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Impact of the process of isolating humic acids from peat on their properties

Article in Canadian Journal of Civil Engineering · February 2009

DOI: 10.1139/S08-052

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 345

Impact of the process of isolating humic acids

from peat on their properties1

..., Janis Sire, Maris Klavins, Juris Kreismanis, and Santa Jansone

Abstract: Humic substances (HS) can be isolated in preparative quantities from low rank: coal, peat, and soil. Tradition­
ally, treatment with solutions of NaOH, KOH, or metal salts (~207) has been used for their isolation. The aim of this ar­
ticle is to study the effectiveness of different technologies in extracting HS from peat as well as the impact of the different
extractive technologies on the properties of the isolated HS. Yields of HS depend very much on the extraction process (ex­
tractant, temperature, pretreatment procedures, solvent, mixing intensity); however, the properties of the substances ob­
tained (molecular mass, number of functional groups, spectral characteristics) differ significantly. Yields of HS can be
associated with the degree of destruction of the peat fibres and intensive destruction technologies provide opportunities to
obtain HS from peat in higher yields than traditional extraction methods. However, during the extraction process, signifi­
cant degradation of the humic molecules takes place.
Key words: extraction, humic substances, peat, properties.
Resume : Les substances humiques peuvent etre isolees en quantites suffisantes pour les essais apartir de charbon de rang
bas, de tourbe et de sol. Habituellement, pour les isoler, elles sont traitees au moyen de solutions de NaOH, KOH ou de
sels metalliques (KiP207). Le but de cet article est d'etudier l'efficacite de differentes technologies pour l'extraction de
substances humiques de la tourbe ainsi que leur impact sur les proprietes des substances humiques isolees. Les quantites
obtenues de substances humiques dependent beaucoup du procede d'extraction (agent d'extraction, temperature, procedures
de pretraitement, solvant, intensite de mixage); toutefois, les proprietes des substances obtenues (masse moleculaire, nom­
bre de groupes fonctionnels, caracteristiques spectrales) different de maniere importante. Les quantites obtenues de subs­
tances humiques peuvent etre associees au niveau de destruction des fibres de tourbes; les technologies de destruction
intensive fournissent des occasions d'obtenir de plus grandes quantites de substances humiques de la tourbe que les metho­
des d'extraction conventionnelles. Les molecules humiques sont toutefois degradees de maniere significative durant Ie pro­
cessus d'extraction.
Mots-eMs : extraction, substances humiques, tourbe, proprietes.
[Traduit par la Redaction]

Introduction tion of HS from their potential sources requires intensive

Humic substances (HS) are a general category of naturally
occurring, biogenic, heterogeneous organic substances that
can be characterized as being yellow to black in color, of
high molecular weight, and refractory (Iqavil}s 1998). HS
are an abundant ingredient in aquatic and soil organic matter
as well as in sedimentary (sapropel, gyttja) and fossil depos­
its (peat and brown coal). Sedimentary and fossil carbon­
containing deposits are a significant source of HS. Extrac­
Received 14 September 2007. Revision accepted 14 September
2008. Published on the NRC Research Press Web site at
cjce.nrc.ca on 13 February 2009.
J. Sire, M. Klavins,2.3 J. Kreismanis,4 and S. Jansone.4
Department of Environmental Sciences, University of Latvia, 19
Raina Blvd, LV 1586 Riga, Latvia.
Written discussion of this article is welcomed and will be
received by the Editor until 30 June 2009.
lA paper submitted to the Journal of Environmental Engineering
and Science.
2Corresponding author (e-mail: maris.klavins@lu.lv).
3Present address: 10 Alberts Str., LV 1010, Riga, Latvia.
4Present address: Faculty of Chemistry, University of Latvia, 19
Raina Blvd., LV 1586, Riga, Latvia.
treatment. Extraction with NaOH and KOH at elevated tem­
peratures has been used most widely (Martin-Neto et a1.
2001; Ran et a1. 2002; Ferreira et al. 2002), although other
extractants have also been used (Senesi and Sipos 1985). To
increase yields, stirring and repeated treatment of the source
material is employed (Moreda-Pifieiro et a1. 2004), including
chemical oxidation with potassium carbonate and maintain­
ing a stable extraction temperature or changing the temper­
ature during the extraction process. One study investigated
extractions using the same extractant, but different sources
of HS (Anaya-Olvera 2004). Optimization of the extraction
procedure of HS from peat is important, considering the
growing interest in industrial production.
Yields of HS often are low, with degradation occurring
during the extraction process and voluminous wastes being
formed. Usually the properties of isolated industrially pro­
duced materials have not been well described and analysed,
especially in comparison with reference HS.
Recently several technologies have been developed that
suggest industrially-relevant approaches to increase the
treatment intensity of the extraction process, but also add
chemical and physical impacts and support a continuous ex­
traction process (Lin and Yen 1993; Mason et al. 2004; Go­
gate et al. 2006). Among prospective technologies for the

