycles of trace metals (Cd, Cu, Fe, Mn, Ni and Zn) in a hypersaline subtropical marsh, geochemical studies of both interstitial and solid phases were conducted on sediment cores from Chiricahueto marsh, SE Gulf of California. The sequential extraction procedure proposed by Tessier was used to estimate the percentages of the metals present in each geochemical phase of the sediment. Metal concentrations in the solid phase were found to be enriched in the upper layers and mainly associated with reactive fractions such as organic matter, Fe–Mn oxyhydroxides and carbonates (46–74% of Ni, Mn and Cd, and 11–19% of Cu and Zn). Principal factor analysis (PFA) and Spearman correlation analysis revealed a strong positive association of metals and their reactive phases with OC (the diagenetic component), and a negative or non-association with the mud content, Al, Fe and Li (the lithogenic component). Diagenetically released metals are mainly mobilized within hypersaline sediments by buoyancy transport (>90% of total flux) in response to an extreme salinity gradient by input of fresh groundwater (3–6 psu cm⁻¹). The molecular diffusion due to the gradient of metals in porewater (maximum and higher levels at 5–7 and below 20 cm depth, respectively) is significantly less important to the advective transport. Most of the metals mobilized by diffusion–advection processes are re-precipitated in the sediments by authigenic minerals, only <10% of most metals are extruded out to the overlying water column. Authigenic accumulation rates were estimated as 1.42–7.09 mg m⁻² a⁻¹ for Cd; 58.8–378 for Cu; 6922–17,985 for Fe; 38.2–345 for Mn; 20.8–263 for Ni; and 282–2956 mg m⁻² a⁻¹ for Zn. The Mn–Fe oxyhydroxides (40–85% of reactive metals) in the upper oxic–suboxic layers (<5 cm below surface) and sulfide minerals (75–97%) in anoxic sediment layers (7–18 cm) constitute the main scavengers for metals.     

First U–Pb SHRIMP age of the Hauterivian stage, Neuquén Basin, Argentina

A high-resolution ion-microprobe (SHRIMP) U–Pb zircon age from a tuff layer intercalated in the ammonoid bearing sedimentary succession of the Neuquén Basin in Argentina provides a robust geochronologic date to add to the absolute ages and to improve the relative chronology of the Early Cretaceous Hauterivian stage. The tuff layer appears interbedded between shales of the upper member (Agua de la Mula) of the Agrio Formation within the Spitidiscus riccardii ammonoid zone (base of the Late Hauterivian) yielding a date of 132.5 ± 1.3 Ma. This date confirms and supports an accurate correlation between the ammonoid biostratigraphy of the Neuquén Basin with the Western Mediterranean Province of the Tethys during the Early Cretaceous and matches with the most recently published time scale. It also casts doubts on the validity of K–Ar ages on glauconite-grains recently reported from the Lower Cretaceous of the Vocontian Basin of France.     

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.     

Flood hazard delineation combining geomorphological and hydrological methods: an example in the Northern Iberian Peninsula

Flood mapping requires the combination and integration of geomorphological and hydrological-hydraulic methods; however, despite this, there is very little scientific literature that compares and validates both methods. Two types of analysis are addressed in the present article. On the one hand, maps of flood plains have been elaborated using geomorphological evidence and historical flood data in the mountainous area of northwestern Spain, covering an area of more then 232 km² of floodplains. On the other hand, a hydrometeorological model has been developed (Clark semidistributed unit hydrograph) in the Sarria River basin (155 km², NW Spain). This basin is not gauged, hence the model was subjected to a goodness-of-fit test of its parameter (curve number) by means of Monte Carlo simulation. The peak flows obtained by means of the hydrological model were used for hydraulic modeling (one-phase, one-dimensional and steady flow) in a 4 km² urban stretch of the river bed. The delineation of surface areas affected by floods since 1918, as well as those analyzed subsequent to the geomorphological study, reveals a high degree of reliability in the delineation of the flooded areas with frequent recurrence intervals (<50 years). If we compare these flooded surface areas with the estimate obtained by the hydrological-hydraulic method we can see that the latter method overestimates the extent of the surface water by 144% for very frequent recurrence intervals (>10 years) and underestimates it as the recurrence interval increases, by up to 80% less floodplain for exceptional events (>500 years). Finally, a management map is put forth combining the most reliable results available by integrating both methods. Originally presented at the Sixth International Conference on Geomorphology.     

Deep-seated gravitational slope deformations and their influence on consequent mass movements (case studies from the highest part of the Czech Carpathians)

Gravitational spreading of mountain ridges displays primary disequilibrium of flysch mountain areas of the Czech Carpathians. The progression of various types of mass movements is a product of long-term ridge disintegration and is predisposed by the geological structure of the area and the upper Tertiary-Quaternary morphogenesis of the mountain area. Deep-seated slope deformations are spatially interconnected by the occurrence of some other types of slope deformations (e.g. debris flows, debris slides, slumps, rock avalanches, etc.), which pose a considerable risk for the existence of human society. An important causative factor in these dynamically developing hazardous processes is, among other factors, the way in which land has been used in the last three centuries. Therefore, the occurrence of various types of slope deformations is studied in terms of their relation to deep-seated gravitational deformations and in terms of other limiting factors (structural geological, morphological and climatic factors, manmade impacts, etc.). The paper presents several case studies of slope deformations (Velká Čantoryje Mt, Lysá hora Mt, Ropice Mt and Smrk Mt) in the area of the Outer Carpathians within the territory of the Czech Republic and also adverts to some consequences in terms of the socioeconomic structure of the landscape.     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

Numerical estimation of REV and permeability tensor for fractured rock masses by composite element method

The Monte Carlo method is used to generate parent stochastic discrete fracture network, from which a series of fractured rock samples of different sizes and orientations are extracted. The fracture network combined with a regular grid forms composite element mesh of the fractured rock sample, in which each composite element is composed of sub‐elements incised by fracture segments. The composite element method (CEM) for the seepage is implemented to obtain the nodal hydraulic potential as well as the seepage flow rates through the fractured rock samples. The application of CEM enables a large quantity of stochastic tests for the fractured rock samples because the pre‐process is facilitated greatly. By changing the sizes and orientations of the samples, the analysis of the seepage characteristics is realized to evaluate the variation of the permeability components, the existence of the permeability tensor and the representative element volume. The feasibility and effectiveness are illustrated in a numerical example. Copyright © 2008 John Wiley & Sons, Ltd.