Environmental risk evaluation of the use of mine spoils and treated sewage sludge in the ecological restoration of limestone quarries

The ecologic restoration criteria in areas degraded from extraction activities require making use of their mine spoils. These materials do not meet fertility conditions to guarantee restoration success and therefore, need the incorporation of organic amendments to obtain efficient substratum. Reducing the deficiencies in the organic material and restoration material nutrients with the contribution of treated sewage sludge is proposed in this work. This experiment was based on a controlled study using columns. The work was conducted with two mine spoils, both very rich in calcium carbonate. The first mineral, of poor quality, came from the formation of aggregates of crushed limestone (Z). The other residual material examined originated in limestone extraction, formed by the levels of interspersed non-limestone materials and the remains of stripped soils (D). Two treatments were undertaken (30,000 and 90,000 kg/ha of sewage sludge), in addition to a control treatment. The water contribution was carried out with a device that simulated either short-duration rain or a flooding irrigation system in order to cover the surface and then percolate through the soil. The collection of leached water took place 24 h after the applications. Different parameters of the leached water were determined, including pH, electrical conductivity, nitrate anions, ammonium, phosphates, sulphates and chlorides. The values obtained for each irrigation application are discussed, and the nitrate values obtained were very elevated.     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.     

Sedimentary petrology and geochemistry of siliciclastic rocks from the upper Jurassic Tordillo Formation (Neuquén Basin, western Argentina): Implications for provenance and tectonic setting

The Upper Jurassic Tordillo Formation is exposed along the western edge of the Neuquén Basin (west central Argentina) and consists of fluvial strata deposited under arid/semiarid conditions. The pebble composition of conglomerates, mineralogical composition of sandstones and pelitic rocks, and major- and trace-element geochemistry of sandstones, mudstones, and primary pyroclastic deposits are evaluated to determine the provenance and tectonic setting of the sedimentary basin. Conglomerates and sandstones derived almost exclusively from volcanic sources. The stratigraphic sections to the south show a clast population of conglomerates dominated by silicic volcanic fragments and a predominance of feldspathic litharenites. This framework composition records erosion of Triassic–Jurassic synrift volcaniclastic rocks and basement rocks from the Huincul arch, which was exhumed as a result of Late Jurassic inversion. In the northwestern part of the study area, conglomerates show a large proportion of mafic and acidic volcanic rock fragments, and sandstones are characterised by a high content of mafic volcanic rock fragments and plagioclase. These data suggest that the source of the sandstones and conglomerates was primarily the Andean magmatic arc, located west of the Neuquén Basin. The clay mineral assemblage is interpreted as the result of a complex set of factors, including source rock, climate, transport, and diagenesis. Postdepositional processes produced significant variations in the original compositions, especially the fine-grained deposits. The Tordillo sediments are characterised by moderate SiO₂ contents, variable abundances of K₂O and Na₂O, and a relatively high proportion of ferromagnesian elements. The degree of chemical weathering in the source area, expressed as the chemical index of alteration, is low to moderate. The major element geochemistry and Th/Sc, K/Rb, Co/Th, La/Sc, and Cr/Th values point to a significant input of detrital volcanic material of calcalkaline felsic and intermediate composition. However, major element geochemistry is not useful for interpreting the tectonic setting. Discrimination plots based on immobile trace elements, such as Ti, Zr, La, Sc, and Th, show that most data lie in the active continental margin field. Geochemical information is not sufficiently sensitive to differentiate the two different source areas recognized by petrographic and modal analyses of conglomerates and sandstones.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

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.     

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.     

Methodology of hydrogeological characterization of deep carbonate aquifers as potential reservoirs of groundwater. Case of study: the Jurassic aquifer of <Emphasis Type="Italic">El Maestrazgo</Emphasis> (Castellón,Spain)

A methodology for the characterization of deep carbonate aquifers has been developed and applied to El Maestrazgo Jurassic aquifer in Castellón, Spain. Characterization of these aquifer formations, located at more than 300 m deep, consisted of a previous phase of compilation, analysis and synthesis of the existing information about the area, followed by a coordinated combination of different speciality studies: geology, stratigraphy, structural analysis, hydrogeology, hydrochemistry, geophysics and remote sensing. Geological studies included geological mapping, definition of stratigraphical units and facies and structural analysis. The aim of the hydrogeology study was to define aquifer formations, recharge area, aquifer points inventory and groundwater flow directions for the establishment of piezometric and water quality observation nets. Special techniques were applied, like thermal infrared aerial images and the evaluation of submarine groundwater discharge by means of natural radium isotopes. Hydrochemical techniques, including majority elements characterization and stable isotopes (¹⁸O, ²H and ³H) determination, allowed classifying hydrochemical facies and establishing a renewal pattern for water within the system. Geophysics was useful in determining the aquifer geometry, the features of the basement and the petrophysical characteristics of the geological formations. Preliminary results show an important tectonic complexity and the possibilities for groundwater uses in the area of study.