Application of dirty-acid wastewater treatment technology in non-ferrous metal smelting industry: Retrospect and prospect.

Dirty-acid wastewater (DW) originating from the non-ferrous metal smelting industry is characterized by a high concentration of H2SO4 and As. During the chemical precipitation treatment, a significant volume of arsenic-containing slag is generated, leading to elevated treatment expenses. The imperative to address DW with methods that are cost-effective, highly efficient, and safe is underscored. This paper conducts a comprehensive analysis of three typical methods to DW treatment, encompassing technical principles, industrial application flow charts, research advancements, arsenic residual treatment, and economic considerations. Notably, the sulfide method emerges as a focal point due to its minimal production of arsenic residue and the associated lowest overall treatment costs. Moreover, in response to increasingly stringent environmental protection policies targeting new pollutants and carbon emissions reduction, the paper explores the evolving trends in DW treatment. These trends encompass rare metal and sulfuric acid recycling, cost-effective H2S production methods, and strategies for reducing, safely disposing of, and harnessing resources from arsenic residue.

Remediation of arsenic contaminated water and soil using mechanically (ball milling) activated and pyrite-amended electrolytic manganese slag.

With the development of industry, heavy metal (HM) pollution of soil has become an increasingly serious problem. Using passivators made of industrial by-products to immobilize HMs in contaminated soil is a promising in-situ remediation technology. In this study, the electrolytic manganese slag (EMS) was modified into a passivator (named M-EMS) by ball milling, and the effects of M-EMS on adsorption of As(V) in aquatic samples and on immobilization of As(V) and other HMs in soil samples were investigated under different conditions. Results demonstrated that M-EMS had a maximum As(V) adsorption capacity of 65.3 mg/g in the aquatic samples. Adding M-EMS to the soil reduced the leaching of As (from 657.2 to 319.8 µg/L) and other HMs after 30 d of incubation, reduced the bioavailability of As(V) and improved the quality and microbial activity of the soil. The mechanism for M-EMS to immobilize As in the soil are complex reactions, ion exchange reaction with As and electrostatic adsorption. This work provides new ideas of using waste residue matrix composites for sustainable remediation of Arsenic in the aquatic environment and soil.

Strategy of optimizing anaerobic digestion of cassava distiller wastewater using a novel automatic biological incubation system.

Due to the drawbacks of using fossil fuels and the need to mitigate global warming caused by increasing greenhouse gas emissions, agricultural biomass for bioenergy production is gaining great interest around the world. This work presented a study at a biochemical plant in Lianyungang, Jiangsu Province, China to maximize methane production from cassava distiller wastewater. The plant's annual production of cassava distiller wastewater is more than 3 million tons and currently was treated using a series of 5000 m3 Internal Circulation (IC) reactors. Modification was applied at No.19 IC reactor by connecting it to two 1 m3 automatic biological incubators called Information Bio-Booster (IBB). The effluent of the IC reactor was fed into the IBBs and iron, cobalt and nickel were added directly in the IBBs. The function of the IBBs was to regulate the microbial community. Afterwards, the microorganisms in the IBBs were pumped back into the IC reactor to participate in the methane production reaction. Daily net increase of methane content and COD removal reached 8.02% and 33% respectively in No.19 IC reactor comparing to the unadjusted reactors. Preliminary lab experiments found that improvements of biogas production, enhanced COD removal and VS removal was closely related to the enhancement of anaerobic microbial communities' diversity and the promotion of enzyme activity through the addition of the metal salts. Daily economic value could be estimated to be $218 which indicated the application potential of using the proposed system to enhance anaerobic digestion at industrial plants for bioenergy production.

Comparative transcriptome combined with metabolome analyses revealed key factors involved in nitric oxide (NO)-regulated cadmium stress adaptation in tall fescue.

