Keywords Mn oxides · Phyllomanganates · Tectomanganates · Sorption · Metals ·
Organics · Remediation
7.1 Introduction
Manganese (Mn) (oxy)hydroxides (hereafter denominated Mn oxides) are ubiquitous in the environment, being encountered in soils (Negra et al. 2005b; Uzochukwu
and Dixon 1986), freshwater (Cerling and Turner 1982), lake (Friedl et al. 1997;
Lienemann et al. 1997; Manceau et al. 2007a) and marine sediments (Aplin and
Cronan 1985; Banerjee et al. 1999; Manceau et al. 2014; Wegorzewski et al. 2015),
as well as in hot (Garvie et al. 2008; Potter and Rossman 1979a) or polar (Dorn et al.
1992) regions. They are also present in many man-made environments, such as sand
used for water filtration (Manceau et al. 2007b). Mn oxides probably originate to a
large extent, at least in surficial environments, from the biotic oxidation of Mn(II) by
the living, as abiotic homogeneous and heterogeneous (that is, catalyzed by mineral
surfaces) oxidation rates are orders of magnitude lower than the oxidation rate
resulting from bacterial activity (Morgan 2005). The assumption of the living
organisms being at the origin of many Mn oxides in surficial environment is
reinforced by the fact that not only many bacterial strains (e.g., Pseudomonas sp.,
Leptothrix sp.) but also many fungal strains and higher living forms are capable of
forming Mn oxides (Grangeon et al. 2010; Jurgensen et al. 2004; Lanson et al. 2008;
Miyata et al. 2006, 2004; Tani et al. 2003; Tebo et al. 2004, 2005; Villalobos et al.
2006; Webb et al. 2005).
In the environment, many Mn oxides are found under the form of black-brown
precipitates forming nodules or coatings on various substrates such as rocks or river
pebbles. They are fine grained in nature and are frequently intermixed with other
minerals. For example, in oceanic ferromanganese nodules, Mn oxides are associated with iron (Fe) oxides and possibly other minerals (e.g., quartz), which form the
underlying sediment and which are embedded in the nodule during its growth. In
soils, Mn oxides can occur under the form of individualized crystals, as coatings on
other mineral particles (Post 1999), and under the form of ferromanganese nodules
(Gasparatos et al. 2005; Manceau et al. 2003; Neaman et al. 2004; Palumbo et al.
2001; Tan et al. 2006; Thresh 1902). These nodules are built of soil particles
cemented by Fe and Mn oxides, forming spherical structures having a high mechanical resistance (Gasparatos et al. 2005; Thresh 1902). The relative proportion of Fe
and Mn oxides is related to the position of the nodules in the soil profile, to the color,
the shape, or the hardness (Sullivan and Koppi 1992; Zhang and Karathanasis 1997).
The varying amounts of Fe and Mn may be related to the fact that these nodules form
during soil alteration and to the fact that Mn is more mobile than Fe and therefore
more easily redistributed in the soil profile during soil weathering (Liu et al. 2002;
Palumbo et al. 2001).
Mn oxides are almost always encountered as nanoparticles, with typical sizes of
5–100 nm (e.g., Bargar et al. 2009), and they often have low crystallinity, which
400
S. Grangeon et al.
Organics · Remediation
7.1 Introduction
Manganese (Mn) (oxy)hydroxides (hereafter denominated Mn oxides) are ubiquitous in the environment, being encountered in soils (Negra et al. 2005b; Uzochukwu
and Dixon 1986), freshwater (Cerling and Turner 1982), lake (Friedl et al. 1997;
Lienemann et al. 1997; Manceau et al. 2007a) and marine sediments (Aplin and
Cronan 1985; Banerjee et al. 1999; Manceau et al. 2014; Wegorzewski et al. 2015),
as well as in hot (Garvie et al. 2008; Potter and Rossman 1979a) or polar (Dorn et al.
1992) regions. They are also present in many man-made environments, such as sand
used for water filtration (Manceau et al. 2007b). Mn oxides probably originate to a
large extent, at least in surficial environments, from the biotic oxidation of Mn(II) by
the living, as abiotic homogeneous and heterogeneous (that is, catalyzed by mineral
surfaces) oxidation rates are orders of magnitude lower than the oxidation rate
resulting from bacterial activity (Morgan 2005). The assumption of the living
organisms being at the origin of many Mn oxides in surficial environment is
reinforced by the fact that not only many bacterial strains (e.g., Pseudomonas sp.,
Leptothrix sp.) but also many fungal strains and higher living forms are capable of
forming Mn oxides (Grangeon et al. 2010; Jurgensen et al. 2004; Lanson et al. 2008;
Miyata et al. 2006, 2004; Tani et al. 2003; Tebo et al. 2004, 2005; Villalobos et al.
2006; Webb et al. 2005).
In the environment, many Mn oxides are found under the form of black-brown
precipitates forming nodules or coatings on various substrates such as rocks or river
pebbles. They are fine grained in nature and are frequently intermixed with other
minerals. For example, in oceanic ferromanganese nodules, Mn oxides are associated with iron (Fe) oxides and possibly other minerals (e.g., quartz), which form the
underlying sediment and which are embedded in the nodule during its growth. In
soils, Mn oxides can occur under the form of individualized crystals, as coatings on
other mineral particles (Post 1999), and under the form of ferromanganese nodules
(Gasparatos et al. 2005; Manceau et al. 2003; Neaman et al. 2004; Palumbo et al.
2001; Tan et al. 2006; Thresh 1902). These nodules are built of soil particles
cemented by Fe and Mn oxides, forming spherical structures having a high mechanical resistance (Gasparatos et al. 2005; Thresh 1902). The relative proportion of Fe
and Mn oxides is related to the position of the nodules in the soil profile, to the color,
the shape, or the hardness (Sullivan and Koppi 1992; Zhang and Karathanasis 1997).
The varying amounts of Fe and Mn may be related to the fact that these nodules form
during soil alteration and to the fact that Mn is more mobile than Fe and therefore
more easily redistributed in the soil profile during soil weathering (Liu et al. 2002;
Palumbo et al. 2001).
Mn oxides are almost always encountered as nanoparticles, with typical sizes of
5–100 nm (e.g., Bargar et al. 2009), and they often have low crystallinity, which
400
S. Grangeon et al.