Journal of Environmental Protection and Ecology 16, No 1, 23–32 (2015)

Water pollution

COMPARATIVE Mn2+ ADSORPTION ON WASTE

LIGNOCELLULOSIC MATERIALS

T. HR. RADOYKOVAa*, S. V. DIMITROVAb, K. I. ALEKSIEVAc,

S. K. NENKOVAa, I. V. VALCHEVa, D. R. MEHANDJIEVd
a
University of Chemical Technology and Metallurgy, 8 Kl. Ohridski Blvd.,
1756 Sofia, Bulgaria
E-mail: nusha_v@uctm.edu
b
Department of Water Supply, Sewerage and Water Treatment, University of
Architecture, Civil Engineering and Geodesy, 1 Christo Smirneneski Blvd.,
Sofia, Bulgaria
c
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Street,
Bl. 11, 1113 Sofia, Bulgaria
d
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences,
Acad. G. Bonchev Street, Bl. 11, 1113 Sofia, Bulgaria

Abstract. The adsorption of Mn2+ ions from samples of hydrolysed lignocellulosic materials (HL)
and alkaline-treated hydrolysed lignin (ААHL), obtained from paulownia, heat straw and maize
stalks was investigated in this article. The adsorption mechanism, adsorption sites specific surface
and the potential for practical application of these materials were examined by BET analysis, IR
spectroscopy and EPR. It was found that the adsorption isotherm of Mn2+ ions on the examined
samples is of Langmuir type, the parameters in Langmuir equation depend on the initial material
and the respective treatment. The EPR spectra of the lignocellulosic materials after a manganese
adsorption consist of six hyperfine splitting lines, specific for Mn2+ ions, which are located so that
there is no interaction between them.
Keywords: adsorption, Mn2+ lignocellulosic materials.

AIMS AND BACKGROUND

The increased interest of bio-ethanol production from vegetal raw materials puts
the question for utilisation of the waste hydrolysed lignin containing some quantity
of cellulose. One possibility to solve this problem is to clarify the potential to use
such materials as adsorbents of metal ions, other elements and organic compounds
from water solutions with the purpose of purifying waste and natural waters. Bio­
sorption is an innovative technology aimed at the removal of toxic metals from
polluted water solutions by using inactive and dead biomasses. Metals entrapment
is due to chemicophysical interactions with active groups present on the cell wall:
*
For correspondence.

23
carboxylic, phosphate, sulphate, amino, amide and hydroxyl groups are the most
commonly found, according to the biosorbent nature. The advantage of biosorption
is that the biomass used, could be a raw material which is either abundant, a waste
from another industrial operation or could be cheaply available1–4. Metal biosorp-
tion is a rather complex process affected by several factors. Mechanisms such as
chemisorption, complexation, adsorption-complexation on surface and pores, ion
exchange, microprecipitation, heavy metal hydroxide condensation, as well as
surface adsorption, are involved in the biosorption process3,4. There are certain
broad range biosorbents which can collect all heavy metals from the solution5–7.
The hydrolysis lignin is used as adsorbent for purification of polluted waste waters
in many publications8–20. The adsorption activity of lignin-contained materials is
due to the availability of different functional groups in the lignin structure. The
adsorption ability that lignin isolated from black liquor has affinity with metal
ions in the following order: Pb(II) > Cu(II) > Cd(II) > Zn(II) > Ni(II) (Ref. 11).
According to the authors the adsorption sites are carboxylic- and phenolic-type
surface OH-groups, the phenolic sites have a higher affinity for metal ions than
the carboxylic sites.
The aim of this article is to investigate adsorption properties of waste hy-
drolysed lignocellulosic materials (HL) and alkaline-treated hydrolysed lignin
(ААHL), obtained from paulownia, heat straw and maize stalks, against Mn2+
ions from water solutions.

