Removal of Metals and Acidity from Acid Mine Drainage Using Municipal Wastewater and Activated Sludge

Co-treatment of acid mine drainage (AMD) and municipal wastewater (MWW) using the activated sludge process is an innovative approach to AMD remediation that utilizes the alkalinity of MWW and the adsorptive properties of the wastewater particulates and activated sludge biomass to buffer acidity and remove metals. The capacity of these materials to treat AMD was investigated in batch mode metal removal tests using high-strength synthetic AMD (pH 2.8, Al 120–200 mg/L, Cu 18–30 mg/L, Fe 324–540 mg/L, Mn 18–30 mg/L, and Zn 36–60 mg/L). Using material from a range of MWW treatment plants, the performance of screened and settled MWW, activated sludges with mixed liquor suspended solids (MLSS) concentrations of 2.0 and 4.0 g/L, and return activated sludges with 6.0 and 7.4 g/L MLSS were compared. Similar trends were observed for the MWW and activated sludges, with removal efficiency generally decreasing in the order Al = Cu > Mn > Zn > Fe. Trends in Fe removal using settled MWW and activated sludges were highly variable, with removal <30 %. Using activated sludges, average removal efficiencies for Al, Cu, Mn, and Zn were 10–65 %, 20–60 %, 10–25 %, and 0–20 %, respectively. Sludge solids concentration was an important controlling factor in metal removal, with removal of Al, Cu, Mn, and Zn increasing significantly with solids concentration. Municipal wastewaters had greater neutralization capacities than activated sludges at high AMD loading ratios. Mixing AMD with screened MWW gave the highest removal efficiency for all metals, achieving average removal of 90–100 % for Al, Cu, and Fe, 65–100 % for Zn, and 60–75 % for Mn. These empirical findings are useful for developing process design parameters in co-treatment systems. Utilizing MWW and activated sludge to remediate AMD can potentially reduce materials and energy requirements and associated costs.     

Activated sludge for the treatment of sulphur-rich wastewaters

The aim of this investigation was to assess the potential of activated sludge for the remediation of sulphur-rich wastewaters. A pilot-scale activated sludge plant was acclimatised to a low load of sulphide and operated as a flow-through unit. Additional sludge samples from different full-scale plants were compared with the acclimatised and unacclimatised sludges using batch absorption tests. The effects of sludge source and acclimatisation on the ability of the sludge to biodegrade high loads of sulphide were evaluated. Acclimatisation to low-sulphide concentrations enabled the sludge to degrade subsequent high loads which were toxic to unacclimatised sludge. Acclimatisation was seen to be an effect of selection pressure on the biomass, suggesting that the treatment capability of activated sludge will develop after acclimation, indicating potential for treatment of acid mine drainage (AMD) by a standard wastewater treatment process. Existing options for biological treatment of AMD are described and the potential of activated sludge treatment for AMD discussed in comparison with existing technologies.     

Removal of Metals and Acidity from Acid Mine Drainage Using Liquid and Dried Digested Sewage Sludge and Cattle Slurry

The metal removal and neutralization capacities of digested sewage sludges from municipal wastewater treatment plants, cattle slurry (liquid manure), and Biofert granules (dried granular anaerobic sludge) were compared under batch conditions using synthetic AMD (pH 2.8) containing high concentrations of Al, Cu, Fe, Mn, Pb, and Zn (100, 15, 270, 15, 2, and 30 mg/L, respectively). The effects of contact time and solids concentration were examined. Metal removal was variable for all materials. Contact time had a significant effect, with total removal often increasing over the experimental time interval (i.e. 30 min to 24 h). Removal efficiency (%) was generally highest for Cu, Pb, and Al, while Mn and Zn were the least removed. Cattle slurry was the best material for metal removal, with the following maximum removals at a solids concentration of 12.9 g/L: Cu >98 %, Al >98 %, Fe >60 %, Mn >18 %, Pb >96 %, and Zn >60 %. Metal removal using digested sewage sludge reached 88 % for Al, 98 % for Cu, 94 % for Pb, and 30 % for Zn. Neutralization was complete within 30 min after AMD was mixed with digested sludges or cattle slurry, with the pH reaching a maximum of 5.5 with the slurry. In contrast, neutralization by the Biofert granules only reached equilibrium after 300 min, and pH remained <4.0 except at high solids concentrations. It appears that recycled waste-derived organic materials can neutralize AMD and remove dissolved metals by adsorption and precipitation, creating a more treatable waste stream or one that could be discharged directly to surface water. Potential methods of safe disposal of metal-enriched organic materials are discussed.     

