Removal of lanthanum, cerium, europium and holmium from water by co-precipitation with iron and aluminium (hydr)oxides

Abstract

Effluents from mining activities may have high concentrations of trace elements such as arsenic, rare earth elements (REE) and actinides, mainly in areas where acid mine drainage (AMD) occurs. Use of lime to neutralise AMD also promote co-precipitation of iron (Fe) and aluminium (Al) (hydr)oxides, increasing the removal of trace elements from water. This study aimed to evaluate the efficiency of Fe/Al (hydr)oxides co-precipitation to remove lanthanum (La), cerium (Ce), europium (Eu) and holmium (Ho) from water under laboratory conditions. Two sets of experiments were performed with individual REE solutions containing Eu and Ho. In these cases, Fe(II) and Al sulphates were used at different Fe:Al:REE molar ratios. Two other sets of experiments with Fe(II) and Fe(III) sulphates were performed in a mixed REE solution containing La, Ce, Eu and Ho. To co-precipitate Fe/Al (hydr)oxides, pH’s were raised to 9.0 and 6.0 with 5 mol L-1 KOH solution. Soluble contents of Fe, Al and REE were periodically measured in supernatants aliquots. Precipitates were collected at the end of the 60-day incubation period and, then, oven-dried, sieved and characterised by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. The stability of REE in precipitates was also assessed by BCR sequential extractions. All treatments presented high REE removal efficiency from water at pH 9.0, but significantly lower at pH 6.0 for Fe(II) treatments. Magnetite precipitation was favoured by lower contents of REE and Al, whereas goethite and lepidocrocite were favoured at higher contents. Segregated phases were not detected for Eu and Ho, but lanthanite and cerianite precipitated at high amounts of La and Ce, respectively. For mixed REE treatments, the mineralogical phases precipitated were mostly poorly crystallised. The presence of magnetite was associated to higher REE stabilities, whereas lepidocrocite decreased the stability as measured by BCR extractions. The presence of segregated phases as cerianite resulted in increased Ce stability, but presence of lanthanite decreased La stability in precipitates.