Journal of Minerals and Materials Characterization and Engineering, 2012, 11, 709-718
Published Online July 2012 (
Characterization and Comparison of Saprist and Fibrist
Newfoundland Sphagnum Peat Soils
Emmanuel S. Asapo1,2*, Cynthia A. Coles1
1Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St. John’s, Canada
2Chemical and Polymer Engineering Department, Faculty of Engineering, Epe Campus,
Lagos State University, Lagos, Nigeria
Email: *
Received April 5, 2012; revised May 21, 2012; accepted June 9, 2012
Saprist and fibrist sphagnum peat soils obtained from the same natural peat bog owned by Traverse Nurseries, Torbay,
Newfoundland, Canada were characterized to study their potential for adsorbing metals. Both peat soils had a pH of 4.2.
The saprist peat had the lower fiber content (68.6% versus 75%), higher cation exchange capacity (70 meq/100g versus
45 meq/100g), higher moisture content (86% versus 82%), higher organic matter content (91% versus 84%), higher wet
bulk density (0.65 g/cm3 versus 0.60 g/cm3) and higher dry bulk density (0.28 g/cm3 versus 0.20 g/cm3). A crystallog-
raphy study showed that the saprist peat was completely amorphous and the metal content analysis showed high cal-
cium and iron concentrations in both types of peat with higher values in the fibrist peat. Carboxylic acid, alcoholic hy-
droxyl, phenolic hydroxyl, amine and amide functional groups were present and these could be responsible for binding
metal ions via ion exchange and or complexation reactions.
Keywords: XRD; SEM; FTIR; NMR; ICP-MS; Functional Groups
1. Introduction
Mining is a major contributor of soil and water pollution
[1] and a high proportion of dissolved metals exist in
areas surrounding mining sites [2] and have been ana-
lyzed in water samples long after the mines have been
closed or abandoned [1]. Aqueous phase metals are
highly mobile and aquatic life around any mine site could
be perpetually endangered if improperly treated waste-
waters are discharged.
Adsorption using low cost adsorbents such as agricul-
tural wastes (orange skins, banana peels, [3]) saw dust
[4], peat [5,6], clay and zeolites [7], is an effective alter-
native to precipitation, membrane technology and floata-
tion for metal removal from wastewater. An adsorbent is
“low cost” if it is readily available, requires minimal or
no processing [8] and is inexpensive or of zero cost.
Peat soils are promising adsorbents for heavy metal
removal [5,6,9], easily harvested and are economical as
can be seen from Table 1. Peat is partially fossilized
plant matter that is formed in poorly oxygenated waters
of marshes, bogs, and swamps where the rate of plant
matterproduction and accumulation exceeds the rate of
microbial oxidation [15]. Though peat is most common
in the northern hemisphere, large deposits exist in Brazil,
Indonesia and South Africa [16]. Peatlands or peat bogs
record environmental and paleoenvironmental evolution
and provide a reference for measuring past and present
global climate change [17].
Since 1922 the von Post scale has been used to classify
peat from poorly decomposed (1 H) to completely de-
composed (10 H) and peat has also been classified as
being highly decomposed (saprist), moderately decom-
posed (hemic) or poorly decomposed (fibrist) [18,19].
Peat characterization has remained a difficult task
since peat soils may form under a variety of conditions of
vegetation and environment [20]. In the past characteri-
zation has provided details on the organic and inorganic
compounds present in the peat, usually obtained through
partial or complete destruction of the peat matrix, and
details on the morphology and particle size. Previous
studies have focused on the humic and fulvic acid frac-
tions extracted from the peat [21-25] but the determina-
tion of the constituents or composition of peat, with
minimal destruction is preferable and may be more real-
istic [26].
Poorly humified or fibrist peat (horticultural peat) has
been well studied as an adsorbent for heavy metals
[27-29] although the highly humified or saprist peat has
not been studied to the same extent and the peat-metal
bonding mechanisms have not been fully understood or
*Corresponding author.
Copyright © 2012 SciRes. JMMCE
Table 1. Relative cost of some adsorbent materials.
