Carmen Mihaela Neculita

Biological treatment of highly contaminated acid mine drainage in batch reactors: Long-term treatment and reactive mixture characterization.

Passive bioreactors involving sulphate-reducing bacteria (SRB) are a practical alternative technology to treat acid mine drainage (AMD). Careful selection of the organic carbon source is important to ensure performance and long-term efficiency of the treatment. However, a rigorous and methodical characterization to predict the biodegradability of organic substrates by SRB still needs to be investigated. In the present study, four natural organic materials were thoroughly characterized to assess their ability to serve as substrates and to find a parameter that links organic carbon sources with their biodegradability. Three reactive mixtures were then comparatively evaluated for their performance to treat a highly contaminated AMD in long-term (152 days) batch experiments. All three mixtures were successful for sulphate reduction and metal (Fe, Ni, Cd, Zn, and Mn) removal (91.8-99.8%). Higher efficiencies were observed in the reactors with 30% (w/w) cellulosic wastes (maple wood chips and sawdust) which decreased sulphate concentrations from 5500 mg/L to <1mg/L, than in reactors with 2-3% cellulosic wastes, where final sulphate concentrations were in the range 2000-2750 mg/L. Organic material characterization indicated that higher C/N ratios, chemical oxygen demand (COD)/SO(4)(2-) ratios and dissolved organic carbon (DOC)/SO(4)(2-) ratios were associated with better sulphate-reducing conditions and metal removal. This work suggests that C/N and DOC/SO(4)(2-) ratios considered together are key parameters to assess the biodegradability of natural organic wastes under sulphate-reducing conditions.

Bioelectrochemical treatment of acid mine drainage dominated with iron

Treatment of acid mine drainage (AMD) dominated with iron (Fe), the most common metal, is a long-term expensive commitment, the goal of which is to increase the pH and remove Fe. In the present study, a proton exchange membrane microbial fuel cell (MFC) showed promise for the efficient treatment of an AMD dominated with ferric iron (pH 2.4±0.1; 500 mg L(-1) Fe(3+)). Briefly, Fe(3+) was reduced to Fe(2+) at the cathode of the MFC, followed by Fe(2+) re-oxidation and precipitation as oxy(hydroxi)des. Oxygen reduction and cation transfer to the cathode of the MFC further caused a rise in pH. A linear relationship was observed between the charge transferred in the MFC and the performance of the system up to 880 C. Optimal conditions were found at a charge of 662 C, achieved within 7 d at an acetate concentration of 1.6 g L(-1) in a membrane MFC. This caused the pH to rise to 7.9 and resulted in a Fe removal of 99%. Treated effluent met the pH discharge limits of 6.5-9. The maximum power generation achieved under these conditions averaged 8.6±2.3 W m(-3), which could help reduce the costs of full-scale bioelectrochemical treatment of AMD dominated with Fe.

Pilot-scale passive bioreactors for the treatment of acid mine drainage: efficiency of mushroom compost vs. mixed substrates for metal removal.

Pilot-scale field-testing of passive bioreactors was performed to evaluate the efficiency of a mixture of four substrates (cow manure compost, mushroom compost, sawdust, and rice straw) relative to mushroom compost alone, and of the effect of the Fe/Mn ratio, during the treatment of acid mine drainage (AMD) over a 174-day period. Three 141 L columns, filled with either mushroom compost or the four substrate mixture (in duplicate), were set-up and fed with AMD from a closed mine site, in South Korea, using a 4-day hydraulic retention time. In the former bioreactor, effluent deterioration was observed over 1-2 months, despite the good efficiency predicted by the physicochemical characterization of mushroom compost. Steady state effluent quality was then noted for around 100 days before worsening in AMD source water occurred in response to seasonal variations in precipitation. Such changes in AMD quality resulted in performance deterioration in all reactors followed by a slow recovery toward the end of testing. Both substrates (mushroom compost and mixtures) gave satisfactory performance in neutralizing pH (6.1-7.8). Moreover, the system was able to consistently reduce sulfate from day 49, after the initial leaching out from organic substrates. Metal removal efficiencies were on the order of Al (∼100%) > Fe (68-92%) > Mn (49-61%). Overall, the mixed substrates showed comparable performance to mushroom compost, while yielding better effluent quality upon start-up. The results also indicated mushroom compost could release significant amounts of Mn and sulfate during bioreactor operation.

