Sulfidogenic biotreatment of synthetic acid mine drainage and sulfide oxidation in anaerobic baffled reactor

The treatment of synthetic acid mine drainage (AMD) water (pH 3.0-6.5) containing sulfate (3.0-3.5 g L(-1)) and various metals (Co, Cu, Fe, Mn, Ni, and Zn) was studied in an ethanol-fed sulfate-reducing 4-compartment anaerobic baffled reactor (ABR) at 32°C. The reactor was operated for 160 days at different chemical oxygen demand (COD)/sulfate ratios, hydraulic retention times (HRT), pH, and metal concentrations to study the robustness of the process. The last compartment of the reactor was aerated at different rates to study the bio-oxidation of sulfide to elemental sulfur. The highest sulfate reduction efficiency (88%) was obtained with a feed sulfate concentration of 3.5 g L(-1), COD/sulfate mass ratio of 0.737, feed pH of 3.0 and HRT of 2 days without aeration in the 4th compartment. The corresponding COD removal efficiency was about 92%. The alkalinity produced in the sulfidogenic ethanol oxidation neutralized the acidic mine water from pH 3.0-4.5 to pH 7.0-8.0. Effluent soluble and total heavy metal concentrations were substantially reduced with removal efficiencies generally higher than 99%, except for Mn (25-77%). Limited aeration in the 4th compartment of ABR promoted incomplete oxidation of sulfide to elemental sulfur rather than complete oxidation to sulfate. Depending on the aeration rate and HRT, 32-74% of produced sulfide was oxidized to elemental sulfur. This study demonstrates that by optimizing operating conditions, sulfate reduction, metal removal, alkalinity generation, and excess sulfide oxidation can be achieved in a single ABR treating AMD.     

Phosphorus removal performance of acid mine drainage from wastewater

Acid mine drainage (AMD) in Yunfu iron sulfide mine contain Fe(2+), Fe(3+), and Al(3+) up to 8000, 1700 and 1200 mg/L, respectively. Phosphorus removal from synthetic wastewater with 10mg/L of total phosphorus (TP) concentration and second municipal effluent with 3.5-4.0mg/L of TP concentration were conducted with the AMD by jar tests. Dosage of the AMD and initial pH of water are the two most important parameters affecting the performance of phosphorus removal of the AMD. The optimal phosphorus removal efficiency and residual iron ions (TFe) concentration are 97.0% and 3.0mg/L, respectively, at 1.61 Fe/P molar ratio and pH 8.03 for synthetic wastewater, and 92.1% and 0.32 mg/L, respectively, for second municipal effluent at 1.41 Fe/P molar ratio and pH 7.3. Resultant heavy metal concentration in effluents and precipitate was very low, and the risk of resultant heavy metal contamination was very small. The phosphorus removal performance of the AMD was much similar to that of ferric sulfate (FS) and polyferric sulfate (PFS), and better than that of FeSO(4). And residual TFe concentration in treated water arising from utilization of the AMD was similar to that of FeSO(4), and higher than that of FS and PFS. The AMD could be used as coagulant for phosphorus removal from wastewater directly due to the presence of Fe(2+), Fe(3+), and Al(3+) largely.     

Removal and recovery of metal ions from acid mine drainage using lignite--A low cost sorbent

Acid mine drainage (AMD), has long been a significant environmental problem resulting from the microbial oxidation of iron pyrite in presence of water and air, affording an acidic solution that contains toxic metal ions. The main objective of this study was to remove and recover metal ions from acid mine drainage (AMD) by using lignite, a low cost sorbent. Lignite has been characterized and used for the AMD treatment. Sorption of ferrous, ferric, manganese, zinc and calcium in multi-component aqueous systems was investigated. Studies were performed at different pH to find optimum pH. To simulate industrial conditions for acid mine wastewater treatment, all the studies were performed using single and multi-columns setup in down flow mode. The empty bed contact time (EBCT) model was used for minimizing the sorbent usage. Recovery of the metal ions as well as regeneration of sorbent was achieved successfully using 0.1 M nitric acid without dismantling the columns.     

Electrodialytic remediation of copper mine tailings

Mining activities in Chile have generated large amounts of solid waste, which have been deposited in mine tailing impoundments. These impoundments cause concern to the communities due to dam failures or natural leaching to groundwater and rivers. This work shows the laboratory results of nine electrodialytic remediation experiments on copper mine tailings. The results show that electric current could remove copper from watery tailing if the potential gradient was higher than 2 V/cm during 21 days. With addition of sulphuric acid, the process was enhanced because the pH decreased to around 4, and the copper by this reason was released in the solution. Furthermore, with acidic tailing the potential gradient was less than 2 V/cm. The maximum copper removal reached in the anode side was 53% with addition of sulphuric acid in 21 days experiment at 20 V using approximately 1.8 kg mine tailing on dry basis. In addition, experiments with acidic tailing show that the copper removal is proportional with time.     

