Mine Wastewater Research Articles

Cultivation of Microalgae (Scenedesmus sp.) Using Coal Mining Wastewater and Separation via Coagulation/Flocculation and Dissolved Air Flotation (DAF)

Algae growth can be carried out in treated mine waters, providing biomass and helping to achieve the standards for water discharge. However, efficient separation of algae from the aqueous medium is crucial. The present work investigated the stability of Scenedesmus sp. in treated acid drainage from coal mining and assessed the harvesting of microalgae via coagulation/flocculation and dissolved air flotation (DAF). Successful algae growth was achieved, with cells remaining suspended in the water at a wide range of pH values, requiring the use of reagents for destabilization/aggregation. Algae coagulation/flocculation was attained with the use of tannin or ferric chloride associated with an anionic polymer flocculant at a pH of 8.0 ± 0.1. When combined with the flocculant, both tannin and the inorganic coagulant proved effective in enhancing floc stability and hydrophobicity for the DAF process. In summary, this operational approach facilitated algae biomass recovery and significantly reduced turbidity in the treated water. Finally, a schematic diagram illustrating the algae cultivation and harvesting process is presented, offering a practical alternative to acid mine drainage (AMD) treatment refinement associated with algae biomass production.

Removal of heavy metal ions from industrial (mining) wastewater using electromagnetically activated carbonaceous sorbent

Mining wastewater, characterized by elevated salt levels, necessitates effective treatment to prevent contamination of underground and surface water. Traditional methods for treating large volumes of mining wastewater with high total dissolved solids are expensive, and cost-effective alternatives are limited. In this study, we propose a solution to this challenge: the sorption of dissolved substances using a carbonaceous sorbent derived from waste, specifically rice husk biochar. To enhance the sorbent’s efficiency, we subjected it to electromagnetic activation, resulting in increased carbon content (from 43.3 to 78.5 % compared to the initial biochar), reduced impurities, and particle size reduction to the nanoscale (1–50 nm) with the formation of mesopores (mean diameter from the adsorption isotherm is 167 Å) and micropores (4.92 Å). This process contributes to improved compositional homogeneity. The effectiveness of the proposed sorbent was validated through the treatment of wastewater from Kirov Mine (Novoshakhtinsk, Rostov Region) under laboratory conditions. The removal rates for dissolved heavy metal ions (iron, zinc, manganese) were found to be 89, 84 and 26 %, respectively. A recommended two-stage sorption treatment involves: (1) static sorption using electromagnetically treated rice husk biochar at a concentration of 0.5 g/dm3; (2) subsequent reagent treatment of the suspension (SKiF-180 reagent, 1.0 mg/dm3), addition of potassium permanganate for manganese removal, settling for 30 min, and non-pressure filtration with a rice husk biochar filter.

The removal of Sb from mine wastewater using biosynthesized Fe-Mn nanoparticles: Function and mechanism

Antimony (Sb) in mine wastewater poses a serious threat to surrounding ecosystems. In this study, biosynthesized iron-manganese nanoparticles (Fe-Mn NPs) were devised to remove Sb species. The resultant removal efficiencies were 100% for Sb(III) and 82.6% for Sb(V) utilizing a Sb(III) and Sb(V) concentration of 1 mg·L−1. To understand the removal process, Fe-Mn NPs before and after exposure to Sb species were characterized by various advanced techniques, which indicated that while both Sb(III) and Sb(V) were adsorbed onto the surface of Fe-Mn NPs, Sb(III) was also partly oxidized to Sb(V). Furthermore, removal of both Sb(III) and Sb(V) followed pseudo-second-order kinetics and best fit the Freundlich adsorption isotherm model, suggesting that the removal process involved non-homogeneous chemisorption. These studies provided the evidence for an adsorption and oxidation mechanism for Sb(III) removal and an adsorption-dominated mechanism for Sb(V) removal by Fe-Mn NPs. When the produced Fe-Mn NPs were applied to remove Sb from mine wastewater, 92.7% removal was attained, demonstrating the significant practical potential of these nanoparticles to Sb species from mine wastewaters. This study provides novel insights for future exploration for Sb removal from mine wastewaters.

Innovative recovery of matrix layered double hydroxide from simulated acid mine wastewater for the removal of copper and cadmium from wastewater.

