Kinetics and mechanisms of the degradation of PPCPs by zero-valent iron (Fe°) activated peroxydisulfate (PDS) system in groundwater.

The abatement of pharmaceuticals and personal care products (PPCPs), including carbamazepine (CBZ), acetaminophen (ACP) and sulfamethoxazole (SMX), by zero-valent iron (Fe°) activated peroxydisulfate (PDS) system (Fe°/PDS) in pure water and groundwater was investigated. The removal rates of CBZ, ACP and SMX were 85.4%, 100% and 73.1%, respectively, within 10 min by Fe°/PDS in pure water. SO4•-, •OH and O2•- were identified in the Fe°/PDS system, and O2•- was indicated to play an important role in the ACP degradation. The degradation of PPCPs increased with increasing dosages of Fe° and PDS or with decreasing pH and initial PPCP concentrations. Interestingly, the degradation of PPCPs by Fe°/PDS was significantly enhanced in groundwater compared with that in pure water, which was partially attributed to SO42- and Cl-. The first-order constants of CBZ, ACP and SMX increased from 0.021, 0.242 and 0.013 min-1 to 0.239, 2.536 and 0.259 min-1, and to 0.172, 1.516 and 0.197 min-1, respectively, with increasing the concentrations of SO42- and Cl- to 100 mg/L and 10 mg/L, respectively. This study firstly reports the unexpected enhancement of groundwater matrix on the degradation of micropollutants by Fe°/PDS, demonstrating that Fe°/PDS can be an efficient technology for groundwater remediation.

Li A ，Wu Z ，Wang T ，Hou S ，Huang B ，Kong X ，Li X ，Guan Y ，Qiu R ，Fang J ... -  《-》

Hydroxyl radical dominated degradation of aquatic sulfamethoxazole by Fe(0)/bisulfite/O(2): Kinetics, mechanisms, and pathways.

In this study, batch experiments were carried out to investigate the key factors on sulfamethoxazole (SMX) removal kinetics in a new AOPs based on the combination of zero valent iron (Fe0) and bisulfite (S(IV)). With the increase of Fe0 from 0.25 mM to 5 mM, the removal rate of SMX was linearly increased in the Fe0/S(IV)/O2 system by accelerating the activation of S(IV) and Fe0 corrosion to accelerate. In the first 10 min of reaction, the increasing concentration of S(IV) inhibited SMX removal after since the high S(IV) concentration quenched reactive oxidative species (ROS). Then SMX removal rate was accelerated with the increase of S(IV) concentration after S(IV) were consumed up. The optimal ratio of S(IV) concentrations to Fe0 concentration for SMX removal in the Fe0/S(IV)/O2 system was 1:1. With SMX concentrations increasing from 1 to 50 μM, SMX removal rate was inhibited for the limitation of ROS yields. Although the presence of SO4- and OH was confirmed by electron paramagnetic resonance (EPR) spectrum, OH was identified as the dominant ROS in the Fe0/S(IV)/O2 system by chemical quenching experiments. Besides, strong inhibitive effects of 1,10-phenanthroline on SMX degradation kinetics by Fe0/S(IV)/O2 proved that the generation of ROS was rely on the release of Fe(II) and Fe(III). The generation of SO4- was ascribed to the activation of S(IV) by Fe(II)/Fe(III) recycling and the activation of HSO5- by Fe(II). And OH was simultaneously transformed from SO4- and generated by Fe0/O2. Density functional theory (DFT) calculation was conducted to reveal special reactive sites on SMX for radicals attacking and predicted intermediates. Finally, four possible SMX degradation pathways were accordingly proposed in the Fe0/S(IV)/O2 system based on experimental methods and DFT calculation.

Du J ，Guo W ，Wang H ，Yin R ，Zheng H ，Feng X ，Che D ，Ren N ... -  《-》

The graceful art, significant function and wide application behavior of ultrasound research and understanding in carbamazepine (CBZ) enhanced removal and degradation by Fe(0)/PDS/US.