Evaluation of engineering properties for the use of leached brown coal ash in soil covers

The need to engineer cover systems for the successful rehabilitation or remediation of a wide variety of solid wastes is increasing. Some common applications include landfills, hazardous waste repositories, or mine tailings dams and waste rock/overburden dumps. The brown coal industry of the Latrobe Valley region of Victoria, Australia, produces significant quantities of coal ash and overburden annually. There are some site-specific acid mine drainage (AMD) issues associated with overburden material. This needs to be addressed both during the operational phase of a project and during rehabilitation. An innovative approach was taken to investigate the potential to use leached brown coal ash in engineered soil covers on this overburden dump. The basis for this is two-fold: first, the ash has favourable physical characteristics for use in cover systems (such as high storage capacity/porosity, moderately low permeability, and an ability to act as a capillary break layer generating minimal leachate or seepage); and second, the leachate from the ash is mildly alkaline (which can help to mitigate and reduce the risk of AMD). This paper will review the engineering issues involved in using leached brown coal ash in designing soil covers for potentially acid-forming overburden dumps. It presents the results of laboratory work investigating the technical feasibility of using leached brown coal ash in engineered solid waste cover systems.     

Water chemistry and ecotoxicity of an acid mine drainage-affected stream in subtropical China during a major flood event

Field and laboratory work was carried out to investigate the chemistry and ecotoxicity of stream water affected by acid mine drainage in a tributary catchment of the Pearl River in subtropical China during a major flood that corresponded to a return period of 100 years. The results indicate that stream water was affected by acid mine drainage from the Dabaoshan mine at least to a distance of 25 km downstream of the mine water discharge point. It appears that H(+) generated from sulfide oxidation in the waste rock dumps was readily available for exporting. The amount of H(+) being discharged into the receiving stream depended on the volume of out-flowing waters. However, there was a lag time for the discharges of the metals. This may be attributed to the slower release of metals, relative to H(+), because it might take more time for the dissolution of heavy metal-bearing compounds, particularly the sparsely soluble jarosites. Fe, Zn and Al were the major metals of potential toxicity contained in the AMD-affected stream water, followed by Mn, Cu, Pb, As, Cd and Ni. The concentrations of these metals in the water decreased rapidly down the stream. This corresponds with an increase in the concentrations of reactive heavy metal fractions in benthic mud down the stream, reflecting the precipitation of heavy metal compounds with increasing pH and their subsequent deposition in the streambed. Toxicity tests show that the AMD-affected stream water at 3.5 km downstream of the discharge point was highly toxic to the test organism. At 25 km downstream of the discharge point where stream water pH was as high as 5.75, marked toxic responses of the test organism were still observed.     

Bioassessment of a combined chemical-biological treatment for synthetic acid mine drainage

In this work, ecotoxicological characteristics of synthetic samples of acid mine drainage (AMD) before and after a combined chemical-biological treatment were investigated by using Lepidium sativum and Daphnia magna. AMD treatment was performed in a two-column apparatus consisting of chemical precipitation by limestone and biological refinement by sulphate reducing bacteria. Synthetic samples of AMD before treatment were toxic for both L. sativum (germination index, G, lower than 10%) and D. magna (100% immobility) due to acid pH and presence of copper and zinc. Chemical treatment (raising pH to 5-6 and eliminating copper) generated effluents with reduced toxicity for L. sativum (G=33%), while 100% immobility was still observed for D. magna. Dynamic trends of toxicity for the first and fifth outputs of the biological column denoted a gradual improvement leading to hormesis for Lepidium (after the initial release of organic excess), while a constant residual toxicity remained for Daphnia (probably due to H(2)S produced by sulphate reducing bacteria).     