This study innovatively added biochar to optimize regulation in the neutralization process of simulated acid mine drainage (AMD) and recovered a new type of matrix layered double hydroxides (MLDH), which can be used to remove copper (Cu(II)) and cadmium (Cd(II)) from wastewater. A series of batch experiments show that MLDH with strong selective removal ability of Cu(II) and Cd(II) can be successfully obtained by adding biochar (BC) at pH = 5 end in the neutralization process. Kinetic and isotherm modeling studies indicated that the removal of Cu(II) and Cd(II) by the MLDH was a chemical multilayer adsorption process. The removal mechanism of Cu(II) and Cd(II) was further analyzed through related characterization analysis with contribution rate calculation: the removal rates of Cu(II) and Cd(II) by ion exchange were 42.7% and 26%, while that by precipitation were 34.5% and 49.9%, respectively. This study can provide a theoretical reference and experimental basis for the recovery and utilization of valuable by-products in AMD and the treatment of heavy metal wastewater.

The Effects of Mine Waste and Rain Water on the Structure of Bacteria Community of Paddy Soils

ABSTRACT Heavy metal contamination of soil has become one of the most important environmental problems worldwide. Heavy metals can affect growth and lead to changes in microbial community composition, which could influence the growth of crops in the soil. In this study, we conducted an experiment to investigate the distribution profile of heavy metals and bacterial communities in soil with the effects of slag and/or water on the top of the soil. Extra heavy metals, acting as selective pressure, led to the loss of sensitive taxa, with tolerant or less sensitive taxa being more abundant in the community. The results showed that the addition of slag on the top of soils did not change the diversity of bacteria but influenced the relative abundance of indigenous members in the community. Water addition, however, improved the homogeneity of the environment vertically in the soil, which consequently led to a lower variation in the bacterial community. This study mimicked the scenario of tailings and abandoned mines in nature, and aimed to study the effects of mines on the soil microbial community with the influence of precipitation on the distribution of heavy metals in the soil. With the effect of precipitation, the transportation of heavy metals in the slag may influence the local bacterial community and subsequently undermine the quality of soil for agriculture. These observations provide evidence of the effects of heavy metals on the soil around abandoned mines without any treatment. Mining causes both heavy metal and water pollution, which may lead to the accumulation of heavy metals in plants and agricultural production. Therefore, it is necessary to take care of tailings with proper procedures instead of exposing them to nature.

Study on harmless treatment and valuable elements recovery of neutralization residue from acid wastewater of copper mine

Recently, the common practice for treating metallurgical acidic wastewater involves neutralization with lime emulsion, resulting in residue that is typically landfilled or stockpiled. This contributes to long-term land occupation and environmental pollution. In this study, neutralization residue from a mine underwent comprehensive analysis using XRD, XRF, SEM-EDS, and other techniques. Utilizing acidic wastewater from the local mine as a leaching agent, the leaching characteristics of the residue were systematically investigated, and subsequent toxicity testing was conducted. Copper and iron, enriched in the leachate, were recovered employing the “pre-iron removal – sulfurization – pH compliance” process. Leaching experiments revealed the feasibility of mitigating toxicity by adjusting the pH of local mine wastewater (pH 1.5) with sulfuric acid and reacting with the residue at a ratio of 3:1 (mL/g), under conditions of 25 °C for 120 min. Under these optimized conditions, the recovery rates for Cu, Fe, As, Zn, and Ni reached 99.42%, 96.71%, 88.89%, 99.23%, and 98.21%, respectively. Toxicity testing classified the leaching residue as non-hazardous general solid waste for discharge. Recovery experiments demonstrated optimal conditions for the process, including pre-iron removal at pH 4, H2O2 10 mL/L 30 min, 25 °C, sulfurization with NaHS at 2 g/L, 20 min, 25 °C, and an emission process at pH 7.5, 60 min and 25 °C. The pre-iron removal residue (grade 45.54%) is conducive to entry into the iron plants for refinement processes aimed at enhancing its grade before entering the market, while the sulfide residue, with a copper grade of 57%, hold commercial potential. The remaining liquid adhere to established discharge standards. This process is characterized by a waste-to-waste and waste-to-treasure paradigm, demonstrating robust process stability.