EXPERIMENTAL
In this investigation the waste hydrolysed lignocellulosic materials (HL) obtained
from steam explosion treatment, followed by enzymatic hydrolysis of wheat straw,
maize stalks and paulownia were used. The steam explosion treatment was per-
formed in special installation at hydromodule ratio 1:10; initial temperature 100°C;
maximum temperature 190°C; pressure 12.8 bar; heating time 60 min and time at
maximum temperature 10 min. Enzymatic treatment conditions are: temperature
50°C, reaction time 72 h, lignocellulosic consistency 10%, pH initial 5.5–6.0 and
5% charge of the cellulase enzyme complex NS 22086 in combination with 0.5%
β-glucosidase NS 22118 (Ref. 21). Samples were labelled as follow: pHL(s) for
samples produced from wheat straw, pHL(m) for samples produced from maize
stalks and pHL(p) for samples produced from paulownia.
The alkaline treatment of waste hydrolysed lignocellulosic materials was
performed at temperature of 180oC for 4 h. An aqueous solution 5% NaOH was
used at lignocellulosic materials: NaOH ratio 1:8. The destructed lignin suspension
obtained by alkaline treatments was filtered. The dissolved part was precipitated
by acidification with HCl (2 mol/l) to pH ~ 1–2 and alkaline-treated lignin was

24
separated. Samples are marked with pААHL(s) – wheat straw, pААHL(m) – maize
stalks, and pААHL(p) – paulownia.
Infrared spectra were measured on a Varian 660 IR spectrometer. Spectra were
collected in the mid-infrared region (4000–400 cm–1). Samples were prepared by
the standard KBr pellets method. The evaluation of the specific surface area of the
samples was carried out by adsorption of nitrogen at 77.4 K. Nitrogen adsorption
isotherms were used to calculate the specific surface area using the BET equation.
The EPR measurements were performed at room temperature on JEOL JES-FA
100 spectrometer operated in X-band. Standard cylindrical cavity ТЕ011 was used.
The powder samples were placed in quartz tubes and directly measured without
any previous sample preparations.
Equilibrium isotherms were obtained by mixing a fixed mass of each sample
(0.2 g) with 50 ml of manganese(II) solutions in conical flasks. A range of Mn2+
concentrations (5 to 60 mg/l) were tested at an initial value of pH 5.5. The flasks
were kept at constant temperature of 20оС for 24 h. The samples were periodically
stirred to establish equilibrium. Then the samples were filtered and pH value of the
filtrate and Mn2+ concentration were measured. The final concentration of Mn2+
was determinate using spectrophotometer (Hach Lange, Model DR 2800) at λ =
525 nm. The equipment was initially calibrated using standardised manganese
solution. The adsorption capacity was calculated as:
(C0 – Ce)V
qe = , (1)
m

where qe is the equilibrium adsorption capacity (mg/g); C0 – the initial Mn2+

concentration in solution (mg/l); Ce – Mn2+ equilibrium concentration in solution
after 24 h (mg/l); V – Mn2+ solution volume (l); m – the mass of the samples (g).

RESULTS AND DISCUSSION

The determination of Klasson lignin was carried out according to TAPPI standard
test method T 222 Ω–1 and results are presented in Table 1.

Table 1. Lignin content in hydrolysed lignocellulosic materials

Waste materials from Lignin content
(%)
Steam explosion and enzymatic hydrolysis of wheat straw 32.60
Steam explosion and enzymatic hydrolysis of maize stalks 38.34
Steam explosion and enzymatic hydrolysis of paulownia 37.39

