EKONOMIA I ŚRODOWISKO • 3 (70) • 2019

Zdenka KOVACOVA • Stefan DEMCAK • Magdalena BALINTOVA

REMOVAL OF COPPER, ZINC AND IRON

FROM WATER SOLUTIONS BY SPRUCE
SAWDUST ADSORPTION

Zdenka Kovacova, Eng. (ORCID: 0000-0003-0676-6050) – Technical University of Kosice,

Faculty of Civil Engineering, Institute of Environmental Engineering
Stefan Demcak, PhD (ORCID: 0000-0001-6660-6142) – Technical University of Kosice, Faculty
of Civil Engineering, Institute of Environmental Engineering
Magdalena Balintova, Prof. (ORCID: 0000-0002-5644-2866) – Technical University of Kosice,
Faculty of Civil Engineering, Institute of Environmental Engineering

Correspondence address:
Vysokoskolska 4, 042 00 Kosice, Slovakia
e-mail: [email protected]

ABSTRACT: The water pollution by toxic elements is one of the major problems threatening human
health as well as the quality of the environment. Sorption is considered a cost-effective method that is
able to effectively remove heavy metals. During past few years, researches have been researching
usage of low-cost adsorbents like bark, lignin, chitosan peat moss and sawdust. This paper deals with
the study of copper, zinc and iron adsorption by adsorption of spruce sawdust obtained as a by-prod-
uct from locally used wood. Raw spruce sawdust was used to remove heavy metal ions from the model
solutions with ion concentration of 10 mg/L during 24 hours or 5, 10, 15, 30, 45, 60, 120 min, respec-
tively. Fourier-transform infrared spectroscopy was applied to determine functional groups of saw-
dust. Sorption efficiency was higher than 67% in short-time experiments and higher than 75% for one
day experiments in all tested cations.

KEY WORDS: adsorption, model solutions, spruce sawdust, heavy metals

No. 3(70) 2019 • pages: 64-74 https://doi.org/10.34659/2019/3/35 JEL: Q25, Q52

EKONOMIA I ŚRODOWISKO 3 (70) • 2019 Studies and materials 65

Introduction

The pollution of air, soil, and water is a result of people’s efforts to

improve their lives. The industrial activities together with technology devel-
opment lead to a release of large quantities of contaminants to the water.
Among a wide range of pollutants contained in wastewater, metals are one of
the most toxic substances. They do not biodegrade and due to their presence
in streams and lakes living organisms accumulate such substances, causing
health problems in animals, plants and human beings – the overall negative
impact on the whole environment. Inorganic pollutants most frequently pre-
sented in wastewaters are copper, nickel, zinc, lead, iron, chromium and cad-
mium. These heavy metals were intensively investigated from the point of
view of persistence and toxicity (Abdel-Raouf, 2016; Larous, 2012; Gogoi,
2018; Simón, 2019).
Copper can be found in high concentration because it is usually used in
many industrial sectors like metal inishing, electroplating, plastics and etch-
ing. Copper is actually one of the most frequently occurring heavy metal con-
taminants in the environment. Water contaminated with copper must be
treated before it is discharged to the environment because of its toxic prop-
erties even at low doses. High concentrations of copper can cause serious
toxicological concerns because it can affect the brain, skin, liver and pancreas.
This can lead to nausea, vomiting, headache, diarrhea, respiratory dif icul-
ties, liver and kidney failure (Al-Saydeh, 2017; Ageena, 2010; Larous, 2012).
Zinc is widely used in electroplating, galvanized pipes, iron, alloy and
brass production and paper production. At trace amounts, zinc is an essential
nutrient for certain biochemical and physiological functions of the organism.
At concentrations beyond the permissible level (2.00 mg/L), zinc can lead to
a malfunction of various systems in the human body and it can cause nausea,
vomiting, epigastric pain, lethargy, fatigue, a short-term illness called “metal-
lic smoke fever» and restlessness. Zinc is also poisonous to plants at high
concentrations and can be damaging in soils because of its high mobility
(Simón, 2019; Udomkitthaweewat, 2019).
Contamination of water with iron can either be geogenic or caused by
industrial ef luents and domestic waste. Although iron is essential for human
and lack of it may lead to anaemia and health problems, its high levels may
cause severe health problems in human beings such as vomiting, liver cancer,
diabetes, cirrhosis of liver, heart diseases, infertility etc. The higher concen-
tration of iron in water corrodes water pipe lines, changes colour of water, its
taste, odour and leaves stains on clothes (Al-Shahrani, 2013; Kumar, 2017).
66 Studies and materials EKONOMIA I ŚRODOWISKO 3 (70) • 2019