Comparative effectiveness of mixed organic substrates to mushroom compost for treatment of mine drainage in passive bioreactors

Bioreactors are one possible best sustainable technology to address the mine-impacted water problems. Several prospective substrates (mushroom compost, cow manure, sawdust, wood chips, and cut rice straw) were characterized for their ability to serve as a source of food and energy for sulfate-reducing bacteria. Twenty bench-scale batch bioreactors were then designed and set up to investigate relative effectiveness of various mixtures of substrates to that of mushroom compost, the most commonly used substrate in field bioreactors, for treating mine drainage with acidic (pH 3) and moderate pH (pH 6). Overall, reactive mixtures showed satisfactory performances in generating alkalinity, reducing sulfate and removing metals (Al>Fe>Mn) (up to 100%) at both pH conditions, for all substrates. The mixture of sawdust and cow manure was found as the most effective whereas the mixture containing 40% cut rice straw gave limited efficiency, suggesting organic carbon released from this substrate is not readily available for biodegradation under anaerobic conditions. The mushroom compost-based bioreactors released significant amount of sulfate, which may raise a more concern upon the start-up of field-scale bioreactors. The correlation between the extent of sulfate reduction and dissolved organic carbon/SO(4)(2-) ratio was weak and this indicates that the type of dissolved organic carbon plays a more important role in sulfate reduction than the absolute concentration and that the ratio is not sensitive enough to properly describe the relative effectiveness of substrate mixtures.

Biochemical passive reactors for treatment of acid mine drainage: Effect of hydraulic retention time on changes in efficiency, composition of reactive mixture, and microbial activity

Biochemical passive treatment represents a promising option for the remediation of acid mine drainage. This study determined the effect of three hydraulic retention times (1, 2, and 4 days) on changes in system efficiency, reactive mixture, and microbial activity in bioreactors under upward flow conditions. Bioreactors were sacrificed in the weeks 8, 17 and 36, and the reactive mixture was sampled at the bottom, middle, and top layers. Physicochemical analyses were performed on reactive mixture post-treatment and correlated with sulfate-reducing bacteria and cellulolytic and dehydrogenase activity. All hydraulic retention times were efficient at increasing pH and alkalinity and removing sulfate (>60%) and metals (85-99% for Fe(2+) and 70-100% for Zn(2+)), except for Mn(2+). The longest hydraulic retention time (4 days) increased residual sulfides, deteriorated the quality of treated effluent and negatively impacted sulfate-reducing bacteria. Shortest hydraulic retention time (1 day) washed out biomass and increased input of dissolved oxygen in the reactors, leading to higher redox potential and decreasing metal removal efficiency. Concentrations of iron, zinc and metal sulfides were high in the bottom layer, especially with 2 day of hydraulic retention time. Sulfate-reducing bacteria, cellulolytic and dehydrogenase activity were higher in the middle layer at 4 days of hydraulic retention time. Hydraulic retention time had a strong influence on overall performance of passive reactors.

Performance of thermally activated dolomite for the treatment of Ni and Zn in contaminated neutral drainage

Intensive research is ongoing for developing low-cost and highly efficient materials in metal removal from contaminated effluents. The present study evaluated dolomite [CaMg(CO3)2], both raw and modified by thermal activation (charring), for Ni and Zn treatment in contaminated neutral drainage (CND). Batch adsorption testing (equilibrium and kinetics) were conducted at pH 6, to evaluate the performance of initial vs. modified dolomite, and to assess potential mechanisms of metal removal. Charring of dolomite led to a rigid and porous material, mainly consisting of CaCO3 and MgO, which showed a sorption capacity increased sevenfold for Zn and doubled for Ni, relative to the raw material. In addition, Freundlich model best described the sorption of the both metals by dolomite, whereas the Langmuir model best described their sorption on charred dolomite. Plausible mechanisms of metal removal include cation exchange, surface precipitation and sorption processes, with carbonate ions and magnesium oxides acting as active centers. Based on these results, charred dolomite seems a promising option for the efficient treatment of Ni and Zn in CND.

Recovery and reuse of sludge from active and passive treatment of mine drainage-impacted waters: a review

The treatment of mine drainage-impacted waters generates considerable amounts of sludge, which raises several concerns, such as storage and disposal, stability, and potential social and environmental impacts. To alleviate the storage and management costs, as well as to give the mine sludge a second life, recovery and reuse have recently become interesting options. In this review, different recovery and reuse options of sludge originating from active and passive treatment of mine drainage are identified and thoroughly discussed, based on available laboratory and field studies. The most valuable products presently recovered from the mine sludge are the iron oxy-hydroxides (ochre). Other by-products include metals, elemental sulfur, and calcium carbonate. Mine sludge reuse includes the removal of contaminants, such as As, P, dye, and rare earth elements. Mine sludge can also be reused as stabilizer for contaminated soil, as fertilizer in agriculture/horticulture, as substitute material in construction, as cover over tailings for acid mine drainage prevention and control, as material to sequester carbon dioxide, and in cement and pigment industries. The review also stresses out some of the current challenges and research needs. Finally, in order to move forward, studies are needed to better estimate the contribution of sludge recovery/reuse to the overall costs of mine water treatment.