Can. J. Civ. Eng. 36: 345-355 (2009) doi: 10. 1139/S08-052 Published by NRC Research Press
346 Can. J. Civ. Eng. Vol. 36, 2009

Table 1. Extraction conditions of humic acids (HA) from peat samples.

Procedure number Extraction procedure Extractant TeC) Time (h)

PI Stirring 5% K2C03 20 24
P2 Stirring 1% NaOH 20 24
P3 Stirring with heating 1% NaOH 100 24
P4 Stirring with heating 1% NaOH 80 24
P5 Stirring with heating 1% K2P4D7 100 24
P6 Extraction in cavitation reactor 1% NaOH 60
P7 Extraction in cavitation reactor 1% KOH 60 1
P8 Treatment with ultrasound 0.07 kW 1% NaOH 30 6
P9 Treatment with ultrasound 0.27 kW 1% NaOH 40 6
PIO Extraction in electrical discharge reactor 1% NaOH 70 0.25
Pll TEHUM NA NA NA
P12 Aldrich NA NA NA
P13 IHSS reference sample 1 M NaOH NA 4

Fig. 1. Change in the concentration of humic substances in the extraction mixture with time depending on the nature of the extraction pro­
cess (extractant 1% NaOH).
-.-P3 -A-P6 -.-P8 - ....-P9 -.-PIO
14

12 ~-

~ 10
/
...~
Q
8

j 6
~
8= 4
Q
U

o 10 20 30 40 50 60 70 80 90 100 110 120

Treatment time, min

extraction of HS from peat, treatment with ultrasound has
been suggested, as well as plasma and electrical discharge,
and cavitation. Cavitation, electric pulse reactors, and sonifi­
cation with ultrasound have not been applied for extraction
on a preparative scale. However, similar approaches are ap­
plied in chemical synthesis (Kurets et al. 1999; He et a1.
2004; Gogate and Pandit 2005; Yasui et a1. 2005), even on
an industrial scale, for the extraction of biologically active
compounds from plant and living materials (Zayas 1985;
Luo et al. 2007; Proestos and Komaitis 2006) and for the de­
contamination of polluted sites (Mason et al. 2004; Furu­
kawa and Tokunaga 2005).
The aim of this article is to study the impact of the ex­
traction process from peat on the properties of the HS ob­
tained.
sample consisted mostly of sphagnum moss (Sphagnum Jus­
cum). The basic properties of the peat were detennined us­
ing soil characterization methods (Tan 2(05) and are as
follows: decomposition degree after von Post - H4; age
(14(: dating) - 2950 years; elemental composition - 50.78%
C, 5.18% H, 1.38 N, 0.69% S, 37.78% 0; ash content ­
4.88%; cation exchange capacity - 0.36 mequiv. Nall00 g,
0.14 mequiv. Klloo g, 5.69 mequiv. Call00 g, 1.10 mequiv.
Mgll00 g.
Analytical quality reagents (Merck Co., Sigma-Aldrich
Co., Fluka Chemie AG RdH Laborchemikalien GmbH Co.)
were used without further purification. Industrially produced
humic acid (HA) (PI2), Aldrich (USA) and TEHUM (Czech
Republic) HA (Pll) and IHSS reference HA (P13) isolated
from Pahokee (USA) peat were used for comparison.