Due to all these reasons, the proper treatment of the wastewaters

before its discharging to the environment is needed.
There are several methods of removing heavy metals from wastewa-
ters, for example:
• precipitation – a simple process based on the fact that some metal salts
are insoluble in water,
• ion – exchange method uses ions to exchange with metal ions in the water
solutions,
• reverse osmosis method utilizes high pressure to ilter out the metal ions
trough a membrane (Simón, 2019; Ageena, 2010).
Due to increased interest in using eco-friendly and economical materials,
researchers are now searching for new adsorbents that can be used for this
purpose. The adsorption process ( igure 1) has been considered as one of the
most ef icient methods with many advantages: low costs, higher lexibility,
high ef iciency, good selectivity, simplicity of design, ease of operation, insen-
sitivity to toxic pollutants, high quality puri ied products and recyclability
(Elkady, 2017; Balintova, 2016; Demcak, 2019).

Figure 1. Realization of adsorption process using sawdust as adsorbent

Source: Ouafi, 2017, p. 117.

In recent years, extensive research has been done to identify new and
cost-saving sorbents that could remove different heavy metal ions. The low-
cost adsorbents including aquatic plants, waste tea leaves, bark, peat moss,
lignin and sawdust have also been reported as ef icient materials. Sawdust is
one of the most appealing timber industry by-products that is available in
large quantities, is cheap and easily regenerated after use (Memon, 2008;
Thapak, 2015; Ince, 2017; El-Saied, 2017).
EKONOMIA I ŚRODOWISKO 3 (70) • 2019 Studies and materials 67
The aim of this research was to investigate application of spruce sawdust
for Cu(II), Zn(II), and Fe(II) removal from aquatic solutions. Copper, zinc, and
iron are metals found in nitrogen rich wastewaters (Zhang, 2019). Due to this
reason these were selected as model ions to test spruce sawdust in the pro-
cess of their removal from aquatic solutions. Spruce sawdust was also tested
by FTIR method in order to determine the changes caused by adsorption/ion
– exchange process.

Research methods

The spruce sawdust (particle size less than 2 mm) from local resources
was used as a sorbent for the removal of selected heavy metals ions from
aqueous solution without any pre-treatment. Wooden sawdust was analysed
by FTIR on Bruker Alpha Platinum-ATR spectrometer (Bruker Optics, Ettin-
gen, Germany). A total of 24 scans were carried out in the range of 4,000–400
cm−1.
Dry spruce sawdust (1 g) was mixed with 100 mL of aquatic solutions.
The water solutions with concentration 10 mg/L of Cu(II), Zn(II) and Fe(II)
were prepared by dissolution of calculated amount of CuSO4.5H2O,
ZnSO4.7H2O and FeSO4.7H2O in deionised water.
The irst experiment focused on interaction between sorbent and sorbate
during 24 hours. The sawdust was initially mixed with the model solution
and left at the room temperature (20±1°C) for the duration of the experi-
ment.
The next step of the research was the study of kinetics, the contact time
between sorbent and sorbate was 5, 10, 15, 30, 45, 60 and 120 min. During
this time spruce sawdust was intensively mixed in the model solution at the
room temperature (20±1°C).
After the experiments, the concentration of heavy metals in the iltrates
was determined by colorimetric method (Colorimeter DR890, Hach Lange,
Germany) with appropriate reagent. Changes of pH were measured by pH
meter (Mettler Toledo FG2, Schwerzenbach, Switzerland). The percentage
ef iciency was calculated by following equations:

ߟൌ
ሺ௖బ ି௖೐ ሻ
ή ͳͲͲǡ (1)
௖బ

where:
η – sorption ef iciency [%],
co – the initial concentration of appropriate ions [mg/L],
ce – equilibrium concentration of ions [mg/L].
68 Studies and materials EKONOMIA I ŚRODOWISKO 3 (70) • 2019

Results of the research

Infrared sprectra
Metal adsorption capacity is in luenced strongly by the surface structures
of C–O and C–OH functional groups which are present in organic materials
(Ricordel, 2001). FTIR method was used to determine active sites existing in
the surface structure of sawdust (El-Saied, 2017). IR spectrum of spruce saw-
dust is shown in igure 2. The main components of sawdust are lignin, cellu-
lose and hemicelluloses. A broad band of 3336 cm-1 represented presence of
hydroxyl groups (−OH), the valence vibration related to aromatic C−H is
shown on the spectrum at the 2883 cm-1. The aromatic functions of lignin are
characterized by infra-red absorption bands, which is characteristic of the
C=C vibrations of the aromatic skeleton of lignin at the 1648 cm-1. Another
bands of lignin (carbonyls (C=O), alcohols and ethers) were observed at
1508, 1451, and at 1316 cm−1. Wavenumbers at 1422, 1367, 1316, 1260,
1026 and 895 cm-1 belong to cellulose. The functional groups of aromatics
were noticed at 895 cm-1 (Salamat, 2018; Schwanninger, 2004).

Figure 2. Infrared spectra of spruce wooden sawdust

Source: author’s own work.

Sorption experiments – results of the 24 hours experiment

Results of the 24 hours experiment with initial concentration of cooper,
zinc and iron ions 10 mg/L are shown in table 1. In all cases, the sorption
ef iciency reached more than 75%. The best removal ef iciency was observed
EKONOMIA I ŚRODOWISKO 3 (70) • 2019 Studies and materials 69
in the case of copper ions (more than 85%). The pH of the aqueous solution
is an important controlling parameter in the adsorption process and thus the
effect of pH has been studied as well (Balintova, 2011). Initial pH of the solu-
tions was in luenced only the type of chemicals used, so adsorption process
was carried out at different pH ranges. In all cases, pH decreased when com-
pared to the initial value. The decrease in pH values could be caused by the
ight for adsorption between metal ions and H+ (Demcak, 2019).

Table 1. Results of the 24 hours experiments

Input value Output value

Sorption
Heavy metal ion
efficiency [%]
co [mg/L] pH ce [mg/L] pH

Cu(II) 10.00 6.3 1.48 5.3 85.2

Zn(II) 10.00 6.2 1.92 5.4 80.8
Fe(II) 10.00 5.9 2.49 5.2 75.1

Source: author’s own work.

Sorption experiments – short-term results

Results of the short-term experiments of copper removal from aquatic
solutions are shown in igure 3. Larous et al. (2005) state that copper adsorp-
tion on sawdust depends on the solution’s pH, temperature, agitation speed,
initial concentration, contact duration, liquid to solid ratio, and ionic strength.
A signi icant increase in sorption was observed at 10 minutes, when ef i-
ciency achieved more than 80%, the rest of the time is characterized by slow
changes in removal ef iciency which can be evaluated as relatively constant.
The highest ef iciency of Cu(II) (≈ 90%) was reached after 60 min. Changes of
pH, due to ion exchange between metal ions in model solutions and func-
tional groups of spruce wood sawdust, are the major mechanism of retention
of copper by sawdust.
Figure 4 shows the results of zinc removal during the experiment (from 5
to 120 min). In all experiments, removal ef iciency was higher than 73%. The
result indicates that zinc removal decreases pH of the solutions in the range
from 6.2 to 5.7. The maximum ef iciency removal of Zn(II) was about 82% at
pH 5.7. Pragati et al. (2015) used the ground sawdust to remove zinc from
aquatic solutions. They found that the maximum level of zinc iones removal
(at pH 5, during 120 min of contact time, and adsorbent dose 0.5g/100 mL)
is about 90%.
70 Studies and materials EKONOMIA I ŚRODOWISKO 3 (70) • 2019

