Drosophilin A methyl ether (DAME) and other chlorinated dimethoxybenzenes in fungi and forest litter from Sweden

Abstract

Fungi and substrates undergoing fungal decomposition were collected from forests in northern and southern Sweden and analyzed for chlorinated dimethoxybenzenes (DMBs). Specimens were fungi fruiting bodies, rotting wood, forest litter and underlying humus. Targeted compounds were DAME (1,2,4,5-tetrachloro-3,6-DMB) and related fungal secondary metabolites. A screening procedure was developed which involved soaking the specimens in ethyl acetate followed by analysis by capillary gas chromatography – mass spectrometry with mass selective detection (GC-MSD). DAME was the most frequently found (62% of 47 specimens) and often the most abundant target compound, with range and mean ± SD concentrations of <0.0017–3.81 and 0.21 ± 0.63 mg kg−1 ww. Based on log-log correlations of partition coefficients of hydrophobic compounds between fungal biomass/water (KD) and octanol/water (KOW), five species of fungi are suggested to produce DAME de novo versus bioaccumulation from forest runoff water. Full-scan mass spectra of some high-concentration specimens indicated the presence of a Cl2DMB and a Cl3DMB, which could not be identified further due to lack of standards, and drosophilin A (DA = 2,3,5,6-tetrachloro-4-methoxyphenol), the precursor to DAME. Tetrachloroveratrole (TeCV = 1,2,3,4-tetrachloro-5,6-DMB) was found in only a few specimens. This study supports our hypothesis of fungi as a source of DAME in terrestrial runoff and indicates that other chlorinated secondary metabolites are present. DAME is widely distributed globally, and it would be good to have a better understanding of its sources and pathways as a marker of terrestrial organochlorines and their availability for bioaccumulation.