Materials and methods Extraction procedures of OS from peat

The efficiencies of five extraction technologies of HS
Study materials from peat have been studied and compared:
In this study, industrially-produced peat from a high-type
Balozu peat bog near Olaine (Latvia) was used. The peat • Conventional extraction procedure: low temperature

Published by NRC Research Press

Sire et aI. 347

Fig. 2. Changes in the concentrations of humic substances in the extraction mixture depending on the nature of the extractants (extraction
performed with heating).
12
-+- NaOH (temp. 100°C) -A- NaOH (temp. 80 "C) - .... - KOH - e - KlP7

10
• • •
..:l
lIIS
...~
~
/
~
~
~~
~-
-.
11:1
~
:= 6
~11:1
u
Col
/
~Iti. ,..---",,­
........ ..... III

11:1
~ ...................
U 4 /-l1li

­ .-.--.­
~-1111 e e
•
••.....
2

o 20 40 60 ~ ~ m ~ ~ ~ ~ ~ ~
Treatment time, min

Fig. 3. Change in the concentration of humic substances in the extraction mixture with time depending on the nature of the extractant and
intensity of the ultrasound treatment.
11
-+-1%KOHUSO.27W - +- 1%KOHUSO.07W
10
- .... -1 % NaOH US 0.27W - .... - 1% NaOH US 0.07W ,..
9 -e-l%KlP7USO.27W- e- 1%KlP7USO.07W /

~-1111.-------
,.. /-l1li
,../'" ,/"+
,../~
,..,/".~
2 Y ..... ------ .... ----
---+

.
.... --.... -- ........- - - - - - - ......... -----_ ......
- - -t: : : ='= : : ~=-=-=-'1::.::-:...-.
1
---=l~.
• ------.
O~_T~~--~~~~-T-~-~-~-~-~-~-=-~-~-~-~-~-~-T·----T---_.---~----T·----r__._,--~~
o 10 20 30 40 50 60 70 so 90 100
Treatment time, min

treatment. Humic acids (HAs) were extracted and puri­
fied using procedures recommended by the International
Humic Substances Society (IHSS) (Tan 2005). Briefly,
20 g of air-dried and finely ground peat sample were
treated under N2 with 1 L of extractant (PI and P2 in Ta­
bles 1 and 2) for 24 h with stirring. The suspension was
filtered and the filtrate was acidified with concentrated
HCI to pH < 2 to precipitate the HAs. The HAs obtained
were further purified by repeatedly dissolving and preci­
pitating them as well as dialyzing against Millipore water
followed by drying. To study the kinetics of the extrac­
tion process, 10 mL of the reaction mixture were re-
moved after appropriate time intervals and the
concentrations were determined using their transmittance
at 410 nm (calibrated using IHSS reference HA).
• Conventional extraction procedure: extraction with heat­
ing (samples P3, P4, and P5). This method is based on
thermal treatment of the peat fibres using the same ex­
tractants as above (heating temperatures 80 and 100 °C).
In this method, high hydroxide concentrations are used.
• Intensive treatment extraction: extraction using cavita­
tion. Based on generation, subsequent growth, and col­
lapse of cavitation, this method results in very high
energy densities of the order of 1 to 1018 kW/m3• Cavita-

Published by NRC Research Press

348 Can. J. Civ. Eng. Vol. 36, 2009

Fig. 4. Peat fibres before 4 h treatment with 1% NaOH at elevated temperatures.

Fig. 5. Peat fibres after 4 h treatment with 1% NaOH at elevated temperatures.

