pH-dependent mechanisms of sulfadiazine degradation by natural pyrite-driven heterogeneous Fenton-like reactions.

The development of a natural pyrite/peroxymonosulfate (PMS) system for the removal of antibiotic contamination from water represented an economic and green sustainable strategy. Yet, a noteworthy knowledge gap remained considering the underlying reaction mechanism of the system, particularly in relation to its pH sensitivity. Herein, this paper investigated the impacts of critical reaction parameters and initial pH levels on the degradation of sulfadiazine (SDZ, 3 mg/L) in the pyrite/PMS system, and elucidated the pH dependence of the reaction mechanism. Results showed that under optimal conditions, SDZ could be completely degraded within 5 min at a broad pH range of 3.0-9.0, with a pseudo-first-order reaction rate of >1.0 min-1. The low or high PMS doses could lower degradation rates of SDZ through the decreased levels of active species, while the amount of pyrite was positively correlated with the removal rate of SDZ. The diminutive concentrations of anions exerted minor impacts on the decomposition of SDZ within the pyrite PMS system. Mechanistic results demonstrated that the augmentation of pH levels facilitated the transition from the non-radical to the radical pathway within the natural pyrite/PMS system, while concurrently amplifying the role of •OH in the degradation process of SDZ. This could be attributed to the change in interface electrostatic repulsion induced by pH fluctuations, as well as the mutual transformation between active species. The stable presence of the relative content of Fe(II) in the used pyrite was ensured owing to the reduced sulfur species acting as electron donors, providing the pyrite/PMS system excellent reusability. This paper sheds light on the mechanism regulation of efficient removal of organic pollutants through pyrite PMS systems, contributing to practical application.

In-situ generation of iron activated percarbonate for sustainable sludge dewatering.

Effective dewatering of sewage sludge could potentially address the issues of high energy consumption and large carbon footprint inherent in the sludge treatment process, advancing toward carbon neutrality in environmental remediation. Yet, the surface hydrophilic characteristics and water-holding interfacial affinity in sludge led to dwindled sludge-water separation performance. Here, the integration of in-situ generation of iron from zero-valent scrap iron (ZVSI) and sodium percarbonate (SPC) was attempted to attenuate the water-retaining interfacial affinity within sludge, thus achieving superior sludge dewatering performance. Results showed that under the optimal conditions, the ZVSI + SPC system led to a remarkable decline of 76.09 % in the specific resistance to filtration of the sludge, accompanied by a notable decline of 34.96 % in the water content. Moreover, the utilization of ZVSI + SPC system could be a viable alternative to the traditional strategies in terms of enhanced sludge dewaterability, offering application potential with stable operating performance, economic feasibility, and reduced carbon emissions. Investigation into dewatering mechanism revealed that ZVSI could maintain the Fe3+/Fe2+ in a stable dynamic cycle and continuously in-situ generate Fe2+, thereby efficaciously fostering the SPC activation for the ceaseless yield of reactive oxygen species. The predominant •OH and 1O2 efficiently decomposed the hydrophilic biopolymers, therefore minimizing the hydrophilic protein secondary structures, along with the hydrogen and disulfide bonds within proteins. Subsequently, the water-holding interfacial affinity was profoundly diminished, leading to intensified hydrophobicity, self-flocculation, and dewaterability. These findings have important implications for the advancement of efficacious ZVSI + SPC conditioning techniques toward sustainable energy and low-carbon prospects.

A highly efficient process to enhance the bioleaching of spent lithium-ion batteries by bifunctional pyrite combined with elemental sulfur.

