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.     

Boundary manifolds for energy surfaces in celestial mechanics

We complete Mc Gehee's picture of introducing a boundary (total collision) manifold to each energy surface. This is done by constructing the missing components of its boundary as other submanifolds. representing now the asymptotic behavior at infinity.It is necessary to treat each caseh=0,h>0 orh<0 separately. In the first case, we repeat the known result that the behavior at total escape is the same as in total collision. In particular, we explain why the situation is radically different in theh>0 case compared with the zero energy case. In the caseh<0 we have many infinity manifold components. and the general situation is not quite well understood.Finally, our results forh0 are shown to be valid for general homogeneous potentials.Paper presented at the 1981 Oberwolfach Conference on Mathematical Methods in Celestial Mechanics.The research conducted in this paper has been partially supported by CONACYT (México), under grant PCCBNAL 790178.Partially supported by an Ajut a l'Investigacio of the University of Barcelona.     

The behavior of trace elements during schwertmannite precipitation and subsequent transformation into goethite and jarosite

Schwertmannite is a ubiquitous mineral formed from acid rock drainage (ARD), and plays a major role in controlling the water chemistry of many acid streams. The formation of schwertmannite was investigated in the acid discharge of the Monte Romero abandoned mine (Iberian Pyrite Belt, SW, Spain). Schwertmannite precipitated from supersaturated solutions mainly owing to the oxidation of Fe(II) to Fe(III) and transformed with time into goethite and jarosite. In a few hours, schwertmannite precipitation removed more than half of the arsenic load from solution, whereas the concentration of divalent trace metals (Zn, Cu, Pb, Cd, Ni, and Co) remained almost unchanged. In the laboratory, natural schwertmannite was kept in contact with its coexisting acid water in a flask with a solid-liquid mass ratio of 1:5 for 353 days. During this time, the pH of the solution dropped from 3.07 to 1.74 and the concentrations of sulfate and Fe increased. During the first 164 days, schwertmannite transformed into goethite plus H₃O-jarosite but, subsequently, goethite was the only mineral to form. Some of the trace elements, such as Al, Cu, Pb, and As were depleted in solution during the first stage as schwertmannite transformed into goethite plus H₃O-jarosite. On the contrary, the transformation of schwertmannite to goethite (with no jarosite) during the second stage released Al, Cu, and As to the solution. Despite the variation in their concentrations in solution, approximately 80% of the total Al and Cu inventories and more than 99% As and Pb remained in the solid phase throughout the entire aging process.     

Sludge weathering and mobility of contaminants in soil affected by the Aznalcollar tailing dam spill (SW Spain)

As a result of the collapse of the Aznalcollar mine tailings dam, a large extension of the Guadiamar valley in SW Spain was covered with a layer of pyrite sludge. Although most of the sludge was removed, a small amount remains in the soil, constituting a potential source of water pollution. A column experiment was carried out in order to determine the rate of sludge oxidation in the soil, and the existence of metal retention processes. The column was filled with a mixture of sludge and a sandy soil common in the region. At different time intervals, the column was leached with water and the resulting solution analysed.

The pH of the water dropped to values around 2 after 260 days and then remained constant due to the buffering role of silicate dissolution. The concentration of Zn, Cd and Co in the leachates matched the expected values from flow-through experiments at atmospheric oxygen pressure. This indicates that oxygen diffusion in the pores was complete. Moreover, no efficient processes existed for retaining Zn, Cd and Co, which formed soluble salts and were entirely incorporated into the infiltrating water. During the first 2 months of the experiment, when pH was higher than 4.5, the concentrations of Fe and Al were very low. Saturation indices showed that the solution was in equilibrium with amorphous Fe(OH)₃ and Al(OH)₃. Subsequently, at lower pH values, jarosite [(Na,K)Fe₃(SO₄)₂(OH)₆] formed. This solid phase was identified by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). Jarosite was also responsible for the depletion of As, Pb, Sb and probably Tl in the water resulting from infiltration.     

