Degradation of geosmin and 2-methylisoborneol in water with UV/chlorine: Influencing factors, reactive species, and possible pathways.

Geosmin (GSM) and 2-methylisoborneol (2-MIB) are two common odor compounds in drinking water. In this paper, the performance of UV/chlorine was compared with that of chlorine and UV to degrade GSM (100 ng L-1) and 2-MIB (100 ng L-1) in water. UV/chlorine was further exploited, and a steady-state kinetic model was used to conduct a detailed study on efficiency, rate, reactive species and pathway. The results showed that UV/chlorine greatly could improve the removal ratio to 90% within 5 min, from approximately 20% with only UV or dark chlorine in 60 min. The removal ratio and rate depended on UV light intensity, free chlorine dosage, reaction time and water quality parameters (e.g. pH, concentrations of HCO3- and Cl-). Among these factors, the first two obviously could accelerate the rate and increase the ratio. The degradation was also significantly improved in an acidic condition, while alkaline conditions and HCO3- had inhibitory effects, and Cl- created no difference. Contributions of OH and Cl to the degradation of 2-MIB and GSM were further revealed, and OH was found to be the most important reactive species. In the UV/chlorine process, 6 degradation byproducts of 2-MIB, including 1 alcohol, 2 ketones, and 3 olefins, were identified, and 14 degradation byproducts of GSM, including 6 ketones, 1 aldehyde, 2 alcohols, 3 naphthenes, and 2 olefins, were found by using solid-phase microextraction coupled to gas chromatography-mass spectrometry. The possible degradation pathways of GSM and 2-MIB in UV/chlorine thus were proposed.

Degradation mechanisms of geosmin and 2-MIB during UV photolysis and UV/chlorine reactions.

We conducted chlorination, UV photolysis, and UV/chlorin reactions to investigate the intermediate formation and degradation mechanisms of geosmin and 2-methylisoborneol (2-MIB) in water. Chlorination hardly removed geosmin and 2-MIB, while the UV/chlorine reaction at 254 nm completely removed geosmin and 2-MIB within 40 min and 1 h, respectively, with lesser removals of both compounds during UV photolysis. The kinetics during both UV photolysis and UV/chlorine reactions followed a pseudo first-order reaction. Chloroform was found as a chlorinated intermediate during the UV/chlorine reaction of both geosmin and 2-MIB. The pH affected both the degradation and chloroform production during the UV/chlorine reaction. The open ring and dehydration intermediates identified during UV/chlorine reactions were 1,4-dimethyl-adamantane, and 1,3-dimethyl-adamantane from geosmin, 2-methylenebornane, and 2-methyl-2-bornene from 2-MIB, respectively. Additionally, 2-methyl-3-pentanol, 2,4-dimethyl-1-heptene, 4-methyl-2-heptanone, and 1,1-dichloro-2,4-dimethyl-1-heptane were newly identified intermediates from UV/chlorine reactions of both geosmin and 2-MIB. These intermediates were degraded as the reaction progressed. We proposed possible degradation pathways during the UV photolysis and UV/chlorine reactions of both compounds using the identified intermediates.

Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light.

The degradation of geosmin and 2-methylisoborneol (2-MIB) by UV irradiation at different wavelengths was investigated under varying boundary conditions. The results showed that conventional UV radiation (254 nm) is ineffective in removing these compounds from water. In contrast to the usual UV radiation UV/VUV radiation (254+185 nm) was more effective in the removal of the taste and odour compounds. The degradation could be described by a simple pseudo first-order rate law with rate constants of about 1.2 x 10(-3) m(2)J(-1) for geosmin and 2-MIB in ultrapure water. In natural water used for drinking water abstraction the rate constants decreased to 2.7 x 10(-4) m(2)J(-1) for geosmin and 2.5 x 10(-4) m(2)J(-1) for 2-MIB due to the presence of NOM. Additionally, the formation of the by-product nitrite was studied. In the UV/VUV irradiation process up to 0.6 mg L(-1) nitrite was formed during the complete photoinitiated oxidation of the odour compounds. However, the addition of low ozone doses could prevent the formation of nitrite in the UV/VUV irradiation experiments.