Francisco Macías

Natural pretreatment and passive remediation of highly polluted acid mine drainage

Acid mine drainage (AMD) from the Iberian Pyrite Belt has high acidity and metal concentrations. Earlier pilot experiments, based on limestone sand dispersed in wood shavings (dispersed alkaline substrate; DAS) have been shown to be an efficient treatment option. However, complete metal removal was not achieved, principally due to the high ferrous iron concentration in the inflow AMD. In order to oxidize and remove iron, a natural Fe-oxidizing lagoon (NFOL) was added prior to treatment with limestone-DAS. The NFOL comprises several pre-existing Fe-stromatolite terraces and cascades, and a lagoon with a volume of 100 m(3) built near the mine shaft. Downstream of the NFOL, the limestone-DAS treatment consists of two reactive tanks of 3 m(3) each filled with limestone-DAS reactive substrate, connected in series with two decantation ponds of 6 m(3) each and several oxidation cascades. The AMD emerging from the mine shaft displayed a pH near 3, a net acidity of 1800 mg/L as CaCO(3) equivalents, and mean concentrations of 440 mg/L Zn; 275 mg/L Fe (99% Fe(II)); 3600 mg/L SO(4); 250 mg/L Ca; 100 mg/L Al; 15 mg/L Mn; 5 mg/L Cu; and 0.1-1 mg/L As, Pb, Cr, Cd, Co, and Ni. The oxidation induced in the NFOL enhanced ferric iron concentration, showing an average of 65% oxidation and 38% retention during the monitoring period. The whole system removed a mean of 1350 mg/L net acidity as CaCO(3) equivalents (71% of inflow); corresponding to 100% of Fe, Al, Cu, Pb and As, and 6% of Zn.

Long term remediation of highly polluted acid mine drainage: a sustainable approach to restore the environmental quality of the Odiel river basin.

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO(3) and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m(3)/day achieving an acid load reduction of 597 g·(m(2) day)(-1), more than 10 times higher than the generally accepted 40 g·(m(2) day)(-1) value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage.

From highly polluted Zn-rich acid mine drainage to non-metallic waters: Implementation of a multi-step alkaline passive treatment system to remediate metal pollution

Complete metal removal from highly-polluted acid mine drainage was attained by the use of a pilot multi-step passive remediation system. The remediation strategy employed can conceptually be subdivided into a first section where the complete trivalent metal removal was achieved by the employment of a previously tested limestone-based passive remediation technology followed by the use of a novel reactive substrate (caustic magnesia powder dispersed in a wood shavings matrix) obtaining a total divalent metal precipitation. This MgO-step was capable to abate high concentrations of Zn together with Mn, Cd, Co and Ni below the recommended limits for drinking waters. A reactive transport model anticipates that 1 m(3) of MgO-DAS (1 m thick × 1 m(2) section) would be able to treat a flow of 0.5 L/min of a highly acidic water (total acidity of 788 mg/L CaCO(3)) for more than 3 years.

Recovery of Rare Earth Elements and Yttrium from Passive-Remediation Systems of Acid Mine Drainage

Rare earth elements and yttrium (REY) are raw materials of increasing importance for modern technologies, and finding new sources has become a pressing need. Acid mine drainage (AMD) is commonly considered an environmental pollution issue. However, REY concentrations in AMD can be several orders of magnitude higher than in naturally occurring water bodies. With respect to shale standards, the REY distribution pattern in AMD is enriched in intermediate and valuable REY, such as Tb and Dy. The objective of the present work is to study the behavior of REY in AMD passive-remediation systems. Traditional AMD passive remediation systems are based on the reaction of AMD with calcite-based permeable substrates followed by decantation ponds. Experiments with two columns simulating AMD treatment demonstrate that schwertmannite does not accumulate REY, which, instead, are retained in the basaluminite residue. The same observation is made in two field-scale treatments from the Iberian Pyrite Belt (IPB, southwest Spain). On the basis of the amplitude of this process and on the extent of the IPB, our findings suggest that the proposed AMD remediation process can represent a modest but suitable REY source. In this sense, the IPB could function as a giant heap-leaching process of regional scale in which rain and oxygen act as natural driving forces with no energy investment. In addition to having environmental benefits of its treatment, AMD is expected to last for hundreds of years, and therefore, the total reserves are practically unlimited.