BACKGROUND: It has been reported that nitric oxide (NO) could ameliorate cadmium (Cd) toxicity in tall fescue; however, the underlying mechanisms of NO mediated Cd detoxification are largely unknown. In this study, we investigated the possible molecular mechanisms of Cd detoxification process by comparative transcriptomic and metabolomic approaches. RESULTS: The application of Sodium nitroprusside (SNP) as NO donor decreased the Cd content of tall fescue by 11% under Cd stress (T1 treatment), but the Cd content was increased by 24% when treated with Carboxy-PTIO (c-PTIO) together with Nitro-L-arginine methyl ester (L-NAME) (T2 treatment). RNA-seq analysis revealed that 904 (414 up- and 490 down-regulated) and 118 (74 up- and 44 down-regulated) DEGs were identified in the T1 vs Cd (only Cd treatment) and T2 vs Cd comparisons, respectively. Moreover, metabolite profile analysis showed that 99 (65 up- and 34-down- regulated) and 131 (45 up- and 86 down-regulated) metabolites were altered in the T1 vs Cd and T2 vs Cd comparisons, respectively. The integrated analyses of transcriptomic and metabolic data showed that 81 DEGs and 15 differentially expressed metabolites were involved in 20 NO-induced pathways. The dominant pathways were antioxidant activities such as glutathione metabolism, arginine and proline metabolism, secondary metabolites such as flavone and flavonol biosynthesis and phenylpropanoid biosynthesis, ABC transporters, and nitrogen metabolism. CONCLUSIONS: In general, the results revealed that there are three major mechanisms involved in NO-mediated Cd detoxification in tall fescue, including (a) antioxidant capacity enhancement; (b) accumulation of secondary metabolites related to cadmium chelation and sequestration; and (c) regulation of cadmium ion transportation, such as ABC transporter activation. In conclusion, this study provides new insights into the NO-mediated cadmium stress response.

Toxicity of soil labile aluminum fractions and aluminum species in soil water extracts on the rhizosphere bacterial community of tall fescue.

Different forms of aluminum (Al) in soil can be toxic to plants and the bacterial community. In our previous study, the distribution and toxicity to plants of soil Al species and soil labile Al fractions were examined. However, the toxicity of different forms of Al on the bacterial community has not been completely studied. In this study, five soil samples (pH: 4.92, 6.17, 6.62, 6.70, 8.51) were collected from Lichuan, China. Tall fescue was planted in rhizosphere boxes with those soils for 120 days. The toxicity of soil Al species and soil labile Al fractions on the bacterial community of near-rhizosphere (NR) soils and far-rhizosphere (FR) soils were analyzed. The effect of different forms of Al on bacterial community between NR and FR soils was small, but the difference was obvious according to the different spatial distribution of samples. An individual bacterial community has eosinophilia, and most bacterial communities are tolerant of heavy metals (e.g., Cu, Zn, Cd). The toxicity of exchangeable Al has a strong effect on the bacterial community. Meanwhile, the toxicity of Al3+ to the bacterial community is strong. In this study, the key finding was that the toxicity of the Al-F- complex toward the bacterial community and plants was different. AlF2+, AlF2+, AlF3, and AlF4- are toxic for the bacterial community, and the correlation decreases with the addition of F-. This finding is of considerable significance to the treatment of acid-contaminated soil and the study of the tolerance mechanism of plants toward Al.

Bioleaching of silicon in electrolytic manganese residue using single and mixed silicate bacteria.

Electrolytic manganese residue (EMR) is a type of industrial solid waste with a high silicon content. The silicon in EMR can be used as an essential nutrient for plant growth, but most of the silicon is found in silicate minerals with very low water solubility, that is, it is inactive silicon and cannot be absorbed and used by plants directly. Thus, developing a highly effective and environmentally friendly process for the activation of silicon in EMR is important both for reusing solid waste and environmental sustainability. The aim of this study was to investigate the desilication of EMR using cultures of Paenibacillus mucilaginosus (PM) and Bacillus circulans (BC). The results showed that the two types of silicate bacteria and a mixed strain of them were all able to extract silicon from EMR with a high efficiency, but the desilication performance of the mixed PM and BC was the best. Fourier transform infrared spectroscopy indicated that silicate bacteria can induce a suitable micro-environment near the EMR particles and release Si into the solution through their metabolism. X-ray diffraction analysis confirmed that layered crystal minerals, such as muscovite and diopside, were more likely to be destroyed by the bacterial action than quartz, which has a frame structure. Scanning electron microscopy-energy dispersive spectrometry proved that the silicate structures were destroyed and that Si in the residue was decreased, indicating the dissolution of silicon under the action of these microorganisms. This study suggests that bioleaching may be a promising method for the activation of silicon in EMR.