Adsorbent material Cost (US $/kg) Source
Chitosan 15.43 [10]
Activated Carbon ~2.54
(production, quality and source dependent)[11]
Zeolites 0.03 - 0.14
(quality and end-use dependent) [12]
Clay 0.03 - 0.375
(quality and type dependent) [13]
Peat 0.024 - 0.052
(peat type and processing level dependent)[14]
established [30], possibly due in part to the destructive
characterization procedures employed. Saprist peat can
be used as an agricultural enhancement for improving the
water holding capacity of sandy soils [23] and possess a
higher metal adsorptive capacity than the widely studied
fibrist peat [31].
This paper describes and compares the properties of
untreated saprist and fibrist peat soils from the same peat
bog. Physico-chemical characterization of the two peat
soils was undertaken using standard laboratory proce-
dures and in addition, was supplemented with non-de-
structive characterization of the two peat soils employing
five types of equipment including an X-Ray Diffracto-
meter (XRD), a Scanning Electron Microscope (SEM), a
Fourier Infrared Spectroscope (FTIR), a Solid State
13Carbon Nuclear Magnetic Resonance (NMR) and an
Inductively Coupled Plasma-Mass Spectrometer (ICP-
MS). The saprist and fibrist peat soils are compared and
the results are discussed in terms of the potential of the
saprist peat to remove metals from wastewater, though
metal removal studies were not a part of this research.
2. Methods
The two peat soils were obtained, courtesy of the Trav-
erse Nursery, from a natural peat bog located between
Torbay and Flat Rock (15 km north of St. John’s), and an
area, which is part of the largest peatland on the Avalon
Peninsula of Newfoundland [32]. The peats were har-
vested at about 0.4 m depth (fibrist) and at about 1.6 m
depth (saprist), transferred in flexi bags to the lab,
weighed, spread on a plastic tray, and air dried at room
temperature (about 23˚C) to remove about 70% of the
original moisture content. Each was then homogenized
by manually mixing after removing pebbles and unde-
composed woody materials. The physico-chemical prop-
erties that could influence metal adsorption of the peat
soils were determined by standard methods [33] as sum-
marized in Table 2. All of the tests were conducted on
the air-dried peat soils except for the wet bulk density
tests that were conducted on the peat fresh from the field,
Table 2. Physico-chemical parameters of the saprist and
fibristpeat soils.
Parameter Method Used
Saprist Fibrist
Degree of decompositionvon Post 8H 3H
pH (in de-ionized water)ASTM D2976-71 4.2 4.2
Fiber content (%) ASTM D1997-91 68.8 75
CEC at 7.0 pH
acetate/chloridea 70 45
Moisture content (%) ASTM D2974-07A 86 82
Organic matter (%) ASTM D2974-07A 91 84
Ash content (%) ASTM D2974-07A 9 16
Wet bulk density (g/cm3 )ASTM D4531-86 0.65 0.60
Dry bulk density (g/cm3)ASTM D4531-86 0.28 0.21
aCalcium acetate/chloride method [34].
and which was homogenized after removing the pebbles
and woody materials. Grain size determination of the air-
dried peats was obtained by sieving triplicate dried peat
samples over a series of mechanically stacked sieves.
To determine the total metallic contents of the air-
dried homogenized saprist and fibric peat soils, each soil
was crushed in a mortar, acidified with 14.5 N HF and 8
N HNO3 and left on a hot plate for several days until
completely digested so that all the organic components
were released. Then 6 N HCl and 8 N HNO3 were added
to dissolve the samples further and this step released the
inorganic components. Finally 8 N HNO3 was added and
diluted with nano-pure water according to the rock dis-
solution procedure [33] in the Earth Sciences Department
at Memorial University of Newfoundland (MUN) where
the samples were finally analyzed with a model ELAN
Micrographs of the peat pore orientation and surface
morphology were obtained using the Hitachi S-570 SEM
(Biology Department, MUN). To prepare the soil sam-
ples for each of the size fractions obtained from the dry
granulometry test but excluding the dust fraction (Table
3) for the saprist and fibrist peat (for a total of twelve
samples), each was spread over a carbon taped stud and
coated with 550× Sputter Coater for gold operated at 20
mA in a vacuum of 0.2 mbar for 2.5 mins resulting in a
15 nm thick coating on the peat.
