Pentachlorophenol and 3,4-dichloroaniline as models for photochemical reactions in seawater

Pentachlorophenol (PCP) and 3,4-dichloroaniline (DCA) were used as models to examine photochemical reactions in seawater.The photolysis of PCP in seawater differed in both rate and product distribution from that in distilled water; rates were slower in seawater due to the photonucleophilic interaction of PCP with chloride ions, demonstrated by the formation of ³⁶Cl-labeled PCP in irradiated PCP solutions containing Na³⁶Cl. DCA showed no rate change and gave identical products in both systems. Both PCP and DCA yielded greater amounts of photoreduction products in seawater than in distilled water, and tetrachloromuconic acid was isolated and identified as a new and unstable PCP photoproduct resulting from ringfission. This study demonstrates the operation of photooxidation, photonucleophilic substitution, and photoreduction reactions which differ in detail between seawater and distilled water and suggests that photochemical reactions can be a major factor in the breakdown of organic pollutants and other chemicals in the marine environment.