Photochemical transformation of ibuprofen into harmful 4-isobutylacetophenone: Pathways, kinetics, and significance for surface waters

• Published in: Water research (Oxford) 2013-10, Vol.47 (16), p.6109-6121
• Main Authors: Ruggeri, Giulia, Ghigo, Giovanni, Maurino, Valter, Minero, Claudio, Vione, Davide
• Format: Article
• Language: English
• Subjects: Acetophenones - chemistry; Applied sciences; Chain reactions; Chains; dissolved organic matter; Drugs; Exact sciences and technology; Formations; Ibuprofen; Ibuprofen - chemistry; Kinetics; Non-steroidal anti-inflammatory drugs; Photochemical; Photochemical Processes; photolysis; Photosensitised transformation; Pollution; propionic acid; Radical reactions; Surface water; Surface-water photochemistry; Transformation by-products and intermediates; Transformations; Water Pollutants, Chemical - chemistry; Water treatment and pollution
• ISSN: 0043-1354; 1879-2448
• DOI: 10.1016/j.watres.2013.07.031

The harmful compound 4-isobutylacetophenone (IBAP) can be formed photochemically from the anti-inflammatory drug ibuprofen (IBP), upon direct photolysis (yield 25 ± 7%, μ ± σ), reaction with OH (yield 2.3 ± 0.1%) and reaction with triplet states of chromophoric dissolved organic matter, 3CDOM* (yield 31 ± 4%). In the latter case, anthraquinone-2-sulphonate was used as CDOM proxy. The three processes would account for most of the photochemical transformation of IBP and IBAP in surface waters. IBAP formation from IBP involves the propanoic acid chain, which is more reactive than the aromatic ring as shown by quantum mechanical calculations. IBAP is expected to undergo slightly faster photochemical transformation than IBP in surface waters, with a modelled pseudo-first order rate constant that is higher by 1.5–1.9 times compared to IBP. Due to fairly high formation yields and depending on IBP emission scenarios, photochemical modelling suggests that IBAP could reach concentration values up to ∼15% of IBP in surface waters, thus being a potentially important transformation intermediate. This issue prompts for the need of field studies that provide information on IBAP environmental occurrence, which is virtually unknown at the present moment. [Display omitted] •Intermediate formation yields from ibuprofen highest for 3CDOM* and lowest for OH.•Intermediate (IBAP) is photodegraded by photolysis, 3CDOM* and OH.•IBAP is photochemically less persistent than ibuprofen (IBP) in surface waters.•IBAP concentration can reach up to 15% of the IBP one in surface water bodies.•Toxic IBAP is an important intermediate of IBP (monitoring required).