tion can occur at millions of microlocations in a reactor
simultaneously and generate microconditions of very
high local temperatures and pressures (pressure of a few
thousand atmospheres and temperature of a few thousand
degrees Kelvin) whereas the overall environment is that
of ambient conditions. Moreover, free radicals are gener­
ated in the process due to the dissociation of vapors
trapped in the cavitation bubbles. Cavitation also results
in the generation of local turbulence and liquid microcir­
culation in the reactor, enhancing the rates of transport
processes (Lin and Yen 1993; Gogate et al. 2006). The
extraction of HAs from peat using a hydrodynamic cavi­
tation reactor (P6 and P7 in Tables land 2) designed as
described previously (Keil and Swany 1999; Gogate et
al. 2006) allows treatment of peat in flow mode under
the intensive hydrodynamic and local heat impacts that
arise during the generation and bursting of cavitation
bubbles. The extraction was performed using 200 g of
peat and 3 L of extractant for 2 h and the extractants
were varied (1 % NaOH or 1% KOH) (Tables 1 and 2).
• Intensive treatment extraction: extraction using electrical
discharge. The extraction of HS from peat is achieved in
flow mode by processing the peat using extractant (KOH
or NaOH) media with electrical discharge (18 kV). Dur­
ing discharge, a plasma field with high temperatures and
a shock wave is formed between the electrodes and this
performs the intensive mixing of the extraction media as
well as degradation of the peat fibres (Kurets et al. 1999;
Gogate et al. 2(06). The extraction of HAs from peat
using an electrical discharge reactor (PlO in Tables 1

Published by NRC Research Press

Sire et al. 349

Fig. 6. Peat fibres after 100 min treatment with ultrasound (0.27 kW power) using 1% NaOH as an extractant.

Fig. 7. Peat fibres after 20 min treatment with cavitation using 1% NaOH as an extractant.

and 2) designed as described (Boiko and Mizinenko
1970; Keil and Swany 1999; Kurets et al. 1999) also al­
lows treatment of peat in flow mode and employs treat­
ment of a dispersion of peat in a solution of extractant
under the impact of strong (18 kV) electrical discharge
conditions (Kurets et al. 1999). The extraction was per­
formed for 15 min using 5 kg of peat and 20 L of 1%
NaOH as extractant (Table 1). The HS obtained at certain
intervals were filtered off and the filtrate was acidified
with concentrated Hel to pH < 2 to precipitate the HAs.
The HAs obtained were further purified by dissolving and
precipitating repeatedly as well as dialyzing against
Millipore water followed by drying.
• Intensive treatment extraction: extraction using ultra­
sound. This method has been proposed to facilitate ex­
traction from plant material (Proestos and Komaitis
2006). In this case pressure variations in the liquid phase
are effected using sound waves (0.07, 0.27 kW power).
The ultrasound method (Mason et al. 2004; Yasui et al.
2005; Gogate et al. 2006) involves sonification of the ex­
tractant-peat mixture in commercial ultrasound baths.
The extraction was performed for 2 h using differing ul­
trasound energies (0.07 and 0.27 kW) (P8 and P9 in Ta­
bles 1 and 2) and 200 g of peat and 3 L of 1% NaOH as
extractant (Table 1) or with a different extraction time
and extractant.

Published by NRC Research Press

350 Can. J. Civ. Eng. Vol. 36, 2009

Table 2. Properties of humic substances isolated using different extraction technologies.

Elemental composition Element ratio -COOH

Procedure
number C (%) H (%) N (%) 0(%) N/C HlC O/C 1WE6 (mequiv.lg) Mw (Da)
PI 53.25 4.27 1.76 40.72 0.03 0.95 0.57 8.00 4.95 4200
P2 50.74 4.24 1.59 43.44 0.03 1.00 0.64 6.43 5.68 3400
P3 53.96 4.52 1.23 40.29 0.02 1.00 0.56 4.93 6.79 1900
P4 52.89 4.32 1.25 41.54 0.02 0.97 0.59 4.93 7.00 1900
P5 51.31 3.50 1.65 43.54 0.03 0.81 0.64 5.89 5.68 2200
P6 39.98 4.00 1.43 54.59 0.03 1.19 1.03 5.82 4.96 1800
P7 42.13 3.68 1.45 52.75 0.03 1.04 0.94 6.09 4.84 3200
P8 47.93 4.21 1.34 46.52 0.02 1.05 0.73 6.00 6.42 3000
P9 45.36 4.90 1.55 48.20 0.03 1.29 0.80 4.76 5.93 1600
PlO 43.60 3.65 1.55 51.20 0.03 1.00 0.88 4.71 4.91 1500
Pl1 60.7 3.7 1.5 34.1 0.02 1.13 0.64 4.51 NA NA
P12 49.89 4.76 2.3 43.05 0.04 1.03 1.35 4 2.15 4100
P13 56.37 3.82 3.69 37.34 0.06 0.81 0.50 5.8 3.59 8500

