Sustained Bauxite Residue Rehabilitation with Gypsum and Organic Matter 16 years after Initial Treatment.

Bauxite residue is a high volume byproduct of alumina manufacture which is commonly disposed of in purpose-built bauxite residue disposal areas (BRDAs). Natural waters interacting with bauxite residue are characteristically highly alkaline, and have elevated concentrations of Na, Al, and other trace metals. Rehabilitation of BRDAs is therefore often costly and resource/infrastructure intensive. Data is presented from three neighboring plots of bauxite residue that was deposited 20 years ago. One plot was amended 16 years ago with process sand, organic matter, gypsum, and seeded (fully treated), another plot was amended 16 years ago with process sand, organic matter, and seeded (partially treated), and a third plot was left untreated. These surface treatments lower alkalinity and salinity, and thus produce a substrate more suitable for biological colonisation from seeding. The reduction of pH leads to much lower Al, V, and As mobility in the actively treated residue and the beneficial effects of treatment extend passively 20-30 cm below the depth of the original amendment. These positive rehabilitation effects are maintained after 2 decades due to the presence of an active and resilient biological community. This treatment may provide a lower cost solution to BRDA end of use closure plans and orphaned BRDA rehabilitation.

Vanadium removal and recovery from bauxite residue leachates by ion exchange.

Bauxite residue is an important by-product of the alumina industry, and current management practices do not allow their full valorisation, especially with regard to the recovery of critical metals. This work aims to test the efficiency of ion exchange resins for vanadium (V) removal and recovery from bauxite residue leachates at alkaline pH (11.5 and 13). As an environmental pollutant, removal of V from leachates may be an obligation of bauxite residue disposal areas (BRDA) long-term management requirements. Vanadium removal from the leachate can be coupled with the recovery, and potentially can be used to offset long-term legacy treatment costs in legacy sites. Kinetics studies were performed to understand the adsorption process. The rate kinetics for the V adsorption was consistent with the pseudo-first-order kinetic model, with a higher adsorption rate for pH 11.5 (1.2 min-1). Adsorption isotherm data fitted better to Freundlich equations than to the Langmuir model. The maximum adsorption capacity (Langmuir value q max) was greatest for pH 13 (9.8 mg V g-1 resin). In column tests, breakthrough was reached at 70 bed volumes with the red mud leachate at pH 13, while no breakthrough was achieved with the effluent at pH 11.5. In regeneration, 42 and 76 % of V were eluted from the resin with 2 M NaOH from the red mud leachate at pH 13 and 11.5, respectively. Further optimization will be needed to upscale the treatment.

Use of bauxite residue (red mud) as a low cost sorbent for sulfide removal in polluted water remediation.

Sulfide is an important pollutant in aqueous systems. Sulfide removal from polluted waters is required prior to discharge. Red mud (RM) is a solid waste of bauxite processing that is rich in reactive iron oxides and consequently has the potential to be used to remove sulfide from aqueous systems. A series of experiments was undertaken using raw and sintered RM to remove sulfide from waters. RM was highly efficient at sulfide removal (average 75% sulfide removal at initial concentration of ∼5 mg L(-1), with 500 mg L(-1) RM addition) due to both physical adsorption (high specific area) and chemical reaction (with amorphous Fe). Sintered RM, which has a lower surface area and lower mineral reactivity, was much less efficient at removing sulfide (∼20% removal under equivalent experimental conditions). Furthermore, concomitant metal release from raw RM was lower than for sintered RM during the sulfide removal process. The results showed that raw RM is a potentially suitable material for sulfide removal from polluted waters and consequently could be used as a low cost alternative treatment in certain engineering applications.

Leaching of copper and nickel in soil-water systems contaminated by bauxite residue (red mud) from Ajka, Hungary: the importance of soil organic matter.

Red mud is a highly alkaline (pH >12) waste product from bauxite ore processing. The red mud spill at Ajka, Hungary, in 2010 released 1 million m(3) of caustic red mud into the surrounding area with devastating results. Aerobic and anaerobic batch experiments and solid phase extraction techniques were used to assess the impact of red mud addition on the mobility of Cu and Ni in soils from near the Ajka spill site. Red mud addition increases aqueous dissolved organic carbon (DOC) concentrations due to soil alkalisation, and this led to increased mobility of Cu and Ni complexed to organic matter. With Ajka soils, more Cu was mobilised by contact with red mud than Ni, despite a higher overall Ni concentration in the solid phase. This is most probably because Cu has a higher affinity to form complexes with organic matter than Ni. In aerobic experiments, contact with the atmosphere reduced soil pH via carbonation reactions, and this reduced organic matter dissolution and thereby lowered Cu/Ni mobility. These data show that the mixing of red mud into organic rich soils is an area of concern, as there is a potential to mobilise Cu and Ni as organically bound complexes, via soil alkalisation. This could be especially problematic in locations where anaerobic conditions can prevail, such as wetland areas contaminated by the spill.

Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility.

Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m(3) of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 â†’ 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5-8.5. This effect was attributed to the reaction of Ca(2+) supplied by the gypsum with OH(-) and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.

Speciation of arsenic, chromium, and vanadium in red mud samples from the Ajka spill site, Hungary.

Results are presented from X-ray absorption spectroscopy based analysis of As, Cr, and V speciation within samples of bauxite ore processing residue (red mud) collected from the spill site at Ajka, Western Hungary. Cr K-edge XANES analysis found that Cr is present as Cr(3+) substituted into hematite, consistent with TEM analysis. V K-edge XANES spectra have E(1/2) position and pre-edge features consistent with the presence of V(5+) species, possibly associated with Ca-aluminosilicate phases. As K-edge XANES spectra identified As present as As(5+). EXAFS analysis reveals arsenate phases in red mud samples. When alkaline leachate from the spill site is neutralized with HCl, 94% As and 71% V are removed from solution during the formation of amorphous Al-oxyhydroxide. EXAFS analysis of As in this precipitate reveals the presence of arsenate Al-oxyhydroxide surface complexes. These results suggest that in the circumneutral pH, oxic conditions found in the Torna and Upper Marcal catchments, incorporation and sorption, respectively, will restrict the environmental mobility of Cr and As. V is inefficiently removed from solution by neutralization, therefore, the red mud may act as a source of mobile V(5+) where the red mud deposits are not removed from affected land.

Dispersal and attenuation of trace contaminants downstream of the Ajka bauxite residue (red mud) depository failure, Hungary.

This paper identifies the spatial extent of bauxite processing residue (red mud)-derived contaminants and modes of transport within the Marcal and Rába river systems after the dike failure at Ajka, western Hungary. The geochemical signature of the red mud is apparent throughout the 3076 km² Marcal system principally with elevated Al, V, As, and Mo. Elevated concentrations of Cr, Ga, and Ni are also observed within 2 km of the source areas in aqueous and particulate phases where hyperalkalinity (pH < 13.1) is apparent. Although the concentrations of some trace elements exceed aquatic life standards in waters (e.g., V, As) and fluvial sediments (As, Cr, Ni, V), the spatial extent of these is limited to the Torna Creek and part of the upper Marcal. Source samples show a bimodal particle size distribution (peaks at 0.7 and 1.3 µm) which lends the material to ready fluvial transport. Where elevated concentrations are found in fluvial sediments, sequential extraction suggests the bulk of the As, Cr, Ni, and V are associated with residual (aqua-regia/HF digest) phases and unlikely to be mobile in the environment. However, at some depositional hotspots, association of As, Cr, and V with weak acid-extractable phases is observed.