Effect of long-term dry-wet circulations on the Solidification/stabilization of Municipal solid waste incineration fly ash using a novel cementitious material.

Solidification/stabilization (S/S) is a typical technique to immobilize toxic heavy metals in Municipal solid waste incineration fly ash (MSWI FA). This study utilized blast furnace slag, steel slag, desulfurization gypsum, and phosphoric acid sludge to develop a novel metallurgical slag based cementing material (MSCM). Its S/S effects of MSWI FA and long-term S/S effectiveness under dry-wet circulations (DWC) were evaluated and compared with ordinary Portland cement (OPC). The MSCM-FA block with 25 wt.% MSCM content achieved 28-day compressive strength of 9.38 MPa, indicating its high hydration reactivity. The leaching concentrations of Pb, Zn and Cd were just 51.4, 1895.8 and 36.1 µg/L, respectively, well below the limit standard of Municipal solid wastes in China (GB 16889-2008). After 30 times' DWC, leaching concentrations of Pb, Zn and Cd for MSCM-FA blocks increased up to 130.7, 9107.4 and 156.8 µg/L, respectively, but considerably lower than those for OPC-FA blocks (689, 11,870.6 and 185.2 µg/L, respectively). The XRD and chemical speciation analysis revealed the desorption of Pb, Zn and Cd attached to surface of C-S-H crystalline structure during the DWC. The XPS and SEM-EDS analysis confirmed the formation of Pb-O-Si and Zn-O-Si bonds via isomorphous replacement of C-A-S-H in binder-FA blocks. Ettringite crystalline structure in OPC-FA block was severely destructed during the DWC, resulting in the reduced contents of PbSO4 and CaZn2Si2O7·H2O and the higher leachability of Pb2+ and Zn2+.

The leaching behavior of hazardous element under different leaching procedure utilizing slag-fly ash-based agent: Chromium, antimony, and lead.

Low-carbon cementitious materials based on blast furnace slag (BFS) and municipal solid waste incineration (MSWI) fly ash play a pivotal role in the construction industry by substituting cement clinker. This innovation significantly reduces CO2 emissions and enables the extensive utilization of both industrial solid waste and hazardous urban waste on a large scale. However, the application of MSWI fly ash as a precursor for alkali-activated cementitious materials presents a significant leaching risk of heavy metal during the extended reaction process, posing a critical barrier to the efficient and widespread utilization of these solid waste. Three static leaching methods [horizontal vibration (HV), sulphuric acid & nitric acid (SN), and acetic acid buffer solution (AAB)], along with acid neutralization capacity (ANC) leaching tests, were applied in BFS-fly ash-based cementitious materials (BFCM) to assess the leaching behavior of high-risk elements-Cr, Sb, and Pb-within MSWI fly ash. The A4 matrix (BFS: MSWI fly ash:FGDG = 70:20:10) exhibits a compressive strength of 72.51 MPa at 180 day, with the leaching concentrations of target elements remaining below the standard limit under chemical attack (H+ and OH-). The critical pH determined is 9.2 from the ANC leaching test results. Visual MINTEQ simulation illustrates the occurrence states of Cr, Sb, and Pb as (CrO4)2-, [Sb(OH)6]-, and Pb(OH)3- within the BFCM system, respectively. The "double salt effect", intended to enhance the dissociation degree of BFS, acts as the driving force behind the long-term hydration reaction. It also serves as an assurance in controlling the long-term leaching risk of object elements. The dissociation degree of BFS within A4 matrix increased by 38.71 %, with the relative content of the typical low-solubility double salt "Ettringite" reaching 29 % at 180 d. This study provides novel theoretical and data-driven evidence to investigate the leaching behavior associated with MSWI fly ash and the accomplishment of replacing cement clinker with low-carbon BFCM.

A review of solid wastes-based stabilizers for remediating heavy metals co-contaminated soil: Applications and challenges.