Application of cobalt-cerium-iron ternary layered double hydroxide for extraction of perfluorooctane sulfonate followed by HPLC-MS/MS analysis

Herein, Ce-doped CoFe layered double hydroxide (LDH), noted as CoCeFe ternary LDH, was prepared using the co-precipitation route. Prosperous synthesis of CoFe LDH and successful partial replacement of iron cations with cerium cations in CoCeFe ternary LDH were confirmed by X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and elemental dot-mapping images. Nanosheet morphology was recognized for both CoFe LDH and CoCeFe ternary LDH from scanning electron microscopy and transmission electron microscopy micrographs. In the following, a dispersive solid phase extraction (DSPE) method was developed using the synthesized CoCeFe ternary LDH as a sorbent for extracting perfluorooctanesulfonic acid (PFOS) from wastewater samples. For the selective analysis of PFOS, high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS) in multiple reaction monitoring mode was used. Analytical parameters such as the limit of detection equal to 0.02 μg/L, with a linear range of 0.05–300 μg/L, the limit of quantification equal to 0.05 μg/L, and an enrichment factor equal to 23.3 were achieved for PFOS at the optimized condition (sorbent: 5 mg of CoCeFe ternary LDH, eluent type and volume: 150 μL mobile phase, pH: 3, adsorption time: 3 min, and desorption time: 5 min). The developed strategy for the analysis of PFOS was tested in real wastewater samples, including copper mine and petrochemical wastewater. The amount of analytes in real samples was calculated using the standard addition method, and good relative recovery in the range of 86%–105% was obtained. The main novelty of this research is the application of CoCeFe ternary LDH to extract the PFOS from wastewater using the DSPE method for determination by HPLC-MS/MS.

Identification of the single and combined acute toxicity of Cr and Ni with Heterocypris sp. and the quantitative structure-activity relationship (QSAR) model.

Mining wastewater with heavy metals poses a serious threat to the ecological environment. However, the acute single and combined ecological effects of heavy metals, such as chromium (Cr) and nickel (Ni), on freshwater ostracods, and the development of relevant prediction models, remain poorly understood. In this study, Heterocypris sp. was chosen to investigate the single and combined acute toxicity of Cr and Ni. Then, the quantitative structure-activity relationship (QSAR) model was used to predict the combined toxicity of Cr and Ni. The single acute toxicity experiments revealed high toxicity for both Cr and Ni. In addition, Cr exhibited greater toxicity compared to Ni, as evidenced by its lower 96-hour half-lethal concentration (LC50) of 1.07 mg/L compared to 4.7 mg/L for Ni. Furthermore, the combined acute toxicity experiments showed that the toxicity of Cr-Ni was higher than Ni but lower than Cr. Compared with the concentration addition (CA) and independent action (IA) models, the predicted results of the QSAR model were more consistent with the experimental results for the Cr-Ni combined acute toxicity. So, the high accuracy of QSAR model identified its feasibility to predict the toxicity of heavy metal pollutants in mining wastewater.

Europium(III) Functionalized Covalent Organic Framework as Sensitive and Selective Fluorescent Switch for Detection of Uranium.

Uranium poses severe health risks due to its radioactivity and chemical toxicity if released into the environment. Therefore, there is an urgent demand to develop sensing materials in situ monitoring of uranium with high sensitivity and stability. In this work, a fluorescent Eu3+-TFPB-Bpy is synthesized by grafting Eu3+ cation onto TFPB-Bpy covalent organic framework (COF) synthesized through Schiff base condensation of monomers 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 5,5'-diamino-2,2'-bipyridine (Bpy). The fluorescence of Eu3+-TFPB-Bpy is enhanced compared with that of TFPB-Bpy, which is originated from the intramolecular rotations of building blocks limited by the bipyridine units of TFPB-Bpy coordinated with Eu3+. More significantly, Eu3+-TFPB-Bpy is a highly efficient probe for sensing UO22+ in aqueous solution with the luminescence intensity efficiently amplified by complexation of UO22+ with Eu3+. The turn-on sensing capability was derived from the resonance energy transfer occurring from UO22+ to the Eu3+-TFPB-Bpy. The developed probe displayed desirable linear range from 5 nM to 5 μM with good selectivity and rapid response time (2 s) for UO22+ in mining wastewater. This strategy provides a vivid illustration for designing luminescence lanthanide COF hybrid materials with applications in environmental monitoring.

