Treatment of antimicrobial azole compounds via photolysis, electrochemical and photoelectrochemical oxidation: Degradation kinetics and transformation products.

The degradation kinetics and transformation products of pharmaceutical azole drugs from Watch List 2020/1161 (fluconazole, FCZ; miconazole, MCZ; clotrimazole, CTZ; and sulfamethoxazole, SMX) are examined individually and as a mixture in Milli-Q water and simulated wastewater (SWW) upon treatment with three different advanced oxidation processes: (i) photolysis (UV), (ii) electrochemical (eAOP), and (iii) photoelectrochemical (eAOP/UV). For individual pollutant degradation, UV was found to be significantly more effective for SMX and CTZ compared to MCZ and FCZ. Whereas when treating the azole drugs mixture, eAOP/UV was determined to be the most effective treatment method. The degradation efficiency was higher in Milli-Q than in SWW because the treatment efficiency depended on the matrix compositions. The degradation products formed under different processes were identified, and the routes of transformation were proposed. The results of this study can assist in the selection of the most suitable treatment technology depending upon the pollutant or matrix.

Anodic oxidation of sulfamethoxazole paired to cathodic hydrogen peroxide production.

A double chamber electrochemical system is developed consisting of a boron-doped diamond (BDD) anode and a graphite cathode, which not only degrades sulfamethoxazole (SMX) but also simultaneously generates hydrogen peroxide (H2O2). The degradation of SMX is carried out by (in)direct oxidation at the BDD anode and H2O2 is produced by two electron oxygen (O2) reduction reaction (ORR) at the cathode. The effect of different parameters on the kinetics of both mechanisms was investigated. The performance of the system at the optimized conditions (pH 3, 0.05 M Na2SO4 as electrolyte, and 10 mA as applied current) showed that after 180 min of electrolysis, SMX was almost fully degraded (95% removal and ∼90% COD reduction) as well as about 535 µM H2O2 was accumulated. With the help of LC-MS, five intermediates formed during SMX electrolysis were properly identified and a degradation pathway was proposed. This study advocates methods for improving the effectiveness of energy use in advanced wastewater treatment.

Recent advances in carbonaceous catalyst design for the in situ production of H2O2 via two-electron oxygen reduction.

The electrochemical oxygen reduction reaction has received increasing attention as a relatively green, safe and sustainable method for in situ hydrogen peroxide (H2O2) production. Recently, significant achievements have been made to explore carbon-based (noble metal-free) low-cost and efficient electrocatalysts for H2O2 electroproduction, which could potentially replace the traditional anthraquinone process. However, to realize industrial-scale implementation, a highly active and selective catalytic material is needed. In this review paper, we first expound on the oxygen reduction reaction (ORR) mechanism, which is the origin of in situ H2O2 production. Then, the recent progress in the development of modified carbon-based catalysts is reviewed and classified, corresponding to their physical or chemical modulation. Furthermore, an overview is provided of the available examples from pilot/large-scale applications. Finally, an outlook on the current challenges and future research prospects to transfer the lab-developed catalysts into pilot or industrial-scale reactors is briefly discussed.

High-resolution MS and MS(n) investigation of ozone oxidation products from phenazone-type pharmaceuticals and metabolites.

Phenazone-type pharmaceuticals, such as aminopyrine, metamizole, phenazone and propyphenazone, are widely used analgesics that have been detected in wastewater treatment plant effluents in µg L(-1) concentrations. Acetamido antipyrine (AAA) and formyl aminoantipyrine (FAA) - the main metabolites of aminopyrine and metamizole - have also been detected in sub µg L(-1) concentrations in environmental water bodies and in resources used to produce drinking water, suggesting their highly persistent character. In this study phenazone, propyphenazone, AAA and FAA were treated with ozone under laboratory conditions and 17 degradation products were identified by an elucidation approach based on high-resolution mass spectrometry (LTQ Orbitrap). Typical oxidation of carbon-carbon double bonds by ozone was observed among other mechanisms of ring opening. It was demonstrated that reactivity of these compounds with ozone is high (rate constants kO3 ranging from 6.5×10(4) to 2.4×10(6) M(-1) s(-1)). The toxicity of the degradation products from ozonation was estimated by quantitative structure-activity relationships (QSAR). It was shown that, when the carbon-carbon double bond is partially oxidized to an epoxy, the toxicity towards fish and daphnids is higher than that of the parent compound. By further oxidizing the molecules, a common degradation product - 1-acetyl-1-methyl-2-phenylhydrazide (AMPH) - was also found to be more toxic than its parent compounds, which is of concern since this compound has previously been reported in environmental waters.