Infancy of peracetic acid activation by iron, a new Fenton-based process: A review.

The exacerbated global water scarcity and stricter water directives are leading to an increment in the recycled water use, requiring the development of new cost-effective advanced water treatments to provide safe water to the population. In this sense, peracetic acid (PAA, CH3C(O)OOH) is an environmentally friendly disinfectant with the potential to challenge the dominance of chlorine in large wastewater treatment plants in the near future. PAA can be used as an alternative oxidant to H2O2 to carry out the Fenton reaction, and it has recently been proven as more effective than H2O2 towards emerging pollutants degradation at circumneutral pH values and in the presence of anions. PAA activation by homogeneous and heterogeneous iron-based materials generates - besides HO• and FeO2+ - more selective CH3C(O)O• and CH3C(O)OO• radicals, slightly scavenged by typical HO• quenchers (e.g., bicarbonates), which extends PAA use to complex water matrices. This is reflected in an exponential progress of iron-PAA publications during the last few years. Although some reviews of PAA general properties and uses in water treatment were recently published, there is no account on the research and environmental applications of PAA activation by Fe-based materials, in spite of its gratifying progress. In view of these statements, here we provide a holistic review of the types of iron-based PAA activation systems and analyse the diverse iron compounds employed to date (e.g., ferrous and ferric salts, ferrate(VI), spinel ferrites), the use of external ferric reducing/chelating agents (e.g., picolinic acid, l-cysteine, boron) and of UV-visible irradiation systems, analysing the mechanisms involved in each case. Comparison of PAA activation by iron vs. other transition metals (particularly cobalt) is also discussed. This work aims at providing a thorough understanding of the Fe/PAA-based processes, facilitating useful insights into its advantages and limitations, overlooked issues, and prospects, leading to its popularisation and know-how increment.

Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry.

In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 µM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 µM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways.

EEM-PARAFAC as a convenient methodology to study fluorescent emerging pollutants degradation: (fluoro)quinolones oxidation in different water matrices.

Commercial (fluoro)quinolones ((F)Qs), ciprofloxacin (CIP), enrofloxacin (ENR), ofloxacin (OFL), oxolinic acid (OA) and flumequine (FLU) (3 µM each), were degraded with solar-photo-Fenton in a compound parabolic concentrator photoreactor (total volume 5 L) in ultra-pure water at pH = 5.0, salty water at pH = 5.0, and simulated wastewater at pH = 5.0 and 7.5. Iron speciation (its hydrolysis and the complexation with (F)Qs 15 µM and/or chlorides 0.5 M) was calculated at pH 5.0, observing, negligible formation of Fe(III)-chloride complexes, and that >99 % of the total (F)Qs are forming complexes stoichiometry 1:1 with Fe(III) (which also increases the percentage of Fe(OH)2+), being minoritarian the free antibiotic form. On the other hand, EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) was employed to simultaneously study the behaviour of: i) 4 structure-related groups corresponding to parent pollutants and slightly oxidised by-products, ENR-like (including CIP), OFL-like, OA-like, FLU-like; ii) intermediates still showing (F)Q characteristics (exhibiting analogous fluorescent fingerprint to ENR-like one, but shifted to shorter wavelengths); iii) humic-like substances. The scores from the 4 PARAFAC components corresponding to the parent pollutants were plotted vs. accumulated energy, exhibiting slower decay than their individual removals (measured with HPLC-UV/vis) due to the contribution of the aforementioned by-products to the overall fluorescence. Moreover, thiabendazole (TBZ) 3 µM was added as fluorescence interference. The presence of (F)Qs greatly enhanced TBZ degradation due to (F)Q-Fe(III) complex formation, keeping iron active at pH = 5.0 for Fenton process. The EEM-PARAFAC model was able to recognise the former six components plus an additional one attributable to TBZ-like.

A Rational Analysis on Key Parameters Ruling Zerovalent Iron-Based Treatment Trains: Towards the Separation of Reductive from Oxidative Phases.

The development of treatment trains for pollutant degradation employing zerovalent iron has been attracting a lot of interest in the last few years. This approach consists of pre-treatment only with zerovalent iron, followed by a Fenton oxidation taking advantage of the iron ions released in the first step. In this work, the advantages/disadvantages of this strategy were studied employing commercial zerovalent iron microparticles (mZVI). The effect of the initial amount of mZVI, H2O2, pH, conductivity, anions and dissolved oxygen were analysed using p-nitrobenzoic acid (PNBA) as model pollutant. 83% reduction of PNBA 6 µM into p-aminobenzoic acid (PABA) was achieved in natural water at an initial pH 3.0 and 1.4 g/L of mZVI, under aerobic conditions, in 2 h. An evaluation of the convenience of removing mZVI after the reductive phase before the Fenton oxidation was investigated together with mZVI reusability. The Fenton step against the more reactive PABA required 50 mg/L of H2O2 to achieve more than 96% removal in 15 min at pH 7.5 (final pH from the reductive step). At least one complete reuse cycle (reduction/oxidation) was achieved with the separated mZVI. This approach might be interesting to treat wastewater containing pollutants initially resistant to hydroxyl radicals.