Fig. 8. Relationships between the HlC and O/C element ratios for humic acids extracted by various extractants and (or) procedures from a
peat sample and for humic acids from several Latvian peat bogs and other sources extracted by the International Humic Sllbstances Society
procedure.
1.6

<l<l
~<lJ
1.4 <l
<l<l
<l ~<l ~
<l
1.2 <Q:]<l ...
~
1.0 ...ct ~ <)

0.8 •
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 15
OIC
<l HA's from different peat bogs in Latvia isolated using procedure recommended by mss
iii HA's extracted with 5% K2CO] I!!!! HA's extracted with 1% NaOH
~ HA's extracted with 1% NaOH under heating
~ HA's extracted with 1% KlP7 <) HA's extracted with cavitation method (1% NaOH)
... HA's extracted with electrical discharge method (1 % NaOH)
• HA's extracted with ultrasound (O.07W, 1% NaOH)
... HA's extracted with ultrasound (O.27W, 1% NaOH)
t) Aldrich HA's () Tehllffi HA's • HA's extracted from Pahokee peat (IHSS)

Physicochemical analysis of HS
Elemental analysis (C, H, N, S, and 0) was carried out
using an Elemental Analyzer Model EA-l108 (Carlo Erba
Instruments). Ash content was measured after heating
50 mg of each HA at 750°C for 8 h. Fourier transform in­
frared (FTIR) spectra were collected using a Nicolet AVA­
TAR 330 (Thermoelectron Co) spectrophotometer and KBr
pellets. Transmittance ratios T340012900 and T 340011600 (trans­
mittance at 3400 characteristic for O-H stretching against
transmittance at 2900 cm- 1 characteristic of aliphatic C-H
stretching and transmittance at 3400 characteristic of aro­
matic C = C stretching against transmittance at 1600 charac­
teristic of a strongly H-bonded C = 0 of a conjugated
ketone) were used to characterize the major functional
groups of HS. Ultraviolet-visible (UV-vis) spectra were re­
corded on a Thermospectronic Helios y UV (Thermoelectron
Co) spectrophotometer in a 1 cm quartz cuvette. The ratio
EJE6 (Chen et aI. 1977), the ratio of absorbances at 465
and 665 nm, has been determined for a solution of 5 mg of
humic or fulvic acid in 10 mL of 0.05 N NaHC0 3 . An auto­
matic titrator TitroLine easy (Schott-Gerate GmbH) was
used to measure the total acidity of each HA. To estimate
total acidity (Tan 2005), the known amount of HA, about
20 mg, was dispersed in 10 mL of 0.1 mollL Ba(OH)z solu­
tion, which was then shaken overnight under N2, filtered,
and washed with water. The filtrates together with the wash­
ing solution were potentiometrically titrated with 0.1 mollL
HCI down to pH 8.4 under N2 flow.
To obtain IH nuclear magnetic resonance (NMR) spectra
of the extracted HAs, 25 mg of dry HAs were weighed and
dissolved in 1 mL of 3% NaOD in D20. The experiments
were performed using an AM 360 MHz spectrometer. Spec­
tra were obtained using a one-pulse experiment. The residual
monodeuterated water (HOD) resonance was set to 4.5 ppm.

Published by NRC Research Press

Sire et al. 351

Fig. 9. Ultraviolet-visible spectra of humic substances isolated using different extraction methods (1 % NaOH, concentration HA = 0.1 gIL).
4.0

--P2 -"-"P6 --- P8 -'-'-PI0

3.5

3.0

1:1 2.5 I
.9
aa 2.0 I
\

~
\
,,
1.5
'" , ,
10 1\ ".
• I'.
... ,
0.5,
I
I
'.
"
~a_
, ... ...........