The remediation of heavy metals/metalloids (HMs) co-contaminated soil by solid wastes-based stabilizers (SWBS) has received major concern recently. Based on the literature reported in the latest years (2010-2023), this review systematically summarizes the different types of solid wastes (e.g., steel slag, coal fly ash, red mud, and sewage sludge, etc.) employed to stabilize HMs contaminated soil, and presents results from laboratory and field experiments. Firstly, the suitable solid wastes for soil remediation are reviewed, and the pros and cons are presented. Thereafter, the technical feasibility and economic benefit are evaluated for field application. Moreover, evaluation methods for remediation of different types of HMs-contaminated soil and the effects of SWBS on soil properties are summarized. Finally, due to the large specific surface, porous structure, and high reactivity, the SWBS can effectively stabilize HMs via adsorption, complexation, co/precipitation, ion exchange, electrostatic interaction, redox, and hydration process. Importantly, the environmental implications and long-term effectiveness associated with the utilization of solid wastes are highlighted, which are challenges for practical implementation of soil stabilization using SWBS, because the aging of soil/solid wastes has not been thoroughly investigated. Future attention should focus on modifying the SWBS and establishing an integrated long-term stability evaluation method.

Simultaneous stabilization of arsenic and antimony co-contaminated mining soil by Fe(â ¡) activated-Fenton sludge: Behavior and mechanisms.

Fenton sludge (FS) with high iron contents that discharged from the Fenton process was rarely studied for soil remediation. Herein, a novel Fe(Ⅱ) activated-Fenton sludge (FS-FeSO4) was proposed to stabilize arsenic (As) and antimony (Sb) co-contaminated soil meanwhile disposing FS. Multiple characteristic analyses revealed that the porous structures and rich functional groups of FS-FeSO4 involved in As and Sb adsorption. Meanwhile, Fe (hydro)oxides played a key role in As and Sb stabilization. Under the optimal application parameters (stabilizers dosage: 5%, incubation time: 60 days), the available As and Sb content decreased by 88.6% and 83.3%, respectively, and the leachability of As and Sb was reduced by 100% and 72.6% for FS-FeSO4 stabilized soil. Moreover, the mobile As and Sb fractions (F1 and F2) were transformed into the most stable fraction (F5). The adsorption of As and Sb on FS-FeSO4 was well fitted by pseudo-second-order kinetic and Langmuir models, while FS-FeSO4 exhibited a better affinity for As than Sb under competition conditions. Poorly crystalline α-FeOOH and amorphous Fe (hydro)oxides provided sufficient active sites for As and Sb, and the generation of Fe-As/Sb and Ca-Sb chemical bonds promoted the stability of As and Sb. This study demonstrated that FS-FeSO4 was a potentially effective stabilizer for As and Sb co-contaminated soil remediation.

Study on Solidification and Stabilization of Antimony-Containing Tailings with Metallurgical Slag-Based Binders.

Blast furnace slag (BFS), steel slag (SS), and flue gas desulfurized gypsum (FGDG) were used to prepare metallurgical slag-based binder (MSB), which was afterwards mixed with high-antimony-containing mine tailings to form green mining fill samples (MBTs) for Sb solidification/stabilization (S/S). Results showed that all MBT samples met the requirement for mining backfills. In particular, the unconfined compressive strength of MBTs increased with the curing time, exceeding that of ordinary Portland cement (OPC). Moreover, MBTs exhibited the better antimony solidifying properties, and their immobilization efficiency could reach 99%, as compared to that of OPC. KSb(OH)6 was used to prepare pure MSB paste for solidifying mechanism analysis. Characteristics of metallurgical slag-based binder (MSB) solidified/stabilized antimony (Sb) were investigated via X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). According to the results, the main hydration products of MSB were C-S-H gel and ettringite. Among them, C-S-H gel had an obvious adsorption and physical sealing effect on Sb, and the incorporation of Sb would reduce the degree of C-S-H gel polymerization. Besides, ettringite was found to exert little impact on the solidification and stabilization of Sb. However, due to the complex composition of MSB, it was hard to conclude whether Sb entered the ettringite lattice.