Recovering and reusing water, H2SO4, nickel and cobalt from gold mining wastewater using air-gap membrane distillation and solvent extraction

Gold mining industry has attracted significant attention for its impact on the environment, encouraging a responsive interest in recovering valuable materials from gold mining wastewater. This study, aligned with the principles of the circular economy, aimed to explore the extraction of water, sulfuric acid, nickel, and cobalt from gold wastewater, employing air gap membrane distillation (AGMD), non-dispersive solvent extraction, and conventional solvent extraction. In the AGMD process, it was demonstrated that 69 % of the wastewater could be reclaimed in the form of high-quality distilled (6.6 ± 1.8 L/m2h). The reclaimed water played a pivotal role in the subsequent non-dispersive extraction stage, acting as a re-extraction agent. Hollow membrane contactors were employed in this stage, achieving a recovery rate of over 95 % for sulfuric acid from the concentrate, with high selectivity over iron (βFe = 488) and magnesium (βMg = 8011;). The acid-depleted stream was then subjected to conventional solvent extraction, wherein Cyanex 272 proved highly effective in extracting nickel, although with limited success in extracting cobalt. The previously used acid current was reintroduced as a re-extractant, demonstrating an 89.3 % re-extraction efficiency. In summary, this study conclusively demonstrated the feasibility of reintroducing water, sulfuric acid, and nickel into the economic cycle through the applied methods. The recovered materials were carefully examined for their potential applications, not only within the gold mining but also across various industrial sectors. This multifaceted approach aligns with the circular economy's objectives, fostering the efficient and sustainable reintroduction of recovered materials into economic processes.

Complexation between butyl xanthate and Cu enhanced peroxydisulfate activation and cation redox cycle by Fe-Cu-LDH/biochar

Butyl xanthate (BX) is one of the most widely used collector in sulfide flotation. It is harmful to human health but its degradability has not been addressed in depth. In this study, Fe-Cu-Layered double hydroxides/Biochar composites (Fe-Cu-LDH/BC) were prepared and firstly used to activate peroxydisulfate (PDS) for degradation of butyl xanthate. More than 90 % of BX could be completely degraded within 10 min under conditions of 20 mg/L BX, 0.2 g/L LDH/BC and 0.1 mM PDS. The high degradation efficiency was owing to the complex formation between catalyst and contaminant molecule by a coordination bond of the Cu in Fe-Cu-LDH/BC and the S in BX. Through DFT calculations, it could be found that this complexation enhanced the adsorption efficiency of LDH/BC on PDS and the reactivity of the Cu site. EPR was applied to analyze the reactive substances in the reaction, and various reactive oxygen species such as O2•−, •OH and SO4•− were detected in the process. In addition, LC-MS was used to analyze and speculate the intermediates and degradation pathways of BX. In conclusion, this material can promote the degradation of BX in water under different conditions and has great potential in treating mine wastewater. Meanwhile, this study proposes new ideas for the synthesis of new catalysts for the efficient degradation of pollutants.

In situ gold adsorption experiment at an acidic hot spring using a blue-green algal sheet

Gold (Au), as one of the most precious metal resources that is used for both industrial products and private ornaments, is a global investment target, and mining companies are making huge investments to discover new Au deposits. Here, we report in situ Au adsorption in an acidic hot spring by a unique adsorption sheet made from blue-green algae with a high preferential adsorption ability for Au. The results of in situ Au adsorption experiments conducted for various reaction times ranging from 0.2 h to 7 months showed that a maximum Au concentration of 30 ppm was adsorbed onto the blue-green algal sheet after a reaction time of 7 months. The Au concentration in the hot spring water was below the detection limit (< 1 ppt); therefore, Au was enriched by preferential adsorption onto the blue-green algal sheet by a factor of more than ~ 3 × 107. Thus, our gold recovery method has a high potential to recover Au even from an Au-poor solution such as hot spring water or mine wastewater with a low impact on the environment.