Fluorescence Spectroscopy and Chemometrics: A Simple and Easy Way for the Monitoring of Fluoroquinolone Mixture Degradation.

In this work, fluorescence excitation-emission matrices (EEMs), in combination with the chemometric tool and parallel factor analysis (PARAFAC), have been proposed as an unexplored methodology to follow the removal of the fluorescent contaminants of emerging concern, fluoroquinolones (FQs). Ofloxacin, enrofloxacin, and sarafloxacin were degraded by different advanced oxidation processes employing simulated sunlight (hν): photolysis, H2O2/hν, and photo-Fenton. All experiments were performed in ultrapure water at three different pH values: 2.8, 5.0, and 7.0. With the obvious advantage of multivariate analysis methods, EEM-PARAFAC allowed the monitoring of degradation from the overall substances (original and formed ones) through simultaneous, rapid, and cost-efficient fluorescence spectroscopy determinations. A five-component model was found to best fit the experimental data, allowing us to (i) describe the decay of the fluorescence signals of the three parent pollutants, (ii) follow the kinetics profile of FQ-like byproducts with similar EEM fingerprints than the original FQs, and (iii) observe the formation of two families of reaction intermediates with completely different EEMs. Results were finally correlated with high pressure liquid chromatography, total organic carbon, and toxicity tests on Escherichia coli, showing good agreement with all the studied techniques.

Significant role of iron on the fate and photodegradation of enrofloxacin.

Enrofloxacin (ENR) belongs to the fluoroquinolone (FQ) antibiotics family, which are contaminants of emerging concern frequently found in effluents. Although many works studying photo-Fenton process for FQ degradation have been reported, there are no reports analysing in deep the effect of iron complexation, as well as other metals, towards FQs' photolysis, which, evidently, also contributes in the overall degradation of the pollutant. Therefore, in this work, we report a comparative study between the photochemical fate of ENR and its complex with Fe(III) under simulated sunlight irradiation. In addition, the effect of dissolved oxygen, self-sensitization process, and H2O2 addition on the studied photochemical systems are also investigated. Results indicate that, for free and iron-complexed ENR, singlet oxygen (1O2) is generated from the interaction of its triplet state with ground state oxygen. Half-life time (t1/2) of ENR under sun simulated conditions is estimated to be around 22 min, while complexation with iron enhances its photostability, leading to a t1/2 of 2.1 h. Such finding indicates that at least the presence of iron, might notably increase the residence time of these pollutants in the environment. Eventually, only with the addition of H2O2, the FQ-iron complex is efficiently degraded due to photo-Fenton process even at circumneutral pH values due to the high stability of the formed complex. Finally, after LC/FT-ICR MS analysis, 39 photoproducts are detected, of which the 14 most abundant ones are identified. Results indicate that photoproducts formation is pH and iron dependent.

Monitoring photolysis and (solar photo)-Fenton of enrofloxacin by a methodology involving EEM-PARAFAC and bioassays: Role of pH and water matrix.

The degradation of enrofloxacin (ENR) by direct photolysis, Fenton and solar photo-Fenton processes has been studied in different water matrices, such as ultra-pure water (MQ), tap water (TW) and highly saline water (SW). Reactions have been conducted at initial pH 2.8 and 5.0. At pH = 2.8, HPLC analyses showed a fast removal of ENR by (solar photo)-Fenton treatments in all studied water matrices, whereas a 40% removal was observed after 120 min of photolysis. However, TOC measurements showed that only solar photo-Fenton was able to produce significant mineralization (80% after 120 min of treatment); differences between ENR removal and mineralization can be attributed to the release of important amounts of reaction by-products. Excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) were employed to gain further insight into the nature of these by-products and their time-course profile, obtaining a 5-component model. EEM-PARAFAC results indicated that photolysis is not able to produce important changes in the fluoroquinolone structure, in sharp contrast with (solar photo)-Fenton, where decrease of the components associated with fluoroquinolone core was observed. Agar diffusion tests employing E. coli and S, aureus showed that the antibiotic activity decreased in parallel with the destruction of the fluoroquinolone core.