Spatio‐temporal variability of the isotopic input signal in a partly forested catchment: Implications for hydrograph separation

The isotopic composition of precipitation (D and ¹⁸O) has been widely used as an input signal in water tracer studies. Whereas much recent effort has been put into developing methodologies to improve our understanding and modelling of hydrological processes (e.g., transit‐time distributions or young water fractions), less attention has been paid to the spatio‐temporal variability of the isotopic composition of precipitation, used as input signal in these studies. Here, we investigated the uncertainty in isotope‐based hydrograph separation due to the spatio‐temporal variability of the isotopic composition of precipitation. The study was carried out in a Mediterranean headwater catchment (0.56 km²). Rainfall and throughfall samples were collected at three locations across this relatively small catchment, and stream water samples were collected at the outlet. Results showed that throughout an event, the spatial variability of the input signal had a higher impact on hydrograph separation results than its temporal variability. However, differences in isotope‐based hydrograph separation determined preevent water due to the spatio‐temporal variability were different between events and ranged between 1 and 14%. Based on catchment‐scale isoscapes, the most representative sampling location could also be identified. This study confirms that even in small headwater catchments, spatio‐temporal variability can be significant. Therefore, it is important to characterize this variability and identify the best sampling strategy to reduce the uncertainty in our understanding of catchment hydrological processes.     

Anticipating the effects of groundwater withdrawal on seawater intrusion and soil settlement in urban coastal areas

Intensive pumping in urban coastal areas is a common threat to water resource quality due to seawater intrusion. In those areas where subsurface water resources are not usually used for human consumption or irrigation, intensive pumping is associated with other activities like the lowering of the water table necessary to support underground structures and building foundations. This activity also increases the likelihood of soil settlement that affects building stability and the corrosion of concrete structures due to groundwater salinity. Under these circumstances, the awareness of a certain municipality (Calonge, NE Spain) of the potential effects of groundwater withdrawal upon foundations has led to an integrated approach to anticipate seawater intrusion related to urban development. Geological mapping and correlation of borehole logs, electrical resistivity tomography, and hydrochemical data provide comprehensive knowledge of the geology and hydrogeology of the area and act as screening tools necessary to discern the influence of hydrological processes in coastal areas. Developing Strack's analytical solution, new comprehensive, dimensionless expressions are herein derived to determine the critical pumping rate necessary to prevent seawater intrusion, as well as to reproduce the evolution of the wedge toe and the water table stagnation point under different withdrawal rates. Furthermore, the Dupuit–Forchheimer well discharge formula allows the estimation of the effects of the water table lowering due to such critical pumping in the surrounding building foundations. Field data from the Calonge coastal plain illustrate this approach and provide assessment criteria for future urban development and planning. Copyright © 2012 John Wiley & Sons, Ltd.     

Coupled thermal, hydraulic and geochemical evolution of pyritic tailings in unsaturated column experiments

The evolution of pore-water and the composition of solid phases in the vadose zone of pyritic tailings was studied by means of unsaturated column experiments. Several columns of water-saturated mine tailings were dried during 125 days under controlled laboratory conditions. The columns were dismantled at four successive drying stages and the evolution of pore-water, mineralogy, water content and temperature was characterized.Sulfide and aluminosilicate minerals present in the waste dissolved, releasing sulfate and other solutes (mainly Fe, Zn, Cu, Al, Mg and Ca) to the pore-water. Evaporation caused a crust of efflorescent, water-soluble sulfates to develop over the complete top surface of the columns and into the pores of the underlying waste material. This crust, which has also been identified in the field, changed the hydraulic properties of the tailings and produced a decrease in the evaporation rate of the columns. Moreover, these water-soluble precipitates (mainly rozenite, szomolnokite, halotrichite, hexahydrite, mirabilite and gypsum) acted as temporary sinks for Cd, Pb, Co and Ni, which could be released to the surface run-off or the groundwaters during rainfall events under field conditions.Pore-water evolution was determined not only by geochemical processes (dissolution of sulfides and aluminosilicates, precipitation of secondary phases) but also by thermal and hydraulic processes. Progressive dilution was observed in the lower part of the columns. Dilution was caused by the thermally driven vapor flux from the top of the column to its colder bottom and subsequent condensation therein. This process, which may also occur in tailings under sub-arid climate, played a key role on the evolution of pore-water with increasing drying.     