200 300 400 500 600 700 800

Wavelength, nm

Fig. 10. Fourier transform infrared spectra of humic substances isolated using different extraction methods.
120
---- P6 ...... P8 _._.- P9 - - PI0

100

~ 80
~
I
I.•
..
I •
\
! \
\

Col
1:1 1\
~
~ 60 I \
\

,
e I
'"
1:1 I I
i.
...f ,
1

~ 1
40 \ 1
i:·· 1
i 1 1
i· l1li1
'•.". r i 'ioI1
20
'. -1; i'
l.~f i'
3400 2950 2850 172 1~20 1040
0
3500 3000 2500 2000 1500 1000 500
Wavenumber, em')

High pressure size exclusion chromatography (HPSEC) pump, a Waters 486 variable wavelength detector and a
was used to determine the weight averaged molecular Waters Protein-Pak 125 modified silica column. Phosphate
weight (Mw) of the HS, which was calculated as follows: buffer (0.028 mol/L, pH 6.8) was used as a mobile phase at
a flow rate of 1 mUmin. The size exclusion chromatogra­
phy (SEC) column was calibrated using polydextrans (kDa:
0.83, 4.4, 9.9, 21.4, 43.5) and sodium polystyrenesulfonates
[1] (kDa: 1.37, 3.8, 6.71, 8.0, 8.6, 13.4, 16.9). The standard kits
were purchased from Polymer Standard Service (Mainz,
Germany). The calibration curve was expanded into the low
molecular weight region by means of mono- and oligosac­
where hi and Mi are the respective peak height and molecu­ charides (180, 342, 504 Da) and glycerol. Blue dextran
lar weight at retention time i. High pressure size exclusion (2000 kDa) served as a void volume probe and methanol as
chromatography was performed using a Waters 510 solvent a permeation volume probe.

Published by NRC Research Press

352 Can. J. Civ. Eng. Vol. 36, 2009

Fig. 11. Fourier transform infrared spectra of industrially produced and humic substances isolated using different extraction methods.
120
- - P 2 - - - - P6 ...... Pll _._.- P12

100

.-
'··r
:
I
I
,, \
\

':1\ ! "
" I
I

II \ ! i'
. :. ,

I '.1'
:
: ,,<I
! I
: I
I
20 , :r"
\, ;
<
3400 2950 2850 1720 1620

3500 3000 2500 2000 1500 1000 suo

Wavenumber, em·!

Fig. 12. lHydrogen nuclear magnetic resonance spectra of humic substances isolated from peat using different extraction methods.

P8
P4
1'9

1'3
P5

PI
J , ..

P7

I I
2 0 I'pm

After the extraction residues of the peat were washed with
distilled water and dried, they were placed in the scanning
electron microscope sample holder and covered with the
gold. Prepared samples were investigated using the JEOL
ISM T-200 scanning electron microscope.
Results and discussion
Extraction of HS from peat
It has been estimated that peat alone can be a source of
up to 500 Gt C of HAs of industrial value for production
(Markov et al. 1998). Peat can be considered a significant
source of HAs, but technologically relevant approaches for
the extraction of HAs have not been studied thoroughly and
most producers do not use peat as a raw material. The effi­
ciency of extraction of HAs depends on the extractant and
the intensity of the treatment. From a wide array of different
extractants recommended in several studies (Martin-Neto et
al. 2001; Olk et al. 1995; Kaschl et al. 2002; Mahieu et al.
2002), hydroxides (NaOH, KOH) and metal salts (Na2C03,

