Long-term interaction of wollastonite with acid mine water and effects on arsenic and metal removal

This paper reports the results of a laboratory experiment conducted to investigate the effects of wollastonite dissolution on removal of potentially toxic trace elements from stream waters affected by acid mine drainage (AMD). Nearly pure wollastonite was treated with natural acid mine water (pH 2.1) for different lengths of time (15, 30, 50 and 80 days). The compositional and textural characterization of the solid reaction products suggests that wollastonite was incongruently dissolved leaving a residual amorphous silica-rich phase that preserved the prismatic morphology of the parent wollastonite. The release of Ca into solution resulted in a pH increase from 2.1 to 3.5, and subsequent precipitation of gypsum as well as poorly crystallized Fe–Al oxy-hydroxides and oxy-hydroxysulfates whose components derived from the AMD solution. A geochemical modeling approach of the wollastonite–AMD interaction using the PHREEQC code indicated supersaturation with respect to schwertmannite (saturation index = 10.7–15.7), jarosite (SI = 8.7–10.2), alunite (SI = 5.1), goethite (SI = 4.7) and jurbanite (SI = 2.2). These secondary phases developed a thin coating on the reacted wollastonite surface, readily cracked and flaked off upon drying, that acted as a sink for trace elements, especially As, Cu and Zn, as indicated by their enrichment relative to the starting wollastonite. At such low pH values, adsorption of As oxyanions on the positively charged solid particles and coprecipitation of metals (mainly Cu and Zn) with the newly formed Fe oxy-hydroxides and oxy-hydroxysulfates seem to be the dominant processes controlling the removal of trace elements.     

Long-term brine impacted fly ash,Part II: Mobility of major species in the ash residues

The leaching of major species from fly ash is a function of the pH of the solution in contact with the fly ash. The aim of this study was to determine the effect of the pH of the leachant on the leaching of species from the ash residues recovered after the long-term fly ash–brine interactions. Acid neutralization capacity (ANC) tests using solutions of different pH values ranging from the initial pH of the ash residues (11–12) to pH 4 were employed in the leaching experiments. The ANC tests revealed that the release of major species from the ash residues depended on the pH of the leachants except for Na and Cl, where the significant concentrations leached were independent of the solution pH. The concentrations of Al and Si in the ANC leachates were very high at pH below 6 while Ca, K, Sr, Mg and B were immediately mobilized from the brine impacted fly ash when in contact with de-ionized water, and leaching increased as the pH decreased. The concentration of SO₄ leached from the brine impacted ash residues at high pH was high, and the leaching increased with decrease in the pH of the leachant. This study shows that most of the major elements captured in the ash residues could be mobilized when in contact with aqueous solutions of various pH. This reveals that the co-disposal of fly ash and brine may not be the best practice as the major elements captured in the ash residues could leach over time.     

Pb and Co removal from paint industries effluent using wood ash

The release of heavy metals into the environment is a worldwide major concern. Different studies have demonstrated that natural agents have a high removal capacity for divalent heavy metal ions. Wood ash is a natural adsorbent and, in comparison with others, has a very low price. In this study, the removal of heavy metals (Pb and Co) from Binalood paint industry (Kerman, Iran) effluent was investigated in batch condition. Pb and Co measurement in samples were done with atomic absorption equipment and test methods were adapted from standard methods for the examination of water and wastewater. The effect of pH and the amount of adsorbent was determined and different adsorption isotherms were also obtained. This study shows that the adsorption process follows the adsorption Langmuir isotherm. The amount of wood ash has a great role in the adsorption rate and adsorption rate increased as wood ash increased. In the study, the reactions reached equilibrium in 3 h contact time. The maximum Pb removal efficiency was 96.1 % at pH 2 with a contact time of 3 h and 100 g/L wood ash and the maximum Co removal efficiency was 99 % at pH 2 with a contact time of 3 h and 100 g/L wood ash. According to the results, wood ash is recommended as a low cost and available adsorbent to remove Pb and Co from municipal and industrial wastewaters.     