25
Fig. 1. Adsorption isotherms of pHL(s) and pAAHL(s) samples at 20оС

Fig. 2. Adsorption isotherms of pHL(m) and pAAHL(m) samples at 20оС

Fig. 3. Adsorption isotherms of pHL(p) and pAAHL(p) samples at 20оС

26
 Equilibrium relationship between the concentration of manganese in the aque-
ous solution and the concentration of adsorbed Mn2+ at a constant temperature for
each of the studied lignocellulosic materials are represented by adsorption isotherms
(Figs 1–3). The Langmuir (equation (2)) and Freundlich (equation (3)) adsorption
models were used for analysis and comparison of experimental absorption data.
qmbCe
qe = ; (2)
1 + bCe
qe = KFCe1/n, (3)
where Ce (mg/l) and qe (mg/g) are the concentrations of metal ions in the liquid and
solid phase, respectively; b (l/g) and qm (mg/g) – the Langmuir coefficients that
represent the adsorbate-adsorbent equilibrium constant and the maximum adsorbed
capacity for a monolayer, respectively; KF (l/g) and n – the Freundlich constants.
The values of qm and b in the Langmuir model can be determined from the slope
and the intercept of a plot of Ce/qe versus Ce. Similarly, KF and n in the Freundlich
model can be obtained from a plot of lg (qe) versus lg (Ce). The calculated isotherm
parameters are given in Table 2.

Table 2. Adsorption parameters

Samples Langmuir isotherm Freundlich isotherm
qm b R2 KF 1/n R2
pHL(s) 2.93 0.249 0.968 0.937 0.292 0.961
pAAHL(s) 1.55 0.063 0.997 0.290 0.413 0.934
pHL(m) 2.60 0.301 0.994 0.895 0.280 0.974
pAAHL(m) 1.33 0.09 0.998 0.716 0.167 0.644
pHL(p) 2.55 0.305 0.998 0.834 0.300 0.926
pAAHL(p) 1.85 0.121 0.998 0.332 0.428 0.962

The adsorption isotherm of Mn2+ ions on the examined samples fits well on
the Langmuir model (isotherm). This is confirmed by the higher values of the
correlation coefficients R2 compared to the Freundlich model as well as observed
similar values of monolayer adsorption capacity qm, which was calculated accord-
ing to the Langmuir equation and the maximum experimental adsorption capacity.
This indicates that all samples provide monolayer and homogeneous adsorption of
Mn2+ ions. It is seen that the adsorption capacity of the hydrolysed lignocellulosic
materials pHL(s), pHL(m) and pHL(p) at saturation is twice as high compared to
the adsorption capacity of the alkaline treated samples pААHL(s), pААHL(m)
and pААHL(p). Therefore, the important factor for the adsorption ability of the
lignocellulosic materials is not only the availability of different adsorption centres,
but also the structure of the lignocellulosic material. For assessment of the adsorp-

27
tion ability of each sample, the specific surface was measured and the adsorption
capacity for unit surface was calculated according to equation (4).
qs = qm/S0 (mg/m2), (4)
where S0 is the specific surface (m2/g); qs – the adsorption capacity for unit surface
(mg/m2); qm – the maximum adsorption capacity (mg/g).
These data are presented in Table 3.

Table 3. Specific surface (S0), and adsorption capacity for unit surface (qs).
Samples Specific surface area (m2/g) qs (mg/m2)
pHL(s) 14.0 0.21
pAAHL (s)   7.0 0.22
pHL(m)   9.4 0.29
pAAHL (m)   5.0 0.27
pHL(p) 16.0 0.16
pAAHL(p)   3.2 0.58

The samples of the alkaline separated lignin have higher adsorption coefficient
for unit surface, consequently the alkaline treatment form more adsorption centres
in lignin structure. An important characteristic for adsorption process is oxidation
state of adsorbed manganese.

10 mT

Fig. 4. EPR spectrum of sample pHL(m) after Mn2+ adsorption

Figure 4 shows an EPR spectrum consisting of six hyperfine splitting lines,

which are characteristic for Mn2+ ions (nuclear spin of 55Mn which is 100% in
the natural abundance is 5/2). EPR spectrum of Mn2+ is characterised with g factor
2.021 and hyperfine splitting constant A0 = 9.5 mT. In addition, a narrow singlet
line with g = 2.001 is observed due to the presence of stable free radicals and is
overlapped with the fourth line of manganese. Accordingly, the oxidation state
of the adsorbed manganese is Mn2+. It is worth to note that the detection of the
six lines of this ion is only when they are located so that there is no interaction
between them. This is confirmed also by the conclusion made of compliance with

28
the adsorption isotherm of Langmuir that the amount of adsorbed manganese ions
is independent of the filling of the surface of the adsorbent.

