Chapter IV Results and Discussion

IV. 1 Comparison the image of SE and BSE mode

Figure IV.1 shows the difference of SEM imaging mode. The images on the left
column of Figure IV.1 are the results of SEM by using the mode SE (Secondary
Electron), while the images on the right column using the mode BSE
(backscattered electron). The results of the SE mode image do not clearly show
the contrast between the grains, while the BSE mode image shows the contrast
between the grain. On the results of SEM with BSE seen some of the light-colored
grains, it is assumed as a sign that these grains contain heavy element (higher
atomic number), while for the SE image is clearer to see the shape of the grains on
the surface (topography).

In this study the SEM image is dominated by the image of BSE, because the
contrast is significant in demonstrating the presence of heavy metals, such as the
research conducted by Nowaczyk (2011) using a BSE image of grain contained in
foraminifera (CaCO3) which appeared darker than the grains that contain
Titanomagnetites. Moreover, according to Trewin (1988) and Nowaczyk (2011),
BSE provides good information about the differences between the composition of
mineral grains and better used to identify remanence carriers within magnetic
extracts and can show the differences in atomic number under 0.12. The size of an
image taken depends on 3 things, the energy of the electron, the atomic number
and density of the grains of the sample. In the BSE image, the energy exchange
between electrons and the reflectance of the sample produces a high-energy
electrons by elastic scattering, BSE is therefore better to show the contrast
between grains with different atomic numbers, especially in this case shows a
large atomic number such as Fe. In the other hand, SE has low energy, making it
easy to escape from the sample, it only can be detected when the electron is
produced at the surface. This is the reason why SE is better to analyze the
topography of the sample. In the process of implementation of this study, the
method of BSE is also well used to indicate the mineral with a high oxygen levels
through the contrast of colors. Figure IV. 2 shows the results of EDS in the two

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regions with contrasting colors on the BSE image. Region 001 (left) has darker
color, contains 36.68% of iron oxide and 38,90%, while for the 002 (right) which
has lighter color with the larger content of iron oxide, 59,58% and has smaller
content of oxygen, 15.26%. As noted by Nowaczyk (2011) the greater of oxygen
content can be found in the darker area.

IV.2 Extraction Method

SEM imaging results are also greatly influenced by the effectiveness of the
method of extraction. In this study the extraction was done in two methods. The
difference lies in the liquid used in the first stage of extraction. The first way to
use alcohol baths and magnetic extraction process is performed only once, while
the second stage using a bath detergent and extraction processes performed more
than once. Results from the first extraction seen in Figure IV. 3. Figure IV. 3. a-b
shows that there are still impurities (clay), whereas for the second extraction of
magnetic minerals is cleaner (Figure IV. 3. c - d).

Several methods of extraction were performed in previous studies is to use a

centrifuge to separate the water content of the sample and then diluted with
ethanol. This method is used by Huliselan (2009) on samples of sludge leachate,
dry ink by Irvan (2005), and Sidoarjo mud (Irvan, 2008). On the other hand, some
studies do the extraction with the use of ethanol in lake sediments (Nowaczyk,
2011) and in soil samples (Safiuddin et al., 2011). Based on the results of this
study, extraction using detergent is better, due to sufactant content which is an
active ingredient that can remove impurities on the surface of the material. In
addition, the effectiveness of extraction is also influenced by the repetition of
magnetic extraction using hand magnet.

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Figure IV. 3 SEM analysis using the two extraction methods: (a) and (b) First
extraction method shows there is still impurities (marked with red
dots), (c) and (d) the second extraction method shows the grain
cleaner than the previous way.

IV. 3 Morphology and Composition of Magnetic Mineral

Morphology of magnetic minerals is a very important indicator to distinguish
between processes and the origin of minerals. In addition, the morphology is also
used to determine the process of diagenesis in that area. SEM and EDX results
obtaining the varies of the shape and composition of magnetic minerals. These
variations are influenced by environmental conditions and its formation process.
Magnetic minerals from lake sediments Towuti have a composition dominated by
iron oxide (FeO) with quietly large mass percentation, more than 65%.

Figure IV.4 is the result of the SEM image of the first samples. This figure shows
that there is mineral grain with a size of about 5 microns, which is an octahedral
shape characteristics of magnetite. Composition of this grain is dominated by FeO

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with very large of mass percentation, about 93.91%. In addition, it is also found
the compound SiO2 but the presentation is relatively very small mass, that is
equal to 3.09%.

