Abiotic chlorination of organic matter in the soil environment: A simulation study

Chlorination of organic matter occurs naturally and is an important part of the chlorine cycle. To investigate the likelihood that inorganic oxidants, (Fe(NO₃)₃, H₂O₂, and hydroxyl radicals (·OH), frequently present in soil environments, could promote the synthesis of chlorinated organic matter in the soil environment, litterfall, humus, and soil (0–20 cm) were collected and used in laboratory based simulation experiments. Results indicate that these inorganic oxidants might promote the synthesis of chlorinated organic matter, but their impact varied due to varying suitable reaction circumstances. Litterfall was the most sensitive to chlorination, likely caused by the presence of abundant amounts of labile organic matter, and the chlorination process was limited by its Cl⁻ level. Hydroxyl radicals showed a dual effect (producing or degrading chlorinated organic matter) on the three materials assessed, which was controlled by both ·OH concentration and the stability of organic matter, and the dual effect was evident in order of litterfall > humus > soil. The Fe(NO₃)₃-mediated chlorination of organic matter was only significant in litterfall due to its labile organic matter composition, while the peroxidative reaction caused by H₂O₂ in the producing chlorinated organic matter was only obvious in soil, most likely due to the presence of metals, facilitating the process. Combined this study sheds light on the chlorine cycle by verifying that inorganic oxidants might mediate abiotic chlorination of organic matter in a natural soil environment.