Interannual variability in the biochemical composition of newly hatched larvae of the spider crab Maja brachydactyla (Decapoda,Majidae)

The spider crab Maja brachydactyla is an important commercial species in Europe and supports intensive fisheries in the NE Atlantic. A field survey was performed to assess long‐term and consecutive interannual (2005–2010) variation of the biochemical composition of newly hatched larvae of M. brachydactyla. Larval biochemical profiles differed significantly among years, with pronounced differences being recorded in 2010. Differences among batches of newly hatched larvae were mainly explained by the contribution of triacylglycerols and, to a lesser degree, by protein and lipid content. The use of different nutrition indices is discussed. The biochemical composition of newly hatched larvae from M. brachydactyla was highly variable, even though surveyed broodstock was obtained from the same local population and was always sampled during the same season. The unpredictable biochemical profiles of newly hatched larvae may condition their survival and recruitment. This largely overlooked aspect of larval variability should be considered in future fisheries management strategies and captive production of marine organisms that still rely on wild seeds.     

The early Cambrian Chahmir shale-hosted Zn–Pb deposit,Central Iran: an example of vent-proximal SEDEX mineralization

The Chahmir zinc–lead deposit (1.5 Mt @ 6 % Zn + 2 % Pb) in Central Iran is one among several sedimentary-exhalative Zn–Pb deposits in the Early Cambrian Zarigan–Chahmir basin (e.g., Koushk, Darreh-Dehu, and Zarigan). The deposit is hosted by carbonaceous, fine-grained black siltstones, and shales interlayered with volcaniclastic sandstone beds. It corresponds to the upper part of the Early Cambrian volcano-sedimentary sequence (ECVSS), which was deposited on the Posht-e-Badam Block during back-arc rifting of the continental margin of Central Iran. Based on crosscutting relationships, mineralogy, and texture of sulfide mineralization, four different facies can be distinguished: stockwork (feeder zone), massive ore, bedded ore, and distal facies (exhalites with barite). Silicification, carbonatization, sericitization, and chloritization are the main wall-rock alteration styles; alteration intensity increases toward the proximal feeder zone. Fluid inclusion microthermometry was carried out on quartz associated with sulfides of the massive ore. Homogenization temperatures are in the range of 170–226 °C, and salinity is around 9 wt% NaCl eq. The size distribution of pyrite framboids of the bedded ore facies suggests anoxic to locally suboxic event for the host basin. δ³⁴S_(V-CDT) values of pyrite, sphalerite, and galena range from +10.9 to +29.8?‰. The highest δ³⁴S values correspond to the bedded ore (+28.6 to +29.8?‰), and the lowest to the massive ore (+10.9 to +14.7?‰) and the feeder zone (+11.3 and +12.1?‰). The overall range of δ³⁴S is consistent with a sedimentary environment where sulfide sulfur was derived from two sources. One of them was corresponding to early ore-stage sulfides in bedded ore and distal facies, consistent with bacterial reduction from coeval seawater sulfate in a closed or semiclosed basin. However, the δ³⁴S values of late ore-stage sulfides, observed mainly in massive ore, interpreted as a hydrothermal sulfur component, leached from the lower part of the ECVSS. Sulfur isotopes, along with the sedimentological, textural, mineralogical, fluid inclusion, and geochemical characteristics of the Chahmir deposit are in agreement with a vent-proximal (Selwyn type) SEDEX ore deposit model.     

Masses for which triple collision is regularizable

We consider the regularization by continuity w.r.t. initial conditions (geometric or Easton method) which has a sense both in physical and computational aspects. Using the idea of triple collision manifold of McGehee we study the values of masses for which the invariant manifolds of equilibrium points coincide. Local analytical equations are continuated numerically. So one gets the masses satisfying a necessary condition. Again analytically we discuss the neighbourhood of t.c.m. at the equilibrium points. A necessary and sufficient condition in terms of integrals along invariant manifolds is found for the rectilinear case. This can be tested for the masses obtained above. Only a countable (symmetric) set of masses remains. Then, due to errors in physical measurements or numerical integrations we can never expect a regular behaviour. Extension to the planar case is also taken into account.Proceedings of the Sixth Conference on Mathematical Methods in Celestial Mechanics held at Oberwolfach (West Germany) from 14 to 19 August, 1978.