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

Mixed-phase titania foams via 3D-printing for pharmaceutical degradation

The continuing accumulation of organic micropollutants, particularly pharmaceuticals, in water is now considered an urgent threat to human health and the environment. Although the photocatalytic degradation of these compounds using slurries of photoactive nanoparticles has been proven to be highly effective at laboratory scale, this technology has not been implemented in industry due to cost and safety concerns. Here, 3D printed titania foams which are nanoparticle-free, mechanically robust and photoactive, are presented for the first time as a viable alternative to slurries for the photocatalytic degradation of pharmaceuticals. By optimizing the resin used to 3D print highly porous gyroid structures and the subsequent sintering conditions, it was possible to obtain a pure titania foam with a high anatase content, leading to the high photoactivity observed. Using carbamazepine, the pharmaceutical most found in waterways around the world, as a model pollutant, the 3D printed foams were tested in a recirculating flow reactor, with a quantum yield and electrical energy per order of 7.6 × 10−3 and 67.6 kW h m−3, respectively, outperforming literature results for titania nanoparticle slurries. These results, along with the reproducibility afforded by 3D printing methods, shows a clear pathway for photocatalysts to be implemented in practice, helping to solve an urgent health problem while addressing the risk of nanoparticulate release in the environment

The role of coagulation on the fate of PFAS, brominated flame retardants and other trace contaminants in tertiary wastewater treatment for phosphorus control

Coagulant dosing to achieve low phosphorus concentrations in wastewater effluents may favour the removal of trace organics such as pharmaceuticals, plasticisers and flame retardants. Nevertheless, the behaviour of trace organics in coagulation processes is currently poorly understood because of the complex interactions between these compounds, the coagulants and dissolved organic matter (DOM). This study assessed the coagulation removal from synthetic secondary effluent of twenty-four compounds including ten PFAS and four brominated flame retardants. Testing involved two coagulants (alum, ferric chloride) and five DOM surrogates (resorcinol, benzoic acid, citric acid, tannic acid, humic acid); DOM surrogates had assorted molecular weights, structures, charges, and hydrophobicity. With coagulant doses of 14 mg Fe/L and 4 mg Al/L, ten trace organics were removed by >30 % in the presence of at least one DOM surrogate. Humic acid effected the highest removals owing to complexation of trace organics and subsequent co-removal by adsorption or sweep floc. For instance, removal extents for three brominated diphenyl ethers were 60 to 75 % with Al and 50 to 88 % with Fe (initial concentration 0.4 to 0.8 ng/L); PFTDA, a long-chain PFAS, was removed by 87 and 91 % with Fe in the presence of tannic or humic acid, respectively (initial concentration 0.03 μg/L). The varying coagulation performance of different treatment works in terms of trace substance removal can be explained because of the site-specific DOM characteristics. Addition of humic acids as complexing agents has the potential to improve the removal of hydrophobic trace substances, including some long-chain PFAS and brominated flame retardants

Simultaneous ozonation of 90 organic micropollutants including illicit drugs and their metabolites in different water matrices.

The ozonation of 90 chemically diverse organic micropollutants (OMPs) including four classes of illicit drugs and their metabolites was studied in pure buffered water, tap water and wastewater effluent at three specific ozone doses and three pH levels. The second order rate constants for the reaction of 40 OMPs with ozone were known and span across 8 orders of magnitude, from below 1 M-1 s-1 to above 107 M-1 s-1. 47 of the tested OMPs were removed to at least 90% at the highest specific ozone dose of 0.3 mM O3 per mM C at pH 7. However, most illicit drugs, including cocainics, amphetamines and ecstasy-group compounds, were ozone-resistant due to their lack of ozone-reactive functional groups. Exceptions included some opioids and the cocaine biomarker anhydroecgonine methylester which contain olefinic bonds and/or activated benzene rings. Different removal trends at different pH for OMPs were due to the combined effect of target compound speciation and ozone stability, leading to elimination of less than 70% for all OMPs at pH 11. In both tap water and wastewater effluent scavenging by matrix components led to lower ozone exposure compared to pure buffered water and consequently lower removal of OMPs. This multi-compound ozonation study utilised liquid chromatography-mass spectrometry to provide a large dataset on the removal of environmentally relevant OMPs, including those of interest for drinking water regulations. Besides including pharmaceutically active compounds that have not been studied with ozone before (e.g. gliclazide, anhydroecgonine methylester, quetiapine, 6-monoacetylmorphine), this study simultaneously shows ozonation data for a wide range of illicit drugs

A Single Tube Contactor for Testing Membrane Ozonation

A membrane ozonation contactor was built to investigate ozonation using tubular membranes and inform computational fluid dynamics (CFD) studies. Non-porous tubular polydimethylsiloxane (PDMS) membranes of 1.0&ndash;3.2 mm inner diameter were tested at ozone gas concentrations of 110&ndash;200 g/m3 and liquid side velocities of 0.002&ndash;0.226 m/s. The dissolved ozone concentration could be adjusted to up to 14 mg O3/L and increased with decreasing membrane diameter and liquid side velocity. Experimental mass transfer coefficients and molar fluxes of ozone were 2.4 &times; 10&minus;6 m/s and 1.1 &times; 10&minus;5 mol/(m2 s), respectively, for the smallest membrane. CFD modelling could predict the final ozone concentrations but slightly overestimated mass transfer coefficients and molar fluxes of ozone. Model contaminant degradation experiments and UV light absorption measurements of ozonated water samples in both ozone (O3) and peroxone (H2O2/O3) reaction systems in pure water, river water, wastewater effluent, and solutions containing humic acid show that the contactor system can be used to generate information on the reactivity of ozone with different water matrices. Combining simple membrane contactors with CFD allows for prediction of ozonation performance under a variety of conditions, leading to improved bubble-less ozone systems for water treatment

A Single Tube Contactor for Testing Membrane Ozonation

A membrane ozonation contactor was built to investigate ozonation using tubular membranes and inform computational fluid dynamics (CFD) studies. Non-porous tubular polydimethylsiloxane (PDMS) membranes of 1.0&ndash;3.2 mm inner diameter were tested at ozone gas concentrations of 110&ndash;200 g/m3 and liquid side velocities of 0.002&ndash;0.226 m/s. The dissolved ozone concentration could be adjusted to up to 14 mg O3/L and increased with decreasing membrane diameter and liquid side velocity. Experimental mass transfer coefficients and molar fluxes of ozone were 2.4 &times; 10&minus;6 m/s and 1.1 &times; 10&minus;5 mol/(m2 s), respectively, for the smallest membrane. CFD modelling could predict the final ozone concentrations but slightly overestimated mass transfer coefficients and molar fluxes of ozone. Model contaminant degradation experiments and UV light absorption measurements of ozonated water samples in both ozone (O3) and peroxone (H2O2/O3) reaction systems in pure water, river water, wastewater effluent, and solutions containing humic acid show that the contactor system can be used to generate information on the reactivity of ozone with different water matrices. Combining simple membrane contactors with CFD allows for prediction of ozonation performance under a variety of conditions, leading to improved bubble-less ozone systems for water treatment