Removal of heavy metals from acid mine drainage (AMD) using coal fly ash, natural clinker and synthetic zeolites

Acid mine drainage (AMD) is a widespread environmental problem associated with both working and abandoned mining operations, resulting from the microbial oxidation of pyrite in presence of water and air, affording an acidic solution that contains toxic metal ions. The generation of AMD and release of dissolved heavy metals is an important concern facing the mining industry. The present study aimed at evaluating the use of low-cost sorbents like coal fly ash, natural clinker and synthetic zeolites to clean-up AMD generated at the Parys Mountain copper-lead-zinc deposit, Anglesey (North Wales), and to remove heavy metals and ammonium from AMD. pH played a very important role in the sorption/removal of the contaminants and a higher adsorbent ratio in the treatment of AMD promoted the increase of the pH, particularly using natural clinker-based faujasite (7.70-9.43) and the reduction of metal concentration. Na-phillipsite showed a lower efficiency as compared to that of faujasite. Selectivity of faujasite for metal removal was, in decreasing order, Fe>As>Pb>Zn>Cu>Ni>Cr. Based on these results, the use of these materials has the potential to provide improved methods for the treatment of AMD.     

Reduction of acidity and removal of metal ions from coal mining effluents using chitosan microspheres

Effluents from coal mining operations are not only highly acid but also depict elevated concentrations of metals which may contaminate the environment. Due to the polybasic characteristic of chitosan, this biopolymer is capable of both neutralizing and removing iron, aluminum and copper ions from such effluents. The present study aimed at evaluating the use of chitosan microspheres for their importance in continuous systems. The microspheres were prepared by the phase inversion method. Their average diameter and morphology were determined. Water samples from decantation pool (DP) and acidic mine drainage (AMD) effluents were treated using different amounts of microspheres. The pH and concentration of Fe, Al and Cu ions were evaluated both before and after treatment of effluent samples. The results revealed that the microspheres were capable of increasing the pH of DP and AMD samples from 2.34 and 2.58, respectively, to 6.20, i.e., close to neutrality. The treatment also resulted in full removal of the metals investigated.     

Modelling temperature-dependent heat production over decades in High Arctic coal waste rock piles

Subsurface heat production from oxidation of pyrite is an important process that may increase subsurface temperatures within coal waste rock piles and increase the release of acid mine drainage, AMD. Waste rock piles in the Arctic are especially vulnerable to changes in subsurface temperatures as the release of AMD normally is limited by permafrost. Here we show that temperatures within a 20 year old heat-producing waste rock pile in Svalbard (78°N) can be modelled by the one-dimensional heat and water flow model (CoupModel) with a new temperature-dependent heat-production module that includes both biological and chemical oxidation processes and heat source depletion over time. Inputs to the model are meteorological measurements, physical properties of the waste rock material and measured subsurface heat-production rates. Measured mean annual subsurface temperatures within the waste rock pile are up to 10 °C higher than the mean annual air temperature of −5.8 °C. Subsurface temperatures are currently decreasing with 0.5 °C per year due to decreasing heat production, which can be modelled using an exponential decay function corresponding to a half-life period of pyrite oxidation of 7 years. Simulations further suggest that subsurface temperatures two years after construction of the pile may have been up to 34.0 °C higher than in 2009 and that the release of AMD may have been more than 20 times higher. Sensitivity simulations show that maximum temperatures in the pile would have been up to 30.5-32.5 °C lower and that the pile would have been frozen 12-27 years earlier if the pile had been initially saturated with water, constructed with a thickness half of the original or a combination of both. Simulation show that the pile thickness and waste rock pyrite content are important factors controlling the internal build up of heat leading to potential self-incineration. However, site specific measurements of temperature-dependent heat production as well as simulation results show that the heat produced from pyrite oxidation alone cannot cause such a temperature increase and that processes such as heat production from coal oxidation may be equally important.     

Removal of arsenic from water using Fe-exchanged natural zeolite

An elevated arsenic (As) content in groundwater imposes a great threat to people worldwide. Thus, developing new and cost-effective methods to remove As from groundwater and drinking water becomes a priority. Using iron/aluminum hydroxide to remove As from water is a proven technology. However, separation of As-bearing fine particles from treated water presented a challenge. An alternative method was to use coarse-grained sorbents to increase the flow rate and throughput. In this research, a natural zeolite (clinoptilolite) was exchanged with iron(III) to enhance its As removal. Batch test results showed a Fe(III) sorption capacity of 144 mmol/kg on the zeolite. The As sorption on the Fe-exchanged zeolite (Fe-eZ) could reach up to 100mg/kg. Columns packed with Fe-eZ were tested for As removal from water collected from acid mine drainage (AMD) and groundwater containing high natural organic matter and high As(III). With an initial concentration of 147 μg/L in the AMD water, a complete As removal was achieved up to 40 pore volumes. However, the Fe-eZ was not effective to remove As from Chia-Nan Plain groundwater due to its high initial As concentration (511 μg/L), high amounts of natural organic matter, as well as its low oxidation-reduction potential, under which the As was in reduced As(III) form.     