Carbamazepine (CBZ) antibiotic organic contamination wastewater poses a huge threat to environmental safety. An advanced oxidation technology (Fe0/PDS/US) of using ultrasound (US) enhanced zero-valent iron/potassium persulfate (Fe0/PDS) can remove CBZ effectively. The optimal reaction conditions were determined by exploring the effect of single-factor experimental conditions such as ultrasonic power, ultrasonic frequency, CBZ concentration, solution pH, PDS dosage, and Fe0 dosage on the removal of CBZ. In addition, we also investigated into the effect of background ions (PO43-, HCO3-, Cl- and HA) on Fe0/PDS/US and analyzed the related results. The mechanism of CBZ removal in Fe0/PDS/US were explored by analyzing CBZ removal efficiency and reaction rates, the ion concentration of S2O82-, SO42-, Fe2+ and Fe3+, pH and the active radicals. The result indicates that US can improve the efficiency of activated PDS and expand the pH range of Fe0/PDS. It has prominent performance in catalytically degrading CBZ when the pH is 10.0. SO4•-, •OH and O2•- all coexist in the Fe0/PDS/US and make contribution to CBZ removal, whereas the SO4•- plays a key role. US can greatly promotes the degradation of target pollutant CBZ by speeding up the dissolution of the outer portion of iron powder, producing sufficient amount of Fe2+ with a continuous and stable way, and better activating S2O82- to generate sufficient SO4•- radicals. The degradation of CBZ may embrace three reaction processes, in which organic intermediate products with low molecular weight and biological toxicity is produced, boosting further mineralization and biodegradation of products. The Fe0/PDS/US is of great potential application value in removal of organic pollution and environmental purification.

Wei W ，Zhou D ，Feng L ，Li X ，Hu L ，Zheng H ，Wang Y ... -  《-》

Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate: implications for remediation of groundwater contaminated by antibiotics.

The wide occurrence of antibiotics in groundwater raised great scientific interest as well as public awareness in recent years due to their potential ability to spread antibiotic resistant gene and pose risk to humans. The present study investigated the ferrous ion (Fe(II)) activated decomposition of persulfate (S2O8(2-)), as a potential in situ chemical oxidation (ISCO) approach, for remediation of groundwater contaminated by antibiotics. Fe(II)-persulfate mediated ciprofloxacin (CIP) degradation was found to be more efficient than sulfamethoxazole (SMX) at near neutral pH (pH6.0), probably due to the higher electric density in CIP molecule and its ability to form complex with Fe(II) as a ligand. Hydroxyl (HO) and sulfate radical (SO4(-)) were determined to be responsible for the degradation of CIP and SMX in Fe(II)-persulfate system by molecular probes. No enhancement in the degradation of CIP was observed when citrate (CA), ethylenediaminetetraacetate (EDTA) and (S,S)-ethylenediamine-N,N'-disuccinate (EDDS) were used as Fe(II) chelating agents in Fe(II)-persulfate system. For SMX, CA and EDTA accelerated the degradation by Fe(II)-persulfate. Degradation of antibiotics in river water matrix was nearly the same as that in Milli-Q water, implying the possibility of using Fe(II)-persulfate for antibiotics depletion under environmentally relevant condition. A comparison of the degradation efficiency of SMX with other sulfonamides and sulfanilic acid indicated that the heterocyclic ring has a large impact on the degradation of sulfonamides. Transformation products of CIP and SMX by Fe(II)-persulfate were analyzed by solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) technique. Based on the intermediate products, Fe(II)-persulfate mediated CIP degradation pathways were tentatively proposed.

Ji Y ，Ferronato C ，Salvador A ，Yang X ，Chovelon JM ... -  《-》

In situ photoreduction of structural Fe(III) in a metal-organic framework for peroxydisulfate activation and efficient removal of antibiotics in real wastewater.

Structural Fe(III) is widely found in various coordination complexes and inorganic compounds. In this work, a typical Fe-based metal organic framework (MOF) (viz. MIL-100(Fe)) was chosen as an example in the activation of peroxydisulfate (PDS) for the removal of antibiotic pollutants. Interestingly, an auto-acceleration effect was observed in the process of MIL-100(Fe) activating PDS aided by visible light irradiation. Compared to the processes with MIL-100(Fe)-activated PDS alone and the photo-activated PDS alone, the degradation efficiency of sulfamethoxazole (SMX) obtained in the visible light assisted PDS activation by MIL-100(Fe) process was enhanced by 2.1 and 5.6 times, respectively. Therein, the photogenerated electrons from MIL-100(Fe) carried out an in situ reduction of the surface structural Fe(III) to form Fe(II), which in turn significantly improved the PDS activation efficiency in the generation of ·OH and O2-· radicals for the removal of SMX. The degradation pathways of SMX were deduced based on the experimental results and theoretical calculations. Acute toxicity estimation indicated the formation of less toxic products after the treatment of SMX. Additionally, degradation of five antibiotics in the real wastewater were investigated to further confirm the advantages of such in situ photoreduced structural Fe(III) in MOFs to activate the PDS process.

Yin R ，Chen Y ，He S ，Li W ，Zeng L ，Guo W ，Zhu M ... -  《-》