Nitric oxide alleviates toxicity of hexavalent chromium on tall fescue and improves performance of photosystem II.

Tall fescue (Festuca arundinacea Schreb) was widely studied for phytoremediation of organic or heavy metal contaminated soils. However, there is still little information concerning toxicity of chromium (Cr) to tall fescue and roles of nitric oxide (NO) in plants against Cr(VI) stress. In this study, different Cr(VI) treatments (0, 1, 5 and 10 mg/L Cr(VI)) and NO treatments were applied with different combinations in hydroponics culture and their interactions to tall fescue were studied. Specifically, 100 µM sodium nitroprusside (SNP) and 100 µM NG-nitro-L-arginine-methyl ester (L-NAME) treatments were used to apply exogenous NO or inhibit synthesis of NO respectively. Our results showed that tall fescue exhibits comparable Cr(VI) tolerance as wheat (Triticum aestivum L.). Additionally, Cr(VI) accumulation in tall fescue leaves were carefully studied and discussed. Moreover, we observed the significantly increased reactive oxygen species (ROS) contents of tall fescue when subjected to Cr(VI) stress, as well as decreased photosynthetic activities induced by Cr(VI) stress by methods of chlorophyll a fluorescence transient, slow chlorophyll fluorescence kinetics and rapid light response curves. Decreased behaviors of photosynthetic activities may due to destruction of antennae pigments by Cr(VI), ROS burst induced by Cr(VI), and down regulation of photosystem II (PSII) by non-photochemical quenching to avoid over reduction of quinone A, which could be considered as an important strategy to cope with Cr(VI) stress. Meanwhile, exogenous NO treatment improves overall physiological and photosynthetic behaviors of tall fescue against Cr(VI) stress. Moreover, increased translocation factors and improved Cr(VI) tolerance of plants under exogenous NO treatment suggest that SNP treatment could be a useful application for Cr phytoremediation.

Transcriptome analysis providing novel insights for Cd-resistant tall fescue responses to Cd stress.

Cadmium (Cd) is a severely toxic heavy metal and environmental pollutant. Tall fescue is a cold season turf grass which has high resistance to Cd as well as the ability to enrich it. To investigate the molecular mechanism underlying the adaptability of tall fescue to Cd stress, RNA-Seq was used to examine Cd stress responses of tall fescue at a transcriptional level. A total of 12 cDNA libraries were constructed from the total RNA of roots or leaves of tall fescue with or without Cd treatments. A total of 2594 (1768 up- and 826 down-regulated) differentially expressed genes (DEGs) were detected in the roots of Cd-stressed tall fescue compared with control roots (R_cd vs R_ck), while only 52 (29 up- and 23 down-regulated) DEGs were found in the leaves of Cd-stressed plants versus the controls (L_cd vs L_ck). The genes encoding glutathione S-transferase (GST), transporter proteins including the ABC transporter, ZRT/IRT-like protein, potassium transporter/channel, nitrate transporter, putative iron-phytosiderophore transporter, copper-transporting ATPase or transporter and multidrug and toxic compound extrusion (MATE) proteins, and numerous transcription factors were found to be significantly induced in Cd-treated roots. In addition, pathogenesis/disease-related gene mRNAs were accumulated in Cd-treated roots of tall fescue. Furthermore, the significantly enriched KEGG pathways in roots were related to 'Glutathione metabolism', 'Ribosome', 'alpha-Linolenic acid metabolism', 'Diterpenoid biosynthesis', 'Sulfur metabolism', 'Phenylpropanoid biosynthesis', 'Protein processing in endoplasmic reticulum', 'Protein export' and 'Nitrogen metabolism'. The study provides novel insights for further understanding the molecular mechanisms of tall fescue responses to Cd stress.

Pretreatment of piggery wastewater by a stable constructed microbial consortium for improving the methane production.

