Stereoselective degradation of aqueous endosulfan in modular estuarine mesocosms: formation of endosulfan gamma-hydroxycarboxylate

J Environ Monit. 2003 Jun;5(3):373-9. doi: 10.1039/b212165d.

Abstract

Solutions of alpha-endosulfan, beta-endosulfan, and technical grade endosulfan (70alpha:30beta) were added to modular estuarine mesocosms; the kinetics and degradation products from each mesocosm are reported. The persistent product endosulfan sulfate was generated in all cases; however, its yield was approximately a factor of three higher from alpha-endosulfan relative to beta-endosulfan. Beta-endosulfan hydrolyzed faster than alpha-endosulfan to endosulfan diol, which then rapidly degraded to endosulfan ether, endosulfan alpha-hydroxyether (major product), and endosulfan lactone. The ring-opened form of the lactone, endosulfan gamma-hydroxycarboxylate, is reported for the first time; it appears to be a terminal product, at least over the timescale of the experiment. The equilibrium between endosulfan gamma-hydroxycarboxylate and endosulfan lactone is dependent on pH, as only the protonated form of the gamma-hydroxy acid undergoes ring-closure. The pKa of the gamma-hydroxy acid was determined to be 5.7, implying that the lactone will quickly open and deprontonate under environmentally relevant conditions.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Biological Availability
  • Endosulfan / chemistry
  • Endosulfan / metabolism*
  • Hydrocarbons, Chlorinated*
  • Hydrolysis
  • Insecticides / chemistry
  • Insecticides / metabolism*
  • Kinetics
  • Models, Theoretical*
  • Molecular Conformation
  • Oxidation-Reduction
  • Water Pollutants, Chemical / metabolism*

Substances

  • Hydrocarbons, Chlorinated
  • Insecticides
  • Water Pollutants, Chemical
  • Endosulfan