Zinc removal in anaerobic sulphate-reducing liquid substrate process

Zinc and sulphate removal from synthetic wastewater was investigated by using four laboratory parallel upflow-mode reactors (referred as R1 to R4; R1 contained carriers to retain biomass, whereas R2–R4 were operated as suspended reactors). All reactors were inoculated with anaerobically digested cow manure. R1 and R2 were first fed with glucose- and sulphate-containing feed for 48 days after which all four reactors were fed with wastewater containing 50 mg l⁻¹ of zinc in R1–R3 and 200 mg l⁻¹ in R4 and operated for 96 days. In all reactors, hydraulic retention time, organic loading rate, and sulphate load were 5–6 d, 0.2–0.4 kg COD m⁻³ d⁻¹ and 3.3–3.8 g SO₄ l⁻¹ d⁻¹, respectively, whereas the zinc load in R1–R3 was 0.074–0.077 and in R4 0.282 g Zn l⁻¹ d⁻¹. During the runs, 30–40% of sulphate and over 98% of zinc was removed, and up to 150–200 mg H₂S was produced in all reactors. Effluent pH dropped in all reactors (feed pH 6.5) to 3–5 by the end of the experiment. No significant effects on zinc removal were observed, despite differences in operating conditions and feed. It was only in the latter part of the runs (i.e. between experiment days 120–142) that zinc removal began to fluctuate, showing a negligible decrease in R3 and R4, whereas in R1 and R2 zinc was removed below the limit of detection (<0.01 mg Zn l⁻¹). Qualitative X-ray diffraction analysis of the reactor sludge at the end of the runs indicated that the compounds precipitated were most probably ZnS (Code 05-0566 Sphalerite), suggesting metal removal through sulphide precipitation; this was supported by the fact that sulphate was reduced and zinc removed simultaneously.     

Changes in Efficiency and Hydraulic Parameters During the Passive Treatment of Ferriferous Acid Mine Drainage in Biochemical Reactors

The objective of this study was to evaluate the effects of different reactive mixtures and hydraulic retention times (HRTs) on hydraulic parameters (hydraulic conductivity, k_sat, and porosity) and the efficiency of passive biochemical reactors (PBRs) for treatment of ferriferous acid mine drainage (AMD). Five 10.7 L PBRs were filled with three reactive mixtures, containing either a carbon-rich substrate (60% w/w) or an inert/neutralizing agent (50% w/w). The PBRs were tested over a 450 day period using two qualities of iron-rich AMD (4 and 1 g L^?1 Fe in AMD1 and AMD2, respectively), and two HRTs, of 5 and 7 days. During the last week of the columns’ operation, a tracer test (5 g L^?1 of NaCl) was also performed, in addition to monthly measurements using the falling head method. Changes in HRT and k_sat were evaluated throughout the experiment. The PBRs increased the pH of AMD influents from 3.5 to 6 and efficiently removed Al, Cd, Cr, Ni, Pb, and Zn (>?90%), whereas Fe was only partially and inconsistently treated. No significant differences were observed among the three tested mixtures, regardless of the HRT or the AMD quality. Results from the tracer test and k_sat measurements showed no significant decrease in the initial values of the hydraulic parameters with time except for column 3, where a slight decrease was observed. Although sorption could have been important during the start-up of the PBRs, post-testing characterization of the spent reactive mixtures showed that the Fe was mainly retained as oxy-hydroxides and sulfides. Given the PBRs’ marginal effectiveness for Fe-rich AMD, pre-treatment removal of the iron is recommended.     

