Abstract

Peroxides and hydrogen peroxide were determined by a fluorometric method in dew and rain collected in the atmosphere of Santiago of Chile city. The measured peroxides comprise hydrogen peroxide (the main component) and peroxides not decomposed by catalase. The collected natural peroxides readily decompose in the natural matrix, rendering difficult an estimation of the values present in real-time. In order to establish the kinetics of the process and the factors that condition their decomposition, the kinetics of the decay at several pHs and/or the presence of metal chelators were followed. The kinetics of hydrogen peroxide decomposition in the water matrix was evaluated employing the natural peroxides or hydrogen peroxide externally added. First-order kinetics was followed, with half decay times ranging from 80 to 2300 min. The addition of Fe(II) in the micromolar range increases the decomposition rate. while lowering the pH ( < 3) notably reduces the rate of the process. The contribution of metals to the decomposition of the peroxides in the natural waters was confirmed by the reduction in decomposition rate elicited by its treatment with Chelex-100. Dew and rain waters were collected in pre-acidified collectors, rendering values considerably higher than those measured in non-treated collectors. This indicates that acidification can be proposed as an easy procedure to stabilize the samples, reducing its decomposition during collection time and the time elapsed between collection and analysis. The weighted average concentration for total peroxides measured in pre-treated collectors was 5.4 mu M in rains and 2.2 mu M in dews. (C) 2000 Elsevier Science Ltd. All rights reserved.