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The present study provided an innovative insight into the formation mechanism of persistent free radicals (PFRs) during the pyrolysis of Fenton-conditioned sludge. Fenton conditioners simultaneously improve the dewatering performance of sewage sludge and catalyze the pyrolysis of sewage sludge for the formation of PFRs. In this process, PFRs with a total number of spins of 9.533×10 19 spins/g DS could be generated by pyrolysis of Fenton-conditioned sludge at 400°C. The direct thermal decomposition of natural organic matter (NOM) fractions contributed to the formation of carbon-centered radicals, while the Maillard reaction produced phenols precursors. Additionally, the reaction between aromatic proteins and iron played a crucial role in the formation of phenoxyl or semiquinone-type radicals. Kinetics analysis using discrete distributed activation energy model (DAEM) demonstrated that the average activation energy for pyrolysis was reduced from 178.28 kJ/mol for raw sludge to 164.53 KJ/mol for Fenton conditioned sludge. The reaction factor (f i ) indicated that the primary reaction in Fenton-conditioned sludge comprised of 27 parallel first-order reactions, resulting from pyrolysis cleavage of the NOM fractions, the Maillard reaction, and iron catalysis. These findings are significant for understanding the formation process of PFRs from NOM in Fenton-conditioned sludge and provide valuable insight for controlling PFRs formation in practical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Arsenic-alkali residue (AAR) from antimony production can pose significant health and environmental hazards due to the risk of arsenic (As) leaching. In this study, geopolymer composite synthesized from fly ash (FA) was investigated for efficient stabilization of high-arsenic-containing AAR (As 2 O 3 of 22.74 wt%). Two industrial wastes, e.g., granulated blast furnace slag (GBFS) with active calcium composition and water-quenched slag (WQS) from lead-zinc smelting with active iron composition, were investigated for the reinforcement of AAR geopolymer solidification. A wide pH stabilization (from pH = 3–pH = 12) of AAR with the geopolymer composite was successfully achieved, and As leaching concentration of geopolymer with the addition of 5 wt% AAR was significantly reduced from 2343.73 mg/L (AAR) to that below 0.18 mg/L, which successfully meet the regulatory limit of Chinese domestic waste landfill (GB, 18598−2019, 1.2 mg/L) and hazardous waste landfill (GB16889-2008, 0.3 mg/L). Johnbaumite (Ca 5 (AsO 4) 3 (OH)) was formed in geopolymer composite and leached samples with initial pH from 2.6 to 6 (final pH from 5.54 to 13.15). Magnetite and iron hydroxide phases with strong adsorption and/or As co-precipitation capability were also observed. As stabilization was also achieved with iron oxidation from As(III) to As(V). This study solves the problem of unstable As leaching at different pH for the solidification of arsenic-bearing solid waste, and provides a promising and practical strategy for efficient solidification/stabilization of AAR as well as other similar arsenic-bearing solid wastes with geopolymer composite. [Display omitted] • A wide pH stabilization of AAR with geopolymer composite was achieved. • As stabilization was achieved with iron oxidation from As(III) to As(V). • As leaching concentration of 0.18 mg/L was obtained. • (Ca 5 (AsO 4) 3 (OH)) was formed in leached samples with initial pH from 2.6 to 6. • The stabilization mechanism of As in geopolymer is mainly physical embedding. [ABSTRACT FROM AUTHOR]

Sulfidated nanoscale zero-valent iron (S-nZVI) has shown excellent removal capacity for the removal of cadmium (Cd) in aqueous phase. Herein, the effectiveness and the mechanism of S-nZVI for the remediation of Cd contaminated soil were investigated for the first time. The results of sequential extraction procedures (SEP) showed that the exchangeable (EX) Cd was decreased by over 97.6% at the optimal dosage of 5 g kg-1 S-nZVI during 30 d incubation and converted to less available Cd such as iron-manganese oxides-bound (OX) and organic matter-bound (OM) fractions. pH has negligible effect on the immobilization of Cd in soil, since OX fraction was stabilized in the range of 72–92% at initial soil pH range from 5.3 to 7.5. SEM-EDS analysis of the separated magnetic particles implied that Cd was successfully enriched on S-nZVI and the distribution of Cd was closely related to Fe, S, and O. CdO and CdS was confirmed as the key products for Cd immobilization in soil. Meanwhile, the S-nZVI was oxided to α-FeOOH, γ-FeOOH, and γ-Fe 2 O 3. The existence of CdO was visibly related to the iron oxides, suggesting the synergetic immobilization effect by iron oxides. Overall, S-nZVI was promising for the remediation of Cd-contaminated soil. [Display omitted] ● S-nZVI could effectively remediate Cd-contaminated soil. ● Exchangeable Cd fraction sharply decreased from 73% to below 1% at 3 h. ● Initial soil pH value showed a slight effect on Cd immobilization by S-nZVI. ● A potential mechanism for Cd immobilization was illustrated. [ABSTRACT FROM AUTHOR]

In this study, the reaction between sulfidated nanoscale zero-valent iron (S-nZVI) and heavy metal cations as well as the role of sulfur were investigated. The results showed the corrosion products of S-nZVI were lepidocrocite (γ -FeOOH) or/and magnetite (Fe 3 O 4), depending on heavy metal species. While the removal of Hg(II), Ag(I), Cu(II), and Pb(II) by S-nZVI was rapid and could achieve over 99% within 5 mins, the removal of Ni(II) and Zn(II) was low in efficiency and unstable. Sulfur was existed as iron sulfides at fresh S-nZVI, but was displaced by the heavy metals and formed the related sulfide compound, or oxidized to S0 and SO 4 2-. The removal mechanisms are strongly dependent on the solubility product constant (K sp) of metal sulfides. For Hg(II) and Ag(I), with K sp of corresponding metal sulfides much lower than that of iron sulfide, the removal mechanism is the displacement reaction. For Cu(II) and Pb(II), with K sp of corresponding metal sulfides moderately lower than that of iron sulfide, the removal mechanisms are the displacement reaction and complexation with surface groups of S-nZVI. For Zn(II) and Ni(II), whose K sp of corresponding metal sulfides slightly lower than that of iron sulfide, are mainly removed by complexation with surface groups of S-nZVI. ga1 The mechanism between heavy metal cations and sulfidated nanoscale zero-valent iron (S-nZVI) • S-nZVI was highly efficient for the removal of Hg(II), Ag(I), Cu(II), and Pb(II). • The role of sulfur during heavy metal cations removal by S-nZVI was investigated. • The removal mechanisms were significantly related to the metal sulfide K sp. [ABSTRACT FROM AUTHOR]