A stable aerobic microbial consortium, established by successive subcultivation, was employed to solubilize the solid organic fraction in swine wastewater. In the 30 days' successive biological pretreatments, 30-38% of volatile solids and 19-28% total solids in raw slurry were solubilized after 10 hours at 37 °C. Meanwhile, soluble chemical oxygen demand (COD) and volatile fatty acid increased by 48%-56% and 600%-750%, respectively. Furthermore, the molecular microbial profile of the consortium in successive pretreatment was conducted by denaturing gradient gel electrophoresis (DGGE). The results indicated that bacterial species of the consortium rapidly overgrew the indigenous microbial community of raw water, and showed a stable predominance at the long-term treatment. As a consequence of biological pretreatment, pretreatment shortened digestion time by 50% and increased biogas production by 45% compared to raw water in the anaerobic process. The microbial consortium constructed herein is a potential candidate consortium for biological pretreatment of swine wastewater to enhance biogas production.

Combined impact of antibiotics and Cr(VI) on antibiotic resistance, ARGs, and growth of Bacillussp. SH-1: A functionl analysis from gene to protease.

The simultaneous selection of antibiotic resistance genes (ARGs) induced by heavy metals and antibiotics has emerged as a growing environmental problem. This study investigated the combined effects of chromium (Cr(VI)) and antibiotics on the ARGs of Bacillus cereus SH-1. As Cr(VI) concentration increased, it triggered reactive oxygen species oxidative stress in SH-1, increased antioxidant enzyme activity, enhanced plasmid conjugative transfer, and reduced the efficiency of Cr(VI) removal by SH-1. Antibiotic resistance varied with increasing tetracycline and amoxicillin minimum inhibitory concentrations (MICs), whereas azithromycin and chloramphenicol MICs decreased with Cr(VI) induction. The overexpression of eight genes of the HAE-1 family of efflux pumps was detected using metagenomics and proteomics. Co-contamination with Cr(VI) and antibiotics has led to the emergence and spread of antibiotic-resistant bacteria. Therefore, resistance gene contamination resulting from Cr(VI)-polluted environments cannot be overlooked.

Bio-stabilization of arsenic in sediments by natural carbon-containing biomass: Performance and microbial metabolites.

The development of sustainable methods for the control and bio-stabilization of arsenic in sediments, without generating secondary pollution, is an urgent technological need. In this study, we utilized three types of natural carbon-containing biomass (NCCB) to explore the stabilization of arsenic through the synergistic action of native sediment microbiomes. We also examined the metabolic pathways of microorganisms following the introduction of NCCB into high-arsenic sediments, aiming to elucidate the biological processes critical for arsenic bio-stabilization. Our findings indicate that humic acid (HA) and soil organic matter (SOM) are effective in preventing the leaching of As(III) from sediments, while fulvic acid (FA) and SOM can significantly reduce the leaching of As(V). Furthermore, the introduction of NCCB into the system altered the biological metabolic processes, with notable upregulation of metabolites such as 8-hydroxyondansetron, 1,2,3,5,6,8-hexathionane, and citric acid. These results hold promise for the application of these findings in the management of arsenic in natural sediments.

Ternary cycle treatment of high saline wastewater from pesticide production using a salt-tolerant microorganism.

The material of this study is provided by biological aerobic treatment of high saline wastewater from pesticide production. The microorganism used for biodegradation has been identified by gene-sequencing as a strain of Bacillus sp. SCUN. The best growth condition for the salt-tolerant microorganism has been studied by varying the pH, immobilized microorganism dosage and temperature conditions. The feasibility of pretreating wastewater in ethyl chloride production containing 4% NaCl has been discussed. It was found that under the pH range of 6.0-8.0, immobilized microorganism dosage of 1.5 g/L, temperature of 30 °C, and NaCl concentration of 0-3%, the microorganism achieves the best growth for biodegradation. After domestication, the strain can grow under 4% NaCl. This salt-tolerant microorganism is effective in the pretreated high saline wastewater. With a newly developed ternary cycle treatment, the chemical oxygen demand removal approaches 58.3%. The theoretical basis and a new method for biological treatments in biodegradation of high saline wastewater in ethyl chloride production are discussed.

Deep insight on mechanism and contribution of arsenic removal and heavy metals remediation by mechanical activation phosphogypsum.

