Sunlight-Driven Chlorate Formation during Produce Irrigation with Chlorine- or Chloramine-Disinfected Water

The increasing use of chlorine- or chloramine-containing irrigation waters to minimize foodborne pathogens is raising concerns about the formation and uptake of disinfection byproducts into irrigated produce. Chlorate has received particular attention in the European Union. While previous research demonstrated the formation of chlorate from dark disproportionation reactions of free chlorine and uptake of chlorate into produce from roots, this study evaluated chlorate formation from solar irradiation of chlorine- and chloramine-containing irrigation droplets and uptake through produce surfaces. Sunlight photolysis of 50 μM (3.6 mg/L as Cl₂) chlorine significantly enhanced the formation of chlorate, with a 7.2% molar yield relative to chlorine. Chlorate formation was much less significant in sunlit chloramine solutions. In chlorinated solutions containing 270 μg/L bromide, sunlight also induced the conversion of bromide to 280 μg/L bromate. Droplet evaporation and the resulting increase in chlorine concentrations approximately doubled sunlight-induced chlorate formation relative to that in the bulk solutions in which evaporation is negligible. When vegetables (broccoli, cabbage, chicory, lettuce, and spinach) were sprayed with chlorine-containing irrigation water in a sunlit field, sunlight promoted chlorate formation and uptake through vegetable surfaces to concentrations above maximum residue levels in the European Union. Spraying with chloramine-containing waters in the dark minimized chlorate formation and uptake into the vegetables.