含氟废水的粉煤灰处理实验研究

进行了影响粉煤灰处理含氟废水的各种条件实验，（pH、水灰比、氟浓度、振荡平衡时间），结果表明最佳处理条件是pH值为2．5、水灰比为小于20、氟浓度小于500mg/l、振荡平衡时间大于2．5h，并研究了粉煤灰处理含氟废水的机理，给出了其吸附等温式。     

Retention studies of chromium (VI) from aqueous solution on the surface of a novel carbonaceous material

In the present study, the retention capacity of carbonaceous material obtained from the diesel engine exhaust mufflers for Cr(VI) removal has been investigated. The physicochemical properties such as density, pH of aqueous slurry, pH at point of zero charge, ash content, moisture content, volatile matter, surface area, scanning electron microscopy and electron dispersive spectroscopy of the carbonaceous material were determined. The capacity of adsorbent for removal of Cr(VI) from aqueous solution was observed under different experimental condition like contact time, initial concentration of metal ions, pH and temperatures on the adsorption capacity of the adsorbent. Maximum adsorption of Cr(VI) ions was found at low pH. The adsorption process was found to follow second-order kinetics. The rate constant was evaluated at different temperatures along with other thermodynamic parameters like activation energy, Gibbs free energy change, enthalpy change and entropy change. Both Langmuir and Freundlich isotherms were used to describe the adsorption equilibrium of carbonaceous material at different temperatures. Langmuir isotherm shows better fit than Freundlich isotherm at given conditions. The result shows that low-cost carbonaceous material from diesel engine exhaust mufflers can be efficiently used for wastewater treatment containing Cr(VI) ions.     

Self-sealing isolation and immobilization: a geochemical approach to solve the environmental problem of waste acidic jarosite

Mimicking geochemical processes to solve environmental problems was implemented in dealing with waste acidic jarosite and alkaline coal fly ash. By placing these two chemically different materials adjacent to one another, a self-sealing layer was formed at the interface between both wastes, isolating and immobilizing chemical constituents in the process. A series of leaching experiments were performed on each material separately to study the release behavior of the principal constituents. Radiotracer experiments were conducted to explore diffusion and reaction of constituents such as Fe³⁺ in a combined jarosite/fly ash system. A model has been developed to simulate the coupled processes of diffusion and precipitation taking into account porosity change due to pore filling by precipitates. The formation of a self-sealing isolation layer in a hypothetical jarosite/fly ash disposal site was modelled. Leaching results indicate that the release of elements from jarosite is much larger than that from fly ash, and that the highly pH dependent release of Fe, Al, and Zn was controlled by the solubility of their hydroxides. Leaching results also suggest that precipitation reactions can be expected to occur at the interface between jarosite and alkaline coal fly ash where a large pH gradient exists. Radiotracer experiments showed that accumulation of constituents occurred at the interface. Modeled Fe³⁺ profiles in layered jarosite/fly ash were well validated by experiments. Modeling results also showed that with the accumulation of constituents at the interface, a new layer with low porosity was formed. Application of this model suggests that there is a potential use to form a self-sealing layer in jarosite/fly ash co-disposal sites.     

Immobilization of toxic elements in mine residues derived from mining activities in the Iberian Pyrite Belt (SW Spain): Laboratory experiments

In the mining environments of the Iberian Pyrite Belt (IPB), the oxidation of sulphide wastes generates acid drainage with high concentrations of SO₄, metals and metalloids (Acid Mine Drainage, AMD). These acid and extremely contaminated discharges are drained by the fluvial courses of the Huelva province (SW Spain) which deliver high concentrations of potentially toxic elements into the Gulf of Cádiz. In this work, the oxidation process of mine tailings in the IPB, the generation of AMD and the potential use of coal combustion fly ash as a possible alkaline treatment for neutralization of and metal removal from AMD, was studied in non-saturated column experiments. The laboratory column tests were conducted on a mine residue (71.6 wt% pyrite) with artificial rainfall or irrigation. A non-saturated column filled solely with the pyrite residue leached solutions with an acid pH (approx. 2) and high concentrations of SO₄ and metals. These leachates have the same composition as typical AMD, and the oxidation process can be compared with the natural oxidation of mine tailings in the IPB. However, the application of fly ash to the same amount of mine residue in another two non-saturated columns significantly increased the pH and decreased the SO₄ and metal concentrations in the leaching solutions. The improvement in the quality of leachates by fly ash addition in the laboratory was so effective that the leachate reached the pre-potability requirements of water for human consumption under EU regulations. The extrapolation of these experiments to the field is a promising solution for the decontamination of the fluvial courses of the IPB, and therefore, the decrease of pollutant loads discharging to the Gulf of Cádiz.     