Biosulfides precipitation in weathered tailings amended with food waste-based compost and zeolite.

Tailings are mine wastes in the form of slurries stacked in mine sites abandoned after the exhaustion of ores. There are approximately 5000 abandoned mine sites in Korea, and tailings have become a serious environmental problem. Long-term environmental exposure of tailings can cause release of acidic and high concentrations of sulfate- and metal-contaminated water (acid mine drainage, AMD). Organic and/or inorganic amendments have been studied for AMD prevention and passive in situ treatment of pore water. This study tests locally available food waste-based compost as a viable amendment, in addition to the need for sustainable ways to dispose of compost, in response to a new environmental law. To examine the feasibility, three bioreactors were constructed, filled with mixtures of tailings, food waste-based compost, and zeolite. During the 4-wk experimental period, feeding water ormedium were poured in one reactor. The leachates were investigated in terms of chemistry and microbiology. Compared with the unamended reactor, the leachate from two mixture-filled reactors showed increased pH, formation of sulfate reduction conditions, and highly efficient metal removal. Black-colored precipitates observed at the end of the experiment suggested the formation of metal biosulfides, following the activity of sulfate reduction mediated by sulfate-reducing bacteria (SRB). Mineralogical analysis of these precipitates confirmed the presence of biosulfides, mainly of Fe and Pb. Moreover, microbial and molecular biological analyses revealed that several species of heterotrophic bacteria (SRB and iron-reducing bacteria) were present in the solids recovered from the bioreactors. Microbial consortium, such as SRB species (), and cellulosic-degrader ( sp.) were identified. This study provides promising results on the application potential of food waste-based compost for prevention of AMD generation and passive in situ treatment of pore water in weathered tailings in Korea and elsewhere.

Impact of fresh tailing deposition on the evolution of groundwater hydrogeochemistry at the abandoned Manitou mine site, Quebec, Canada

The abandoned Manitou mine site has produced acid mine drainage (AMD) for several decades. In order to limit the detrimental environmental impacts of AMD, different rehabilitation scenarios were proposed and analyzed. The selected rehabilitation scenario was to use fresh tailings from the neighboring Goldex gold mine as monolayer cover and to maintain an elevated water table. In order to assess the impact of the Goldex tailing deposition on the hydrogeochemistry of the Manitou mine site, a network of 30 piezometers was installed. These piezometers were used for continuous measurement of the groundwater level, as well as for water sampling campaigns for chemical quality monitoring, over a 3-year period. Hydrochemical data were analyzed using principal component analysis. Results clearly showed the benefic impact of fresh tailing deposition on the groundwater quality around the contaminated area. These findings were also confirmed by the evolution of electrical conductivity. In addition to the improvement of the physicochemical quality of water on the Manitou mine site, new tailing deposition induced an increase of water table level. However, at this time, the Manitou reactive tailings are not completely submerged and possible oxidation might still occur, especially after ceasing of the fresh tailing deposition. Therefore, complementary rehabilitation scenarios should still be considered.

Using fluorescence-based microplate assay to assess DOM-metal binding in reactive materials for treatment of acid mine drainage.

One potential drawback of compost-based passive bioreactors, which is a promising biotechnology for acid mine drainage (AMD) treatment, is the transport of dissolved organic matter (DOM)-metal complexes in surface waters. To address this problem, the objective of this study was to assess the maximum capacity of organic substrates to release soluble DOM-metal complexes in treated water. The reactivities of DOM in maple wood chips and sawdust, composted poultry manure, and leaf compost were quantified toward Cd2+, Ni2+, Fe2+, and Cu2+ using fluorescence quenching. The DOM showed the highest reactivity toward Fe, but a limited number of available sites for sorption, whereas DOM-Cd complexes exhibited the lowest fluorescence quenching. Overall, the DOM from a mixture of wastes formed higher concentrations of DOM-metal complexes relative to sole substrates. Among DOM-metal complexes, the concentrations of DOM-Ni complexes were the highest. After reaching steady-state, low concentrations of DOM-metal complexes were released in treated water, which is in agreement with theoretical predictions based on geochemical modeling. Therefore, in addition to physicochemical characterization, fluorescence quenching technique is recommended for the substrate selection of bioreactors.