Treatment of Mine Water for Sulphate and Metal Removal Using Barium Sulphide

Abstract.   The integrated barium sulphide process consists of: preliminary treatment with lime, sulphate precipitation as barium sulphate, H₂S-stripping, crystallization of CaCO₃, and recovery of barium sulphide. Our tests showed that during lime pre-treatment, sulphate was lowered from 2 800 mg/L to 1 250 mg/L by gypsum crystallization; metals were precipitated as hydroxides. The BaS treatment then lowered sulphate to less than 200 mg/L. Sulphide was lowered from 333 to less than 10 mg/L (as S) in the stripping stage, using CO₂ gas for stripping. The stripped H₂S-gas was contacted with Fe (III)-solution and converted quantitatively to elemental sulphur. The alkalinity of the calcium bicarbonate-rich water was reduced from 1 000 to 110 mg/L (as CaCO₃) after CO₂-stripping with air due to CaCO₃ precipitation. Fe (II), after sulphur production, was re-oxidized to Fe (III) using an electrolytic step. The running cost of the BaS process is R2.12/m³ (US$1 = SAR6.5) for the removal of 2 g/L of sulphate.     

Barium Carbonate Process for Sulphate and Metal Removal from Mine Water

Abstract.  The removal of sulphate and metals from mine water was assessed using the integrated barium carbonate process and the co-precipitation of barium sulphate with calcium carbonate. The rate of sulphate removal was influenced by the BaCO₃ concentration and the cation associated with sulphate, and increased with increasing BaCO₃-concentration. BaCO₃ can only be used for removal of sulphate that is associated with calcium, as calcium is needed to remove the added carbonate associated with the barium cation. Sulphate removal was only marginally influenced by alkalinity. Sulphide can be stripped with CO₂ from a BaS-solution. The (CO₂ dosed/sulphide removed) molar ratio was close to unity for the first 50% of sulphide in solution. The stripped H₂S-gas can be absorbed into zinc acetate. BaSO₄ and CaCO₃ can be converted simultaneously to BaS and CaO, respectively at an optimum temperature of 1050°C. The CaCO₃/BaSO₄ molar ratio has little influence on the yield of BaS. The running cost of the barium carbonate process for the removal of 2 g/L of sulphate totalled ZAR1.28/m³ (US$1.00 = ZAR7.0, Feb 2007), the capital redemption cost was R1.08/m³, and the value of the products (water and sulphur) totalled R2.76/m³.     

A Bench-scale Assessment of a Combined Passive System to Reduce Concentrations of Metals and Sulphate in Acid Mine Drainage

Abstract  Passive treatment of acid mine drainage (AMD) requires a combined strategy to minimize the effect of climatic variability on the treatment performance of the system. A vertical-flow combined passive treatment system was developed and evaluated in a bench-scale laboratory test for a 290-day period. The combined system consisted of four components with specific treatment functions: an oxidation/precipitation basin for excess iron removal; a peat biofilter for heavy metal sorption and the establishment of anoxic conditions; a bioreactor for alkalinity generation and sulphate reduction; and an anoxic limestone drain for alkalinity addition. The benchscale system was dosed with moderate strength synthetic AMD at a surface loading of 95 L/m²/d, and operated under continuous flow conditions. Removal efficiencies were 99.7%, 99.9%, 99.9%, 98.6%, 98.2%, and 99.9% for Fe, Al, Zn, Mn, Ni, and Cu, respectively, while Cd remained more mobile with a removal efficiency of 66.5%. Sulphate concentrations were reduced from 3030 mg/L to 814.9 mg/L and the acidic drainage was neutralized to an effluent pH of 7.2 and an alkalinity of 1353.6 mg/L (as CaCO₃).     