Stability and leaching of cobalt smelter fly ash

The leaching behaviour of fly ash from a Co smelter situated in the Zambian Copperbelt was studied as a function of pH (5–12) using the pH-static leaching test (CEN/TS 14997). Various experimental time intervals (48 h and 168 h) were evaluated. The leaching results were combined with the ORCHESTRA modelling framework and a detailed mineralogical investigation was performed on the original FA and leached solid residues. The largest amounts of Co, Cu, Pb and Zn were leached at pH 5, generally with the lowest concentrations between pH 9 and 11 and slightly increased concentrations at pH 12. For most elements, the released concentrations were very similar after 48 h and 168 h, indicating near-equilibrium conditions in the system. Calcite, clinopyroxenes, quartz and amorphous phases predominated in the fly ash. Various metallic sulfides, alloys and the presence of Cu, Co and Zn in silicates and glass were detected using SEM/EDS and/or TEM/EDS. The leaching of metals was mainly attributed to the dissolution of metallic particles. Partial dissolution of silicate and glass fractions was assumed to significantly influence the release of Ca, Mg, Fe, K, Al and Si as well as Cu, Co and Zn. The formation of illite was suggested by the ORCHESTRA modelling to be one of the main solubility-controlling phases for major elements, whereas Co and Zn were controlled by CoO and zincite, respectively. Sorption of metals on hydrous ferric oxides was assumed to be an important attenuation mechanism, especially for the release of Pb and Cu. However, there is a high risk of Co, Cu, Pb and Zn mobility in the acidic soils around the smelter facility. Therefore, potential local options for “stabilisation” of the fly ash were evaluated on the basis of the modelling results using the PHREEQC code.     

Removal of Cu(Ⅱ) From Aqueous Solutions Using Colloidal Pyrite Calcined Under Inert Atmosphere

A natural colloidal pyrite calcined in N2 atmosphere was utilized to remove Cu(II) from aqueous solutions in present work. Effect of calcination temperature, initial solution pH, reaction time, initial Cu(II) concentration, sorption temperature, foreign ions and the dissolved oxygen (DO) on Cu(II) removal was investigated. The results showed that colloidal pyrite calcined at 500-550°C (CCPy) has a most promising potential for Cu(II) removal. The increase of pH, initial Cu(II) concentration and reaction time benefited the improvement of Cu(II) removal efficiency. The isothermal adsorption data of CCPy was well described by Langmuir isotherms and the thermodynamic parameters (ΔG<0, ΔH>0), indicating the endothermic nature of Cu(II) sorption on CCPy. The presence of most common ions in acid mine drainage and DO just had little influence on the Cu(II) uptake. The observation implied that CCPy is a low-cost, abundant material for Cu removal from Cu waters.     

粉煤灰处理含氟废水的正交试验研究

对粉煤灰处理含氟废水进行了正交试验研究。结果表明各因素对F-去除率的影响顺序为:pH>V/M>T>CF-,极差R分别为49.6、9.1、4.9和3.6;在pH=5、V/M=10、T=3h时,粉煤灰对于CF-<500 mg/L的废水具有较好的去除效果;粉煤灰吸附F-的行为符合Langmuir等温方程,方程为Ce/qe=0.251 8Ce+6.087 3。     

黄豆脲酶诱导碳酸钙沉淀多变量试验研究

植物源脲酶诱导碳酸钙沉淀（enzyme induced carbonate precipitation,简称EICP）可以显著改善砂土的工程力学特性,但在具体操作时,参数取值无对应规范,固化效果有待提升。基于黄豆脲酶,研究了温度、脲酶浓度、尿素浓度、钙浓度、pH值、钙源种类等变量对脲酶活性与碳酸钙沉淀的影响,并进行了沉淀物（碳酸钙晶体）的扫描式电子显微镜（scanning electron microscope,简称SEM）与X射线衍射（X-ray diffraction,简称XRD）测试,在此基础上开展了黄豆脲酶固化砂的无侧限抗压强度与固化效果试验研究。结果表明：脲酶活性随脲酶浓度的增加而线性增长,但存在温度阈值,温度超过阈值后,脲酶将完全失活,且阈值随脲酶浓度的增大而降低;尿素浓度与pH值共同影响脲酶活性,二者存在一个最优组合,当尿素浓度在0.1～1.0 mol/L时最优pH值为7,当尿素浓度在1.0～1.5 mol/L时最优pH值为8。脲酶是沉淀反应的催化剂,脲酶浓度越高,反应越完全,碳酸钙沉淀率越高;尿素与钙溶液则主要通过掺入量影响碳酸钙沉淀量,掺量比例宜为1:1,且二者浓度与pH值可通过影响脲酶活性来影响碳酸钙的沉淀情况;不同钙源对碳酸钙沉淀量的影响幅度不大。不同钙源沉淀碳酸钙晶体的成分与密度基本相同,但晶体结构差异较大,氯化钙沉淀碳酸钙晶体以块状为主,表面分布球状、类球状晶体,胶结面大,可作为EICP技术中较为理想的钙源。基于黄豆脲酶和氯化钙钙源固化砂的无侧限抗压强度约为掺粉煤灰砂样的6倍,通过SEM图像可发现,沉淀碳酸钙晶体包裹并黏结砂粒成为整体,固化效果非常理想。     