脂肪酸捕收剂气浮浓缩不同剩余活性污泥的研究

根据矿物浮选原理, 研究了添加脂肪酸捕收剂对3种不同废水处理工艺所产生的剩余污泥气浮浓缩效果的影响。主要考察了捕收剂的种类和用量等因素对不同种类污泥浓缩的影响规律。结果表明, 在3种不同工艺产生的剩余活性污泥中添加脂肪酸捕收剂, 都可以实现污泥的气浮浓缩, 同时降低浓缩污泥的含水率, 极大地改善了气浮浓缩的效果。特别是添加捕收剂ZFS12且用量为75 mg/L时效果最佳, 相对应的3种浓缩污泥的含水率分别为97.26%, 96.64%, 96.44%, 水回收率分别为77.65%, 80.62%, 85.41%。     

Alkalinity Generation in a Novel Multi-stage High-strength Acid Mine Drainage and Municipal Wastewater Passive Co-treatment System

Passive co-treatment of high-strength acid mine drainage (AMD) and municipal wastewater (MWW) was examined in a laboratory-scale, four-stage continuous flow reactor system with a total residence time of 6.6 d. Synthetic AMD of pH 2.60 and an acidity of 1,870 mg/L (as CaCO₃) was mixed at a 1:2 ratio with raw MWW (pH 7.67, 288 mg/L alkalinity (as CaCO₃), and 265 mg/L BOD₅) from the City of Norman, Oklahoma and introduced into the system. Alkalinity generated by limestone dissolution and bacterial SO₄ ²⁻ reduction (BSR) processes was sufficient to support various metal removal processes and produce an effluent with circumneutral pH (6.98) and a net alkalinity of 10.4 mg/L (as CaCO₃). Alkalinity generation from limestone dissolution was comparable with conventional AMD passive treatment systems. BSR proceeded at a relatively high rate (0.56 mol/m³ day) despite inhibitory pH and metals concentrations. Results indicate that the diverse electron donors in the MWW may be as suitable for BSR and their supporting microbial communities as commonly used substrates, presenting an opportunity to use a common waste as a resource for passive treatment.     

煤液化高浓度污水处理厂中VOCs污染水平及其归趋

探讨了VOCs在煤液化高浓度污水处理过程中的去除规律、污染水平和分布行为,采用顶空-气相色谱/质谱法（HS/GC/MS）进行分析检测,结果表明,各工艺段出水中累计检出26种目标VOCs,且均以苯、乙苯、苯乙烯、甲苯、二甲苯（邻、间、对）等苯系物为主,ΣVOCs总浓度在339.28~562.36 μg/L;4个产泥工艺段产出污泥中均以苯或苯乙烯含量为最高,ΣVOCs吸附量以及各VOCs单体的Kd值均以3T活性污泥段为最高;在吸附剂相对稳定时,污泥更倾向于吸附辛醇-水系数（Kow）大的VOCs污染物。污水处理过程中ΣVOCs的主要归趋途径为随水排出（60.33%）,其次为污泥吸附（22.95%）和挥发降解（16.72%）;随着lg Kow的增大VOCs出水排放率逐渐降低,吸附去除率逐步增大,挥发降解去除率则出现先增后减的变化趋势,并在lg Kow值为3.5左右时达到最大值。     

Enhancement of Sludge Sedimentation Properties in a Concentrated Acid Mine Drainage Using Nano- and Micro-magnetite Particles

Conventional treatment of AMD involves neutralization with consequent precipitation of metals as hydroxides. In AMD with a high concentration of metals, the settling rate of the sludge/water interface is low. We investigated the use of nano- and micro-magnetite particles to assist the settling and thickening of floc particles. The magnetite was produced from ferrous sulphate crystals (melanterite, Fe₂SO₄·7H₂O) obtained by leaching pyrite from a coal mine. AMD was obtained from the treatment plant at the same mine and the water was neutralized with Ca(OH)₂ at pH 8.7?±?0.1. Laboratory studies were conducted in 1 L test tubes with and without the addition of magnetite particles and a flocculant. Sedimentation curves (interface settling) were generated to evaluate the rate of sedimentation. For the studied effluent, the best option was 4 g L^?1 of magnetite particles and 5 mg L^?1 of high molecular weight anionic polyacrylamide. The magnetite particles were recovered magnetically from the sludge with ≈ 90% efficiency. Thus, the combined use of magnetite and a flocculant increased the sludge settling rate and, consequently, reduced the area needed for settling basins.