Neutralizing Coal Mine Effluent with Limestone to Decrease Metals and Sulphate Concentrations

Abstract.   This paper describes pilot scale tests of a novel process for the neutralisation of acidic mine water. Leachate from a waste coal dump was neutralised with limestone, and iron, aluminium, and sulphate were removed. Specific aspects studied were: the process configuration; the rates of iron oxidation, limestone neutralisation, and gypsum crystallisation; the chemical composition of the effluents before and after treatment; the efficiency of limestone utilisation; and the sludge solids content. The acidity was decreased from 12,000 to 300 mg/L (as CaCO₃), sulphate from 15,000 to 2,600 mg/L, iron from 5,000 to 10 mg/L, aluminium from 100 to 5 mg/L, while the pH increased from 2.2 to 7.0. Reaction times of 2.0 and 4.5 h were required under continuous and batch operations respectively for the removal of 4 g/L Fe (II). The iron oxidation rate was found to be a function of the Fe (II), hydroxide, oxygen, and suspended solids (SS) concentrations. The optimum SS concentration for iron oxidation in a fluidised-bed reactor was 190 g/L. Up-flow velocity had no influence on the rate of iron oxidation in the range 5 to 45 m/h. Sludge with a high solids content of 55% (m/v) was produced. This is high compared to the typical 20% achieved with the high density sludge process using lime. It was determined that neutralisation costs could be reduced significantly with an integrated iron oxidation and limestone neutralisation process because limestone is less expensive than lime, and a high-solids-content sludge is produced. Full scale implementation followed this study.     

Treatment of Mine Water by a Microbial Mat: Bench-scale Experiments

Abstract.   We investigated the treatment of acid mine drainage (AMD) by a blue-green algae-microbial consortium and substrate (containing powdered goat manure, wood chips, and soil) in 1 m³ bench scale biological treatment test cells. The microbial mat resulted from the interaction of bacteria and filamentous blue-green algae (predominantly Oscillatoria spp). The experiments were carried out for different water column heights, and were evaluated for 24, 48, 72, 96, and 168 hours of retention. Within 24 hours of retention, the pH increased from 2.93 to 6.78 as net alkalinity went from -125 mg/L to 197 mg/L as CaCO₃. Turbidity decreased by 33–54%, sulphate decreased by 23–29%, and hardness decreased by 19 to 26%. We also observed that: 95% of the Fe, 79–97% of the Cu, 84–86% of the Zn, 88% of the Pb, 59–83% of the Co, 22–62% of the Ni, and 28–45% of the Mn were removed. A blue-green algae/microbial mat consortium may be a cost–effective treatment technique for removing metals from AMD.     

Optimizing the Effluent Treatment at a Coal Mine by Process Modelling

Abstract:   The water network of a coal mine was audited and simulated by an interactive steady state model and the results were used to optimise the mines water management strategy. Simulation of the interactions showed that calcium carbonate powder could be used as an alternative to lime for neutralization of acid water at a reagent cost saving of 56%. Gypsum crystallization would reduce sulphate concentrations in the neutralization plant by 30% and in the coal processing plant by 60%. The capital cost for a neutralization/gypsum crystallization plant for separate treatment of coal discard leachate and less polluted streams would cost 3.0 million Rand (R), compared to R10.3 million for combined treatment. Only slightly less (8.9 t/d vs. 9.5 t/d) sulphate removal would be achieved during separate treatment. The over-saturation index (OSI) value can be controlled effectively by removing sulphate from the feed water for coal processing. Sulphate has to be lowered to 350 mg/L in a flow of 222 m³/h to obtain an OSI value less than 1. The capital cost of a 222 m³/h biological sulphate removal plant was estimated at R21.8 million (R4.1 million/(ML/d)); the running cost was estimated at R13.7 million/a (R4.10/m³). Pre-washing of the coal would reduce capital and running costs.     