Environmental assessment and management of metal-rich wastes generated in acid mine drainage passive remediation systems

As acid mine drainage (AMD) remediation is increasingly faced by governments and mining industries worldwide, the generation of metal-rich solid residues from the treatments plants is concomitantly raising. A proper environmental management of these metal-rich wastes requires a detailed characterization of the metal mobility as well as an assessment of this new residues stability. The European standard leaching test EN 12457-2, the US EPA TCLP test and the BCR sequential extraction procedure were selected to address the environmental assessment of dispersed alkaline substrate (DAS) residues generated in AMD passive treatment systems. Significant discrepancies were observed in the hazardousness classification of the residues according to the TCLP or EN 12457-2 test. Furthermore, the absence of some important metals (like Fe or Al) in the regulatory limits employed in both leaching tests severely restricts their applicability for metal-rich wastes. The results obtained in the BCR sequential extraction suggest an important influence of the landfill environmental conditions on the metals released from the wastes. To ensure a complete stability of the pollutants in the studied DAS-wastes the contact with water or any other leaching solutions must be avoided and a dry environment needs to be provided in the landfill disposal selected.

Acid mine drainage in the Iberian Pyrite Belt: 2. Lessons learned from recent passive remediation experiences

The Iberian Pyrite Belt (IPB), SW Spain and Portugal, contains about 100 abandoned mine wastes and galleries that release acid mine drainages (AMD) to the Tinto and Odiel rivers. In situ passive remediation technologies are especially suitable to remediate the drainages of these orphan sites. However, traditional remediation systems, designed for coal mines, have been demonstrated inefficient to treat the IPB mine waters. Due to their high acidity and metal loads, large amount of solids precipitate and fast clogging of porosity or passivation (coating) of the reactive grains occurs. To overcome these problems, the dispersed alkaline substrate (DAS) a mixture of fine-grained limestone sand and a coarse inert matrix (e.g., wood shavings) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate. The high porosity retards clogging. However, calcite dissolution only raises pH to values around 6.5, at which the hydroxides of trivalent metals (Al and Fe) precipitate, but it is not high enough to remove divalent metals. Caustic magnesia (MgO) buffers the solution pH between 8.5 and 10. A DAS system replacing limestone with caustic magnesia has been tested to be very efficient to remove divalent metals (Zn, Cd, Mn, Cu, Co, Ni, and Pb) from the water previously treated with calcite.

Pollutant flows from a phosphogypsum disposal area to an estuarine environment: An insight from geochemical signatures.

Phosphogypsum wastes from phosphate fertilizer industries are stockpiled in stacks with high contamination potential. An assessment of the environmental impact, including the use of geochemical tracers such as rare earth elements (REE) and Cl/Br ratios, was carried out in the phosphogypsum stack located at the Estuary of Huelva (SW Spain). Inside the pile, highly polluted acid pore-waters flows up to the edge of the stack, emerging as small fluvial courses, known as edge outflows, which discharge directly into the estuary. The disposal area is divided into four zones; two unrestored zones with surface ponds of industrial process water and two a priori already-restored zones. However, an extensive sampling of edge outflows conducted in the perimeter of the four zones demonstrates the high potential of contamination of the whole stack, including those zones that were supposedly restored. These solutions are characterized by a pH of 1.9 and concentrations of 6100 mg/L for P, 1970 mg/L for S, 600 mg/L for F, 200mg/L for NH4(+), 100mg/L for Fe, 10-30 mg/L for Zn, As and U, and 1-10mg/L for Cr, Cu and Cd. Preliminary restoration actions and those planned for the future prioritize removal of ponded process water and cover of the phosphogypsum with artificial topsoil. These actions presuppose that the ponded process water percolates through the porous medium towards the edge up to reach the estuary. However, geochemical tracers rule out this connection and point to an estuarine origin for these leachates, suggesting a possible tidal-induced leaching of the waste pile in depth. These findings would explain the ineffectiveness of preliminary restoration measures and should be considered for the development of new action plans.

