837

*
Author to whom all correspondence should be addressed. E-mail: auyanik@omu.edu.tr.
Effect of the Adsorptive Character of Filter Papers on the Concentrations
Determined in Studies Involving Heavy Metal Ions
Mehmet Soner Engin, Ahmet Uyanik
*
, Seydahmet Cay and Hasan Icbudak Department of
Chemistry, Science & Arts Faculty, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey.
(Received 15 September 2010; revised form accepted 14 December 2010)
ABSTRACT: Analytical filter papers are generally made of fibrous cellulose
which has the potential to adsorb metal ions. In this study, blue band ashless
filter paper was used to demonstrate one of the sources of error in the
determination of the concentration of Fe
2+
, Co
2+
, Mn
2+
, Cd
2+
, Cu
2+
, Pb
2+
and
Zn
2+
ions. For this purpose, the metal ion content of standard solutions in the
1100 mg/ concentration range was analysed via FAAS before and after the
filtration process. The corresponding results and the calculated percentage errors
due to adsorption are presented. The effect of pH on the adsorption process was
also investigated. Activated carbon and soil samples were spiked with each
metal ion and the solid phases from the resulting solutions were separated by
both filter paper methods and centrifugation. In the statistical estimation of the
results, the paired t-test was applied for non-filtered and filtered solutions in the
concentration range 1100 mg/ using the data analysis tools available in MS
Excel