Controlled low-strength material using fly ash and AMD sludge

Controlled low-strength material (CLSM) is a cementitious material with properties similar to stabilized soil. After hardening, CLSM provides adequate strength in bearing capacity and support but can also be easily excavated. To be classified as a CLSM, the material must have a compressive strength between 450 kPa (65 psi) and 8400 kPa (1200 psi). Typical CLSM contains coal-combustion fly ash (FA), cement, water and fine or coarse aggregate. In this paper, physical and strength properties of CLSM formed by combining sludge, a by-product from the treatment of acid mine drainage (AMD), with Class F FA are investigated. The sludge is a lime-based waste product that when combined with FA, exhibits self-hardening characteristics similar to cement. A main focus of this research is to develop a CLSM mix in which by-product material utilization is maximized while satisfying workability and performance requirements. A mixture of 10% AMD sludge, 2.5% Portland cement (PC), 87.5% Class F FA (dry wt.%) with water provided unconfined compressive strength values within the range for classification as CLSM. This mixture satisfies the excavatability and walkability requirements as well as the hardening time and stability criteria.     

CCB-based encapsulation of pyrite for remediation of acid mine drainage

Acid mine drainage (AMD) from abandoned coal mines continues to be one of the most significant environmental problems. Remediation of AMD requires an addition of lime source to decrease the acidity, and grouting the entire mine and encapsulating the pyrite by calcium-rich additives is often employed. Utilization of alkaline coal combustion by-products (CCBs) has gained acceptance in such remediation applications because of their cost-effectiveness. A study was conducted to investigate the effectiveness of CCBs to abate acid mine drainage by encapsulation of pyrite. Geomechanical, hydraulic, and environmental tests were performed on grouts prepared with various ratios of CCBs as well as an alternative free lime source, lime kiln dust (LKD). The results indicated that the mechanical properties of grouts were dependent on their free lime contents. Hydraulic conductivities of pyrite-grout columns were relatively high due to the coating of the pyrite rock with the grout rather than the filling of all of the void spaces, as commonly experienced in field applications. The leaching tests indicated that the presence of high amounts of lime in a grout is not solely sufficient to improve the quality of AMD, since the rate of dissolution of a high lime content grout may be slow due to its rapid hardening. Therefore, it is recommended that grouts be selected with consideration of their hardening capacities, as well as the percentage of lime content present in the mixture.     

Computational modelling of final covers for uranium mill tailings impoundments

To properly design a final cover for uranium mill tailings impoundments the designer must attempt to find an effective geotechnical solution which addresses the radiological and non-radiological potential impact and prevents geochemical processes from occurring within the tailings. This paper presents a computer-based method for evaluating the performance of engineered final covers for the remediation of uranium mill tailings impoundments. Three hypothetical final covers were taken from scientific literature to investigate the proposed method: (i) a compacted clay liner (CCL); (ii) a composite liner (CL) and (iii) a capillary barrier (CB). The processes investigated: (i) the saturated hydraulic flux; (ii) the unsaturated hydraulic flux (exclusively for the capillary barrier) and (iii) the radon exhalation to the atmosphere. The computer programs utilised for the analyses are: (i) Hydrologic Evaluation of Landfill Performance (HELP); (ii) SEEP/W and (iii) RADON. The site considered for the development of the research presented herein was the uranium mill tailings impoundment located at the Brazilian city of Poços de Caldas, in the Minas Gerais State.     

Immobilization of Cu, Pb and Zn in mine-contaminated soils using reactive materials

Immobilization processes were used to chemically stabilize soil contaminated with Cu, Pb and Zn from mine tailings and industrial impoundments. We examined the effectiveness of ordinary Portland cement (OPC), phosphoric acid and MgO at immobilizing Cu, Pb and Zn in soil contaminated by either mine tailings or industrial and mine wastes. The effectiveness was evaluated using column leaching experiments and geochemical modelling, in which we assessed possible mechanisms for metal immobilization using PHREEQC and Medusa numerical codes. Experimental results showed that Cu was mobilized in all the experiments, whereas Pb immobilization with H(3)PO(4) may have been related to the precipitation of chloropyromorphite. Thus, the Pb concentrations of leachates of pure mining and industrial contaminated soils (32-410 μg/l and 430-1000 μg/l, respectively) were reduced to 1-60 and 3-360 μg/l, respectively, in the phosphoric acid experiment. The mobilization of Pb at high alkaline conditions, when Pb(OH)(4)(-) is the most stable species, may be the main obstacle to the use of OPC and MgO in the immobilization of this metal. In the mining- and industry-contaminated soil, Zn was retained by OPC but removed by MgO. The experiments with OPC showed the Zn decrease in the leachates of mining soil from 226-1960 μg/l to 92-121 μg/l. In the industrial contaminated soil, the Zn decrease in the leachates was most elevated, showing >2500 μg/l in the leachates of contaminated soil and 76-173 μg/l in the OPC experiment. Finally, when H(3)PO(4) was added, Zn was mobilized.     