Anaerobic Bioremediation of Acid Mine Drainage using Emulsified Soybean Oil

Abstract  Batch incubation and flow-through column experiments were conducted to evaluate the use of emulsified soybean oil for in situ treatment of acid mine drainage. Addition of soybean oil, soluble substrates, and a microbial inoculum to the batch incubations resulted in complete depletion of SO₄, 50% reduction in Fe, and an increase in pH to >6. A one time injection of emulsified soybean oil, lactate, yeast extract, and a microbial inoculum stimulated SO₄ and metal ion reduction for ≈300 days in laboratory columns packed with mine tailings receiving influent solutions with a pH≈3 and≈5. In all emulsion treated columns, SO₄ and Fe were reduced, pH increased to >6, and Al, Cu and Zn removal efficiency was 99% or greater. Cu, Fe, Mn and Zn were removed as metal sulfides and/or carbonates with removal efficiency decreasing with increasing metal sulfide solubility. The low pH and high heavy metals concentrations did not significantly inhibit biological activity. However, SO₄ removal with associated precipitation of metal sulfides may have been limited by the short hydraulic retention time (6-7 days) of the columns. There was a significant hydraulic conductivity loss in one of the four treated columns, indicating that hydraulic conductivity loss may be an issue under certain conditions.     

The Use of Measured and Calculated Acidity Values to Improve the Quality of Mine Drainage Datasets

Abstract:  The net acidity of a water sample can be measured directly by titration with a standardized base solution or calculated from the measured concentrations of the acidic and basic components. For coal mine drainage, the acidic components are primarily accounted for by free protons and dissolved Fe²⁺, Fe³⁺, Al³⁺, and Mn²⁺. The base component is primarily accounted for by bicarbonate. A standard way to calculate the acidity for coal mine drainage is: Acid^calc = 50*(2*Fe²⁺/56 + 3*Fe³⁺/56 + 3*Al/27 + 2*Mn/55 + 1000*10^-pH)—alkalinity, where acidity and alkalinity are measured as mg/L CaCO₃ and the metals are mg/L. Because such methods of estimating acidity are derived by independent laboratory procedures, their comparison can provide a valuable QA/QC for AMD datasets. The relationship between measured and calculated acidities was evaluated for 14 datasets of samples collected from mine drainage discharges, polluted receiving streams, or passive treatment systems, containing a total of 1,484 sample analyses. The datasets were variable in nature, ranging from watersheds where most of the discharges contained alkalinity to ones where all of the discharges were acidic. Good relationships were found to exist between measured and calculated acidities. The average acidity measurement was 239 mg/L CaCO₃ and the average acidity calculation was 226 mg/L CaCO₃. Linear regressions were calculated for individual datasets and for the entire dataset. The linear regression for the entire dataset was: Acid^calc = 0.98 * Acid^meas – 8, r² = 0.98. The good correlation between calculated and measured acidity is the basis for an easy and inexpensive QA/QC for AMD data. Substantial variation between measured and calculated acidities can be used to infer sampling or analytical problems.     

Removal of Sulphate, Metals, and Acidity from a Nickel and Copper Mine Effluent in a Laboratory Scale Bioreactor

Abstract  Mine effluents should be treated so that they can either be re-used (e. g. for mining activities or irrigation purposes) or discharged into a river system. The results of this study showed that applying laboratory scale biological sulphate removal technology to a nickel/copper mine effluent (BCL mine, Botswana) consistently lowered sulphate concentrations from an average of 2000 to 450 mg/L, and increased the pH from 5.8 to 6.5. During this period, the hydraulic retention time varied from 24 to 12 h. The Ni and Zn concentrations were reduced from a maximum of 5.86 to 0.15 mg/L and from a maximum of 38 mg/L to 0.03 mg/L, respectively, presumably precipitated as metal sulphides.     

Buffering of Acidic Mine Lakes: The Relevance of Surface Exchange and Solid- Bound Sulphate

Abstract.  Buffering mechanisms in an acidic mine lake in Lusatia, Germany were investigated. The titration curve has four sections with different buffering mechanisms: (1) buffering by free hydrogen ions and hydrogen sulphate (pH = 2.55-2.9), (2) buffering by Fe with bound SO₄ (pH = 2.9-4.3), (3) buffering by Al with bound SO₄ (pH = 4.3-5.5), and (4) buffering by surface exchange of SO₄ and basic cations (pH > 5.5). Three different phase models were applied to simulate the titration curve: (1) an iron and aluminium hydroxide model; (2) an iron and aluminium hydroxysulphate model; and (3) an iron hydroxide model with surface exchange for SO₄, Ca, and Mg, coupled with an aluminium hydroxysulphate model. The uncertainty of model input parameters was accounted for in a sensitivity analysis. Only the third model, which considers surface exchange, was able to adequately reproduce the measured titration curve.     