The mineral content was analyzed for each of the same
twelve size fractions of the saprist and fibrist peat sam-
ples that micrographs had been taken of. Samples were
packed on a vertically placed stud of the Rigaku Rotaflex
D/Max 1400 rotating anode powdered XRD (Earth Sci-
ences Department, MUN) with Cu-Kα radiation source
Copyright © 2012 SciRes. JMMCE
E. S. ASAPO, C. A. COLES 711
Table 3. Dry granulometry resultsfor the two peat types.
Average % retained by weight
Sieve No. Sieve size (µm)
Saprist Fibrist
4 4750 13 15
8 2000 - 19
20 850 52 -
40 425 15 45
50 300 5 -
60 250 - 9
100 150 6 4
200 75 3 6
Smaller dust 6 2
operated at 40 kV and 100 mA from Rigaku/MSC—Ja-
pan equipped with an X-ray stream 2000 low tempera-
ture system. The spectra obtained were matched through
the JADE data software (Earth Sciences Department,
The functional group content of the same twelve frac-
tions of the saprist and fibrist peat soils that were ana-
lyzed with a SEM and an XRD was identified using the
Bruker TENSOR 27 FTIR (Chemistry Department, MUN)
equipped with a MIRacle ATR accessory coated with
crystallized ZnSe with absorbance range from 4000 and
650 cm1. A few grains of each air dried homogenized
peat sample was placed on the pressure tip, compressed
onto the sampling area at the center of the ZnSe crystal
plate, and was scanned for one minute in transmission
mode double sided forward/backward at a spectral reso-
lution of four wavenumbers. The equipment incorporates
a KBr beam splitter, aperture (6 mm setting) and detector.
Solid state 13C NMR of a peat samples were taken from
fraction < 425 µm to identify the dominant functional
groups. The spectra were obtained at 298 K using a
Bruker Avance II 600 spectrometer, equipped with a SB
Bruker 3.2 mm MAS triple-tuned probe operating at
600.33 MHz for 1 H and 150.97 MHz for 13C. Chemical
shifts are referenced to tetramethylsilane (TMS) using
adamantane as an intermediate standard for 13C. The sam-
ples were spun at 20 kHz for 13C NMR spectra. Cross-
polarization spectra were collected with a Hartmann-
Hahn match at 62.5 kHz and 100 kHz 1 H decoupling.
The recycle delay was 2 s. The contact time was 2000 ms
for 13C NMR.
3. Results and Discussion
3.1. Physico-Chemical Properties
The physico-chemical properties of the two peat types
are summarized in Table 2. On the von Post scale of
classification, the saprist peat was 8H while the fibrist
peat was 3 H. Both peat samples were acidic and had
relatively high fiber contents, with the fiber content being
greater in the fibrist peat (as would be expected).
The cation exchange capacity (CEC) was 70 meq/100g
for the saprist peat compared to 45 meq/100 for the fi-
brist peat. The higher CEC of the saprist peat suggests
that it could be a better adsorbent for metal removal
though it is the fibrist peat that has been the most widely
tested as an adsorbent for metals. Both peats had high
moisture holding capacities with the saprist peat having
the higher value. Since CEC influences uptake of hy-
drated cations, CEC is also related to moisture holding
capacity and so the results are reasonable.
The organic content was greater in the saprist peat,
which can be attributed to the higher degree of decompo-
sition [35], longer exposure to weathering (including me-
chanical activities such burrowing by worms, soil move-
ment and coverage), and deeper zone of formation [20].
Consequently the ash or inorganic content was greater in
the fibric peat (since the one test gives both the organic
and inorganic fractions and their sum is the total mate-
The bulk density (wet and dry) of the saprist peat was
higher as this peat was dominated by more of the smaller
particle size fractions (as shown in Table 2). This is also
related to the greater water retaining capacity that the
saprist peat exhibited as the smaller particles would con-
tribute to a greater overall surface area.