Characterization and Hydration Mechanism of Ammonia Soda Residue and Portland Cement Composite Cementitious Material.

The use of ammonia soda residue (ASR) to prepare building materials is an effective way to dispose of ASR on a large scale, but this process suffers from a lack of data and theoretical basis. In this paper, a composite cementitious material was prepared using ASR and cement, and the hydration mechanism of cementitious materials with 5%, 10%, and 20% ASR was studied. The XRD and SEM results showed that the main hydration products of ASR-cement composite cementitious materials were an amorphous C-S-H gel, hexagonal plate-like Ca(OH)2 (CH), and regular hexagonal plate-like Friedel's salt (FS). The addition of ASR increased the heat of hydration of the cementitious material, which increased upon increasing the ASR content. The addition of ASR also reduced the cumulative pore volume of the hardened paste, which displayed the optimal pore structure when the ASR content was 5%. In addition, ASR shortened the setting time compared with the cement group, and the final setting times of the pastes with 5%, 10%, and 20% ASR were 30 min, 45 min, and 70 min shorter, respectively. When the ASR content did not exceed 10%, the 3-day compressive strength of the mortar was significantly improved, but the 28-day compressive strength was worse. Finally, the hydration mechanism and potential applications of the cementitious material are discussed. The results of this paper promote the use of ASR in building materials to reduce CO2 emissions in the cement industry.

Decomposition of refractory aniline aerofloat collector in aqueous solution by an ozone/vacuum-UV (O3/VUV) process.

The degradation of refractory aniline aerofloat (AAF) collector was investigated by an ozone/Vacuum-UV (O3/VUV) process. The effects of O3 dosage and initial pH on the AAF degradation were studied. The total organic carbon (TOC) and concentrations of S O 4 2 - , P O 4 3 - and N O 3 - anions were measured to evaluate the AAF mineralization. The solid phase extraction and gas chromatography-mass spectrometry (SPE/GC-MS) was developed to identify byproducts. The results showed that 99.84% of AAF could be removed by the O3/VUV, and the AAF degradation was enhanced at higher O3 dosage and initial solution pH. The radical scavenging tests revealed that most of AAF was degraded by OH• radicals, and the O3/UV254nm made the main contribution in AAF degradation in the O3/VUV system. The mineralization extents of C, S, P and N elements of AAF at 180 min reached 47.74%, 93.94%, 17.71% and 45.81%, respectively. At initial pH > 10.0, the EE/O values of AAF degradation by the O3/VUV was below 7.0 kWh m-3 per order, showing the energy consumption was acceptable. The SPE/GC-MS analysis showed that toxic aniline was generated in the O3/VUV oxidation of AAF, but it was further degraded at a longer time. Compared to the ozonation, the O3/VUV had a much lower content of aniline at 180 min. The possible degradation pathways of AAF by the O3/VUV were proposed.

Feasibility of using fly ash-slag-based binder for mine backfilling and its associated leaching risks.

As a binder to completely replace Portland cement for mine backfilling, the use of clinker-free cementitious materials combined with municipal solid waste incineration (MSWI) fly ash is proposed to achieve the targets of low-cost green backfilling, safe disposal and resource utilisation of bulk urban hazardous waste and metallurgical solid waste. This study balances the positive and negative effects of adding MSWI fly ash to the backfill by controlling its quantity in the binders, thus establishing an optimal concentration of 49 wt.% steel slag (SS), 21 wt.% blast furnace slag (BFS), 10 wt.% MSWI fly ash and 20 wt.% flue gas desulfurisation (FGD) gypsum. It is also reported that the filling performance of slurry (A2) satisfied strength requirements and is very suitable for long-distance transportation according to filling parameters. The leaching levels of the target elements (Cr, Ni, Zn, As, Cd, Sb, Pb, Hg and dioxins) for A2 matrix are lower than the required maximum concentration limits for the underground class Ⅲ water standard. Furthermore, the risk of leaching harmful constituents is mainly controlled by the pH of the environmental and the excellent buffering capacity of the matrix can reduce the potential leaching risk. The encapsulation, precipitation and adsorption of low-solubility double salts, such as hydrate calcium chloroaluminate (HCC) and ettringite, are the solidification/stabilisation (S/S) mechanism of series A on harmful substances. In addition, the high degree of polymerization(Ca/Si = 1.18 < 1.2, at 90d), the formation of long-chain C-S-H gels in binder A2-2, the dense pore structure lead to very stable growth in strength and control of leaching risks in subsequent periods.