     

Study on microwave-induced thin-layer drying of municipal sludge for fuel reclamation

Since the adverse factors such as deficient penetration and long reaction time have restricted the complete microwave-used drying of municipal sludge, the microwave-induced drying is considered, which has advantages in such aspects. The investigation of the microwave-induced drying to uncover the mechanism bears great meaning for its development and utilization. The effects of temperature and microwave cracking in municipal sewage sludge drying characteristics are studied through municipal sewage sludge drying experiment. Experiments shows that higher drying temperature would lead to a more acutely changing drying rate (D _R). The D _R had increased from 0.005 g/(g·min) to 0.060 g/(g·min), which was 12 times enlarged, while the temperature rose from 70 °C to 160 °C. The higher the temperature was, the earlier the peak value of D _R appeared. The experiments indicated that the temperature was the decisive factor affecting the D _R. The microwave-induced sludge reached the highest D _R at the moisture rate (M _R) of 40%, with a 20% grade promotion compared with that of the original one. The molecular fracture caused by microwave radiation had obviously accelerated the drying process and the DR was rising in proportion to the microwave radiation dose. The diffusion coefficient had been calculated according to Fick??s law. In comparison to that of the original one, the diffusion coefficient of microwave-induced sludge was obviously enlarged more than two times. By fit examinations, Model Weibull was proven to be the most fit one for thermal thin-layer drying of municipal sludge. By means of Arrhenius equation, the obtained average activation energy of municipal sludge was 37.1 kJ/(mol·K).     

Removal of Turbidity from Travertine Processing Wastewaters by Coagulants,Flocculants and Natural Materials

The sedimentation behaviour of travertine-processing wastewater containing a high concentration of suspended solids was investigated using different coagulation and flocculation methods. In batch experiments, four types of coagulants [FeC1₃, Al₂(SO₄)₃, PACl, NaAlO₂], six types of flocculants (40% MMW–40% HMW cationic, 30% MMW, 40% MMW, 40% HMW anionic and nonionic) and three types of natural materials (NMs) (sepiolite, zeolite, and pumice) were used to treat wastewater with an initial turbidity of 570–880 NTU. The optimum process conditions (dosage, mixing time/speed, sedimentation time, and pH) were investigated for each. Sedimentation performance was assessed by the effluent turbidity (T _eff) values of the treated water. The best performances obtained were 99.3% (T _eff?=?4 NTU), 99.1% (T _eff?=?8 NTU), and 97.8% (T _eff?=?18 NTU) with 40% HMW anionic-cationic flocculants, zeolite, and FeCl₃, respectively. Sludge properties, including sludge settling velocity (mm/min), sludge density (g/cm³), suspended solids (SS) content (mg/L), and sludge solids (%) were determined and compared under optimized conditions. The type of additive significantly affected performance. Travertine processing wastewater flocculation with polymeric materials and NMs, especially zeolite, was more favourable than coagulants in terms of both turbidity removal and sludge quality. Since zeolite is a NM, additional studies on using and recycling of the generated sludge as an industrial feedstock would be worthwhile.     

Biotreatment of As-containing simulated acid mine drainage using laboratory scale sulfate reducing upflow anaerobic sludge blanket reactor

Heavy metal contamination of water sources can occur from the discharge of acid mine drainage (AMD). This study assessed sulfidogenic treatment of As-, Fe-, Zn-, Ni- and Cu-containing AMD in an upflow anaerobic sludge blanket (UASB) reactor, operated for approximately 500 days. Sulfate reducing granules were successfully enriched with synthetic wastewater and sulfate concentration decreased from 2000 mg/L in the influent to 100–200 mg/L in the effluent. The pH increased from 3–4 to 6–8 as a result of biogenic alkalinity production. Arsenic removal was not detected in the absence of heavy metals, possibly due to the high dissolved sulfide concentration. In the presence of heavy metals, and at low dissolved sulfide concentrations, As removal efficiency increased to 98–100% likely due to the formation of arsenopyrite (FeAsS) or the adsorption of As on metal sulfide precipitates. Fe, Cu, Ni and Zn removal efficiencies approached 99% in the presence of dissolved sulfide. When hydrogen sulfide generation was insufficient to precipitate all of the metals, Fe was detected in the UASB effluent. The results showed that As-, Fe-, Zn-, Ni- and Cu-containing AMD can be effectively treated by sulfate reducing granules in UASB reactors.     