The particle size distributions of the air-dried homo-
genized peat soils (in Table 3) are showing that only
13% of the saprist peat had particles > 2000 μm whereas
34% of the fibric peat had particles > 2000 μm. Fractions
> 2000 µm in the fibrist peat were woody undecomposed
materials. Fractions < 2000 μm and >850 µm were mostly
fibre of unidentifiable decomposing materials.
3.2. Metal Content
The average metal concentrations in each peat sample are
presented in Table 4. Also detected at concentrations
below 1 mg/kg were As, Co, and Pb. Although the pres-
ence of these metals could be due to both natural and
anthropogenic sources, the results show that these peat
soils have a natural affinity for the detected metals with
calcium and iron being the predominant metals.
3.3. Surface Morphology
The micrographs of the twelve peat fractions ranged in
resolution from 150 times to 2200 times but the at 1000
times it was easiest to identify pores without damaging
the structure so these micrographs are presented and the
fractions 425 µm gave the best images of the pores and
Copyright © 2012 SciRes. JMMCE
Table 4. Metals detected by ICP-MS analysis of the two
peat types.
Concentration (mg/kg)
Saprist Fibrist
Ca 2392 2743
54Fe 1012 971
Ti 34 98
Zn 15 88
Sn 8 8
Mn 7 27
52Cr 4 NDa
Ni 4 0.7
Cu 2 0.3
77Se 1 NDa
anot detected.
structure. Therefore the 425 µm fractions are shown in
Figures 1(a) (saprist peat) and (b) (fibrist peat).
While taking the SEM images it was observed that the
pores were interlinked, collapsed and overlapped. For
example on Figure 1(a), no single pore could be identi-
fied as each pore is also surrounded by a larger pore of
similar shape so they are concentric pores but they are
also slightly deformed due to compression. This pattern
enhances the water holding capacity of the saprist peat
and the small opening in Figure 1(a) would allow the
passage of water and also the interaction of the pore
walls with aqueous heavy metal ions. The wavy patterns
in the bottom right corner of Figure 1(a) are the con-
stantly overlapping pores. Each pore consists of a unique
internal cellular structure depending on the parent mate-
Most of the pores in the fibrist peat (Figure 1(b)) to a
large extent retain their original shape, and could have
originated directly from the plant forming materials and a
study [5] reported this pore structure to be cellular. The
pore structure in the saprist peat could be resulting from
the compressive forces and it has been reported [36] that
greater decomposition reduced the pore fraction, smaller
particles were more packed together, and the bulk density
was increased. This was evident in this study as the fi-
brist peat had the smaller bulk density and moisture con-
tent (Table 2). With increasing decomposition, pore sizes
become smaller and inseparable (powder-like) resulting
in a compact peat matrix with a higher water holding
capacity. The fibrist peat normally has a higher porosity,
which makes it favoured in gardening and horticulture
where fast percolation of water is needed.
Figure 1. (a) Micrograph of saprist peat 425 µm; (b) Mi-
crograph of fibrist peat 425 µm.
3.4. Peat Crystallography
The diffractograms (Figure 2(a)) are for saprist peat
fractions retained on the 425 μm mesh, Figure 2(b) for
fibric peat retained on the 425 μm mesh and Figure 2(c)
for fibric peat fractions < 75 μm. The diffractograms
were similar for all fractions obtained from the dry
granulometry for both peat types with no unique or iden-
tifiable crystal peaks except for the fraction < 75 µm of
the fibrist peat, which showed the presence of calcium
and silicon oxide. The hump-shaped peak occurring be-
tween 18˚ and 32˚ is a unique characteristic of peat [37].
The saprist peat was more amorphous as no mineral
peak was identified compared to the fibrist peat. Known
minerals in peat such as quartz and feldspar in a New
York woody peat [6] and calcite, kaolinite and quartz in
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Copyright © 2012 SciRes. JMMCE
Figure 2. (a) Diffractograms of saprist peat fractions 425 µm; (b) Diffractograms of fibrist peat fractions 425 µm; (c) Dif-
fractograms of fibrist peat fractions < 75 µm.
an Alder-peat from Poland [38] have been reported, but
in this study no known minerals and especially clays
were detected by matching the peaks with the JADE
software database.