Influence of calcium hydroxide addition on arsenic leaching and solidification/stabilisation behaviour of metallurgical-slag-based green mining fill.

In this study, metallurgical-slag-based binder (MSB) with different dosages of calcium hydroxide (CH) was mixed with high-arsenic-containing mine tailings (HAMT) to form green mining fill samples (GMFs) for As solidification/stabilisation (S/S). The As leaching characteristics of the GMFs were evaluated using pH-dependent leaching tests, semi-dynamic leaching tests and toxicity leaching tests. The effective diffusion coefficient (De) decreased from 6.98 × 10-14 to 5.90 × 10-15 cm2/s and the leachability index (LI) increased from 13.53 to 14.73 after 3 wt.% CH was added to the GMFs. The GMFs containing 0 wt.% CH (GMF-0C) and those containing 3 wt.% CH (GMF-3C) reached pH = 2 with acid addition amounts of 9.0 meq/g-dry and 9.3 meq/g-dry at 90 d curing time, and the maximum As leaching concentrations of GMF-0C and GMF-3C reached 10.47 mg/L and 7.47 mg/L, respectively, indicating that GMF-3C exhibited better acid neutralisation and As retention capacities than GMF-0C. Further, a Tescan Integrated Mineral Analyser (TIMA) was used to analyse the dominant hydration products of GMF-3C, which revealed that calcium silicate hydrate, CASH, ettringite and zeolite phases represented approximately 22.5 wt.% of the products. These results provide an understanding regarding the safe large-scale utilisation of GMFs.

In-Situ Immobilization of Cd-Contaminated Soils Using Ferronickel Slag as Potential Soil Amendment.

The current study investigated the efficiency and mechanisms of in situ immobilization of artificially Cd-contaminated soils with ferronickel slag (FNS). The available Cd content of soil was measured and the modified European Community Bureau of Reference (BCR) sequential extraction procedure (SEP) was adopted to quantify the evolutions of Cd chemical speciation after the immobilization by the FNS. The results showed that the addition of FNS (5%‒15%) remarkably reduced the available Cd content and increased the pH and cation exchange capacity of soils. The passivation rate of Cd increased from 58.13% to 73.25% as the spiked Cd content rose from 10 to 120 mg kg‒1. The BCR SEP test revealed that the FNS addition substantially reduced the acid soluble fraction and increased the residual fraction of Cd, indicating the reduction of mobility and bioavailability of Cd in soils. The chemical precipitation, ion exchange and surface complexation might be involved in in situ immobilization of Cd-contaminated soils by the FNS.

UV185+254 nm photolysis of typical thiol collectors: decomposition efficiency, mineralization and formation of sulfur byproducts.

The decomposition of toxic flotation reagents upon UV185+254 nm irradiation was attractive due to operational simplicity and no dosage of oxidants. In this work, the degradation of typical thiol collectors (potassium ethyl xanthate (PEX), sodium diethyl dithiocarbamate (SDD), O-isopropyl-N-ethyl thionocarbamate (IET) and dianilino dithiophoshoric acid (DDA)) was investigated by UV185+254 nm photolysis. The degradation efficiencies and mineralization extents of collectors were assessed. The formation of CS2 and H2S byproducts was studied, and the mechanisms of collector degradation were proposed under UV185+254 nm irradiation. The PEX, SDD and IET were decomposed with nearly 100% removal upon 75 min of UV185+254 nm irradiation. The decomposition rate constants decreased in the order SDD > PEX > IET ≫ DDA, and the DDA was the refractory collector. After 120 min of UV185+254 nm irradiation, 15-45% of carbon and 25-75% of sulfur of collectors were completely mineralized, and the mineralization extent decreased in the order PEX > SDD > IET > DDA. The percentage of gaseous sulfur (CS2 and H2S) ranged from 0.48 to 4.85% for four collectors, showing the fraction of emitted sulfur byproducts was small. The aqueous CS2 concentration increased in the first 10-20 min, and was decreased to a low level of 0.05-0.1 mg l-1 at 120 min. Two mechanisms, i.e. direct UV254 nm photolysis and indirect oxidation with free radicals, were responsible for collector decomposition in the UV185+254 nm photolysis.

