Low-toxicity natural pyrite on electro-Fenton catalytic reaction in a wide pH range.

The resource utilization of natural pyrite not only reduces secondary pollution but also brings certain environmental benefits. However, the green and efficient use of pyrite presents certain challenges. In this study, a novel electro-Fenton (EF) system was constructed utilizing copper modified graphite felt (GF/Cu) as cathode and natural pyrite (com-FeS2) as catalyst. The results demonstrated that the system exhibited a remarkable stability over an extensive pH range (3.0-10.0) and remained effective even under adverse environmental conditions, such as high salinity or elevated antibiotic concentration. After optimizing the reaction conditions, 0.2 mM sulfamerazine (SMZ) was almost completely degraded within 1.5 h. The results highlighted the catalytic role of Fe(II) on the com-FeS2 surface. Combined with quenching experiments and quantitative analysis of reactive oxygen species (ROS), the removal of SMZ was primarily attributed to the generation of •OH, ordered by 1O2 > â€¢O2- > â€¢OHads, a possible degradation pathway was proposed by HR-LC-MS. The biological toxicity after the reaction was detected, and the introduction of polyvinylpyrrolidone (PVP) was beneficial to reduce the biological toxicity of iron dissolution. This work provides new insights into the green and efficient resource utilization of natural pyrite and significantly expands the pH applicability range of the Fenton process, demonstrating the large-scale industrial application potential of pyrite.

Natural pyrite and ascorbic acid co-enhance periodate activation for inactivation of antibiotic resistant bacteria and inhibition of resistance genes transmission: A green disinfection process dominated by singlet oxygen.

The transmission of antibiotic resistance genes (ARGs) and the propagation of antibiotic resistant bacteria (ARB) threaten public health security and human health, and greener and more efficient disinfection technologies are expected to be discovered for wastewater treatment. In this study, natural pyrite and ascorbic acid (AA) were proposed as environmental-friendly activator and reductant for periodate (PI) activation to inactivate ARB. The disinfection treatment of PI/pyrite/AA system could inactivate 5.62 log ARB within 30 min, and the lower pH and higher PI and natural pyrite dosage could further boost the disinfection efficiency. The 1O2 and SO4•- were demonstrated to be crucial for the inactivation of ARB in PI/pyrite/AA system. The disinfection process destroyed the morphological structure of ARB, inducing oxidative stress and stimulating the antioxidant system. The PI/pyrite/AA system effectively reduced the intracellular and extracellular DNA concentration and ARGs abundance, inhibiting the propagation of ARGs. The presence of AA facilitated the activation of PI with natural pyrite and significantly increased the concentration of Fe2+ in solution. The reusability of natural pyrite, the safety of the disinfection by-products and the inhibition of ARB regeneration indicated the application potential of PI/pyrite/AA system in wastewater disinfection.

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.

Natural pyrite-stimulative periodate activation: efficiency and mechanism study.

Natural pyrite (NP) is an alternative catalyst for wastewater purification via advanced oxidation processes (AOPs). However, the activation performance and mechanism of periodate (PI) by NP have not yet been revealed. Herein, this work examines the activation performance of NP towards PI and its application in the degradation of antibiotic wastewater. Interestingly, 95.69% of chlortetracycline (CTC) was degraded by NP within 20 min via PI activation. Besides, NP shows effective degradation of various pollutants such as rhodamine B (65.81%), sulfamethoxazole (89.04%), and sodium butylxanthate (99.77%) within 20 min. The active species quenching experiment suggested that the active species ∙ OH , IO 3 ∙ , 1O2 and the active complex of PI bonded with NP surface participated in CTC degradation. In addition, Fe(II) on NP surface is the main active site for PI activation, while Sn2- species accelerates the reduction of Fe(III) to Fe(II) and promotes sustained PI activation. This work provides new ideas for the application of NP in environmental pollution control.

Insight into mechanism of peroxydisulfate activation by natural pyrite: Participation of Fe(IV) and regulation of Fe(III)/Fe(II) cycle by sulfur species.

