Passive co-treatment of phosphorus-depleted municipal wastewater with acid mine drainage: Towards sustainable wastewater management systems.

Industrial processes typically produce large wastewater volumes, which, if left untreated, greatly affect receiving ecosystems. However, wastewater treatment can be costly and energy-intensive, with the developing world particularly struggling with wastewater management. As such, simple and cost-effective solutions are urgently required with the passive (no energy or reagents) co-treatment of different wastewater matrices holding great promise. Here, wastewater from a phosphorus recovery system (chemical precipitation) was co-treated with acid mine drainage (AMD). Specifically, phosphorus-rich municipal wastewater was treated with hydrated lime, as to synthesize a wastewater-derived phosphorus product, i.e., calcium phosphate (Ca3(PO4)2), also producing a phosphorous-depleted alkaline effluent. The feasibility of valorising this effluent is examined here by using it for the passive co-treatment of real AMD. Different liquid-to-liquid (v/v) ratios were considered, with the optimum ratio (AMD to phosphate-depleted wastewater) being 1:9. The pH of the co-treated effluent was adjusted to 8.4 (from an initial value of 11.5 in the phosphorus-depleted wastewater and 2.2 in AMD), while metals (∼100% reduction of Fe, Mn, Ni, Cu, Pb, ≥99.5 for Al, Zn, and Mg, 80% for Cr, and 75% for As) and sulphate (89.26% reduction) contained in AMD were greatly removed. This was also the case for the remaining orthophosphate that was contained in the phosphorus-depleted wastewater (93.75% reduction). The electrical conductivity was also reduced in both the AMD (88.75%) and the phosphorus-depleted wastewater (69.21%), suggesting the removal of contaminants from both matrices. Results were underpinned by state-of-the-art analytical techniques, including FE-SEM/FIB/EDX, FTIR, and XRD, along with geochemical modelling (PHREEQC). Contaminants were removed through complexation, (co)adsorption, crystallization, and (co)precipitation. Overall, results suggest that the co-treatment of these wastewater matrices is feasible and could be directly scaled up (e.g., using waste stabilization ponds), while opportunities for the beneficiation of the produced sludge and for water reclamation (e.g., through membrane filtration) could also arise, further promoting the sustainably of this passive co-treatment method.

Wastewater treatment valorisation by simultaneously removing and recovering phosphate and ammonia from municipal effluents using a mechano-thermo activated magnesite technology.

Phosphate and nitrate enrichment largely impair aquatic ecosystem functions and services, thus comprising an emerging problem of environmental concern. The problem pertains to developing countries where their discharge to surface water is on the rise due to a rapid growth in population. Herein, these pollutants (phosphate and ammonia) were removed from real municipal wastewater using a simple, fast, and cost-effective process. Raw cryptocrystalline magnesite, a mineral abundant in South Africa, was simply milled and calcined (mechano-thermo processing) in order to produce the activated magnesite (feed). The feed was then used in batch processing for pollutants adsorption and precipitation from real wastewater. The process was optimised by varying the treatment or contact time, feed dosage, concentration, pH, and temperature. The feed and product mineral (produced sludge) were characterised using X-ray Diffraction (XRD), field emission scanning electron microscopy (FESEM) compatible with energy dispersive spectroscopy (EDS), and Fourier Transform Infrared Spectrometer (FTIR). It was identified that the optimal conditions differed for each pollutant, highlighting the importance of tailoring the process to fit the local wastewater characteristics and as part of a treatment train system. Specifically, maximum P removal was achieved after 5 min of mixing, using 1 g  L-1 of feed, 123 mg  L-1 initial phosphate concentration, pH 8 - 10, and was not affected by temperature variations; whereas, for ammonia removal, optimal conditions were 180  min, 16 g  L-1 feed dosage, 80 mg  L-1 initial concentration, pH 10 and temperature > 45 °C. The optimal conditions for the removal of both pollutants from real wastewater were 30 min, 6 g  L-1 dosage, and ambient temperature and pH. Furthermore, Mg and Ca concentration was found to influence the process. Reduction in total dissolved solids (TDS) and electrical conductivity (EC) suggest an attenuation of chemical species. Characterisation revealed that the product mineral obtained under the optimal conditions for pollutants removal is rich in quartz, periclase, brucite, calcite, magnesite, and struvite. This was further supported by the FTIR results, which indicated the presence of Mg-O, PO43-, N-H and OH stretches. In addition, the EDS verified the presence of Mg, Ca and P in product mineral. Results are suggestive of the high efficiency of the mechano-thermo activated magnesite treatment process for phosphate and ammonia removal and struvite crystallization. Thus, this technology could valorise municipal wastewater effluents and open new horizons for the effective and sustainable management of wastewater effluents, since struvite can replace the mined phosphate fertilizers, which are rapidly depleting, in the agriculture industry.

Co-treatment of acid mine drainage and municipal wastewater effluents: Emphasis on the fate and partitioning of chemical contaminants.