Chemical and Biological Oxidation of Iron in Acid Mine Water

Abstract.   Prior to limestone neutralization of acid water, ferrous iron needs to be oxidized to prevent downstream oxidation and the formation of acid. This study assessed the effect of various parameters on the biological and chemical rate of iron oxidation, both chemically and biologically. In batch experiments, it was found that although the use of support media had no effect on the chemical iron oxidation rate, it was important when iron was oxidised biologically. Under continuous flow conditions, the highest oxidation rate occurred when the initial Fe (II) concentration was between 4.5 to 4.8 g/L, geotextile was used as the support medium, and when nutrients were added to the reactor. The optimal iron oxidation rate was achieved at a hydraulic retention time of 8 h. The chemical iron oxidation rate depends on the concentration of suspended Fe(OH)₃ and CaSO₄, which act as catalysts. The biological iron oxidation rate was dependent on the bacterial growth, which was influenced by several parameters (support media, nutrients, CO₂, and oxygen).     

Design Criteria for Limestone Neutralization at a Nickel Mine

Abstract.   Design criteria were developed for the construction of a full-scale limestone neutralization plant to treat leachate from the waste rock of a nickel mine, using data from laboratory studies, pilot-scale studies, and operation of a full-scale limestone handling and dosing facility. We learned that: limestone powder can be slurried to a constant slurry density of 60 g/L; Fe (II) can be oxidised at low pH (2.5) at a rate of 16.1 g/(L/d) using geotextile as a medium; and that the integrated Fe (II)-oxidation and limestone neutralization process allows neutralization, Fe (II)-oxidation, and gypsum crystallization to take place at the same time, provided that the solids concentration is high (greater than 30 g/L). A full-scale plant with a capacity of 50 m³/h was designed and constructed. The plant consists of the following stages: biological Fe (II)-oxidation, a fluidised-bed limestone neutralization reactor, a complete-mix gypsum crystallization reactor, and a clarifier.     

Using Calcium Carbonate/Hydroxide and Barium Carbonate to Remove Sulphate from Mine Water

This study evaluated the effectiveness of using barium bicarbonate to remove sulphate from neutralized AMD. The Ba(HCO₃)₂ was produced by dosing a BaCO₃ solution with CO₂ to form Ba(HCO₃)₂. This greatly increased the barium ion concentration, which rapidly removed sulphate linked to either calcium or magnesium. Following sulphate removal, the Ca(HCO₃)₂ or Mg(HCO₃)₂ containing water can be stabilised by CO₂ stripping with air, which results in CaCO₃ precipitation. The MgCO₃ remains in solution.     

Fate of sulphate removed during the treatment of circumneutral mine water and acid mine drainage with coal fly ash: Modelling and experimental approach

The treatment of acid mine drainage (AMD) and circumneutral mine water (CMW) with South African coal fly ash (FA) provides a low cost and alternative technique for treating mine wastes waters. The sulphate concentration in AMD can be reduced significantly when AMD was treated with the FA to pH 9. On the other hand an insignificant amount of sulphate was removed when CMW (containing a very low concentration of Fe and Al) was treated using FA to pH 9. The levels of Fe and Al, and the final solution pH in the AMD–fly ash mixture played a significant role on the level of sulphate removal in contrast to CMW–fly ash mixtures. In this study, a modelling approach using PHREEQC geochemical modelling software was combined with AMD–fly ash and/or CMW–fly ash neutralization experiments in order to predict the mineral phases involved in sulphate removal. The effects of solution pH and Fe and Al concentration in mine water on sulphate were also investigated. The results obtained showed that sulphate, Fe, Al, Mg and Mn removal from AMD and/or CMW with fly ash is a function of solution pH. The presence of Fe and Al in AMD exhibited buffering characteristic leading to more lime leaching from FA into mine water, hence increasing the concentration of Ca²⁺. This resulted in increased removal of sulphate as CaSO₄·2H₂O. In addition the sulphate removal was enhanced through the precipitation as Fe and Al oxyhydroxysulphates (as shown by geochemical modelling) in AMD–fly ash system. The low concentration of Fe and Al in CMW resulted in sulphate removal depending mainly on CaSO₄·2H₂O. The results of this study would have implications on the design of treatment methods relevant for different mine waters.     