Ozone and ozone/vacuum-UV degradation of diethyl dithiocarbamate collector: kinetics, mineralization, byproducts and pathways.

The diethyl dithiocarbamate (DDC) collector, a precursor of toxic N-nitrosamines, is detected in flotation wastewaters usually at the ppm level. In this study, the O3 and O3/Vacuum-UV (O3/VUV) processes were compared to investigate the efficient removal of DDC with a low risk of N-nitrosamine formation. The results showed that 99.55% of DDC was removed at 20 min by O3/VUV, and the degradation rate constant was 3.99 times higher than that using O3-alone. The C, S and N mineralization extents of DDC using O3/VUV reached 36.36%, 62.69% and 79.76% at 90 min, respectively. O3/VUV achieved a much higher mineralization extent of DDC than O3-alone. After 90 min of degradation, O3/VUV achieved lower residual concentrations of CS2 and H2S, and released lower amounts of gaseous sulfur byproducts compared to O3-alone. The solid phase extraction and gas chromatography-mass spectrometry (SPE/GC-MS) analysis indicated that the main byproducts in O3/VUV degradation of DDC were amide compounds without the detection of N-nitrosamines. The avoidance of N-nitrosamine formation might be attributed to exposure of UV irradiation and enhanced formation of ˙OH radicals in the O3/VUV system. The degradation pathways of DDC were proposed. This work indicated that O3/VUV was an efficient alternative treatment technique for the removal of DDC flotation collector with low risk of N-nitrosamine formation.

Vertically aligned Pt/TiO2 nanobelt films on Ti sheets for efficient degradation of a refractory ethyl thionocarbamate collector.

Noble metal modified TiO2 nanostructures on a substrate featuring a two-dimensional (2D) morphology are of great interest in wastewater remediation due to high photocatalytic activity and avoidance of separating powder catalysts from water. In this work, vertically aligned Pt/TiO2 nanobelt films (Pt/TNFs) on Ti sheets were fabricated via a synthesis strategy including an alkaline hydrothermal treatment and electrostatic self-assembly. The Pt/TNFs had a BET specific surface area of 93.35 m2 g-1, showing high adsorption capacity in removing an ethyl thionocarbamate (ETC) flotation collector. After the deposition with Pt nanoparticles, the photocatalytic activity of the TNFs increased by 94.98% with the enhanced mineralization of the ETC collector. Moreover, the Pt/TNFs on Ti sheets exhibited strong substrate adhesion enabling superior photocatalytic stability in the cyclic degradation of ETC. The solid phase extraction and gas chromatography-mass spectrometry (SPE/GC-MS) analysis revealed that seven byproducts still remained even when 100% of ETC was degraded, showing the difficulty in the complete mineralization of the ETC collector. The Pt/TNF can serve as a promising photocatalyst to treat mineral flotation wastewaters containing organic reagents.

Removal of aqueous Cu2+ ions with Fe0/C ceramsites fabricated by direct reduction roasting of magnetite, coal, and paper mill sludge.

