UV-visible degradation of boscalid--structural characterization of photoproducts and potential toxicity using in silico tests.
BACKGROUND
Boscalid is a carboximide fungicide mainly used for vineyard protection as well as for tomato, apple, blueberry and various ornamental cultivations. The structural elucidation of by-products arising from the UV-visible photodegradation of boscalid has been investigated by gas chromatography/multi-stage mass spectrometry (GC/MS(n) ) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) couplings. The potential toxicities of transformation products were estimated by in silico calculations.


METHODS
Aqueous solutions of boscalid were irradiated up to 150 min in a self-made reactor equipped with a mercury lamp. Analyses were carried out using a gas chromatograph coupled with an ion trap mass spectrometer operated in both electron ionization (EI) and chemical ionization (CI) modes and a liquid chromatograph coupled with a quadrupole time-of-flight (Q-TOF) mass spectrometer operated in electrospray ionization (ESI) mode. Multiple-stage collision-induced dissociation (CID) experiments were performed to establish dissociation pathways of ions. The QSAR (Quantitative Structure-Activity Relationship) T.E.S.T. program allowed the estimation of the toxicities of the by-products.


RESULTS
Eight photoproducts were investigated. Chemical structures were proposed not only on the interpretation of multi-stage CID experiments, but also on kinetics data. These structures led us to suggest photodegradation pathways. Three photoproducts were finally detected in Lebanon in a real sample of grape leaves for which routine analysis had led to the detection of boscalid at 4 mg kg(-1).


CONCLUSIONS
With one exception, the structures proposed for the photoproducts on the basis of mass spectra interpretation have not been reported in previous studies. In silico toxicity predictions showed that two photoproducts are potentially more toxic than the parent compound considering oral rat LD50 while five photoproducts may induce mutagenic toxicity. With the exception of one compound, all photoproducts may potentially induce developmental toxicity.
Laboratoire des Mécanismes Réactionnels UMR-7651, École Polytechnique, 91128, Palaiseau Cedex, France.
Yannick
Y
Lassalle
Aziz
A
Kinani
Ahmad
A
Rifai
Yasmine
Y
Souissi
Carine
C
Clavaguera
Sophie
S
Bourcier
Farouk
F
Jaber
Stéphane
S
Bouchonnet
D000818:Animals; D001713:Biphenyl Compounds / Q000737:chemistry / Q000528:radiation effects* / Q000633:toxicity*; D002853:Chromatography, Liquid; D003198:Computer Simulation; D052918:Environmental Restoration and Remediation; D008401:Gas Chromatography-Mass Spectrometry; D009536:Niacinamide / Q000031:analogs & derivatives* / Q000737:chemistry / Q000528:radiation effects / Q000633:toxicity; D010782:Photolysis; D051381:Rats; D012989:Soil Pollutants / Q000737:chemistry / Q000528:radiation effects* / Q000633:toxicity*; D053719:Tandem Mass Spectrometry; D014466:Ultraviolet Rays
D001713:Biphenyl Compounds; D012989:Soil Pollutants; D009536:Niacinamide; C550088:2-chloro-N-(4-chlorobiphenyl-2-yl)nicotinamide