Arsenic-containing wastewater and arsenic-contaminated soil can cause serious environmental pollution. In this study, phosphogypsum with partial mechanical activation of calcium oxide was used to prepare a new phosphogypsum-based passivate (Ca-mPG), and its remediation performance on arsenic-contaminated soil was evaluated in terms of both effectiveness and microbial response. The results showed that the optimum conditions for the preparation of the passivate were optimized in terms of single factor and response surface with a ball milling speed of 200 r/min, a material ratio of 6:4 and a ball milling time of 4 h. Under these conditions, the adsorption capacity was 37.75 mg/g. The leaching concentration of arsenic (As) in the contaminated soil after Ca-mPG modification decreased from 25.75 µg/L to 5.88 µg/L, which was lower than the Chinese national standard (GB/T 5085.3-2007); Ca-mPG also showed excellent passivation effect on other heavy Metals (copper, nickel, cadmium, zinc). In addition, As-resistant bacteria and passivators work together to promote the stabilization effect of contaminants during the remediation of As-contaminated soil. The mechanisms of Cu, As(III)/As(V), Zn, Cd, and Ni removal were related to ion exchange, electrostatic adsorption of substances on heavy metals, calcium binding to other substances to produce precipitation; and microbially induced stabilization of HMs, oxidized. Overall, this study demonstrates an eco-friendly "waste-soil remediation" strategy to solve problems associated with solid waste reuse and remediation of HM-contaminated soils.

Simultaneous immobilization of multiple heavy metals in polluted soils amended with mechanical activation waste slag.

Heavy metal soil contamination has become an increasingly serious problem in industrial development. However, industrial byproducts used for remediation are one aspect of green remediation that can contribute to sustainable practices in waste recycling. In this study, electrolytic manganese slags (EMS) were mechanically activated and modified into a passivator (M-EMS), and the heavy metal adsorption performance of M-EMS, heavy metal passivation ability in soil, dissolved organic matter (DOM) change and its effect on the microbial community structure of soil were investigated. The findings revealed that the maximum adsorption capacities of As(V), Cd2+, Cu2+ and Pb2+ were 76.32 mg/g, 301.41 mg/g, 306.83 mg/g and 826.81 mg/g, respectively, indicating that M-EMS demonstrated remarkable removal performance for different heavy metals. The Langmuir model fits Cd2+, Cu2+ and Pb2+ better than the Freundlich model, and monolayer adsorption is the main process. Surface complexation played a major role in the As(V) adsorption's on the surface of metal oxides in M-EMS. The passivation effect was ranked as Pb > Cr > As>Ni > Cd > Cu, with the highest passivation rate of 97.59 % for Pb, followed by Cr (94.76 %), then As (71.99 %), Ni (65.17 %), Cd (61.44 %), and the worst one was Cu (25.17 %). In conclusion, the passivator has the effect of passivation for each heavy metal. The addition of passivating agent can enhance the diversity of microorganisms. Then it can change the dominant flora and induce the passivation of heavy metals through microorganisms. XRD, FTIR, XPS and the microbial community structure of soil indicated that M-EMS can stabilize heavy metals in contaminated soils through four main mechanisms: ion exchange, electrostatic adsorption, complex precipitation and the microbially induced stabilization. The results of this study may provide new insights into the ecological remediation of multiple heavy-metal-contaminated soils and water bodies and research on the strategy of waste reduction and harmlessness by using EMS-based composites in combination with heavy metals in soil.

Preparation of phosphogypsum-copper smelting slag-based consolidating body with high compressive strength.

Phosphogypsum (PG) is an industrial waste residue produced during the production of phosphoric acid through the wet process. With strong acidity and a large amount of toxic impurities, PG is difficult to reuse. In this study, the solidified body (PG-S) was made by mechanical compression of the mixture of PG, copper smelting slag (CSS), CaO, NaOH, and water. Results indicate that the composition of the material phases in the PG-S samples changed with hydrated calcium silicate and amorphous silicate derivatives were formed during the reaction; Fe and Ca in the material were transformed; and the prepared geopolymer material had a dense internal structure with the materials being cemented to each other. The highest compressive strength of PG-S cured for 28 days could reach 21.3 MPa with a fixation efficiency of PO43-and F-reaching 99.81 and 94.10%, respectively. The leaching concentration of heavy metals of the PG-S cured for 28 days met the requirements of the Comprehensive Wastewater Discharge Standard (GB 8978-1996). The simulation results of the geochemical model verified the feasibility of the whole immobilization process from the thermodynamic point of view. This work directly uses copper smelting slag and phosphogypsum for coupled immobilization/stabilization treatment not only to achieve the immobilization of pollutants in both solid wastes but also to obtain colloidal masses with certain compressive strength, which also provides a new option for resource utilization of phosphogypsum and copper smelting slag. This work also shows great potential in turning the actual mine backfill into cementitious material.