浮选捕收剂气浮浓缩城市污水处理厂剩余污泥的研究

以浮选捕收剂SESN为表面活性剂,用气浮法对某大型城市污水处理厂的剩余活性污泥进行浓缩试验。结果表明,气浮时SESN的用量、pH值是影响污泥的水回收率及浓缩污泥的含水率的主要因素。当SESN用量为37.5mg/L时,气浮10min,水回收率为79.6%;浓缩污泥含水率从气浮前的99.44%降低到96.8%。用红外光谱及SEM对表面活性剂与污泥的作用机理进行研究,结果表明,表面活性剂SESN和污泥发生了化学吸附。     

The application of wood ash as a reagent in acid mine drainage treatment

The paper deals with a possible utilisation of wood ash as a reagent in treating acid mine drainage (AMD) from opencast mining of brown coal. Wood ash samples were obtained having combusted deciduous and coniferous tree wood in a household furnace. The dominant mineral phases in wood ash are calcite, quartz, lime and periclase. The used AMD is characteristic of high contents of sulphates, iron, manganese, heavy metals and low pH. The AMD treatment process included dosing of wood ash to adjust pH values about 8.3 (a dose of 0.5 g l⁻¹) or calcium hydroxide (a dose of 0.2 g l⁻¹) for comparison. The reaction time was 20 min. Dosing of wood ash in AMD resulted in an increase of pH in solution from 3.5 to 8.3, which caused the removal of metal ions mainly by precipitation, co-precipitation and adsorption. Comparing the application of Ca(OH)₂ in AMD treatment, at an almost identical pH value the concentrations fell in both cases for Fe, Mn, As, Co, Cu, Ni, Zn, Mg, Al and Mo. Applying wood ash the drop was even more distinct in Mn, Zn and Mg. The results of sedimentation tests in an Imhoff cone confirm that the settling capacities of sludge using wood ash are significantly better than when using calcium hydroxide in acid mine drainage treatment.     

Competitive Removal of Metals from Wastewater by Maghemite Nanoparticles: A Comparison Between Simulated Wastewater and AMD

Maghemite nanoparticles (γ-Fe₂O₃) produced using a recently developed, single-step method proved to be highly effective for selective removal of Cu, Ni, Mn, Cd(II), and Cr(VI) from acid mine drainage (AMD) and simulated wastewater. An average particle size of about 14 nm was estimated for the maghemite nano-particles using transmission electron microscopy. Their adsorption characteristics proved to be highly pH dependent, allowing facilitated selective adsorption of the studied metals, all of which followed the Langmuir adsorption model. In both simulated wastewater and AMD, Cr(VI) adsorption was best at 70 °C and pH = 2.6. Adsorption peaked at pH = 8.5 for Ni(II), 10 for Cd(II), 8.5 for Mn(II), and 6.5 for Cu(II).     

Sequential precipitation of Cu and Fe using a three-stage sulfidogenic fluidized-bed reactor system

The exposure of sulfides, such as pyrite (FeS₂) to water and air leads to the formation of acidic metal and sulfate containing waters, generally referred to as acid mine drainage (AMD). Under anaerobic conditions and in the presence of a suitable electron and carbon source, sulfate-reducing bacteria (SRB) can reduce sulfate to hydrogen sulfide which can precipitate metals as low-solubility sulfides. In the present study, a three-stage fluidized-bed reactor (FBR) system was operated at 35 °C with ethanol as an electron and carbon source for SRB to sequentially precipitate Cu and Fe from synthetic AMD. The system consisted of two pre-settling tanks before a sulfidogenic FBR for the sequential precipitation of Cu and Fe with biogenic H₂S gas and HS⁻ containing effluent, respectively. Cu and Fe precipitation efficiencies were over 99% and sulfate and COD removals 60-90%. Biologically produced alkalinity increased the initial pH of the AMD from 3.0 to neutral values.     