Published by NRC Research Press

Sire et al.
K2C03, ~207) have been used. However, intensive treat­
ment technologies suggested recently (Gogate et al. 2006)
have not been used for the extraction of HS. Depending on
the intensity of treatment, the following five extraction ap­
proaches have been studied:
• Low temperature peat treatment with NaOH or KOH
with mixing. Although these methods do not require spe­
cial machinery or energy inputs, each extraction cycle
takes a comparatively long time and requires high hydro­
xide concentrations and, in addition, these extractions
cannot be performed in flow mode. This method is well
suited for laboratory experiments when small amounts of
HS are needed.
• Extraction with heating is based on thermal treatment of
the peat fibres using the same extractants. As in tradi­
tional methods, this uses high hydroxide concentrations,
but the extraction time can be radically decreased (up to
4 h).
• Extraction using cavitation is based on the generation,
subsequent growth, and collapse of cavitation resulting
in very high energy densities and the generation of local
turbulence and increasing circulation in the reactor, thus
enhancing the rates of transport processes. High doses of
kinetic and thermal energy that are released in a very
small area can cause complete destruction of the peat fi­
bres as well as mixing of the extraction medium. Cavita­
tion increases the velocity of chemical reactions and can
be performed in flow mode.
• The electrical discharge method is based on extraction of
HS from peat in flow mode by processing the peat-ex­
tractant media with electrical discharge, generating a
plasma field between the electrodes with high tempera­
tures and a shock wave, which performs the intensive
mixing of the extraction media as well as degradation of
the peat fibres.
• The ultrasound method involves sonification of an extrac­
tant-peat mixture in commercial ultrasound baths. Ultra­
sound not only shreds the peat fibres, but also provides
intensive mixing of the extraction environment.
Changes in the isolation efficiency of HS (their concentra­
tion in the extraction mixture) with time (Fig. 1) show that
differences in the extraction efficiencies depend on the treat­
ment intensity.
The use of electrical discharge and cavitation allows us to
obtain comparatively high concentrations (11 and 13 gIL, re­
spectively) of HS much faster and more efficiently than by
other methods. In addition, these methods are very effective;
concentrations of about 7 gIL can be obtained during the
first few extraction minutes. The effectiveness of ultrasound
is proportional to its power, but in general this process is
much slower and less effective than the two methods men­
tioned previously. Using ultrasound of 0.27 kW power, a
concentration similar to that obtained with electrical dis­
charge can be reached only after 120 min of treatment.
The yields of HS depend on the properties of the extrac­
tant and the intensity of treatment (Figs. 2, 3). Sodium hy­
droxide appears to be the most effective extractant and the
effectiveness of ultrasound is closely related to its power; ul­
trasound treatment with 0.27 kW power is 4 times more ef­
fective than treatment with 0.07 kW power when NaOH is
353
used (Fig. 3). When different extractants are compared, so­
dium hydroxide is about 20% more effective than potassium
hydroxide, but potassium pyrophosphate is ineffective be­
cause the concentrations of HS obtained are at least 5 times
lower than when using NaOH or KOH.
To evaluate the impact of different extraction methods on
the peat fibres, scanning electron microscopy was used
(Figs. 4-6). In Fig. 4 the appearance of the peat fibres be­
fore treatment can be seen. The surface and stomatas of the
sphagnum moss leaf with no damage are clearly visible.
Treatment with 1% NaOH at elevated temperatures breaks
down the structure of the peat particles. In Fig. 5 a slightly
changed form and shape of the stomatas can be seen, and
the surface layer of peat fibres has been broken and partly
ripped off. Processing peat with ultrasound promotes the
degradation of its structural elements as the treatment addi­
tionally destroys the plant and moss remains of the peat, in­
creasing the yield of HS. After yet more intensive treatment
with cavitation (Fig. 7), a completely eroded surface layer as
well as altered internal structures can be seen. It may be that
intensive treatment technologies promote significantly
higher yields of HS compared with traditional extraction
methods and that the efficiency can be explained by the de­
struction of the peat fibres during treatment.
Properties of US depending on the extraction procedure
The impact of the isolation process on the properties of
HAs isolated from peat has been analyzed using elemental,
functional, molecular mass, and spectral (UV, IR, IH NMR)
analysis. The nature of the isolation process does have a ma­
jor impact on the properties of the HAs as is evident from
their elemental analysis (Table 2). Depending on the inten­
sity of the treatment, the amount of carbon in the HS and
the molecular masses of the HAs are reduced, proportional
to the EJE6 ratio. The analysis of the impact of the isolation
procedure has been performed using van Krevelen graphs,
which have been widely applied for the analysis of the basic
