摘要
Gibberellic acid(GA_(3))is widely used in agriculture and maybe transfer with groundwater flow,which is an endocrine disruptor,but few studies have focused on the transformation pathway and toxicity assessment of GA_(3)and its products.Here,GA_(3)and its transformation products in aqueous solution were identified and quantified by liquid chromatography mass spectrometry hybrid ion trap time-of-flight(LCMS-IT-TOF)and high-performance liquid chromatography(HPLC),respectively.The results showed that the half-life of GA_(3)transformation in ultrapure water was 16.1–24.6 days at p H=2.0–8.0,with the lowest half-life occurring at p H=8.0 and highest half-life occurring at p H=3.3.Isomerized gibberellic acid(Iso-GA_(3))and gibberellenic acid(GEA)were the main transformation products with a little hydroxy gibberellic acid(OH-GA_(3)).In North China groundwater,the mass balance of GA_(3)and its products was 76.2%,including Iso-GA_(3)(58%),GEA(7.9%),GA_(3)(7.3%)and OH-GA_(3)(3%)after reaching transformation equilibrium.Using Gaussian 09 for chemical computation,it was found that the transformation mechanism of GA_(3)was dependent upon the bond energy and the stereochemical feature of its molecular structure.GA_(3)always isomerized from theγ-lactone ring due to the lowest bond energy between the oxygen terminus of theγ-lactone ring and A ring.While GA_(3)and its transformation products all had developmental toxicity,the predicated LC 50(96 hr)and LD 50 of the main products of GA_(3)were much lower than those of GA_(3),indicating GA_(3)would be transformed into higher toxicity derivatives in water environments,posing a significant health risk to humans and the environment.
基金
supported by the National Natural Science Foundation of China(No.41772245)
the National Key Research and Development Program of China(No.2019YFC1805400)
the Fundamental Research Funds for the Central Universities(No.2020ZDPY0201)。