Fig. 5. IR spectra of pHL(m) and pHL(s)

Fig. 6. IR spectra of pAAHL(m) and pAAHL(s)

29
Fig. 7. IR spectra of pHL(p) and pAAHL(p) samples

The IR spectra of the studied lignocellulosic materials and separated from them
alkaline lignin (Figs 5–7) are similar to the spectra of our previous investigation
for Cu2+ adsorption from similar hydrolysed materials20. The new band, which is
due to chemistry bond between metal and functionally group from lignocellulosic
materials, is not observed. In the amorphous compounds the small differences
in the spectra due to the presence of part of the groups in complex formation is
not clearly expressed. The involvement of OH groups in complex formation is
difficult to be registered by IR spectra because they take part in the formation of
hydrogen bonds in the initial sample, too. This is seen in the broad band in the
zone 3500–3100 cm–1, which is due to stretching vibrations of the alcohol and
phenol hydroxyl groups included in hydrogen bonds. The free OH groups show
absorption at 3600 cm–1. The visible band profile change in this zone could be due
to change in the strength of the hydrogen bonds as a result of their participation in
complex formation with metals ions. The zone 1600–1760 cm–1 is characteristic
for the carbonyl absorption. The next bands that appear in the spectra of almost
all lignins are at 1600 and 1510 cm–1, the second being usually stronger. These
bands are connected with skeleton vibrations of the aromatic rings and in this
reason are more intensive in the alkaline separated lignin spectra (Figs 6, 7а and
b). It is thought that the bands at 1460 cm–1, as well as at 1412 cm–1 are related to
CH deformation vibrations in the methoxyl groups of the lignin. The band at 832
cm–1 is ascribed to deformation vibrations of the С–Н bonds in siringyl groups in
position 2 and 6 of the lignin.

30
CONCLUSIONS
It can be concluded that the waste hydrolysed lignocellulosic materials were found
to be efficient adsorbent for heavy metals removal from aqueous solutions. The
adsorption isotherms of Mn2+ on the examined samples are of Langmuir type. The
detection of the six lines of this ion in the EPR spectrum confirms the conclusion
made of compliance with the adsorption isotherm of Langmuir that the amount of
adsorbed manganese ions is independent of the filling of the surface of the adsorbent
and they are located so that there is no interaction between them. The hydrolysed
lignocellulosic materials have greater adsorption capacity for 1g compared to that
retained by the separated lignin after alkaline treatment of these materials. The
samples of alkaline separated lignin have higher adsorption coefficient for unit
surface since the alkaline treatment form more adsorption sites in lignin structure.