Geochemistry and Isotopic Composition of H2S-rich Water in Flooded Underground Mine Workings,Butte, Montana,USA

Abstract.   Groundwater being pumped from the flooded West Camp mine workings of Butte, Montana, is elevated in hydrogen sulfide (H₂S), has a circum-neutral pH, and has high arsenic but otherwise low metal concentrations. The daily flux of H₂S and As pumped from the extraction well are each estimated at roughly 0.1 kg. Isotopic analysis of coexisting aqueous sulfide and sulfate confirms that the H₂S was produced by bacterial sulfate reduction. the mine waters are close to equilibrium saturation with amorphous FeS, amorphous ZnS, siderite, rhodochrosite, calcite, and goethite, but are undersaturated with orpiment (As₂S₃). The higher solubility of orpiment relative to other mental sulfides allows concentrations of dissolved arsenic (~ 100 g/L) that are well above human health standards. The West Camp waters differ markedly from the acidic and heavy metal-rich mine waters of the nearby Berkeley pit-lake. These differences are partly attributed to geology, and partly to mining history.     

Performance of a Natural Wetland Treating Acid Mine Drainage in Arid Conditions

Abstract  A wetland naturally formed in the discharge from a copper mine tailing impoundment in Rajasthan, India. The wetland is abundantly vegetated. This study investigated changes that occurred in the seepage as it travelled 180 and 380 m (P₁ and P₂) through the wetland. The pH increased from 6.17 to 7.10 at P₁ and 7.34 at P₂ in the pre-monsoon season, 6.53 to 7.36 at P₁ and 7.77 at P₂ in the post-monsoon season, and from 6.20 to 6.63 at P₁ and 6.89 at P₂ in the winter. Contaminant removal at P₂ ranged from 40 to 95%.     

Effects of a Barite Mine on Ground Water Quality in Andhra Pradesh,India

Abstract.  An investigation was undertaken to determine the effects of a large barite mining operation on local ground water quality near Mangampeta,Andhra Pradesh, India.Water samples were collected from drinking water wells in the mining and adjacent regions. The drinking water in the mining region had sulphate concentrations that ranged from 211 to 589 mg/L, compared to sulphate concentrations of 25 mg/L or less in the non-mined areas. The natural existence of barite and the widespread mine waste dumps at Mangampeta are believed to be responsible for the higher levels of sulphate in the ground water.     