Manipulate an air–cathode fuel cell toward recovering highly active heterogeneous electro-Fenton catalyst from the Fe(II) in acid mine drainage

The recovery of iron oxides from acid mine drainage (AMD) has attracted extensive research attention due to the double advantage of waste minimization and resource recovery. Recently a novel air–cathode fuel cell approach was proposed to in-situ utilize ferrous iron (Fe(II)) in the AMD for the fabrication of Fe₃O₄/graphite felt (GF) composite as the cathode of electro-Fenton process. In the present work, the influence of fuel cell operating parameters, including solution pH, carbonate concentration and Fe(II) concentration, on the catalytic activity of prepared Fe₃O₄/GF composite is adequately elucidated. The highest activity is observed on the composite obtained from the fuel cell operated with 30 mM Fe(II) and 50 mM carbonate at pH 7.5. The activity of Fe₃O₄/GF is strongly dependent upon iron loading and Fe₃O₄ morphology in the composite. Higher iron loading generally induces higher catalytic activity, and the Fe₃O₄ aggregate is catalytically less reactive relative to the well-dispersed one. The precipitation of Fe(III) oxides on the GF through electrochemical oxidation of Fe(II) plays a key role in determining the structure of Fe₃O₄/GF composite. Solution pH and composition in the fuel cell affect such a process by manipulating the distribution of Fe(II) species in aqueous solution and on the GF.     

用浸出工艺回收酸性矿山废水沉淀渣中金属元素

酸性矿山废水沉淀渣的处置一直是废水处理工程面临的难题。以广东省大宝山矿槽对坑尾矿库外排废水处理厂产生的沉淀渣为例,开展沉淀渣中有价金属元素酸浸与回收试验。淀渣铁、锰、铜、锌、镍、铅品位分别为40 919.6,14 320.6,4 681.4,7 557.4,149.3,360.9 g/t,杂质成分主要为石英、方解石。在硫酸浓度为20%、固液比为0.33 g/mL、浸出时间为8 h、浸出温度为30 ℃条件下,铜、锌、镍、铅、锰和铁的浸出率分别为99.49%、21.41%、51.21%、4.45%、55.86%、34.25%。采用硫酸浸出工艺回收沉淀渣中有价金属元素在技术经济上可行,同时可缓解废水处理厂的环保压力。     

Valorisation of acid mine drainage treatment sludge as remediation component to control acid generation from mine wastes,part 1: Material characterization and laboratory kinetic testing

In operating mines, acid mine drainage (AMD) is often treated using lime treatment. This process generates a significant amount of sludge that contains metal hydroxide precipitates, gypsum, and unreacted lime. The sludge may have interesting geotechnical and geochemical properties to be used as a part of covers (oxygen barriers) to prevent AMD generation from waste rocks and tailings. The main results of a project aiming to evaluate the use of sludge from the Doyon mine site (Canada) as a material in mine site rehabilitation are presented. The first part of the project involved detailed characterization of sludge, waste rock, and tailings samples. Then, laboratory column leaching tests were performed to evaluate the performance of the mixtures to control AMD produced by tailings and waste rocks. It was found that a sludge–waste rock mixture placed over waste rock reduces the metal loads in the column effluent, which remained acidic, as well as a mixture of sludge and tailings deposited over tailings can reduce metal content in effluents from tailings.     

Valorization of acid mine drainage treatment sludge as remediation component to control acid generation from mine wastes,part 2: Field experimentation

The possibility of using acid mine drainage (AMD) treatment sludge as a cover component to control AMD generation from mine wastes was investigated through laboratory characterization and kinetic column testing (companion paper). The results showed that mixtures of sludge and waste rock, and sludge and tailings, may be integrated in an AMD prevention and control strategy at Doyon mine site (northwestern Quebec, Canada). In order to further investigate these scenarios in realistic climatic conditions, instrumented field test cells were installed on site to evaluate the performance of the mixtures to control AMD generation from tailings and waste rock under natural field conditions. The main findings from two seasons of monitoring are presented in the paper. The waste rock-sludge mixture placed over waste rock was able to reduce the generation of AMD from the waste rock, therefore confirming lab results, and was able to produce a neutral effluent with low concentrations of dissolved metals. The tailings-sludge mixture placed over tailings, with an evaporation protection layer, maintained a high volumetric water content and reduced sulphide oxidation from the tailings as exhibited by a neutral effluent. Monitoring of the field cells will continue to provide valuable information on the possible sludge valorization options.