Municipal solid waste incineration fly ash (MSWI FA) and granulated lead smelting slag (GLSS) are toxic industrial wastes. In the present study, granulated lead smelting slag (GLSS) was pretreated as a geopolymer precursor through the high-energy ball milling activation process, which could be used as a geopolymeric solidification/stabilization (S/S) reagent for MSWI FA. The S/S process has been estimated through the physical properties and heavy metals leachability of the S/S matrices. The results show that the compressive strength of the geopolymer matrix reaches 15.32 MPa after curing for 28 days under the best parameters, and the physical properties meet the requirement of MU10 grade fly ash brick. In addition, the toxicity characteristic leaching procedure (TCLP) test results show that arsenic and heavy metals are immobilized effectively in the geopolymer matrix, and their concentrations in the leachate are far below the US EPA TCLP limits. The hydration products of the geopolymer binder are characterized by X-ray diffraction and Fourier transform infrared methods. The results show that the geopolymer gel and Friedel’s salt are the main hydration products. The S/S mechanism of the arsenic and heavy metals in the geopolymer matrix mainly involves physical encapsulation of the geopolymer gel, geopolymer adsorption and ion exchange of Friedel’s salt.

Arsenic sulfide residue (ASR), a by-product from the treatment of arsenic-bearing acidic wastewater, is abundantly generated but not properly disposed of in China. The utilization of such high-content arsenic waste residue is limited by the market. The traditional methods of stabilization/solidification (S/S) by lime cement or iron salt have a large mass/volume addition, high dumping cost and secondary pollution risk. In this paper, hydrothermal technology was used to treat three kinds of ASRs obtained from different smelters to minimize waste. The leaching toxicity and chemical speciation of the generated products was also evaluated by TCLP and BCR analyses. It was found that the hydrothermal treatment could greatly reduce the volume and moisture content of the ASRs. TCLP tests showed that the leachability of arsenic and heavy metals significantly decreased after the treatment. According to the BCR analysis, most of the unstable As, Cd and Cr transformed into a residual fraction. Finally, XRD, SEM, Raman and XPS techniques were carried out to reveal the mechanism. As a result, hydrothermal treatment can efficiently achieve the dehydration, volume reduction and stabilization/solidification of ASRs.

Non-ferrous metal smelting enterprises produce hundreds of thousands of tons of arsenic sulfide sludge (ASS) each year in China. Most of the ASS are stored at the companies without enough preventive measures. During the storage and natural drying process, arsenic sulfide is easily oxidized, thereby causing secondary pollution and increasing environmental risks. In this paper, experiments of simulated storage were used to study the release characteristics of heavy metals. During the simulated storage, the release concentrations of As, Pb, and Cd increased rapidly at first and then slowly. Although the total amount of arsenic released was the largest, the release ratio was in the order of Cd > Pb > As. The effects of different atmospheres and conditions on the release of arsenic and heavy metals were explored. The more the H₂SO₄ in the sludge, the higher the release concentration, and the addition of an appropriate amount of Ca(OH)₂ is beneficial for reducing the release of heavy metals. Finally, SEM, XRD and TG-DTG techniques were carried out to confirm that the release of heavy metals was caused by the oxidation process resulting from the residual H₂SO₄ in the ASS and the air.

Sulfide precipitation has been widely applied to remove arsenic from acidic wastewater containing As(III) and As(V), due to its simple process and high efficiency. However, the characteristics and composition of the precipitates are also of importance for its further treatment and disposal. To explore the characteristics of elemental S formed by reduction and the combined form of the generated S and As₂S₃, the characteristics of precipitates sulfurized from As(III) and As(V) and the effects of temperature, the S(-II) to As ratio (S/As), Cl⁻ concentration (c_Cl−), and the volume fraction of H₂SO₄ (φ_H2SO4(v)) on the sulfurization of As(III) and As(V) were investigated in detail. The results showed that the contents of As and S were 60.37% and 39.73% in precipitate-As(III), while they accounted for 47.46% and 52.64% in precipitate-As(V); both precipitate-As(III) and precipitate-As(V) were mainly composed of amorphous As₂S₃, while the latter contained elemental S. Temperature and S(-II)/As(III) slightly affected the sulfurization process of As(III), while for As(V), as the temperature increased, the content of As₂S₃ in precipitate-As(V) increased significantly. Additionally, with the S(-II)/As(V) increasing, the content of A₂S₃ increased continuously. This study provides a further clarification of the specific composition and structure of the complex precipitates of arsenic sulfide, which will benefit the efficient stabilization of the arsenic sulfide sludge.

Lead smelting slag (LSS) has been identified as general industrial solid waste, which is produced from the pyrometallurgical treatment of the Shuikoushan process for primary lead production in China. The LSS-based geopolymer was synthesized after high-energy ball milling. The effect of unconfined compressive strength (UCS) on the synthesis parameters of the geopolymer was optimized. Under the best parameters of the geopolymer (modulus of water glass was 1–1.5, dosage of water glass (W(SiO₂+Na₂O)) was 5% and water-to-binder ratio was 0.2), the UCS reached 76.09 MPa after curing for 28 days. The toxicity characteristic leaching procedure (TCLP) leaching concentration of Zn from LSS fell from 167.16 to 93.99 mg/L after alkali-activation, which was below the limit allowed. Meanwhile, C-S-H and the geopolymer of the hydration products were identified from the geopolymer. In addition, the behavior of iron was also discussed. Then, the hydration process characteristics of the LSS-based geopolymer were proposed. The obtained results showed that Ca²⁺ and Fe²⁺ occupied the site of the network as modifiers in the glass phase and then dissociated from the glass network after the water glass activation. At the same time, C-S-H, the geopolymer and Fe(OH)₂ gel were produced, and then the Fe(OH)₂ was easily oxidized to Fe(OH)₃ under the air curing conditions. Consequently, the conclusion was drawn that LSS was an implementable raw material for geopolymer production.