Aqueous ozonation of furans:Kinetics and transformation mechanisms leading to the formation of α,β-unsaturated dicarbonyl compounds

Despite the widespread occurrence of furan moieties in synthetic and natural compounds, their fate in aqueous ozonation has not been investigated in detail. Reaction rate constants of seven commonly used furans with ozone were measured and ranged from kO3 = 8.5 × 104 to 3.2 × 106 M−1 s−1, depending on the type and position of furan ring substituents. Transformation product analysis of the reaction of furans with ozone focusing on the formation of toxic organic electrophiles using a novel amino acid reactivity assay revealed the formation of α,β-unsaturated dicarbonyl compounds, 2-butene-1,4-dial (BDA) and its substituted analogues (BDA-Rs). Their formation can be attributed to ozone attack at the reactive α-C position leading to furan ring opening. The molar yields of α,β-unsaturated dicarbonyl compounds varied with the applied ozone concentration reaching maximum values of 7% for 2-furoic acid. The identified α,β-unsaturated dicarbonyls are well-known toxicophores that are also formed by enzymatic oxidation of furans in the human body. In addition to providing data on kinetics, transformation product analysis and proposed reaction mechanisms for the ozonation of furans, this study raises concern about the presence of α,β-unsaturated dicarbonyl compounds in water treatment and the resulting effects on human and environmental health.</p

Effect of Solution pH on the Dual Role of Dissolved Organic Matter in Sensitized Pollutant Photooxidation

[Image: see text] Dissolved organic matter (DOM) has a dual role in indirect phototransformations of aquatic contaminants by acting both as a photosensitizer and an inhibitor. Herein, the pH dependence of the inhibitory effect of DOM and the underlying mechanisms were studied in more than 400 kinetic irradiation experiments over the pH range of 6–11. Experiments employed various combinations of one of three DOM isolates, one of two model photosensitizers, the model antioxidant phenol, and one of nine target compounds (TCs), comprising several aromatic amines, in particular anilines and sulfonamides, and 4-cyanophenol. Using model photosensitizers without antioxidants, the phototransformation of most TCs increased with increasing pH, even for TCs for which pH did not affect speciation. This trend was attributed to pH-dependent formation yields of TC-derived radicals and their re-formation to the parent TC. Analogous trends were observed with DOM as a photosensitizer. Comparison of model and DOM photosensitizer data sets showed increasing inhibitory effects of DOM on TC phototransformation kinetics with increasing pH. In systems with anilines as a TC and phenol as a model antioxidant, pH trends of the inhibitory effect could be rationalized based on the reduction potential difference (ΔE(red)) of phenoxyl/phenol and anilinyl/aniline couples. Our results indicate that the light-induced transformation of aromatic amines in the aquatic environment is governed by the pH-dependent inhibitory effects of antioxidant phenolic moieties of DOM and pH-dependent processes related to the formation of amine oxidation intermediates

Simplified in-situ tailoring of cross-linked self-doped sulfonated polyaniline (S-PANI) membranes for nanofiltration applications

Sulfonated polyaniline (S-PANI) membranes could have wide-ranging applications due to their electrical tunability, antifouling behaviour and chlorine resistance. However, S-PANI membranes below the ultrafiltration (UF) separation range have not been successfully established. This study presents a scalable approach to produce the first in-situ cross-linked S-PANI membranes at nanofiltration (NF) range. S-PANI membranes were produced by non-solvent induced phase separation (NIPS). The presence of sulfonic groups as polymer cross-linking anchors and controlling the coagulation bath's acidic strength resulted in instant stabilisation of the selective layer, which hindered the solvent/non-solvent exchange rate. This enabled the production of a tailored membrane morphology with a dense skin layer, suppressed macro-voids, reduced porosity, enhanced tensile strength, increased hydrophilicity and solvent stability. S-PANI membranes cast in 3 M HCl(aq) with MWCO≈680 g mol−1 (sucrose octa-acetate) showed a rejection of 99 % for PEG 1000 g mol−1 and 91–100 % for dye solution (MW range of 320–1017 g mol−1) compared to 34 % and 74–85 % rejection for a commercial fluoropolymer membrane (nominal MWCO 1000 g mol−1), respectively. The reported approach is simple and can be applied to design new classes of cross-linked solvent stable S-PANI NF membranes

Photocatalytic foams for water treatment: A systematic review and meta-analysis

Photocatalysis has proven to be highly effective for the removal of recalcitrant organic micropollutants at the lab scale. However, drawbacks such as the need for downstream removal of nanoparticle slurries and low surface areas of immobilised catalyst have, so far, hindered large-scale application. Photocatalytic foams have the potential to address these issues and advance the field towards large scale deployment. This review offers the first comprehensive overview of the state-of-the-art in this growing research field while simultaneously addressing two key issues which are slowing down further progress: The lack of classification nomenclature for foams, particularly regarding pore size and production method, and the use of kinetics as the defining feature of a photocatalyst, when alternate figures of merit, such electrical and quantum efficiencies, may be more appropriate. These were particular evident from a semi-quantitative comparison of the literature reported here, which highlighted the need for standardisation of experimental methods within the field. Finally future perspectives and best practices are discussed and recommended