Insights into pH-dependent transformation of gibberellic acid in aqueous solution: Transformation pathway, mechanism...

Gibberellic acid (GA₃) 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 GA₃ and its products. Here, GA₃ 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 GA₃ transformation in ultrapure water was 16.1-24.6 days at pH=2.0-8.0, with the lowest half-life occurring at pH=8.0 and highest half-life occurring at pH=3.3. Isomerized gibberellic acid (Iso-GA₃) and gibberellenic acid (GEA) were the main transformation products with a little hydroxy gibberellic acid (OH-GA₃). In North China groundwater, the mass balance of GA₃ and its products was 76.2%, including Iso-GA₃ (58%), GEA (7.9%), GA₃ (7.3%) and OH-GA₃ (3%) after reaching transformation equilibrium. Using Gaussian 09 for chemical computation, it was found that the transformation mechanism of GA₃ was dependent upon the bond energy and the stereochemical feature of its molecular structure. GA₃ always isomerized from the γ-lactone ring due to the lowest bond energy between the oxygen terminus of the γ-lactone ring and A ring. While GA₃ and its transformation products all had developmental toxicity, the predicated LC₅₀ (96 hr) and LD₅₀ of the main products of GA₃ were much lower than those of GA₃, indicating GA₃ would be transformed into higher toxicity derivatives in water environments, posing a significant health risk to humans and the environment.