ABSTRACT
An alternative sample preparation method for photochemical studies, which overcomes all the disadvantages associated with classical approaches, is proposed. The method is based on Solid Phase Microextraction (SPME) and can be considered as being within the scope of "green photochemistry", especially when it is combined with sunlight irradiation. To demonstrate the potential of the procedure, photochemical studies of synthetic pyrethroids were carried out. Photodegradation pathways for five dihalogenovinyl-substituted pyrethroid pesticides: permethrin, deltamethrin, cyfluthrin, cypermethrin and lambda-cyhalothrin, are proposed, and kinetic curves and parameters provided. This information, obtained by rapidly carried out, green experiments, allows us to corroborate photoproducts reported by other authors and to identify the photoproducts proposed for the first time in the present study.
Subject(s)
Photochemistry/methods , Pyrethrins/chemistry , Solid Phase Microextraction/methods , Kinetics , Pyrethrins/radiation effects , Spectrophotometry, Ultraviolet , Ultraviolet Rays , Water Pollutants, Chemical/chemistryABSTRACT
In this work the photochemical behaviour of a technical mixture of polybrominated diphenyl ethers (PBDEs) (BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) has been studied. The mixture of BDEs was extracted from aqueous solutions using SPME fibers that were subsequently exposed to different UV irradiation times, procedure so-called Photo-SPME. PBDEs photochemical studies in such medium have been accomplished for the first time. Twenty one different photoproducts, all of them generated by successive bromine atoms losses, have been identified, being their photoformation-photodegradation curves easily determined by the Photo-SPME technique.
Subject(s)
Flame Retardants , Phenyl Ethers/chemistry , Polybrominated Biphenyls/chemistry , Bromine/chemistry , Dimethylpolysiloxanes/chemistry , Gas Chromatography-Mass Spectrometry , Oxidation-Reduction , PhotochemistryABSTRACT
Photodegradation kinetics of four nitro musks (musk xylene, musk tibetene, musk ketone and musk moskene) in solid-phase microextraction (SPME) fibres ("photo-SPME") and in an aqueous system were studied by means of gas chromatography-mass spectrometry (MS) detection. Musks fragrances were extracted from aqueous solutions using SPME fibres that subsequently were exposed to different UV irradiation times, generating photoproducts easily characterized by their mass spectra. Aqueous photodegradation studies followed by SPME were also performed and compared to photo-SPME. The same fourteen photoproducts have been detected in both media. The potential of this approach to readily calculate apparent rate constants (from 10(-4) to 10(-3) s(-1)), half-life times (from 3 to 32 min) and reaction orders (n = 1) in both media is stated. The main photoreaction determined was photocyclization, but products of photoreduction and photorearrangement have also been detected. Tentative photodegradation pathways for musk moskene and musk tibetene are proposed for the first time.