Figure IV.5 shows the result of SEM analyses of the second sample. There are
two grains in this figure, one has prism-shaped with a smooth surface, and grain
size of about 5 microns. This mineral is dominated by iron oxide with a very large
mass, equal to 89.25%, in the other hand, there is SiO2 compound with very small
mass percentation, equal to 4.05%. Grain 2 has size approximately two times
larger than grain 1, equal to 10 microns, with a prism-shaped morphology with
fractures on the surface. The composition of grain 2 is dominated by iron oxide
with mass percentage of 89.11%, SiO2 compound is also found with a very small
percentage, equal to 2.78%. Both of these grains are assumed to be magnetite.

Figure IV.6 is the result of SEM image of the grain sample 3, there are three
mineral grains of different sizes. Grain 1 has size of about 10 microns, with the
top of the prism-shaped corner looks like a truncated prism. Grain 2 and 3 have
similar size and morphology, prism-shaped with a smooth surface and size of
about 5 microns. These three grains are assumed to be magnetite.

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Figure IV.9 is the result of SEM image of the grain sample 5, there are three
mineral grains with different shape and size. Grain 1 has size of about 10 microns,
dodecahedron-shaped with composition is dominated by iron oxide of about
99.03%, this grain is assumed as magnetite. Grain 2 has approximately 10
microns in size, with a hexagonal-shaped. The composition is dominated by iron
oxide with 97.36%, SiO2 also found with a very small percentage, that is equal to
2.64%, this mineral is assumed as hematite. While grain 3, has oval-shaped
morphology with slightly rough surface and some cracks on its surface. The
composition is dominated by grains of iron oxide that is equal to 98.90%. This
grain is assumed as magnetite, as well as grain 1.

1 3

Figure IV. 9 The SEM image of the grain sample 5. (1) a dodecahedron-shaped,
(2) a hexagonal-shaped grain. (3) The oval-shaped grain with
slightly rough and cracks on its surface. Grain 1 and 3 were
assumed to be the magnetite, while the grain 2 is the hematite.

Figure IV.10 shows the SEM image of the grain sample 6. The grain on the left
has about 10 microns size, a prism-shaped with a slightly rough surface. The grain
on the right has a size approximately equal to the grain 1, 10 microns, has a

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perfect hexagonal shape. Both grains are dominated by iron oxide with the mass
percentage of 79.86%. The left grain is assumed as magnetite while the grain on
the right image is assumed as hematite.

Figure IV. 10 SEM morphology of grains in the sample 6. Left: a prism-shaped

mineral grains with a slightly rough surface, assumed as a
magnetite. Right: a nearly perfect hexagonal-shaped mineral grains,
its composition is dominated by iron oxide, assumed as hematite.

Study of morphology and mineral composition plays an important role in

predicting the source or origin of magnetic minerals. Morphology of magnetic
minerals at this core TOW 9 generally has a shape similar to lake sediment
magnetic mineral on research conducted by Nowaczyk (2011) in Lake Kinneret,
Israel, which has angle and prism-shaped. In addition some of the mineral is
found also elliptical, according Huliselan (2009), round or oval-shaped mineral
derived from anthropogenic processes. The differences in the morphology of
mineral grains is presumably due to the formation, deposition and transport of
environmental conditions. According to the pattern morphology and composition
of magnetic minerals, this TOW 9 core is divided in two parts, upper (0-506 cm)
and bottom (507 cm - 1 143 cm). At the top of this core, the morphology of
magnetic minerals was dominated by prismatic and octahedral-shaped also
assumed as magnetite with average size of about 5 microns. At the bottom of this
core, still found magnetite, and hematite and maghemite with approximately the
same size, 10 microns. It is also found grains interpreted as evidence of magnetite

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dissolution (blue circle in figure IV.8, figure IV.11 and left of figure IV.10).
Maghemite is allegedly arising from the process of the maghemitization of
magnetite. It is shown by magnetite grain with maghemite-striated (Figure IV.
12). According to Nowaczyk (2011), the maghematization is the process of
oxidation of (Titano-) magnetite at low temperatures (T <250 C), but in general,
this process is caused by the migration of Fe ions out the lattices which causes the
shrinkage effects resulting the changes of magnetic properties of maghemite.
While the mineral hematite is found by the oxidation process of maghemite.