Selective recovery of copper from copper tailings and wastewater using chelating resins with bis-picolylamine functional groups

Industrial and mining wastewater, along with copper tailings, are typically highly acidic and contain copper and other heavy metals, which may contaminate and damage the environment. Copper (Cu) is, however, a valuable metal, making its removal and recovery from such wastewater and tailings environmentally and economically advantageous. Chelating ion exchange resins featuring bis-picolylamine functional groups are especially suitable for application requiring selective recovery of Cu(II) from highly acidic media. In this study, and for the first time, the kinetics, binding capacity and selectivity of Lewatit MDS TP 220 chelating resin towards Cu(II) are reported. The resin was characterized by Zeta potential, scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Factors including pH, initial concentration, contact time, temperature, and selectivity were investigated to assess the adsorption performance of the chelating resin. The adsorption kinetics tests revealed fast adsorption within the first 5–30 min and fitted the pseudo-second-order model, signifying chemisorption process. The adsorption isotherm followed the Langmuir model, implying monolayer adsorption process. The maximum adsorption capacity (qm) for Cu(II) determined by the Langmuir model was 103.9 mg/g. The adsorption thermodynamics showed an endothermic and spontaneous adsorption. FTIR and XPS studies suggested coordination or chelation as the possible adsorption mechanism. Lewatit MDS TP 220 exhibited excellent Cu(II) adsorption, desorption with 2 M ammonium hydroxide (NH4OH), and selectivity in multi-metal ions solution. Additionally, the resin demonstrated excellent reusability after five regeneration steps. This chelating resin is a potential adsorbent for effective and recurrent recovery of Cu(II) from copper tailings and wastewater, thereby contributing to environmental remediation.

OPTIMAL CONDITIONS FOR LIME TREATMENT OF MINE WASTEWATER FROM POLYMETALLIC ORE MINES

Mine waters of polymetallic mines are multicomponent systems containing ions of heavy non-ferrous metals, calcium, magnesium, iron, ammonium, as well as chlorides, sulfates, fluorides and other components in a wide range of concentrations. As a rule, water purification of this type is carried out by the lime method, which provides a fairly high degree of extraction of the most toxic pollutants (metals), with relatively small material costs. Taking into account the large volume, complexity and variation of the composition of mine waters, the tasks of optimizing reagent consumption, methods of its supply and effective control of the purification process still do not lose their relevance. The article presents the results of laboratory studies to determine the optimal conditions for processing model solutions that provide the maximum degree of purification for specific conditions of the Irtysh mine (East Kazakhstan). Experimental data obtained on model solutions are confirmed by the results of purification of real mine waste water. The results of experiments with mine water confirmed that the selected pH region of 9.5–10.5 can be accepted as optimal, which will allow achieving a high degree of purification of mine water.

Weibull Technique for Evaluation of Swelling: Composite Graphite Resin Electrode for Electrochemical Treatment of Gold Mining Wastewaters

This paper evaluated the swelling of graphite resin electrodes developed for utilization in the electrochemical treatment of gold mining wastewater. Graphite-resin electrodes were developed from used dry cells and resin using non-heat treatment processes (segregation). The Microstructure of the electrode was determined using a scanning electron microscope (Carl Zeiss Smart Evo 10) to ascertain the composition of the electrode. The swelling property of the electrodes was measured using the standard method through a combination of gold mining wastewater and chloride salt solutions. Effects of operational factors (particle size, percentage binder and compressive “compacting” pressure) on the swelling of the electrodes were monitored and evaluated statistically (using analysis of variance). Weibull probability distribution (2 and 3 parameters) was applied to the swelling through Microsoft Excel Solver and Moment Likelihood Method to ascertain the usefulness of the electrode in environmental pollution control through computation of reliability. The study revealed that the swelling was in the range of 1.48 % to 2.24 %, particle size (F5,20 =196.48, p = 2.76 x 10-16), percentage binder (F4,12 =181.58, p = 1.27 x 10-10), and compressive pressure (F3,12 = 106.69, p = 6.43 x 10-9) were significant factors that influence swelling of graphite-resin electrode at 95 % confidence level. the values of α and β for 2-parameters Weibull distribution are 63.162 and 15.098, and 1.265 and 10.089 for MSE and MLM methods, respectively. The Table shows that the values of α, β and θ for 3-parameters Weibull distribution are 3.679, 8.097 and 0.168, and 4.350, 7.165 and 0.198 for MSE and MLM methods, respectively. It was concluded that particle size and compacting pressure are significant factors that had an effect on the swelling of graphite resin electrodes for treatment water and wastewater.