The co-management of different wastewater matrices can lead to synergistic effects in terms of pollutants removal. Here, the co-treatment of real municipal wastewater (MWW) and acid mine drainage (AMD) is comprehensively examined. Under the identified optimum co-treatment condition, i.e., 15 min contact time, 1:7 AMD to MWW liquid-to-liquid ratio, and ambient temperature and pH, the metal content of AMD (e.g., Al, Fe, Mn, Zn) was grossly (~95%) reduced along with sulphate (~92%), while MWW's phosphate content was practically removed (≥99%). The PHREEQC geochemical model predicted the formation of (oxy)-hydroxides, (oxy)-hydro-sulphates, metals hydroxides, and other mineral phases in the produced sludge, which were confirmed using state-of-the-art analytical techniques such as FE-SEM-EDS and XRD. The key mechanisms governing pollutants removal include dilution, precipitation, co-precipitation, adsorption, and crystallization. Beneficiation and valorisation of the produced sludge and co-treated effluent could promote resource recovery paradigms in wastewater management. Overall, the co-treatment of AMD and MWW appear to be feasible, yet not practical due to the excessive volume of MWW that is required to attain the desired treatment quality. Future research could focus on chemical addition for the control of the pH and the use of (photo)-Fenton for enhancing treatment efficiency.

Effective removal of arsenate from wastewater using aluminium enriched ferric oxide-hydroxide recovered from authentic acid mine drainage.

This study explored an eco-friendly approach for the synthesis of novel aluminium enriched ferric oxide-hydroxide (Fe/AlO(OH)) from authentic acid mine drainage (AMD). The synthesized Fe/AlO(OH) was subsequently tested for arsenate removal capabilities. Fe/AlO(OH) was synthesized from bona fide AMD via selective precipitation, thermal activation, and vibratory ball milling. One-factor-at-a-time (OFAAT) method was used to optimize operational parameters, which include adsorbent dosage, concentration, pH, agitation time, and temperature. Optimized conditions were observed to be 150 ppm of As(V), Solid: Liquid ratio - 1 g: 250 mL, contact time of 60 min, and ambient temperature and pH. Limited temperature and pH effects on adsorption were observed. Equilibrium data fits using Langmuir-, Freundlich-, Two surface Langmuir-, Dubinin-Radushkevich-, and Dubinin-Astokov isotherm models showed highly favorable adsorption conditions, the highest known maximum adsorption capacity for As(V) of 102-129 mg g-1, and coupled physisorption/diffusion limited adsorption. Thermodynamic analysis showed positive Gibbs free energy (ΔG°), negative enthalpy change (ΔH°), and positive entropy change (ΔS°) - likely a result of an inner sphere complexation of the As(V) with the Fe/Al surface. Considering the obtained results, valorization of AMD for the synthesis of Fe/AlO(OH) was viable and effective. This initiative could potentially minimize the footprints of AMD and arsenic pollution.

Calcined magnesite as an adsorbent for cationic and anionic dyes: characterization, adsorption parameters, isotherms and kinetics study.

The ability of calcined magnesite for Methylene Blue (MB), Direct Red 81 (DR81), Methyl Orange (MO) and Crystal Violet (CV) dye removal was evaluated in this study. The experiments were designed to test the hypothesis that alkaline earth carbonates can remove dyes from water through a combination of sorption and coagulative reactions involving Mg2+. To achieve that, several operational factors like residence time, dosage, adsorbent concentration and temperature were appraised. The batch study proved that calcined magnesite is effective in the treatment of MB, DR81, CV and MO contaminated water and moreover it performed well in terms of color removal. The adsorption equilibrium data were analysed by the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models, and the Dubinin-Radushkevich and Temkin models were found to be the most appropriate fit to MB and MO dyes respectively. The adsorption kinetics process primarily followed the Elovich and Pseudo-second order model, a possible indication that chemisorption was the rate limiting step during the dye uptake process. With the adsorption-desorption cycle repeated four times, the calcined magnesite regeneration efficiency for DR81 and MO loaded dyes remained very high. According to the results of this study, it can be concluded that calcined magnesite can be used effectively for the adsorption of MB, DR81, CV and MO from wastewater.

Synthesis of cryptocrystalline magnesite/bentonite clay composite and its application for removal of phosphate from municipal wastewaters.

In the present study, nanocomposite of cryptocrystalline magnesite-bentonite clay was used as a novel technology for removal of phosphates from municipal effluents. Vibratory ball miller was used for fabrication of the composite. Removal of phosphate from an aqueous solution was achieved using batch experimental procedures. The parameters optimized include time, dosage, concentration and pH. An optimization experiment revealed that 30 mins of shaking time, 1 g of composite, 100 mg L(-1) of phosphate, 1: 100 S/L ratios, 250 rpm, pH 10 and room temperature are the optimum conditions for removal of phosphate. Adsorption data fitted well to the Langmuir adsorption isotherm than Freundlich adsorption isotherms, thus confirming monolayer adsorption. Adsorption kinetics data fitted well to pseudo second-order kinetics than first-order kinetics, thus suggesting chemisorption. This comparative study showed better adsorption of the composite as compared to conventional methods of phosphate removal. The results suggest that the fabricated composite has the potential for remediation of phosphate-contaminated waters.