Figure IV. 11 SEM image of grains in the sample 4. Red circle shows a grain
predicted as a evidence of magnetite dissolution.

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Figure IV. 12 SEM image of grains in the sample 5. Shown an oval-shaped
magnetite magnetite grain with maghemite-striated. This grain is
assumed as the result of maghemitization process.

Elements that appear beside iron oxide and is Magnesium (Mg) with a range of
percentage 1.85% to 36% on top of the core and 1.57% to 27% in the bottom core.
Silicate elements are almost always found in every grain that contains iron oxide,
with a percentage range of 4% to 40% in the top core. At the bottom of core, the
presence of silicate varies of about 1% -38%, for the grain with higher content of
silicate has smaller content of iron, this probably indicates, the surface of the
magnetic minerals are covered by silicate matrix. At bottom core, the abundance
of Carbon (C) was found of about 54.92% which is assumed as siderite (Figure.
IV. 13).

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Figure IV. 13 The morphology and composition of the grain in sample 6. Shows
a cube (in red circle) with a rough surface with a composition
dominated by elemental carbon of 54.92%. Probably this mineral is
Siderite.

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Lately, a lot of diagenesis studies using SEM analysis. Diagenesis means
chemical and physical changes at the sediment deposited. In this study, the
process of diagenesis is only visible to the physical changes of grains, like the
shape and size of the grains, but not too significant. Chemical changes in the
magnetic grains is only visible in the same class, such as the oxidation of
magnetite becomes maghemite, as well as the oxidation of maghemite becomes
hemitite at the bottom of the core.

In this study, there were no changes from iron oxide to iron sulfide. Iron sulfide
can provide a picture of magnetostatigraphy and could be an important role in
providing a significant effect of diagenesis. Iron sulfide minerals are generally
found in the anoxic sediment layer. This TOW 9 did not reveal any iron sulfide
magnetic minerals, it indicates three possibilities; first possibilities, this TOW 9
core is located at the oxic sediment layer, the second TOW 9 core is located at the
anoxic in non-sulphic condition and the third possibility is extraction the samples
were not effective enough. Iron sulfides supposedly required a particular way due
to the nature of the magnetism of iron sulphide is much weaker than the iron
oxide.

Compared with research conducted by Nowaczyk (2011), iron sulfide can be

found by extraction with alcohol and ultrasound, iron sulfide can also be found
using detergent extraction as well, this indicates that the presence of iron sulfide
in core TOW 9 is very low, moreover, according to geochemistry study held by
Dr. James Russel from Brown University (communication through electronic
mail), the presence of iron sulfide in TOW9 core is very low as well. According to
Canfield and Berner (1987), areas with low susceptibility can be attributed to the
dissolution of magnetite and can also be associated with sulfate conditions, where
at high H2S conditions, the dissolution of magnetite is accompanied by
replacement of pyrite, in contrast, at low H2S conditions, the dissolution of
magnetite is not accompanied by replacement of pyrite. This is consistent with
SEM results at the bottom of the core which shows the dissolution of magnetite in
an area with low susceptibility values (table 1). In addition, according to Leslie et

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al. (1990), magnetite dissolution occurs in sediments, especially in suboxic and
anoxic condition. The existence of siderite at the bottom of the core also
strengthens the case that the bottom of the sediment deposition zone TOW9 is in
anoxic zone, because siderite formed in zones of low oxygen or anoxic zone.
According to Kearey (1993), anoxic is a low level of dissolved oxygen
environment. Anaerobic organism use other oxidants to break down organic
matter, such as nitrate, iron oxide and sulphate, after the available oxygen has
been utilized.

Overall, the extraction method used in this study resulting good images of SEM
analysis, grain shape and grain can be seen clearly, moreover, compared to study
conducted by Nowaczyk (2011), the extraction method is more economical and
more easily to obtain. In the context of magnetic minerals, the study Nowaczyk,
(2011) found an abundance of iron oxides and iron sulfides that provide good
information for the process of diagenesis. In this study, there was an abundance of
magnetite, but in contrast, there was no iron sulfide, therefore the process of
diagenesis is only visible in iron oxides.

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