Magnetic separation for arsenic and metal recovery from polluted sediments within a circular economy.

Several metals and metalloids (e.g., As, Cd, Cu, Pb, Zn) are toxic at low concentrations, thus their presence in sediments can raise environmental concern. However, these elements can be of economic interest, and several techniques have been used for their recovery and some of them have been widely applied to mining or to industrial soils, but not to sediments. In this work, wet high-intensity magnetic separation (WHIMS) was applied for As, Cd, Cu, Pb and Zn recovery from polluted sediments. A composite sample of 50 kg was taken in the Avilés estuary (Asturias, North Spain) with element concentrations above the legislation limits. Element distribution was assessed using wet-sieving and ICP-MS analysis, revealing that the 125-500 µm grain-size fraction accounts for the 62 w% of the material and that element concentration in this fraction is lower than in the other grain size fractions. Subsequently, WHIMS was applied at three different voltage intensities for the 125-500 µm and <125 µm fractions, revealing excellent recovery ratios, especially for the coarser material. Furthermore, magnetic property measurements coupled to microscopy analysis revealed that the success of the technique derives from concentrating metal-enriched iron oxides particles (ferro- and para-magnetic material) in a mixture of quartz and other minerals (diamagnetic particles). These results indicate the feasibility of the magnetic separation for metal and metalloid recovery from polluted sediments, and thus offer a double benefit of coastal area restoration and valuable material recovery in the context of a circular economy.

Nanoscale zero-valent iron-assisted soil washing for the removal of potentially toxic elements.

The present study focuses on soil washing enhancement via soil pretreatment with nanoscale zero-valent iron (nZVI) for the remediation of potentially toxic elements. To this end, soil polluted with As, Cu, Hg, Pb and Sb was partitioned into various grain sizes (500-2000, 125-500 and <125 µm). The fractions were pretreated with nZVI and subsequently subjected, according to grain size, to Wet-High Intensity Magnetic Separation (WHIMS) or hydrocycloning. The results were compared with those obtained in the absence of nanoparticles. An exhaustive characterization of the magnetic signal of the nanoparticles was done. This provided valuable information regarding potentially toxic elements (PTEs) fate, and allowed a metallurgical accounting correction considering the dilution effects caused by nanoparticle addition. As a result, remarkable recovery yields were obtained for Cu, Pb and Sb, which concentrated with the nZVI in the magnetically separated fraction (WHIMS tests) and underflow (hydrocyclone tests). In contrast, Hg, concentrated in the non-magnetic fraction and overflow respectively, while the behavior of As was unaltered by the nZVI pretreatment. All things considered, the addition of nZVI enhanced the efficiency of soil washing, particularly for larger fractions (125-2000 µm). The proposed methodology lays the foundations for nanoparticle utilization in soil washing operations.

Comprehensive waste characterization and organic pollution co-occurrence in a Hg and As mining and metallurgy brownfield.

The abandonment of Hg-As mining and metallurgy sites, together with long-term weathering, can dramatically degrade the environment. In this work it is exemplified the complex legacy of contamination that afflicts Hg-As brownfields through the detailed study of a paradigmatic site. Firstly, an in-depth study of the former industrial process was performed to identify sources of different types of waste. Subsequently, the composition and reactivity of As- and Hg-rich wastes (calcines, As-rich soot, stupp, and flue dust) was analyzed by means of multielemental analysis, mineralogical characterization (X-ray diffraction, electronic, and optical microscopy, microbrobe), chemical speciation, and sequential extractions. As-rich soot in the form of arsenolite, a relatively mobile by-product of the pyrometallurgical process, and stupp, a residue originated in the former condensing system, were determined to be the main risk at the site. In addition, the screening of organic pollution was also aimed, as shown by the outcome of benzo(a) pyrene and other PAHs, and by the identification of unexpected Hg organo-compounds (phenylmercury propionate). The approach followed unravels evidence from waste from the mining and metallurgy industry that may be present in other similar sites, and identifies unexpected contaminants overlooked by conventional analyses.

High intensity magnetic separation for the clean-up of a site polluted by lead metallurgy.

The industrial history in the district of Linares (Spain) has had a severe impact on soil quality. Here we examined soil contaminated by lead and other heavy metals in "La Cruz" site, a brownfield affected by metallurgical residues. Initially, the presence of contaminants mainly associated with the presence of lead slag fragments mixed with the soil was evaluated. The subsequent analysis showed a quasi-uniform distribution of the pollution irrespective of the grain-size fractions. This study was accompanied by a characterization of the lead slag behavior under the presence of a magnetic field. Two main magnetic components were detected: first a ferromagnetic and/or ferrimagnetic contribution, second a paramagnetic and/or antiferromagnetic one. It was also established that the slag was composed mainly of lead spherules and iron oxides embedded in a silicate matrix. Under these conditions, the capacity of magnetic separation to remove pollutants was examined. Therefore, two high intensity magnetic separators (dry and wet devices, respectively) were used. Dry separation proved to be successful at decontaminating soil in the first stages of a soil washing plant. In contrast, wet separation was found effective as a post-process for the finer fractions.

Feasibility study on the use of soil washing to remediate the As-Hg contamination at an ancient mining and metallurgy area.

Soils in abandoned mining sites generally present high concentrations of trace elements, such as As and Hg. Here we assessed the feasibility of washing procedures to physically separate these toxic elements from soils affected by a considerable amount of mining and metallurgical waste ("La Soterraña", Asturias, NW Spain). After exhaustive soil sampling and subsequent particle-size separation via wet sieving, chemical and mineralogical analysis revealed that the finer fractions held very high concentrations of As (up to 32,500 ppm) and Hg (up to 1600 ppm). These elements were both associated mainly with Fe/Mn oxides and hydroxides. Textural and geochemical data were correlated with the geological substrate by means of a multivariate statistical analysis. In addition, the Hg liberation size (below 200 µm) was determined to be main factor conditioning the selection of suitable soil washing strategies. These studies were finally complemented with a specific-gravity study performed with a C800 Mozley separator together with a grindability test, both novel approaches in soil washing feasibility studies. The results highlighted the difficulties in treating "La Soterraña" soils. These difficulties are attributed to the presence of contaminants embedded in the soil and spoil heap aggregates, caused by the meteorization of gangue and ore minerals. As a result of these two characteristics, high concentrations of the contaminants accumulate in all grain-size fractions. Therefore, the soil washing approach proposed here includes the grinding of particles above 125 µm.

Analysis of soil washing effectiveness to remediate a brownfield polluted with pyrite ashes.

Soil in a brownfield contaminated by pyrite ashes showed remarkably high concentrations of several toxic elements (Hg, Pb, Zn, Cu, Cd, and As). Initially, we assessed various physical, chemical and mineralogical properties of this soil. The data obtained, and particularly multivariate statistics of geochemical results, were useful to establish the predominant role of the soil organic matter fraction (6%) and iron oxyhydroxides in the binding of heavy metals and arsenic. In addition, we studied the viability of soil washing techniques to reduce the volume of contaminated soil. Therefore, to concentrate most of the contaminants in a smaller volume of soil, the grain-size fraction below 125 microm was treated by hydrocycloning techniques. The operational parameters were optimized by means of a factorial design, and the results were evaluated by attributive analysis. This novel approach is practical for the global simultaneous evaluation of washing effectiveness for several contaminants. A concentration factor higher than 2.2 was achieved in a separated fraction that contained less than 20% of the initial weight. These good yields were obtained for all the contaminants and with only one cycle of hydrocycloning. Hence full-scale soil washing is a plausible remediation technique for the study site.