The porous metallic iron/carbon (Fe0/C) ceramsites, with virtues of low cost and 'green' fabrication, were prepared by direct reduction roasting of magnetite, coal, and paper mill sludge. The X-ray diffraction data revealed that Fe0 was generated in situ by reducing the magnetite at 1,200 °C. Scanning electron microscopy with energy-dispersive X-ray spectroscopy indicated that Fe0 particles, with a size of <10 µm, were highly dispersed on carbon particles to form an integrated anode (Fe0) and cathode (C) structure of microelectrolysis filters. The effects of initial solution pH and Fe/C mass ratio on Cu2+ removal were investigated. The extent of Cu2+ removal increased from 93.53% to 99.81% as initial pH rose from 2.5 to 7.0. The residual Cu2+ concentration was as low as <0.2 mg/L. The highest extent of Cu2+ removal was achieved at Fe/C mass ratio of 6.8:1. The pseudo-second-order kinetic model fitted well for Cu2+ removal by the ceramsite, revealing the chemisorption as a limiting step. The Cu2+ adsorption equilibrium data were well described by the Langmuir isotherm, with a maximum adsorption capacity of 546.45 mg/g at initial pH 3.0.

Porous Fe0/C ceramsites for removal of aqueous Pb(ii) ions: equilibrium, long-term performance and mechanism studies.

This study reports the equilibrium, long-term performance and mechanisms in removing Pb(ii) ions by metallic iron/carbon (Fe0/C) ceramsites (FCC). The Pb(ii) removal equilibrium data was analyzed using the Langmuir, Freundlich and Dubinin-Radushkevich isotherms. At the FCC dosage of 1.14 g L-1, 95.97% of Pb(ii) ions were removed from 50 mg L-1 Pb(ii) solution at initial pH 6.0. The Langmuir isotherm could fit well with the data at initial pH 3.0 with a maximum monolayer adsorption capacity of 112.36 mg g-1 at 25 °C, while the data obtained at initial pH 6.0 could be described by the Freundlich model, indicating multilayer adsorption of Pb species on the FCC. Column tests demonstrated that FCC achieved the highest Pb(ii) removal of 65.86% after 12 days' run compared to 32.35% for Fe0/activated carbon couples and only 1.24% for activated carbon. The X-ray diffraction and X-ray photoelectron spectroscopy analysis revealed that the PbO (dominant Pb species), Pb0, asisite and plumbojarosite appeared after Pb(ii) removal. Scanning electron microscopy with energy dispersive X-ray spectroscopy showed that PbO particles with numerous structures were deposited on the FCC surface in a high amount. The decrease of the Fe/C mass ratio from 7.5 : 1 to 0.298 : 1 revealed that microscale Fe0 could been readily corroded by forming galvanic couples between Fe0 and carbon. The mechanisms of Pb(ii) removal by the FCC were proposed.

VUV-Photocatalytic Degradation of Bezafibrate by Hydrothermally Synthesized Enhanced {001} Facets TiO2/Ti Film.

In the present study, a novel TiO2/Ti film with enhanced {001} facets was synthesized by the hydrothermal technique followed by calcination for studying the removal of bezafibrate (BZF), from an aqueous environment. The synthesized photocatalyst was characterized by FE-SEM, XRD, HR-TEM, and PL-technique. The second-order rate constant of (•)OH with BZF was found to be 5.66 × 10(9) M(-1) s(-1). The steady state [(•)OH] was measured as 1.16 × 10(-11) M, on the basis of oxidation of terephthalic acid. The photocatalytic degradation of BZF followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model (k1 = 2.617 mg L(-1) min(-1) and k2 = 0.0796 (mg L(-1))(-1)). The effects of concentration and the nature of various additives including inorganic anions (NO3(-), NO2(-), HCO3(-), CO3(2-), Cl(-)) and organic species (fulvic acid) and initial solution pHs (2, 4, 6, 9) on photocatalytic degradation of BZF were investigated. It was found that the nature and concentration of studied additives significantly affected the photocatalytic degradation of BZF. The efficiency of the photocatalytic degradation process in terms of electrical energy per order was estimated. Degradation schemes were proposed on the basis of the identified degradation byproducts by ultraperformance liquid chromatography.