『Abstract
We have conducted a series of laboratory studies to investigate
the generation of ferrous iron and reactive oxygen species when
solutions of seawater containing natural organic matter (NOM)
and ferric iron are exposed to simulated sunlight. Total ferrous
iron and hydrogen peroxide were measured at nanomolar concentrations
with high temporal resolution using chemiluminescence-based methods.
In all cases, ferrous iron concentrations rapidly peaked at several
nanomoles per litre after a few minutes, and then declined over
time, while hydrogen peroxide concentrations increased in a non-linear
manner. Although concentrations of both species depended on the
concentration of NOM, hydrogen peroxide concentrations were only
minimally affected by the presence of iron. Increasing the NOM
concentration while the total iron concentration was maintained
constant led to an increase in the maximum ferrous iron concentrations,
suggesting that superoxide-mediated reduction of iron may be a
major pathway for ferrous iron formation. This was supported by
measurements of superoxide production from irradiation of NOM
in the absence of iron and kinetic calculations, as well as as
experiment in which superoxide dismutase was added. Further analysis
of the data suggested that dissolved oxygen and photo-produced
hydrogen peroxide were the primary oxidants of the Fe(II) formed.
Thus we propose that superoxide and ferrous iron may be intricately
coupled in the system, and that their generation is determined
by the supply of NOM available to harvest light and donate electrons.』
1. Introduction
2. Experimental section
2.1. General
2.2. Experimental apparatus and procedure
2.3. Determination of ferrous iron, hydrogen peroxide and superoxide
2.4. Ferrozine-trapping experiment
3. Results and discussion
3.1. Photo-generation of ferrous iron and hydrogen peroxide
by simulated sunlight
3.2. Speciation of iron during irradiation
3.3. Reduction of Fe(III) to Fe(II)
3.4. Re-oxidation of Fe(II) to Fe(III)
3.5. Production versus consumption of ferrous iron
4. Conclusions
Acknowledgments
Appendix A. Supplementary data
References