Compression Behavior of Mine Tailings Amended with Cementitious Binders

The objective of this study was to evaluate the effect of fly ash amendment on the compression behavior of mine tailings. Natural and synthetic (i.e., laboratory prepared) mine tailings were used to assess the effects of tailings composition and tailings solids content on compressibility. Three types of off-specification fly ashes and Type I–II Portland cement were used as cementitious binders. Tailings-fly ash mixtures were prepared at solids content of 60–75% (water content = 33–67%), water-to-binder ratios of 2.5 and 5, and were cured for 0.1 days (2 h), 7, and 28 days. Bi-linear compression curves on semi-log plots were observed in most of the binder-amended tailings specimens. The break in slope on the compression curve was identified as the breaking stress, whereupon cementitious bonds were broken. The breaking stress increased with an increase in fly ash content, which was attributed to a lower water-to-binder ratio and void volume-to-binder volume ratio that produced more effective particle bonding. Breaking stress also increased with an increase in CaO content and CaO-to-SiO₂ ratio of fly ash, which resulted in more effective bonding between particles. The effect of curing time on the breaking stress of fly ash amended specimens was characterized by (1) an increase in breaking stress via increase in curing time and cementitious bond formation or (2) a constant breaking stress with curing time due to competing mechanisms during loading. Specimens cured under a vertical stress showed an increase in breakings stress with applied load water removal prior to cementitious bond formation that reduced the water-to-binder ratio and led to more effective cementation.     

Lead and nickel biosorption with a fungal biomass isolated from metal mine drainage: Box–Behnken experimental design

The Pb(II) and Ni(II) biosorption of a fungal biomass isolated from mine drainage of metal-processing industries in Balya (Bal?kesir province, Turkey) was optimized using a response surface methodology by altering parameters such as pH, initial metal concentration, contact time and biosorbent dosage. This strain was shown to be highly similar to Penicillium sp. Furthermore, zeta potential measurements and Fourier transform infrared spectroscopy were performed to understand the adsorption mechanism. A Box–Behnken design with 29 experiments was used to evaluate the interactions between independent variables. The results showed that the fungal biomass isolated from the metal mine drainage could have a significant environmental impact through the biosorption of Pb(II) and Ni(II) in waters polluted with heavy metals, particularly in the drainage from metal mines. The maximum removal values were 76 and 47 % at pH 4.5 for both Pb(II) and Ni(II), with 123 and 33 mg/L initial metal concentrations, 65 and 89 min contact times and 0.2 and 1.6 g/L biosorbent, respectively.     

Nettle ash as a low cost adsorbent for the removal of nickel and cadmium from wastewater

This study was focused on nettle ash as an alternative adsorbent for the removal of nickel (II) and cadmium (II) from wastewater. Batch experiments were conducted to determine the factors affecting adsorption of nickel (II) and cadmium (II). The adsorption process is affected by various parameters such as contact time, solution pH and adsorbent dose. The optimum pH required for maximum adsorption was found to be 6. The experimental data were tested using Langmuir, Freundlich and Tempkin equations. The data were fitted well to the Langmuir isotherm with monolayer adsorption capacity of 192.3 and 142.8 mg/g for nickel and cadmium, respectively. The adsorption kinetics were best described by the pseudo second order model. The cost of removal is expected to be quite low, as the adsorbent is cheap and easily available in large quantities. The present study showed that nettle ash was capable of removing nickel and cadmium ions from aqueous solution.     