Bioleaching technologies have been shown to be an environmentally friendly and economically beneficial tool for extracting metals from spent lithium-ion batteries (LIBs). However, conventional bioleaching methods have exhibited low efficiency in recovering metals from spent LIBs. Therefore, relied on the sustainability principle of using waste to treat waste, this study employed pyrite (FeS2) as an energy substance with reducing properties and investigated its effects in combination with elemental sulfur (S0) or FeSO4 on metals bioleaching from spent LIBs. Results demonstrated that the bioleaching efficiency was significantly higher in the leaching system constructed with FeS2 + S0, than in the FeS2 + FeSO4 or FeS2 system. When the pulp densities of FeS2, S0 and spent LIBs were 10 g L-1, 5 g L-1 and 10 g L-1, respectively, the leaching efficiency of Li, Ni, Co and Mn all reached 100%. Mechanistic analysis reveals that in the FeS2 + S0 system, the activity and acid-producing capabilities of iron-sulfur oxidizing bacteria were enhanced, promoting the generation of Fe (Ⅱ) and reducible sulfur compounds. Simultaneously, bio-acids were shown to disrupt the structure of the LIBs, thereby increasing the contact area between Fe (Ⅱ) and sulfur compounds containing high-valence metals. This effectively promoted the reduction of high-valence metals, thereby enhancing their leaching efficiency. Overall, the FeS2 + S0 bioleaching process constructed in this study, improved the leaching efficiency of LIBs while also effectively utilizing waste, providing technical support for the comprehensive and sustainable management of solid waste.

Defluorination of perfluorooctanoic acid and perfluorooctane sulfonic acid by heterogeneous catalytic system of Fe-Al2O3/O3: Synergistic oxidation effects and defluorination mechanism.

In this study, catalytic ozonation by Fe-Al2O3 was used to investigate the defluorination of PFOA and PFOS, assessing the effects of different experimental conditions on the defluorination efficiency of the system. The oxidation mechanism of the Fe-Al2O3/O3 system and the specific degradation and defluorination mechanisms for PFOA and PFOS were determined. Results showed that compared to the single O3 system, the defluorination rates of PFOA and PFOS increased by 2.32- and 5.92-fold using the Fe-Al2O3/O3 system under optimal experimental conditions. Mechanistic analysis indicated that in Fe-Al2O3, the variable valence iron (Fe) and functional groups containing C and O served as important reaction sites during the catalytic process. The co-existence of 1O2, OH, O2- and high-valence Fe(IV) constituted a synergistic oxidation system consisting of free radicals and non-radicals, promoting the degradation and defluorination of PFOA and PFOS. DFT theoretical calculations and the analysis of intermediate degradation products suggested that the degradation pathways of PFOA and PFOS involved Kolbe decarboxylation, desulfonation, alcoholization and intramolecular cyclization reactions. The degradation and defluorination pathways of PFOA and PFOS consisted of the stepwise removal of -CF2-, with PFOS exhibiting a higher defluorination rate than PFOA due to its susceptibility to electrophilic attack. This study provides a theoretical basis for the development of heterogeneous catalytic ozonation systems for PFOA and PFOS treatment.

Triclocarban transformation and removal in sludge conditioning using chalcopyrite-triggered percarbonate treatment.

Herein, a facile combination approach of chalcopyrite and sodium percarbonate (CuFeS2+ SPC) was established to augment both TCC removal efficiency and sludge dewatering. Results showed that utilizing the CuFeS2 dosage of 600 mg/g total solids (TS) under the optimal condition, along with the SPC dosage of 12.5 mg/g TS, an initial pH of 4.0, and a reaction duration of 40 min, led to a substantial reduction of 53.9% in the TCC content within the sludge, accompanied by a notable decrease of 36.9% in the water content. Compared to well-studied iron-based advanced oxidation processes, CuFeS2 + SPC treatment proved to be more cost-effective and environmentally friendly. Mechanistic findings demonstrated that •OH oxidation played a significant role in TCC removal, with O2•- and 1O2 acting as secondary factors. During the CuFeS2 + SPC process, the received •OH, O2•-, and 1O2 destroyed the main binding sites of extracellular polymeric substances to TCC, including tryptophan-like protein, amide, CO stretch, and -COO- functional groups. As a result, approximately 50% of TCC was partially degraded within the solid sludge phase after the attack of radicals. Meanwhile, the decreased macromolecular organic compounds in solid sludge attenuated the binding efficacy of TCC, giving rise to the transfer of partial TCC to the liquid phase. Ultimately, the TCC in sludge was successfully removed, and five transformation products were identified. This study significantly contributes to our understanding regarding TCC transformation and removal in the sludge conditioning process.