Recovery and purification of copper sulfide nanoparticles from acid mine drainage by biological sulfate reduction and microfiltration using low-cost ceramic membrane

Clean Technologies and Environmental Policy - Acid mine drainage (AMD) typically has a high amount of copper that can be recovered in pure form for different industrial applications. This study...     

Laboratory studies using naturally occurring "green rust" to aid metal mine water remediation

Green rust, an Fe (II) and (III) oxyhydroxy salt, can alter the aqueous oxidation state, mobility and toxicity, of inorganic contaminants and thus could have applications in water treatment. This paper discusses a series of stirred, open batch experiments designed to evaluate green rust, and its oxidised equivalent in this context comparing it to a ferrihydrite/goethite 'ochre'. Natural green rust was added to different mine waters as either a wet, reduced material or a dry, partially oxidised material. Experiments showed that the addition of either form accelerated the removal of potentially harmful elements from solution. Within one hour Fe, Al and Cu were completely removed from mine waters with initial concentrations of 80, 70 and 8.5mg/L, respectively, and Zn was reduced from 60 to <5mg/L. These experiments show the potential of green rust in mine water treatment, especially as it is able to remove problematic elements such as Al and Zn. The material is effective even after being dried and mostly oxidised. Changes to the pH and ORP of the mine waters and surface catalysis are the suggested mechanisms of accelerated removal of contaminants.     

Mechanism of arsenate coprecipitation at the solid/liquid interface of ferrihydrite: A perspective review

Arsenate (As(V)) is a toxic element in acid mine drainage and has to be removed during the neutralization process. Coprecipitation with ferrihydrite is the main mechanism for As(V) removal from acid mine drainage. To improve treatment efficiency, a quantitative understanding of the coprecipitation mechanism is required. Coprecipitation can incorporate more As(V) into ferrihydrite than adsorption. The results of XRD (X-ray Diffraction) and XANES (X-ray Adsorption Near Edge Structure) analysis confirmed that the formation of poorly crystalline ferric arsenate increased when the initial As/Fe molar ratio increased in the coprecipitation with ferrihydrite. EXAFS (Extended X-ray Adsorption Fine Structure) analysis at the iron K-edge showed that the proportion of octahedral structures in ferrihydrite increased when the initial As/Fe molar ratio increased. Moreover, EXAFS analysis at the arsenic K-edge, assuming three kinds of surface complexes for the AsFe bond, revealed that the coordination number for AsFe with an atomic distance of 2.85 × 10⁻¹⁰ m increased and that for As-Fe with an atomic distance of 3.24 × 10⁻¹⁰ m decreased as the initial As/Fe molar ratio increased. Thus, for more efficient wastewater treatment, active control of coprecipitation phenomena according to mechanistic details is essential.     

Anaerobic biodegradation of an organic by-products leachate by interaction with different mine tailings

Deinking by-products from paper recycling have been used as cover materials on acid-producing tailings. Due to residual cellulose, anaerobic degradation leads to the production of an organic-rich leachate, which may percolate through the tailings. This study aims at describing the influence of the tailings’ characteristics on the attenuation of organic matter in leachate and at discussing the degradation mechanisms. To this end, leachate was mixed with different types of tailings, including three unoxidized tailings with varying acid generation potentials and one tailing in three states of oxidation. Regularly, selected biochemical parameters were analyzed to access the evolution of organic components. The results show that when leachate from deinking by-products was placed in contact with tailings, phase and acid–base balance reactions took place in the beginning. Subsequently, oxidation–reduction reactions dominated the chemistry of the system. The type, the constituents, and the state of oxidation of the mine tailings condition the mechanisms of biodegradation of organic components. Methanogenesis was predominant in the control sample (pure organic leachate) but was absent in all leachate-tailings mixtures. No biodegradation was observed in the liquid phase for oxidized tailings and the organic concentration remained constant for unoxidized tailings, independently of the acid-generation potential. The biodegradation efficiency was optimal when the leachate was in contact with a mixture of oxidized and unoxidized tailings due to sulfate-reduction.     

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.