3.5. Functional Groups
The FTIR spectra of all size fractions of the saprist peat
had similar profiles to the spectra of the fibrist peat frac-
tions 425 µm as shown in Figure 3. Similar spectra
suggest a similar chemical composition, thus the chemical
composition of the fibrist and saprist peats from the same
bog contained similar chemical compounds especially at
fractions 425 µm. Larger fractions (>850 µm) of the
fibrist peat showed very broad spectra with fewer distinct
The probable functional groups present in the peat
samples and their corresponding wavenumbers are pre-
sented in Table 5. Lange’s handbook of Chemistry [39]
was the primary source used to identify the probable peaks
and where indicated, John Coates in the Encyclopaedia of
Analytical Chemistry [40] was also consulted.
The functional groups in the saprist and fine grain fi-
brist peat appear to be dominated by the presence of or-
ganic oxygenated species such as carboxylic acid, alco-
holic and phenolic hydroxyls and ethers in addition to
amines. All of these groups are comprised of active elec-
tron sites in their primary structures and their fluctuating
polarization can allow their electrons to be positioned and
shared with the incoming metals deficient in electrons.
These reactions may governthe peat metal binding chem-
istry, with complexation of metals being the main path of
metal uptake, and ion exchange occurring at a much
slower rate.
The measured peaks and their corresponding functional
groups are slightly different from values reported in other
studies. One of the unique characteristics of this New-
foundland peat is the abundance of amine groups as sug-
gested by the FTIR spectra. The amine group may be
particularly important in complexation reactions with a
number of metals (such as Cu, Pb, Cd, Ni, Zn and Al) at a
neutral pH [43].
These differences in composition and orientation of
the compounds can be attributed to different parent ma-
terials from which the peat is derived, varying climatic
and environmental conditions under which the peat is
formed, and the different levels of pre-treatments applied
to the peat. For example, in one study [38], the peat sam-
ple was heated to 350˚C prior to analytical analysis and
this could have altered the chemical composition, while
in this study, the pre-treatment consisted of only air dry-
ing at room temperature (23˚C). Humic and fulvic acids
may be damaged during the harsh processes under which
they are extracted from peat and so their FTIR spectra
may be only partially comparable with peat FTIR spectra.
This study and the work by Orem et al., [41] are two of
the very few studies that analyzed peat in close to its
natural state.
One study [36] observed the Si-O stretching group
(1086 cm1) in a Brazilian peat. The silicate ion also ap-
peared to be present in the peat in this study at a
wavenumber of 915 cm1. In addition, according to the
XRD results (Figure 2(c)) silicon oxide was also present.
Figure 3. FTIR spectra of saprist peat (fraction 425 µm) (similar for all fractions < 425 µm for both saprist and fibrist peats).
Copyright © 2012 SciRes. JMMCE
E. S. ASAPO, C. A. COLES 715
Table 5. Probable functional groups from FTIR spectra.