structures of HAs (Barancikova et al. 1997). The van Kreve­
len graph (Fig. 8) shows that the variability among HAs iso­
lated from different sources (peat from different bogs) is less
than the variability in the elemental composition of HAs iso­
lated using different extraction (treatment) procedures. The
position in the van Krevelen graphs allows the identification
of major processes affecting the structure and properties of
organic matter - dehydration, dehydratation (reduction of
HlC ratio), decarboxylation (reduction of O/C ratio) and de­
methylation (Barancikova et al. 1997). From this perspec­
tive, the intensive isolation approaches resulted first in
dehydratation and decarboxylation of HS. The same trend is
evident in analyzing the functional characteristics and mo­
lecular mass differences among the isolated HAs; intensive
treatment methods (ultrasound, electrical discharge, and cav­
itation as well as treatment with higher concentrations of hy­
droxides) yield humic material with a reduced number of
carboxyl groups (Table 2).
The molecular masses of HS isolated using intensive
treatment methods are significantly lower than those isolated
using a conventional extraction approach. The UV-vis spec­
tra of HAs isolated by different methods differ significantly
(Fig. 9). However, the EJE6 ratio (Table 2) used to estimate
the molecular mass confirms the nature of the structural
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354
changes in the HAs depends on the intensity of the peat
treatment.
The IR spectra (Figs. 10, 11) reveal that the nature of the
changes in the structures of the HAs depends on the isola­
tion process. A comparison of IR spectra shows differences
in the relative amounts of -OH groups (absorption maximum
at 3400 cm-i ) with respect to -CH2 groups (maximum at
2950 cm-i ). Similarly significant are the impacts of the iso­
lation process on the presence of aromatic C = C and conju­
gated carbonyl C = 0 groups (absorption maximum at
1620 cm-i ), carboxyl and ketonic carbonyl stretching band
intensities (1720 cm-i ) and the presence of carbohydrates
(stretching band of carbohydrate or alkoholic -OH at
1040 cm-i ). For example, isolation of the HAs via ultra­
sound results in a significantly reduced intensity of signals
characteristic of carboxyl groups and carbohydrate hydroxyl
groups. The IR spectra also indicate a significant reduction
in the number of hydroxyl groups characteristic of carbohy­
drates when the extraction has incorporated electrical dis­
charge and cavitation.
The iH NMR spectra of the HAs from peat (Fig. 12) are
known to display the following resonances. The region be­
tween 0.8 and 3.0 ppm is commonly assigned to aliphatic
protons (peat assignments as in Barancikova et al. 1997).
In particular, the resonances centered at 0.9 and 1.3 ppm
can be assigned to the protons of methyl groups of highly
branched aliphatic structures and to terminal methyl groups
of methylene chains, respectively. The signals at 1.3 ppm
have also been attributed to hydrogens, which are attached
to benzene rings. The second region between 3.0 and
4.5 ppm arises from protons on C atoms attached to an
oxygen atom and they are attributed to sugar-like compo­
nents, polyether or methoxyl groups. Finally, the third re­
gion between 6.0 and 8.5 ppm can be attributed to the
presence of both heterocyclic and highly substituted aro­
matic ring hydrogens, and the intensity of signals for all
of the HAs studied is weak in this range. The changes ob­
served in the spectra of the HA in Fig. 12 can be attributed
to chemical changes during the extraction process. During
intensive extraction procedures, a reduction in the number
of resonances assigned to sugar-like components can be ob­
served.
Conclusions
Analysis of the properties of HAs isolated from peat de­
pends on the nature of the isolation procedure and shows
that intensive mixing technologies (electrical discharge, cav­
itation, and ultrasound) promote significantly higher yields
and can operate in flow mode (electrical discharge plasma,
cavitation). Therefore, these technologies can be applied to
develop highly efficient production processes. However, de­
pending on the intensity of the treatment process, significant
changes in the structure of HS occur, evidently correspond­
ing to the degradation of more labile structures, principally
the carbohydrates associated with HS. The effectiveness of
the extraction of HS is directly dependent on the capability
to degrade the raw material, as well as on the extractant.
The most effective methods are cavitation and electrical dis­
charge, but the most effective extractant is NaOH, which
gives approximately twofold higher yields compared with
Can. J. Civ. Eng. Vol. 36, 2009
KOH and provides much better results than all other extrac­
tants, such as ~207.
In large-scale production it is very important to achieve
the highest yields possible using the least amounts of raw
materials, time, and energy. For these criteria the best suited
technologies are the cavitation and electrical discharge
methods.
Acknowledgements
The European Social Fund is gratefully acknowledged for
financial support to J. Sire. We acknowledge the help of
Professor S. Tsyfansky.
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