105
6,4
90
6,2
75
6
Efficiency [%]

¼
60
5,8
pH

pH
45 5,6
30 5,4

15 5,2

0 5
0 15 30 45 60 75 90 105 120

Time [min]

Figure 3. Dependence of sorption efficiency η and changes of pH over time when removing
copper from aquatic solutions
Source: author’s own work.

90
6,4
75
6,2

60 6
Efficiency [%]

5,8
45
pH

5,6
30
5,4
¼
15
pH 5,2

0 5
0 15 30 45 60 75 90 105 120

Time [min]

Figure 4. Dependence of sorption efficiency η and changes of pH on time during

experiment on zinc removal from aquatic solutions
Source: author’s own work.
EKONOMIA I ŚRODOWISKO 3 (70) • 2019 Studies and materials 71
The results of iron removal in short-term experiments indicated the
removal ef iciency higher than 67% (5 minutes), the highest ef iciency was
observed at 45 minutes at about 76% ( igure 5). The value of pH was decreas-
ing from 6.3 to 5.3 due to ion exchange. Senin et al. (2007) found that the
maximum adsorption ef iciency by sawdust was found to be 71.7% which
corelates with the results of the experiment.

90
6,4
75
6,2

60 6
Efficiency [%]

¼ 5,8
45
pH

pH
5,6
30
5,4
15
5,2

0 5
0 15 30 45 60 75 90 105 120

Time [min]

Figure 5. Dependence of sorption efficiency η and changes of pH on time during

experiment on iron removal from aquatic solutions
Source: author’s own work.

Conclusions

In terms of treatment of ef luents, the current international tendency

towards environmentally friendly standards and solutions favours cheap and
harmless systems. Adsorption is one of the most effective techniques for
removal of pollutants from aqueous solutions. Inexpensive and easily availa-
ble materials like wood sawdust can be used as sorbent for puri ication of
wastewaters.
The Fourier-transform infrared spectroscopy of spruce sawdust con-
irmed the presence of the functional groups that they are able to bind heavy
metals ions.
72 Studies and materials EKONOMIA I ŚRODOWISKO 3 (70) • 2019

Under the 24 hours experiments, the highest removal ef iciency of ions

was recorded for copper – more than 85%, and the lowest ef iciency was
recorded for iron ions – more than 75%.
In all experiments Cu(II), Zn(II) and Fe(II) removal rate was more that
67%. In case of copper, zinc and iron the equilibrium concentration of ions
was highest at 60 minutes (1.01 mg/L) for Cu(II), 120 min (1.72 mg/L) for
Yn(II) and 45 min (2.41 mg/L) for Fe(II). Changes in pH values in the pro-
cesses of adsorption and ion exchange in all experiments shown a decreasing
tendency.
The sorption experiments showed the huge potential of the spruce saw-
dust in removing heavy metals ions from water solutions. The results of the
experiments are promising in terms of using sawdust to reduce pollution by
heavy metals.

Acknowledgements
This work has been supported by the Slovak Grant Agency for Science
(Grant No. 1/0419/19).

The contribution of the authors

Zdenka Kovacova – 40% (carried out the experiments and contributed to the inal
version of the manuscript).
Stefan Demcak – 30% (conceived and planned the experiments, carried out the
experiments and contributed to the inal version of the manuscript).
Magdalena Balintova – 30% (conceived and planned the experiments, supervised the
paper).

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