Feasibility of low-intensity ultrasound treatment with hydroxylamine to accelerate the initiation of partial nitrification and allow operation under intermittent aeration.

Partial nitrification is a key aspect of efficient nitrogen removal, although practically it suffers from long start-up cycles and unstable long-term operational performance. To address these drawbacks, this study investigated the effect of low intensity ultrasound treatment combined with hydroxylamine (NH2OH) on the performance of partial nitrification. Results show that compared with the control group, low-intensity ultrasound treatment (0.10 W/mL, 15 min) combined with NH2OH (5 mg/L) reduced the time required for partial nitrification initiation by 6 days, increasing the nitrite accumulation rate (NAR) and ammonia nitrogen removal rate (NRR) by 20.4% and 6.7%, respectively, achieving 96.48% NRR. Mechanistic analysis showed that NH2OH enhanced ammonia oxidation, inhibited nitrite-oxidizing bacteria (NOB) activity and shortened the time required for partial nitrification initiation. Furthermore, ultrasonication combined with NH2OH dosing stimulated EPS (extracellular polymeric substances) secretion, increased carbonyl, hydroxyl and amine functional group abundances and enhanced mass transfer. In addition, 16S rRNA gene sequencing results showed that ultrasonication-sensitive Nitrospira disappeared from the ultrasound + NH2OH system, while Nitrosomonas gradually became the dominant group. Collectively, the results of this study provide valuable insight into the enhancement of partial nitrification start-up during the process of wastewater nitrogen removal.

Comprehensive insights into the gallic acid assisted bioleaching process for spent LIBs: Relationships among bacterial functional genes, Co(III) reduction and metal dissolution behavior.

Despite the growing demand for resource recovery from spent lithium-ion batteries (LIBs) by bioleaching, low Co leaching efficiency has hindered the development and application of this technology. Therefore, a novel process was designed, combining gallic acid (GA) and mixed culture bioleaching (MCB), to enhance the removal of metals from spent LIBs. Results indicated that the GA + MCB process achieved 98.03% Co and 98.02% Li leaching from spent LIBs, simultaneously reducing the biotoxicity, phytotoxicity and leaching toxicity of spent LIBs under optimal conditions. The results of mechanism analysis demonstrated that functional microorganisms adapted to the leaching system through various strategies, including oxidative stress reduction, DNA damage repair, heavy metal resistance and biofilm formation, maintaining normal physiological activities and the continuous production of biological acid. The biological acid erodes the surface of waste LIBs, causing some Co and a large amount of Li to be released, while also increasing the contact area between GA and Co(III). Therefore, GA is beneficial for reducing insoluble Co(III), forming soluble Co(II). Finally, biological acid can effectively promote Co(II) leaching. Collectively, the results of this study provide valuable insight into the simultaneous enhancement of metal extraction and the mitigation of environmental pollution from spent LIBs.

Iron-rich digestate biochar toward sustainable peroxymonosulfate activation for efficient anaerobic digestate dewaterability.

In this study, a suite of Fe-rich biochars derived from Fenton-like treated digestate (Fe-BC) were fabricated under different pyrolysis temperatures (300, 500, and 800 °C), which were firstly utilized as peroxymonosulfate (PMS) activators for promoting digestate dewaterability with wide applicability. Results showed that compared to the Fe-BC300/Fe-BC500 + PMS treatments, Fe-BC800 + PMS process performed superior digestate dewaterability in which specific resistance to filtration reduction and water content reduction improved by > 12.5% and > 130%, respectively, under the optimal conditions. Mechanistic results demonstrated that in Fe-BC800 + PMS system, HO• and SO4•- oxidation played a pivotal role on promoted digestate dewaterability, while HO• and 1O2 oxidation was dominated in Fe-BC300/Fe-BC500 + PMS treatments. Fe-BC800 containing higher Fe and CO contents could efficiently interact with PMS to generate numerous HO• and SO4•- via iron cycle. These highly reactive oxygen species proficiently reduced the hydrophilic biopolymers, protein molecules, and amino acids in extracellular polymeric substances, leading to remarkable decrease in particle size, hydrophilicity, adhesion, network strength, and bound water of digestate. Consequently, the flowability and dewaterability of digestate could be significantly enhanced. The cost-benefit result indicated the Fe-BC + PMS treatment possessed desirable reusability, applicability, and economic viability. Collectively, the Fe-BC + PMS is a high-performance and eco-friendly technique for digestate dewatering, which opens a new horizon towards a closed-loop of digestate reutilization.