Limestone Drain Design Parameters for Acid Rock Drainage Mitigation

Abstract.  Limestone drains are an integral component of some of the most efficacious passive systems for the treatment of acid rock drainage (ARD). A critical design parameter for a limestone drain is the mass of limestone that will be required for effective treatment. This in turn depends on the flow rate, limestone dissolution rate, and associated hydraulic detention time necessary to achieve a certain effluent alkalinity for a given design life. Rates of alkalinity generation and limestone dissolution, and the quality of the limestone in terms of weight fraction of CaCO₃ and percentage CaCO₃ available must be known to determine the required mass of limestone. These parameters were experimentally determined for a natural and synthetic suite of ARD waters. The experimental results show that the empirical change in the alkalinity over time cannot simply be modeled as a first-order process. During the initial stage, the concentration increase is extremely fast, giving a linear and steep rise in the alkalinity. Alkalinity concentrations peaked at elapsed times of 90 to 180 minutes and then declined to a nearly constant value. The decline in alkalinity corresponds with a decline in concentrations of dissolved iron and aluminum, implying that the consumption of alkalinity by the hydrolysis of these metals is faster than the rate of alkalinity production by the dissolution of limestone, so that the reaction appears zero order in the early stage and pseudo-first order later. Because the changes in concentration were complex, considerable uncertainty exists in the rate constants for estimating alkalinity concentration. This causes problems in design equations based solely on a limestone dissolution rate that is estimated from alkalinity generation rates. A more applicable design procedure, combining the kinetics of alkalinity production and consumption with the hydraulics and chemical equilibrium of the system, is illustrated. Research was conducted while the first and third authors were with Ecology and Environment, Inc, Dallas, TX, USA;     

Geochemistry of Perched Water in an Abandoned Underground Mine, Butte, Montana

Abstract.  The Lexington tunnel is the last accessible underground mine working in the Butte, Montana mining district. Used as recently as 1993, the tunnel and adjacent workings have been abandoned for over 10 years. Although the Lexington tunnel is over 200 m above the regional water table, perched water is present over much of its extent. Mine water near the portal is moderately acidic (pH 4 to 5), with extremely high concentrations of metals, including Cu (up to 1000 mg/L) and Zn (up to 1400 mg/L). In the middle reaches of the tunnel, the quality of the water is much better, with near-neutral pH, high bicarbonate alkalinity, and lower concentrations of heavy metals. The low acidity and metal content is attributed to a lack of pyrite and other sulfides in this portion of the mine, as well as the presence of carbonate minerals, such as rhodochrosite (MnCO₃), in exposed veins. Sulfide minerals are more widespread further back in the tunnel, and are now oxidizing rapidly, leading to pockets of severe acid drainage (pH< 3, dissolved Zn up to 5000 mg/L). Geochemical modeling suggests that the near-neutral waters—the most voluminous type encountered in the Lexington tunnel—are close to equilibrium saturation with rhodochrosite and hydrous Zn-carbonate (ZnCO₃•H₂O). The Eh of these waters is most likely controlled by redox reactions involving dissolved Mn²⁺ and secondary, Zn-rich, hydrous Mn-oxides. In contrast, the Eh of the acidic waters appears to be controlled by reactions involving Fe²⁺ and Fe³⁺. Most of the acidic waters are saturated with K-jarosite, which forms delicate, straw-like dripstones at several localities. Decaying mine timbers could be an important renewable source of organic carbon for heterotrophic microorganisms, such as iron- and sulfate-reducing bacteria, especially deeper in the mine workings where the ground is saturated with anoxic ground water.     

The Hydrogeochemistry of Arsenic in the Clara Mine,Germany

Abstract.   The oxidative dissolution of primary arsenic-bearing sulfide minerals in barite-fluorite veins is a potential source of arsenic in the Clara Mine. Geological structures, especially the mineral veins, provide potential pathways for the water. The highest arsenic concentrations are found in ground water within the eastern part of the mine. Arsenic and major ions are positively correlated and provide evidence that arsenic is likely derived locally from the water-vein/water-rock interaction. Geochemical modeling with PHREEQC shows all the arsenate mineral phases to be significantly undersaturated, although secondary arsenate minerals are common in the oxidized part of the deposit. The mine waters plot near the boundary of Fe(OH)₃ and Fe²⁺ in the pH-Eh diagram for the As-Fe-S-H₂O-system. Arsenic occurs as the 5-valent species and . Statistical analysis illustrates a strong association between As, Fe, pH, and HCO₃. Oxidation of the primary As-bearing minerals, such as pyrite and arsenopyrite, and the subsequent behavior of the oxyanion, arsenate, generally controls the distribution and speciation of arsenic. The low concentrations of dissolved As is due to co-precipitation and adsorption of arsenate by Fe, Al, and Mn (oxy)hydroxides.