In this study, natural pyrite (NP) was used to activate peroxydisulfate (PDS) for imidacloprid (IMD) degradation. NP was characterized by X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Effects of key reaction parameters (NP dosage, PDS concentration and initial pH) and co-existing ions on IMD degradation in the NP/PDS system were investigated. Quenching experiments and electron spin resonance (ESR) tests identified the existence of sulfate radical (SO4•-), hydroxyl radical (•OH), singlet oxygen (1O2) and superoxide radical (O2•-). The cumulative concentration of SO4•- and •OH were quantified by the formation of benzoquinone (BQ) and p-hydroxybenzoic acid (HBA), respectively. Meanwhile, more than 60% of methylphenyl sulfoxide (PMSO) was selectively converted to methylphenyl sulfone (PMSO2), revealing that Fe(IV) was dominant in the NP/PDS system. The order of contribution of the three reactive species in the NP/PDS system was Fe(IV) > â€¢OH > SO4•- (contributions of 1O2 and O2•- were negligible). Fe(II) released from NP played a crucial role in PDS activation, and sulfur species in NP could also boost Fe(III)/Fe(II) cycle and contribute to the generation of reactive species. Further, the possible degradation pathways of IMD have been proposed based on the detected intermediates using high-performance liquid chromatography-mass spectrometry (HPLC-MS), and the toxicity (including acute toxicity, developmental toxicity and mutagenicity) of these intermediates have been predicted using Toxicity Estimation Software Tool (T.E.S.T). Moreover, NP/PDS system was applied in four natural water bodies and IMD degradation efficiency reached more than 97% after adjusting the pH to 3. The fluorescence excitation-emission matrix (EEM) spectra showed that in addition to IMD, NP/PDS system could also remove other impurities.

Central composite design optimization of pilot plant fluidized-bed heterogeneous Fenton process for degradation of an azo dye.

Optimization of Acid Yellow 36 (AY36) degradation by heterogeneous Fenton process in a recirculated fluidized-bed reactor was studied using central composite design (CCD). Natural pyrite was applied as the catalyst characterized by X-ray diffraction and scanning electron microscopy. The CCD model was developed for the estimation of degradation efficiency as a function of independent operational parameters including hydrogen peroxide concentration (0.5-2.5 mmol/L), initial AY36 concentration (5-25 mg/L), pH (3-9) and catalyst dosage (0.4-1.2 mg/L). The obtained data from the model are in good agreement with the experimental data (R(2 )= 0.964). Moreover, this model is applicable not only to determine the optimized experimental conditions for maximum AY36 degradation, but also to find individual and interactive effects of the mentioned parameters. Finally, gas chromatography-mass spectroscopy (GC-MS) was utilized for the identification of some degradation intermediates and a plausible degradation pathway was proposed.

Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite.

Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD) was removed within 120 min when 50 mmol/L H2O2 and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD5/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were achieved. The COD removal efficiency was less sensitive to initial pH than was the classic Fenton process. Excessive amounts of pyrite and H2O2 did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H2O2 (<5 mmol/L). Fluorescence excitation emission matrix analyses illustrated that H2O2 facilitated the reduction by natural pyrite of organic molecules containing an electron-withdrawing group to electron-donating group. Thus, the Fenton-like process catalyzed by pyrite can remediate wastewater containing organic pollutants under mild reaction conditions and provide an alternative environmentally friendly method by which to reuse natural pyrite.

Cr(VI)-contaminated groundwater remediation with simulated permeable reactive barrier (PRB) filled with natural pyrite as reactive material: Environmental factors and effectiveness.

Permeable reactive barriers (PRBs) are efficient technologies for in situ remediation of contaminated groundwater, the effectiveness of which greatly depends on the reactive media filled. Natural pyrite is an iron sulfide material with a very low content of iron and sulfur, and a mining waste which is a potential material for Cr(VI) immobilization. In this study, we conducted a series of batch tests to research the effects of typical environmental factors on Cr(VI) removal and also simulated PRB filled with natural pyrite to investigate its effectiveness, in order to find a both environmentally and economically fine method for groundwater remediation. Batch tests showed that pH had the significant impact on Cr(VI) removal with an apparently higher efficiency under acidic conditions, and dissolved oxygen (DO) would inhibit Cr(VI) reduction; a relatively high initial Cr(VI) concentration would decrease the rate of Cr(VI) sorption; ionic strength and natural organic matter resulted in no significant effects on Cr(VI) removal. Column tests demonstrated that the simulated PRB with natural pyrite as the reactive media was considerably effective for removing Cr(VI) from groundwater, with a sorption capability of 0.6222 mg Cr per gram of natural pyrite at an initial Cr(VI) concentration of 10mg/L at pH 5.5 in an anoxic environment.