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(Levy et al., 2005; Maeda et al., 1992) or to generate energy to
support cellular growth (Mateos et al., 2010; Oremland and Stolz,
2003). Microbial biotransformation of highly toxic As
III
includes
oxidation to As
V
and methylation to MetAs forms.
2.1. Oxidation of arsenite by microorganisms
Oxidation of As
III
to As
V
is an energy-producing reaction since
As
III
can serve as electron donor in this process (Mateos et al., 2010;
Páez-Espino et al., 2009). Over the past decade, many microorganisms, including eubacteria and archaea, have been reported
to be using energy generated from the oxidation or reduction
of As oxyanions (Oremland and Stolz, 2003). Microbial mats
predominantly composed of filamentous microorganisms (algae,
presumably Cyanidium and bacteria, similar to Hydrogenobacter acidophilus) have been reported to be responsible for rapid oxidation
of As
III
in a hot spring ecosystem within the Yellowstone National
Park (Langner et al., 2001). A study by Kulp et al. (2008) presented the evidence for As
III
-supported anoxygenic photosynthesis
in naturally-occurring microbial mats of photosynthetic bacteria from Mono Lake (California). They also provided evidence of
photoautotrophic growth of purple bacteria supported by As
III
oxidation to As
V
. The mechanisms of As
III
oxidation by microorganisms
include chemolithoautotrophic metabolism where As
III
is used as
an energy source (Santini et al., 2000) and extracellular oxidation
of As
III
via an arsenite oxidase (Langner et al., 2001).
2.2. Reduction of arsenate by microorganisms
Biomethylation of iAs has been commonly observed in prokaryotic and eukaryotic photosynthetic microorganisms such
as microalgae and cyanobacteria (Ye et al., 2012). Because of
physicochemical similarities between As
V
and phosphate, these
photosynthetic microorganisms actively take up As
V
through the
PO
3−
4
uptake system and then biotransform As
V
inside their cells
(Fig. 1A) (Hasegawa et al., 2001; Suhendrayatna and Maeda, 2001;
Yin et al., 2011). The toxicity of As
V
is due to binding of AsO
3−
4
at
places where PO
3−
4
is essential inside the cells (Hellweger et al.,
2003). To reduce the toxic effect, the photosynthetic microorganisms biotransform As
V
inside their cells in a process that involves a
two-electron reduction of pentavalent As
V
to trivalent As
III
, mediated by glutathione (Fig. 1B) (Hughes, 2002).
2.3. Biomethylation of iAs by phytoplankton
Inside the cells of photosynthetic organisms, As
V
is reduced to
As
III
followed by oxidative methylation of intermediate trivalent
MetAs species (MMA
III
and DMAIII
) to pentavalent MetAs species
(MMA
V
and DMAV
) (Hughes, 2002). A number of freshwater and
marine phytoplankton have been reported to biomethylate iAs
(Caumette et al., 2011; Hirata and Toshimitsu, 2005; LlorenteMirandes et al., 2010; Miyashita et al., 2011; Slejkovec et al., 2006).
The concentrations of different arsenic species in phytoplankton
and macroalgae is listed in Table 1. A study by Hasegawa et al.
(2001) showed that a freshwater phytoplankton (Closterium aciculare) converts As
V
predominantly (∼80%) into the less toxic
pentavalent methylated intermediate (DMA
V
), with trace concentrations of trivalent MetAs. The biotransformation of As
V
by marine
and freshwater phytoplankton is discussed in detail elsewhere
(Rahman and Hasegawa, 2011).
Arsenate reduction and methylation rates in freshwater environments are often dependent on the dynamics of phytoplankton
blooms, which are affected by nutrient enrichment and seasonal
variables such as light and temperature (Hasegawa et al., 2010;
Hasegawa et al., 2009; Rahman and Hasegawa, 2012). Sohrin et al.
(1997) reported seasonal variations of As speciation in Lake Biwa,
Japan, where the concentrations of As
III
increased in spring and
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