Insight into the role and mechanism of polysaccharide in polymorphous magnesium oxide nanoparticle synthesis for arsenate removal.

The low cost and non-toxic of magnesium oxides make it a potential eco-friendly material for arsenic removal. Polysaccharide is a kind of green modifier to obtain nanoscale MgO particles with a higher adsorption affinity. In this study, the impact of chain structures of polysaccharides on the morphology features and arsenate removal efficiency of MgO-NPs were investigated. Pullulan and starch facilitated the synthesis of flower-like MgO-NPs, and pectin facilitated the synthesis of plate-like ones. Although the two kinds of flower-like MgO-NPs undergone similar time to reach equilibrium, the one obtained from the starch-synthesis route showed a higher arsenate adsorption capacity (98 mg g-1), due to that their bushy and smaller petals on the surface provide more active sites for arsenic adsorption. The pectin-synthesis route also produced MgO-NPs with higher arsenate adsorption capacity (101 mg g-1), ascribed to stacking of nano-plates on their surfaces facilitated to form defect surfaces. However, due to their lower BET area, the plate-like MgO-NPs took twice times to reach equilibrium for arsenic adsorption compared with the others. In the stage for the hydrolysis of MgO, hydroxyl groups on the polymer chain provide active sites to physically trap or bond with MgO particles and then to produce hydrolyzed precursors. The poly chain containing inter- and intra-hydroxyl groups directed MgO molecular growing into hydroxide crystals with 3D frameworks during their nucleation and growth. However, pectin only provides inter-hydroxyl groups and directs to form hydroxides with 2D frameworks. Furthermore, the rapid-nucleation vs. slow-growth model in the stage of pyrolysis of hydroxide crystals successfully interprets the thinner petals and complex chemical phases of the final nanoparticles obtained from the pullulan-synthesis route. This work may provide direction and perspectives for the rational design of well-performing MgO materials for arsenate removal.

Highly efficient removal of Cr(VI) from aqueous solution by pinecone biochar supported nanoscale zero-valent iron coupling with Shewanella oneidensis MR-1.

Nanoscale zero-valent iron (nZVI) has been extensively used to remove various pollutants. However, the rapid deactivation due to aggregation and surface passivation severely limits its practical application. In this study, a novel composite with nZVI supported by pinecone biochar (nZVI-PBC) was successfully synthesized and used for the removal of high concentration Cr(VI) from aqueous solution in the presence of Shewanella oneidensis MR-1 (MR-1). The results showed that the nZVI-PBC coupling with MR-1 (nZVI-PBC/MR-1) exhibited an excellent removal performance for high concentration Cr(VI) compared to the nZVI-PBC alone. Under optimal conditions, 100 mg/L Cr(VI) could be removed completely by nZVI-PBC/MR-1 within 48 h, while only 39.50% of Cr(VI) was removed by nZVI-PBC alone. The improvement of Cr(VI) removal is due to the dissolution of the surface passivation layer of nZVI-PBC, formation of sorbed Fe(II) in the presence of MR-1, and an important role of extracellular polymeric substance (EPS) derived from MR-1. X-ray photoelectron spectroscopy (XPS) and Cr K-edge X-ray absorption near-edge structure spectra (XANES) confirmed that most Cr(VI) was reduced to insoluble Cr(III) and formed Cr2O3, CrxFe1-x(OH)3 and FeCr2O4 precipitates, and a small amount of unreduced Cr(VI) was immobilized through adsorption and complexation. The results suggest that nZVI-PBC/MR-1 can effectively overcome the limitations of nZVI and achieve highly efficient removal of high concentration Cr(VI).