A bacterial consortium isolated from an Icelandic fumarole displays exceptionally high levels of sulfate reduction and metals resistance.

The soils of three fumaroles and one mining site, all with high metal content, were surveyed for the presence of metal-resistant sulfate-reducing bacteria and their potential application in the bioremediation of acid mine drainages. By means of selective soil enrichments a bacterial consortium was isolated from an Icelandic fumarole that displayed very high sulfate reduction in the presence of a mixture of 0.75 g/L of Fe, 0.20 g/L of Zn and 0.080 g/L of Cu. Under these conditions the bacterial consortium reduced 91% of the added 3.9 g/L of sulfate after 28 days, precipitating 100% of the Fe, 96% of the Zn and 97% of the Cu during the same time. Both total bacterial numbers and numbers of culturable sulfate-reducing bacteria remained unchanged when grown in media containing metals, suggesting low or absent inhibitory effects of the metals on the bacterial consortium. PCR-DGGE profiles of the sulfate reducing bacterial communities obtained from the Icelandic fumarole sample showed that bacterial diversity decreased significantly after metal addition: from the original 12 ribotypes only two were detected in the metal-tolerant culture. Phylogenetic analysis of 16S ribosomal RNA gene sequences revealed that these two ribotypes were affiliated with the genera Clostridium and Desulfovibrio, with C. subterminale, C. pascui, C. mesophilum and C. peptidovorans and D. desulfuricans identified as their closest relatives.

Long term fluctuations of groundwater mine pollution in a sulfide mining district with dry Mediterranean climate: Implications for water resources management and remediation

Water resources management and restoration strategies, and subsequently ecological and human life quality, are highly influenced by the presence of short and long term cycles affecting the intensity of a targeted pollution. On this respect, a typical acid mine drainage (AMD) groundwater from a sulfide mining district with dry Mediterranean climate (Iberian Pyrite Belt, SW Spain) was studied to unravel the effect of long term weather changes in water flow rate and metal pollutants concentration. Three well differentiated polluting stages were observed and the specific geochemical, mineralogical and hydrological processes involved (pyrite and enclosing rocks dissolution, evaporitic salts precipitation-redisolution and pluviometric long term fluctuations) were discussed. Evidencing the importance of including longer background monitoring stage in AMD management and restoration strategies, the present study strongly advise a minimum 5-years period of AMD continuous monitoring previous to the design of any AMD remediation system in regions with dry Mediterranean climate.

Hydrochemical performance and mineralogical evolution of a dispersed alkaline substrate (DAS) remediating the highly polluted acid mine drainage in the full-scale passive treatment of Mina Esperanza (SW Spain)

Abstract Acid mine drainage remediation is an unresolved matter in abandoned mining districts around the world. Development and implementation of passive treatment systems in these areas are commonly focused on engineering and water quality aspects. Neoformed mineral phases precipitated within the reactive material of these passive treatments account for the removal of pollutants but also can cause clogging and passivation of the reactive substrate. After 20 months of operation and monitoring, the limestone-based passive treatment system implemented in Mina Esperanza (SW Spain) was sampled to study the relationship between water chemistry, mineral composition of the neoformed precipitates, and treatment performance. Water chemical profiles show the existence of three precipitation zones controlled by Fe, Al, and Zn hydrochemistry and also a migration with time of precipitation zones downward into the reactive material. These precipitation zones were also confirmed by a mineral study performed on the solid samples where either schwertmannite and goethite or hydrobasaluminite and Zn-rich green rust were the mineral phases that controlled the metal removal in the three precipation (Fe, Al, or Zn) zones. Iron and Al precipitates were observed to play a critical role in the time evolution of the reactive material hydraulic conductivity. Furthermore, Al precipitates passivated to some extent the limestone grains by armoring, although migration of the Fe precipitation zone and Al redissolution later activated the limestone grains. A higher proportion of limestone in the reactive mixture and the addition of new reagents to the bottom section of the reactive material (to enhance the reducing environment and to promote divalent metal removal) are proposed on the basis of this hydrochemical and mineralogical study for a future design for the Mina Esperanza passive treatment system.