To probe the reactivity of 2,4,6-trimethylphenol with humic triplet excited states, we investigated its influence on the humic substances-mediated photooxygenation offurfuryl alcohol. Elliott soil humic and fulvic acids were employed for these experiments. When added in the concentration range of 10(-4) - 10(-3) M, 2,4,6-trimethylphenol inhibited furfuryl alcohol photooxygenation to an extent depending on its concentration. The inhibiting effect decreased as the oxygen concentration was increased. By postulating that 2,4,6-trimethylphenol competes with oxygen for reaction with humic triplet excited states and with furfuryl alcohol for reaction with singlet oxygen, we obtained kinetic laws describing the consumption profiles of furfuryl alcohol and 2,4,6-trimethylphenol. Experimental rates of 2,4,6-trimethylphenol and furfuryl alcohol loss could be satisfactorily fitted with 1.09-1.16 for the ratio k2/k3, where k2 and k3 are the reaction rate constants of humic triplet excited states with oxygen and 2,4,6-trimethylphenol, respectively. These types of experiments could be extended to a variety of substrates to measure their reaction rate constants with humic triplet excited states.

The IHSS soil humic acid (HA) standard and two HAs from soils of very different origin (Chernozem and Ranker) were fractionated by tandem size-exclusion chromatography-polyacrylamide gel electrophoresis. From each HA, three fractions with different molecular sizes (MSs) and electrophoretic mobilities were obtained and investigated for their fluorescence properties and abilityto photoinduce the transformation of 2,4,6-trimethylphenol and herbicide fenuron. Regardless of the source of the HA, the two high MS fractions were found to be very weakly fluorescent. They photoinduced the degradations of fenuron and 2,4,6-trimethylphenol less efficiently than the bulk HA (10-50-fold and 1.4-5.3-fold, respectively). In contrast, the low MS fraction was proved to be fluorescent and to photoinduce the transformation of probes as least as efficiently than the bulk HA. These results show that (i) most of fluorophores and a great part of photoinductive chromophores are located in the low MS fractions of soil HAs and (ii) this distribution of photochemically active constituents may be characteristic across broad soil types.