Potentially Toxic Elements’ Contamination of Soils Affected by Mining Activities in the Portuguese Sector of the Iberian Pyrite Belt and Optional Remediation Actions: A Review

Both sectors of the Iberian Pyrite Belt, Portuguese and Spanish, have been exploited since ancient times, but more intensively during and after the second half of the 19th century. Large volumes of polymetallic sulfide ore were extracted in open pits or in underground works, processed without environmental concerns, and the generated waste rocks and tailings were simply deposited in the area. Many of these mining sites were abandoned for years under the action of erosive agents, leading to the spread of trace elements and the contamination of soils, waters and sediments. Some of these mine sites have been submitted to rehabilitation actions, mostly using constructive techniques to dig and contain the contaminated tailings and other waste materials, but the remaining soil still needs to be treated with the best available techniques to recover its ecosystem functions. Besides the degraded physical structure and poor nutritional status of these soils, they have common characteristics, as a consequence of the pyrite oxidation and acid drainage produced, such as a high concentration of trace elements and low pH, which must be considered in the remediation plans. This manuscript aims to review the results from studies which have already covered these topics in the Iberian Pyrite Belt, especially in its Portuguese sector, considering: (i) soils’ physicochemical characteristics; (ii) potentially toxic trace elements’ concentration; and (iii) sustainable remediation technologies to cope with this type of soil contamination. Phytostabilization, after the amelioration of the soil’s properties with organic and inorganic amendments, was investigated at the lab and field scale by several authors, and their results were also considered.

Industrial Heap Bioleaching of Copper Sulfide Ore Started with Only Water Irrigation

Sulfuric acid solution containing ferric iron is the extractant for industrial heap bioleaching of copper sulfides. To start a heap bioleaching plant, sulfuric acid is usually added to the irrigation solution to maintain adequate acidity (pH 1.0–2.0) for copper dissolution. An industrial practice of heap bioleaching of secondary copper sulfide ore that began with only water irrigation without the addition of sulfuric acid was successfully implemented and introduced in this manuscript. The mineral composition and their behavior related to the production and consumption of sulfuric acid during the bioleaching in heaps was analyzed. This indicated the possibility of self-generating of sulfuric acid in heaps without exogenous addition. After proving by batches of laboratory tests, industrial measures were implemented to promote the sulfide mineral oxidation in heaps throughout the acidifying stages, from a pH of 7.0 to 1.0, thus sulfuric acid and iron was produced especially by pyrite oxidation. After acidifying of the heaps, adapted microbial consortium was inoculated and established in a leaching system. The launch of the bioleaching heap and finally the production expansion were realized without the addition of sulfuric acid, showing great efficiency under low operation costs.

Lithological controls on the expansion of unbound aggregates in Dublin, eastern Ireland: two contrasting cases

Pyrite-bearing unbound fills, widely used in eastern Ireland have heaved, causing serious structural damage to thousands of buildings. This study compares calcareous mudstones that degenerated rapidly, causing severe structural damage, with argillaceous limestones that did not. Framboidal pyrite in the mudstones is widely dispersed – every aggregate particle contains abundant framboidal pyrite. Oxidation of this produced sulfuric acid that reacted with calcite producing supersaturated solutions of CaSO4 and CO2 gas. It is suggested that the latter exerted pressures approaching 5 MPa within rock particles, creating micro-fractures into which gypsum crystallised. Antitaxial growth of gypsum continued expansion, a process analogous to the formation of mineral veins in rocks. Heave of the fill took place since all the loadbearing particles expanded. The limestones have a lower pyrite content, which occurs mainly in the shaly seams and is concentrated in the fines; limestones suffered similar oxidation, but the coarser aggregate remains unaltered, and gypsum is mainly pore-filling; little expansive force was generated. It is concluded that the actual amount of pyrite present is a less important factor controlling expansion of unbound fills than its crystal size, and its distribution throughout the aggregate.

Hydrogeochemical Evolution of an Aquifer Regulated by Pyrite Oxidation and Organic Sediments

Detailed full-scale groundwater monitoring was carried out over a period of nine years, sampling at selected points along the groundwater flow direction in its final stretch. This established the hydrogeochemical evolution along the flow of a natural system formed by a calcareous aquifer which discharges and then passes through a quaternary aquifer of lake origin which is rich in organic matter. This evolution is highly conditioned by the oxidation of pyrites that are abundant in both aquifers. In the first aquifer, one kilometre before the discharge location, oxidizing groundwater crosses a pyrite mineralization zone whose oxidation produces an important increase in sulphates and water denitrification over a short period of time. In the quaternary aquifer with peat sediments and pyrites, water experiences, over a small 500 m passage and residence time of between three and nine years, a complete reduction by way of pyrite oxidation, and a consequent increase in sulphates and the generation of hydrogen sulphuric acid. This is an example of an exceptional natural hydrogeological environment which provides guidance on hydrogeochemical processes such as denitrification.