REFERENCES
1. K. KRISHNANI, Х. MENG, L. DUPONT: Metal Ions Binding onto Lignocellulosic Biosorbent.
J Environ Sci Health A Tox Hazard Subst Environ Eng, 44 (7), 688 (2009).
2. X. LIU, H. ZHU, Ch. QIN, J. ZHOU, JOE R. ZHAO, S. WANG: Adsorption of Heavy Metal Ion
from Aqueous Single Metal Solution by Aminated Epoxy-lignin. Bioresourses, 8 (2), 2257 (2013).
3. J. L. GARDEA-TORRESDEY, G. de la ROSA, J. R. PERALTA-VIDEA: Use of Phytofiltration
Technologies in the Removal of Heavy Metals: A Review. Pure Appl Chem, 76 (4), 801 (2004).
4. B. VOLESKY: Detoxification of Metal-bearing Effluents: Biosorption for the Next Century.
Hydrometallurgy, 59, 203 (2001).
5. I. H. BUKHARI, G. SHABBIR, J. REHMAN, M. RIAZ, N. RASOOL, M. ZUBAIR, Q. U. AIN,
S. MUNIR, M. A. SHAHEEN: Biosorption of Pb(II), Cu(II) and Mn(II) Metal Ions from Aque-
ous Solutions by Using Typha Latifolia Waste Biomass. J Environ Prot Ecol, 14 (2), 453 (2013).
6. J.-G. CAO, X.-M. LI, YUZHU OUYANG, WEI ZHENG, QI YANG: Manganese Waste Water
Treatment: Biosorption of Manganese by Serratia sp. J Environ Prot Ecol, 12 (2), 661 (2011).
7. C. BUMBA, E. PENA LEONTE, C. DUMITRESCU, I. GHITA, M. STEFANESCU: Heavy
Metals Removal Using Residual Fungal Biomass. J Environ Prot Ecol, 11 ( 3), 822 (2010).
8. M. KARSHEVA, J. HRISTOV, S. NENKOVA: Adsorption of Lead from Aqueous Solutions
onto Technical Hydrolysis Lignin. Hung J Ind Chem, 28, 151 (2000).
9. G. HARMAN, R. PATRICK, T. SPITTLER: Removal of Heavy Metals from Polluted Waters
Using Lignocellulosic Agricultural Waste Products. Ind Biotechnol, 366 (2007).
10. G. N. DALIMOVA: Modification of Hydrolysed Lignin in Acid And Basic Media. Chem Nat
Compd, 42 (1), 88 (2006).
11. X. GUO, S. ZHANG, X. SHAN: Adsorption of Metal Ions on Lignin. J Hazard Mater, 151,
134 (2008).
12. S. NENKOVA, E. TZOLOVA: Adsorption of Heavy Metals Ions from Soil in Presence of Natural
Polymer Products. J Univ Chem Tech Met, XXXVIII (I), 11 (2003).
13. J. E. PENARANDA, A. MARCOS, A. SABINO: Effect of the Presence of Lignin or Peat in IPN
Hydrogels on the Sorption of Heavy Metals. Polym Bull, 65, 495 (2010).
14. N. TAZROUTI, M. AMRANI: Chromium (VI) Adsorption onto Activated Kraft Lignin Produced
from Alfa Grass (Sipta tenacissima). Bioresources, 4 (3), 740 (2009).
15. N. T. ABDEL-GHANI, M. HEFNY, G. A. F. El-CHAGHABY: Removal of Lead from Aqueous
Solution Using Low Cost Abundantly Available Adsorbents. Int J Environ Sci Tech, 4 (1), 67
(2007).

31
16. S. J. ALLEN, B. KOUMANOVA, Z. KIRCHEVA, S. NENKOVA: Adsorption of 2-nitrophenol
by Technical Hydrolysis Lignin – Kinetics, Mass Transfer and Equilibrium Studies. Ind Eng
Chem Res, 7, 2281 (2005).
17. S. NENKOVA: Sorption of Oil by Lignin Fiber Composites. Bioresources, 2 (3), 408 (2007).
18. K. FLOGEAC, E. GUILLON, E. MARCEAUB, M. APLINCOURT: Speciation of Chromium
on a Straw Lignin: Adsorption Isotherm, EPR, and XAS Studies. New J Chem, 27, 714 (2003).
19. Y. WU, S. ZHANG, X. GUO, Y. H. HUANG: Adsorption of Chromium(III) on Lignin. Biore-
source Technol, 99, 7709 (2008).
20. T. H. RADOYKOVA, S. V. DIMITROVA, K. I. ALEKSIEVA, S. K. NENKOVA, I. V. VALCHEV,
D. R. MEHANDJIEV: Adsorption Properties of Waste Lignocellulosic Materials Produced in
Reprocessing of Wheat Straw and Maize Stalks Biomass. J Int Sci Publ: Materials, Methods &
Technologies, 7 (2), 190 (2013).
21. P. TSEKOVA, S. PETRIN, I. VALCHEV, S. NENKOVA, V. BLYAHOVSKI, G.RADEVA:
Comparative Consideration of the Pretreatment Methods Used in Bioethanol Production on the
Basis of Wheat Straw and Maize. In: Italic 6, Science &Technology of Biomass: Advances and
Challenges from Forest and Agricultural Biomass to High Added Value Products: Processes and
Materials, September 5–8, Viterbo, Italy, 2011, 311–314.
Received 19 December 2014
Revised 17 January 2015

32