Chlorination Kinetics of 11-Nor-9-carboxy-Δ⁹-tetrahydrocannabinol: Effects of pH and Humic Acid

The main psychoactive compound in marijuana, Δ⁹-tetrahydrocannabinol (THC), and its metabolites are emerging organic contaminants that have been detected in waste and surface waters. As legalization of marijuana for medical and recreational use continues, the effects of increased use and potency of marijuana on water and wastewater treatment processes and the environment should be considered. This study examined degradation kinetics of the main urinary metabolite of THC, 11-nor-9-carboxy-Δ⁹-tetrahydrocannabinol (THC-COOH) with chlorine. THC-COOH was rapidly removed from both deionized (DI) water at pH 5.6 ± 0.2 and Suwannee River humic acid (SRHA) at pH 5.1 ± 0.2 using low doses of chlorine (0.1 to 0.50 mg free Cl₂/L), with half-lives calculated from second-order kinetics constants (k₂) of 8 s for DI and 42 s for DI with SRHA. Kinetic rates increased with an increase in pH from 5 to 9 in both DI water and SRHA and no interference from phosphate was observed. The chlorination pathway of electrophilic substitution of Cl at the ortho or para position of the phenol structure of THC-COOH was confirmed by detection of monochlorinated byproduct fragmentation ions using flow injection analysis with orbitrap mass spectrometry.