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etc. The major sources of free radicals such as the superoxide ion (O 2 - ) and
the hydroperoxyl radical (HO 2
) are modest leakages from the electron trans-
port chains of mitochondria, chloroplasts and the endoplasmic reticulum
(Miller et al. 1990 ; Paradies et al. 2000 ; Blokhina et al. 2003 ). The HO
,
alkoxyl radical (RO
), and H 2 O 2 produced from the
autooxidation of biomolecules such as ascorbate, catecholamines or thiols, can
damage the macromolecules such as DNA, proteins and lipids in biological
systems (Miller et al. 1990 ; Buettner and Jurkiewicz 1996 ; Cadet et al. 1999 ;
Blokhina et al. 2003 ; Berlett and Stadtman 1997 ; Morse et al. 1977 ; Radtke
et al. 1992 ; Abele-Oeschger et al. 1994 ). These events have implications for
numerous human health problems. Autoxidation reactions would mostly be
catalyzed by transition metal ions (Fe 2 + , Cu + ), and by semiquinones which
can act as electron (e - ) donors (Buettner and Jurkiewicz 1996 ; Blokhina
et al. 2003 ). Four-electron reduction of oxygen in the respiratory electron
transport chain (ETC.) is generally associated with a partial one- to three-elec-
tron reduction, yielding reactive oxygen species such as O 2
), peroxyl radical (ROO
- , HO
, H 2 O 2 , sin-
- and HO 2
glet oxygen ( 1 O 2 ) and O 3 (Blokhina et al. 2003 ). Both O 2
undergo
spontaneous dismutation to produce H 2 O 2 . In the presence of reduced transi-
tion metals such as Fe 2 + or its complexes that are quite common in biological
systems, the HO
radical can be produced by the Fenton reaction. A mecha-
nistic scheme for the generation of HO
in biological systems can be depicted
as follows (Eqs. 6.1 - 6.3 ) (Buettner et al. 1978 ; Buettner 1987 ; Buettner and
Jurkiewicz 1996 ; Blokhina et al. 2003 ):
FE 3 + -CHELATE + O 2 •− / ASCH FE 2 + -CHELATE + O 2 / ASC •−
(6.1)
FE 2 + -CHELATE + H 2 O 2 FE 3 + -CHELATE + OH + HO
(6.2)
BIOMOLECULES + HO + O 2 FE 3 + -CHELATE + OH + HO
(6.3)
Fig. 9 H 2 O 2 concentration
during photoirradiation of
Suwannee River Fulvic Acid
(10 mg L
1 ) solutions in
the absence ( , average of
five experiments) and the
presence (
, average of three
experiments) of Fe (10 μ M)
at pH 6.0. Data source
Southworth and Voelker
( 2003 )
Irradiation times (hours)
 
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