Bioaccumulation and Bound-Residue Formation of a Branched 4-Nonylphenol Isomer in the Geophagous Earthworm Metaphire guillelmi in a Rice Paddy Soil

Nonylphenols (NPs) are the breakdown products of the nonionic surfactants nonylphenol ethoxylates and are toxic pollutants. Here we studied the bioaccumulation, elimination, and biotransformation of NP (12.3 mg kg?1 soil dry weight) in a typical Chinese geophagous earthworm, Metaphire guillelmi, in a rice paddy soil, using 4-[1-ethyl-1,3-dimethylpentyl]phenol (4-NP111), the main constitute of technical NP, radiolabeled with 14C. Earthworms rapidly bioaccumulated 14C-4-NP111 following a two-compartment first-order kinetics model. At steady state (after 20 days exposure), the normalized biota-soil accumulation factor amounted to 120, and 77% of the accumulated radioactivity were present as nonextractable bound residues. The total radioactivity was eliminated from the earthworm following an availability-adjusted decay model and controlled by the elimination rate of the bound residues (half-life = 22.6 days). The extractable residues consisted mainly of one less-polar metabolite (37%) and polar compounds (50%), including glucuronide conjugates of 4-NP111 and the metabolite; and free 4-NP111 accounted for only 9% of the total extractable residues. This study provides the first results of the toxicokinetics and biotransformation of 4-NP in a terrestrial organism, and underlines the significant underestimation of the bioaccumulation and risk assessment based only on free NP in earthworms. Nonylphenols (NPs) are the breakdown products of the nonionic surfactants nonylphenol ethoxylates and are toxic pollutants. Here we studied the bioaccumulation, elimination, and biotransformation of NP (12.3 mg kg?1 soil dry weight) in a typical Chinese geophagous earthworm, Metaphire guillelmi, in a rice paddy soil, using 4-[1-ethyl-1,3-dimethylpentyl]phenol (4-NP111), the main constitute of technical NP, radiolabeled with 14C. Earthworms rapidly bioaccumulated 14C-4-NP111 following a two-compartment first-order kinetics model. At steady state (after 20 days exposure), the normalized biota-soil accumulation factor amounted to 120, and 77% of the accumulated radioactivity were present as nonextractable bound residues. The total radioactivity was eliminated from the earthworm following an availability-adjusted decay model and controlled by the elimination rate of the bound residues (half-life = 22.6 days). The extractable residues consisted mainly of one less-polar metabolite (37%) and polar compounds (50%), including glucuronide conjugates of 4-NP111 and the metabolite; and free 4-NP111 accounted for only 9% of the total extractable residues. This study provides the first results of the toxicokinetics and biotransformation of 4-NP in a terrestrial organism, and underlines the significant underestimation of the bioaccumulation and risk assessment based only on free NP in earthworms.