Effective removal of Cr(VI) and Pb(II) ions from mining wastewater using eco-friendly synthesized magnesium oxide nanoparticles incorporated rice husk ash

This study explored the effective adsorptive performance of magnesium oxide (MgO) nanoparticles incorporated rice husk ash (RHA) to address the removal of Chromium (VI) and Lead (II) from mining wastewater from aqueous environment. MgO nanoparticles were synthesized using a magnesium salt precursor and moringa oleifera leaf extract and then impregnated onto RHA to create MgO-RHA nano composite. Different analytical techniques were employed to characterize the RHA and MgO-RHA nanocomposites. The prepared adsorbents were used in batch adsorptive studies and the concentrations of the metal ions were measured before and after treatment using atomic absorption spectrophotometry. Morphological analysis confirmed that the adsorbents developed exhibited a dispersed and porous nature. BET analysis revealed that RHA, MgO, and MgO-RHA had surface areas of 93.04, 32.02, and 102.71 m2/g, respectively. MgO-RHA outperforms RHA in removing metal ions due to its increased surface area and functionality. MgO-RHA demonstrated higher removal percentages of up to 79.20 % and 96.02 % for Cr(VI) and Pb(II), respectively. The Pseudo-second order kinetics and Langmuir isotherm demonstrated the highest degree of conformity to the experimental data, considering the coefficient of determination (R2), smallest value of SSE and chi-square (ᵪ2). Thermodynamic results indicated that the adsorption process was characterized by endothermicity, spontaneity and chemisorption controlled. In summary, the performance of the MgO-RHA nanocomposite surpassed that of RHA alone, which serves as a better adsorbent for metal ion removal.

Hydrogen-Bonded Organic Cocrystal-Encapsulated Perovskite Nanocrystals as Coreactant-Free Electrochemiluminescent Luminophore for the Detection of Uranium.

Lead halide perovskite nanocrystals with excellent photophysical properties are promising electrochemiluminescence (ECL) candidates, but their poor stability greatly restricts ECL applications. Herein, hydrogen-bonded cocrystal-encapsulated CsPbBr3 perovskite nanocrystals (PeNCs@NHS-M) were synthesized by using PeNCs as nuclei for inducing the crystallization of melamine (M) and N-hydroxysuccinimide (NHS). The as-synthesized composite exhibits multiplicative ECL efficiencies (up to 24-fold that of PeNCs) without exogenous coreactants and with excellent stability in the aqueous phase. The enhanced stability can be attributed to the well-designed heterostructure of the PeNCs@NHS-M composite, which benefits from both moiety passivation and protection of the peripheral cocrystal matrix. Moreover, the heterostructure with covalent linkage facilitates charge transfer between PeNCs and NHS-M cocrystals, realizing effective ECL emission. Meanwhile, the NHS and M components act as coreactants for PeNCs, shortening the electron-transport distance and resulting in a significant increase in the ECL signal. Furthermore, by taking advantage of the specific binding effect between NHS-M and uranyl (UO22+), an ECL system with both a low detection limit (1 nM) and high selectivity for monitoring UO22+ in mining wastewater is established. The presence of UO22+ disrupted the charge-transfer effect within PeNCs@NHS-M, weakening the ECL signals. This work provides an efficient design strategy for obtaining stable and efficient ECLs from perovskite nanocrystals, offering a new perspective for the discovery and application of perovskite-based ECL systems.

Dual Shield: Bifurcated Coating Analysis of Multilayered WO3/BiVO4/TiO2/NiOOH Photoanodes for Sustainable Solar-to-Hydrogen Generation from Challenging Waters.