Uptake of arsenic(V) using iron and magnesium functionalized highly ordered mesoporous MCM-41 (Fe/Mg-MCM-41) as an effective adsorbent.

Mesoporous silica (MCM-41) is widely used as a supporting material due to its large specific surface area and good stability, but it cannot remove heavy metals due to the lack of adsorption active sites. In this study, the MCM-41 (a mesoporous SiO2 material) decorated with iron and magnesium oxide (Fe/Mg-MCM-41) was found to be an excellent adsorbent to remove arsenic(V) from water. FTIR, BET, TEM-EDS, XRD, XPS, etc. were applied for characterization analysis. Adsorption isotherms were fitted well by the Langmuir model and the experimental maximum adsorption capacity of Fe/Mg4-MCM-41 (magnesium accounts for 4%) was 71.53 mg/g at pH = 3. Thermodynamics analysis suggested exothermic nature of adsorption behavior. Kinetic process was well described by the pseudo-second-order model and adsorption rate was controlled by intraparticle diffusion and film diffusion. Moreover, the adsorption behavior of As(V) onto Fe/Mg4-MCM-41 was investigated under different reaction conditions, such as pH, temperature, Mg-doping and competing ions. The results showed that loading a certain amount of magnesium can significantly improve arsenic removal efficiency. Additionally, Fe/Mg4-MCM-41 exhibits high arsenic(V) removal in the wide pH range of 3-10. The Fe/Mg4-MCM-41 can be regenerated and used after four consecutive cycles. The high arsenic(V) sorption capacity, wide range of pH applications, ability to regenerate, and reusability of Fe/Mg4-MCM-41 confirmed that this adsorbent is promising for treating As-contaminated wastewater.

Mechanochemical activation on selective leaching of arsenic from copper smelting flue dusts.

A novel application, including mechanochemical pre-treating and alkali leaching, for arsenic selective leaching from copper smelter flue dusts (CSFUs) was developed to overcome the disadvantages of hydrometallurgical methods. Compared with raw CSFU powders, the mechanical-activated ones showed higher maximum arsenic leaching efficiency (increased by ~20%), and lower apparent activation energy (decreased by ~7 kJ·mol-1). Furthermore, this novel process only consumed half of alkali and sulfides and needed one-third of the leaching time to compare with the ones used in the traditional alkali leaching process. The promoting effect of mechanical force on arsenic leaching firstly relied on the physical property changes of CSFU powders, including a decrease of particle sizes and an increase of the specific surface. Secondly, mechanochemical force converted As5+ species into reduced phases (e.g. As2O3, NaAsO2), and thio-arsenates (e.g. AsO2S23-, AsO3S3-), which could spur its leaching due to their stronger mobilities in the alkali solution within sulfides. Finally, mechanochemical activation could be facilitated to separate discrete soluble arsenic species or incorporated ones from sulfate minerals in the CSFUs. This work may have important implications for the development of new eco-friendly technologies for purifying arsenic-bearing materials.

A novel method for solidification/stabilization of Cd(II), Hg(II), Cu(II), and Zn(II) by activated electrolytic manganese slag.

This study was aimed at removing and stabilizing heavy metals (HgII, ZnII, CuII, and CdII). A novel material (named A-EMS) for heavy metal removal was proposed by ball grinding activated electrolytic manganese slag (EMS) with low content of sodium hydroxide. For different application scenarios, the two physical properties of the materials were developed: the powdery A-EMS (powder) was used to remove heavy metals from wastewater. In addition, the blocky A-EMS (porous brick) was used to build barrier walls for tailings ponds to prevent heavy metals from flowing out. The maximum removal amount of Hg(II) Cd(II), Zn(II), and Cu(II) by A-EMS were 475.35, 77.72, 259.70, and 203.20 mg/g in 30 min. The heavy metals ions were removed and fixed on A-EMS mainly through ion exchange and some forms of electrostatic adsorption and hydroxyl complexation. After consolidating the heavy metals, the compressive strength of the materials can reach 20 Mpa and the leaching toxicity met the national standard of China (GB/T 3838-2002) in 60 days. These excellent properties made A-EMS widely used to remove heavy metals in wastewater and to intercept and solidify heavy metals in mine wastewater.