High-efficiency treatment of electroless nickel plating effluent using core-shell MnFe2O4-C@Al2O3 combined with ozonation: Performance and mechanism.

Heterogeneous catalytic ozonation (HCO) has been widely applied for the treatment of wastewater. In order to maintain the structural stability and surface catalytic activity of heterogeneous catalysts during the HCO treatment of electroless nickel plating effluent (ENPE), a MnFe2O4-C@Al2O3 catalyst with a core-shell structure was synthesized. MnFe2O4-C@Al2O3 was characterized and applied in the removal of total nickel (TNi) and organic contaminants from actual ENPE, using a coupled system of HCO combined with a magnetic dithiocarbamate chelating resin (MnFe2O4-C@Al2O3/O3-MDCR). Results show that embedding Al2O3 with C and MnFe2O4 significantly increased the TNi removal efficiency (99.3%), enhanced the O3-utilization efficiency and improved the generation of reactive oxygen species (ROS). The reaction rate (k = 0.7641 min-1) and O3-utilization efficiency established for TNi removal (ΔTNi/ΔO3 =0.221) by the MnFe2O4-C@Al2O3/O3-MDCR system, were 220% and 140% higher than the Al2O3/O3-MDCR system, respectively. Catalytic mechanism analysis demonstrated that surface hydroxyl groups, oxygen vacancy, metals, the carbon surface and its functional groups, can all potentially serve as catalytic active sites, with 1O2 and •OH considered to the predominant ROS. Overall, these findings verify that the synthesized MnFe2O4-C@Al2O3 catalyst possesses excellent catalytic capabilities and outstanding structural stability, making it suitable for practical application in the treatment of wastewater effluent.

Dewaterability improvement and environmental risk mitigation of waste activated sludge using peroxymonosulfate activated by zero-valent metals: Fe0 vs. Al0.

The stabilization and dewaterability of waste activated sludge (WAS) are essential factors for downstream disposal or reuse. Herein, two types of zero-valent metals, zero-valent iron (Fe0) and zero-valent aluminum (Al0), were compared for their ability to activate peroxymonosulfate (PMS) during the WAS conditioning process, with the effects of PMS activation by these two metals on WAS dewaterability and the potential environmental risks evaluated. Results showed that compared to Al0/PMS treatment, Fe0/PMS treatment achieved superior WAS dewaterability and reduced operational costs. Using PMS combined with Fe0 and Al0 treatments under optimal conditions, the water content (Wc) of dewatered sludge decreased to 55.7 ± 2.7 wt% and 59.4 ± 1.3 wt%, respectively. Meanwhile, application of the Fe0/PMS treatment system reduced the total annual cost by approximately 33.1%, compared to the Al0/PMS treatment. Analysis of the dewatering mechanism demonstrated that in the Fe0/PMS treatment, Fe3+/Fe2+ flocculation played an important role in the enhancement of WAS dewatering, while sulfate radical (SO4•-) oxidation was the dominant factor for WAS dewaterability improvement in Al0/PMS treatment. The greater enhancement of WAS dewaterability by Fe0/PMS treatment, was mainly attributed to more efficient reduction of hydrophilic extracellular polymeric substances (EPS) and an increase in surface charge neutralization. Environmental risk evaluation results indicated that Fe0/PMS and Al0/PMS treatments both effectively alleviated the environmental risks of heavy metals and faecal coliforms in dewatered sludge. Overall, this study proposes a novel perspective for the selection of an optimal PMS activator in sludge treatment.