Wavenumber (cm1) Probable Functional Group Assigned Band, cm1 Comparable Studies
3518 Primary amines (aliphatic) 3550 - 3300 (m)a
Secondary amines 3550 - 3400 (w)
3352 Normal polymeric OH stretch1 [21]
3270 Ammonium ion 3300 - 3030 (s)b
2918 Carboxylic acids -CO2H, OH stretching 3000 - 2500 [41]
2850 Carboxylic acids -CO2H, OH stretching 3000 - 2500 [41]
Methylene (CH2) C-H asymmetric/symmetric stretch1 [21]
2360 Tertiary amines R1R2R3NH+ 2700 - 2250
2341 Aliphatic CN
1620 Primary amines (aliphatic) 1650 - 1560 (m)a
C=C conjugated with aromatic ring 1640 - 1610 (m) [41]
α, β unsaturated carbonyl compounds 1640 - 1590 (m)
1412 Ammonium ion 1430 - 1390 (s)b
Vinyl C-H in-plane bend1
1375 =C(CH3)2 Alkane residues attached to C 1380 (m) [41]
Nitro C-NO2 aromatic 1380 - 1320 (s)c
1242 Aromatic ethers, aryl –O stretch (Φ-O-H)1 [42]
1150 Tertiary alcohol C-O stretch1 [21]
1034 Hydroxyl O-H primary aliphatic alcohols 1085 - 1030d [41,42]
-O-CH3 ethers (w-m) c 1030
Peroxides -O-O- 1150 - 10301e (m-s) Alkyl [41,42]
915 Silicate ion1
845 Nitro C-NO2 aromatic 865 - 835c
825 Peroxides -O-O- 900 - 830 (w)e
767 -CH2- Rocking vibration
720 Saturated CH2c 720 [42]
667 Hydroxyl O-H primary aliphatic alcohols 700 - 600d
1John Coates in Encyclopedia of Analytical Chemistry; aprimary amine bands at 3550 - 3300 and 1650 - 1560; bam-
monium ion bands at 3300 - 3030 and 1430 - 1390; cnitro C-NO2 aromatic bands at 1380 - 1320 and 865 - 835; dpri-
mary aliphatic alcohols bands at 1085 - 1030 and 700 - 600; eperoxide bands at 1150 - 1030 and 900 - 830.
Analysis of the 13C NMR spectra as shown in Figure 4
(similar for all other fractions for both peat types), for the
fraction 425 µm supported the functional groups iden-
tified by the FTIR spectra as shown in Table 6.
4. Conclusions
Characterization of a saprist peat was undertaken as a
prelude to its evaluation as an adsorbent for removing
metals from wastewaters. The CEC (70 meq/100g) was
higher than that of the poorly humified peat (45 meq/100g)
making the highly humified peat a better cation exchanger.
Although the metal content of the fibrist peat was greater
this could have been due to its closer contact to the upper
layer of the bog and exposure to windblown transport. The
ash content of the fibrist peat was almost twice that of
saprist peat, which might be due to the different zones of
formation and accumulation of inorganic materials such
s silicon oxide at the upper layer of the bog. a
Copyright © 2012 SciRes. JMMCE
Figure 4. NMR spectra of saprist peat (fraction 425 µm) (similar for all other fractions for saprist and fibrist peats of
fractions < 425 µm).
Table 6. Probable functional groups from 13C NMR spectra
of saprist peat.
Chemical shift
range (ppm) Probable functional groups Similar studies
18.05 - 40.06 CH3 (in long polymeric chains) [44-46]
56.28 - 84.15 Amine Carbon, Alcohol, ethers,
methoxyl [44-47]
100.37 - 129.43 Phenol, N-substituted aromatic [44,46]
150.78 - 173.38 Carboxyl, amide, esters [44,46,47]
The chemistry of metal binding in the two peat types
might be different with the poorly humified peat being
more influenced by inherent inorganic compounds present,
a fact supported by the detection of silicon oxide (SiO2) in
the XRD spectrum of fraction < 75 µm. With the absence
of clay minerals and any known inorganic substances in
the highly humified peat (compared to the poorly humi-
fied peat sample), any metal uptake in this peat type may
be due to the functional group chemistry and the readily
available exchangeable cations initially present in this
amorphous material. Since the highly humified peat was
more homogeneous in physical nature, it might be easier
to study the peat metal binding chemistry from this peat
5. Acknowledgments
The authors appreciate the financial support from NSERC
and MUN and are grateful to Mr. R. Traverse of Traverse
Gardens, Torbay, for supplying the peat soils. Also ap-
preciated are the contributions of MUN laboratory tech-
nicians, Ms L. Men and Ms. A. Hillier (SEM) of the Bio-
logical Science Department, and Ms. H. Gillespie (XRD)
and Ms. P. King (ICP-MS) of the Earth Science Depart-
ment and Dr Celine Schneider (NMR) of Chemistry De-
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