Coupled physicochemical and bacterial reduction mechanisms for passive remediation of sulfate- and metal-rich acid mine drainage

Treatment of acid mine drainage (AMD) highly rich in sulfate and multiple metal elements has been investigated in a continuous flow column experiment using organic and inorganic reactive media. Treatment substrates that composed of spent mushroom compost (SMC), limestone, activated sludge and woodchips were incorporated into bacterial sulfate reduction (BSR) treatment for AMD. SMC greatly assisted the removals of sulfate and metals and acted as essential carbon source for sulfate-reducing bacteria (SRB). Alkalinity produced by dissolution of limestone and metabolism of SRB has provided acidity neutralization capacity for AMD where pH was maintained at neutral state, thus aiding the removal of sulfate. Fe, Pb, Cu, Zn and Al were effectively removed (87–100%); however, Mn was not successfully removed despite initial Mn reduction during early phase due to interference with Fe. The first half of the treatment was an essential phase for removal of most metals where contaminants were primarily removed by the BSR in addition to carbonate dissolution function. The importance of BSR in the presence of organic materials was also supported by metal fraction analysis that primary metal accumulation occurs mainly through metal adsorption onto the organic matter, e.g., as sulfides and onto Fe/Mn oxides surfaces.     

Manganese removal from mine waters – investigating the occurrence and importance of manganese carbonates

Manganese is a common contaminant of mine water and other waste waters. Due to its high solubility over a wide pH range, it is notoriously difficult to remove from contaminated waters. Previous systems that effectively remove Mn from mine waters have involved oxidising the soluble Mn(II) species at an elevated pH using substrates such as limestone and dolomites. However it is currently unclear what effect the substrate type has upon abiotic Mn removal compared to biotic removal by in situ micro-organisms (biofilms). In order to investigate the relationship between substrate type, Mn precipitation and the biofilm community, net-alkaline Mn-contaminated mine water was treated in reactors containing one of the pure materials: dolomite, limestone, magnesite and quartzite. Mine water chemistry and Mn removal rates were monitored over a 3-month period in continuous-flow reactors. For all substrates except quartzite, Mn was removed from the mine water during this period, and Mn minerals precipitated in all cases. In addition, the plastic from which the reactor was made played a role in Mn removal. Manganese oxyhydroxides were formed in all the reactors; however, Mn carbonates (specifically kutnahorite) were only identified in the reactors containing quartzite and on the reactor plastic. Magnesium-rich calcites were identified in the dolomite and magnesite reactors, suggesting that the Mg from the substrate minerals may have inhibited Mn carbonate formation. Biofilm community development and composition on all the substrates was also monitored over the 3-month period using denaturing gradient gel electrophoresis (DGGE). The DGGE profiles in all reactors showed no change with time and no difference between substrate types, suggesting that any microbiological effects are independent of mineral substrate. The identification of Mn carbonates in these systems has important implications for the design of Mn treatment systems in that the provision of a carbonate-rich substrate may not be necessary for successful Mn precipitation.     

利用高铝粉煤灰制备氢氧化铝的实验

以无水碳酸钠为助剂,分解高铝粉煤灰中的莫来石和铝硅酸盐玻璃相。经中温烧结、酸浸使硅铝分离,调节pH值为5～6纯化含铝滤液,通入CO₂气体酸化等工序,可制备氢氧化铝粉体。采用X射线粉末衍射、扫描电镜、化学分析方法对制品进行表征,结果表明：制备的氢氧化铝为球形颗粒,其粒径为200 nm左右,性能达到GB/T4294-1997的三级标准。实验所采用的工艺路线是高铝粉煤灰资源化高效利用的有效途径之一。     

Retention of fly ash-derived copper in sediments of the Pandu River near Kanpur,India

A coal-based thermal power plant is situated on the bank of the Pandu River, which is a tributary to the Ganges near Kanpur. River sediments downstream from the ash pond outfall are contaminated by fly ash. In order to establish the role of soils and sediments in retaining fly ash-derived heavy metals, copper was investigated as a model metal. A maximum concentration of 70 ppm Cu could be leached from the fly ash, confirming that it is a major source of this metal. Soil samples and river sediments were examined for Cu adsorption in the natural state as well as after treatment with H₂O₂, EDTA, and H₂O₂ followed by EDTA. The organic fraction of the samples was determined, and it had a major control on removal of Cu from a solution with 10^–4 M initial concentration. Further characterization of organic matter indicated that with reference to natural samples, the humic acid fraction had a copper enrichment factor in the range 9.1–15.1. The factor for fulvic acids, in contrast, was between 3.5 and 5.5. This leads to the conclusion that river deposits rich in humic acids would withstand relatively high metal loads. Only when the metal input exceeds the maximum retention potential, would the metal be fractionated into the aqueous phase and act as a potential biocide.