The heterostructure WO3/BiVO4-based photoanodes have garnered significant interest for photoelectrochemical (PEC) solar-driven water splitting to produce hydrogen. However, challenges such as inadequate charge separation and photocorrosion significantly hinder their performance, limiting overall solar-to-hydrogen conversion efficiency. The incorporation of cocatalysts has shown promise in improving charge separation at the photoanode, yet mitigating photocorrosion remains a formidable challenge. Amorphous metal oxide-based passivation layers offer a potential solution to safeguard semiconductor catalysts. We examine the structural, surface morphological, and optical properties of two-step-integrated sputter and spray-coated TiO2 thin films and their integration onto WO3/BiVO4, both with and without NiOOH cocatalyst deposition. The J-V experiments reveal that the NiOOH cocatalyst enhances the photocurrent density of the WO3/BiVO4 photoanode in water splitting reactions from 2.81 to 3.87 mA/cm2. However, during prolonged operation, the photocurrent density degrades by 52%. In contrast, integrated sputter and spray-coated TiO2 passivation layer-coated WO3/BiVO4/NiOOH samples demonstrate a ∼88% enhancement in photocurrent density (5.3 mA/cm2) with minimal degradation, emphasizing the importance of a strategic coating protocol to sustain photocurrent generation. We further explore the feasibility of using natural mine wastewater as an electrolyte feedstock in PEC generation. Two-compartment PEC cells, utilizing both fresh water and metal mine wastewater feedstocks exhibit 66.6 and 74.2 μmol/h cm2 hydrogen generation, respectively. Intriguingly, the recovery of zinc (Zn2+) heavy metals on the cathode surface in the mine wastewater electrolyte is confirmed through surface morphology and elemental analysis. This work underscores the significance of passivation layer and cocatalyst coating methodologies in a sequential order to enhance charge separation and protect the photoanode from photocorrosion, contributing to sustainable hydrogen generation. Additionally, it suggests the potential of utilizing wastewater in electrolyzers as an alternative to freshwater resources.

UV-initiated polymerization of cationic organic flocculants and its application and mechanism in coal mine wastewater treatment

In this study, in order to improve the flocculation efficiency of natural organic flocculant in coal mine wastewater, guar gum (GG) and [2-(methacryloyloxy) ethyl] trimethyl ammonium chloride (DMC)were used to synthesize a type of graft copolymer of GG with DMC (GG-g-DMC) with flocculating function by free radical polymerization under ultraviolet (UV) light initiation conditions. Performance testing and structural characterization of the composites including FTIR, NMR, XRD, SEM, TG, and XPS were conducted to verify the synthesis of the graft polymer. The GG-g-DMC was applied to treat coal mine wastewater, according to the sedimentation index and the optimal flocculation solution was determined, and the flocculation settling mechanism was studied using focused beam reflectance measurement (FBRM), Zeta potentiometer and adhesion force meter. The results indicated that GG-g-DMC synthesis by UV-initiated polymerization was feasible and the settling effect increased significantly; 0.5 mg/g(s) GG-g-DMC 4 was excellent in all aspects, its sedimentation speed reached 20.64 cm/min, the light transmittance was 95.00%, and the compression layer thickness was 1.89 cm; the mechanism is mainly the synergy of charge neutralization, bridging, and improve hydrophobicity.

Self-hydrolyzing Submerged Flow Technology for Acid Coal Mine Drainage Treatment: Effective Removal of Iron Ions

In this study, mine wastewater from Leiyang, Hunan Province was taken as the research object to investigate the effect of using the method of self-hydrolytic submerged sedimentation to treat acid coal mine drainage. It was found in this study that the removal rate of sulfate ions and iron ions from the acidic coal mine drainage stock solution at pH=2.7 was very limited by self-hydrolytic sedimentation experiments relying only on pure vertical sedimentation flow treatment, but the hydrolytic treatment could greatly improve the solution environment and promote the formation of secondary minerals of sulfate ions and iron ions in the acidic coal mine drainage, which greatly improved the removal rate of iron ions. Both suspended and precipitated materials produced in the self-hydrolysis sedimentation experiments were hydroxylated iron sulfate secondary minerals- Schwertmannite [Fe8O8(OH)8-2X(SO4)X (1 ≤ x ≤ 175)], the formation of which is inextricably linked to the low pH environment and high concentration of sulfate and iron ions in coal mine wastewater. Self-hydrophoretic submerged flow can remove iron ions from acidic coal mine drainage at low cost and high efficiency, and the total iron removal rate of this system can reach 90.93% after 24 h of treatment, which has a favorable comprehensive utilization value.