. The use of filter paper caused systematic errors, particularly at lower

metal concentrations, and hence centrifugation or a filtering process using
techniques other than filter paper is favoured as a better approach towards
estimating the concentration of heavy metal ions from aqueous solution.
INTRODUCTION
Solid materials of mineral, synthetic, carbonaceous or biological origin have been of immense
interest in the removal of heavy metal ions as pollutants from natural, industrial and household
effluents. The adsorbent materials used for this purpose include various types of activated carbon,
zeolites, alumina, silica gel, ferric oxide, biomasses and agricultural wastes containing lignin
and/or cellulose, synthetic resins and polymer beads (Wang and Chen 2009; An et al. 2001; Kwon
et al. 2010; Say et al. 2006; Qi and Aldrich 2008; Pitcher et al. 2004; Park et al. 2007; Aklil et al.
2004; Yuan et al. 2008; Dimitrova and Mehanjiev 2000).
In previous studies, the adsorption efficiencies of the investigated solid materials have generally
been determined by preparing and analysing a series of standard metal ion solutions in the
laboratory. Thus, in the first step, standard metal ion solutions of known concentration were mixed
with a given amount of solid adsorbent material and stirred for a period of time in order to attain
adsorption equilibrium. Following adsorption, the exhausted adsorbents were removed from the
solutions whose final concentrations were determined from the resulting filtrates. The efficiency
of the adsorption process was then deduced from the difference between the initial and final
concentration measurements of the treated solutions.
For the separation of the exhausted solid adsorbent materials, analytical filter papers, filters made
from materials other than paper and centrifugation processes are commonly used in this particular
order according to the majority of reports. Only recent reports are referred to herein in order to point
out that an important source of systematic error is still omitted from those methods in which various
types of filters are used. Thus, for example, soil (Jan et al. 2010; Singh and Agrawal 2010),
vegetables, foodstuffs, irrigation water (Sharma et al. 2007; Singh et al. 2010), plant samples (Koz
et al. 2010; Kafel et al. 2010), fly ash (Shi and Kan 2009) and sunflower oil (Ansari et al. 2009) have
been digested or processed in order to determine their heavy metal ion content, with the resulting
solutions being passed through Whatman No. 42 blue band or equivalent filter papers. In other
studies, acid-washed filter paper and Whatman No. 1 filter paper have been used to estimate the
removal of heavy metal ions by pine barks (Khokhotva and Waara 2010) and olive oil waste (Garcia
et al. 2006), respectively. In other experiments, although filtration was also used in the separation,
no information was provided regarding the filter papers employed (Tavakoli and Yoshida 2010; Zou
et al. 2008; Gyliene et al. 2002; Akieh et al. 2008; B ozi c et al. 2009; Kolodyn ska et al. 2008;
Kolodyn ska and Hubicka 2009; Wang et al. 2008; Gupta and Babu 2009). In some cases, liquid
waste samples to be analysed for low levels of heavy metal ions were filtered prior to analysis using
an anonymous filter paper (Lee et al. 2006). In some reports, no clear description was provided as
to how the solid and aqueous phases were separated in the adsorption experiments (Dhakal et al.
2005; Bayramo glu and Arca 2008; Haroun et al. 2009; Tan and Xiao 2009; Keskinkan et al. 2004).
However, significant numbers of researchers have been aware of the drawbacks associated with the
use of filter papers and have, accordingly, used centrifugation instead of filtration (Anirudhan and
Suchithra 2008; Inglezakis et al. 2005; Asc et al. 2010) or, alternatively, column methods (Ghimire
et al. 2008), membrane (Kameda et al. 2008; Zhang et al. 2008) or Teflon filters (Li et al. 2009)
because they usually adsorb no metal ions.
Normally, the errors involved in centrifugation and with other types of filters are negligible.
However, when filter paper is used, differences in the metal ion concentrations before and after the
adsorption process are generally attributed to the adsorbent materials employed, with the adsorptive
character of the filter paper itself being not taken into account. It should be remembered that filter
papers of any kind used for analytical chemistry purposes are generally made of pure or modified
fibrous cellulose. Cellulose and its derivatives are composed of large polymeric molecules
containing acidic functional groups with many carbonyl and OH groups acting as metal ion
adsorbents (Acemioglu and Alma 2001; Annadurai et al. 2002). Unmodified cellulose is said to
have a low heavy metal ion adsorption capacity (OConnell et al. 2008), but the adsorption of
divalent metal ions by filter papers via an ion-exchange mechanism has long been recognised as a
common phenomenon upon which paper chromatography is mainly based (Pickering 1960a,b;
Frew and Pickering 1970). Furthermore, the adsorptive character of any adsorbent depends on
numerous parameters such as the temperature, contact time, solution pH and the type of metal ion
studied. Unless the filter papers employed in analysis are specially treated or produced, it is not
possible to rely on the use of filter papers in heavy metal ion studies without assessing the
experimental conditions. Hence, the adsorptive character of filter papers should be taken into
consideration in studies of heavy metal ions in order to lower the intrinsic systematic errors.
It will be seen from the above that that adsorptive character of filter papers is still not
recognised by many researchers. Hence, the present study has been conducted in order to draw
attention to the fact that the use of filter papers causes extra systematic errors in the low
concentration determination of Fe
2+
, Co
2+
, Mn
2+
, Cd
2+
, Cu
2+
, Pb
2+
and Zn
2+
ions in heavy metal
ion studies. In all the experiments discussed below, blue band ashless filter papers as commonly
used by researchers were employed.
838 M.S. Engin et al./Adsorption Science & Technology Vol. 28 No. 10 2010
MATERIALS AND METHODS
Equipment and reagents
A Unicam 929 flame atomic absorption spectrometer (FAAS) operating with an air/acetylene
flame and equipped with Fe and Pb (Cathodeon), Cd (Photron), Co, Zn, Cu and Mn (Unicam)
hollow cathode lamps at 12, 8, 4, 12, 8, 4 and 9.6 mA current settings, respectively, were
employed. All pH values were measured using a Jenway model 3040 pH meter combined with a
glass electrode (standardised by the use of pH buffers at 4.00 and 8.00). A Mistral 2000 model
centrifuge was employed at 2500 rpm in order to separate activated carbon and soil from the
solutions in spiked samples. The laboratory temperature was 19 5 C throughout. Analytical
reagent grade metal salts [MnCl
2
4H
2
O, CuCl
2
2H
2
O, ZnCl
2
, FeCl
3
6H
2
O, CdCl
2
H
2
O, Pb(NO
3
)
2
,
Co(NO
3
)
2
6H
2
O], HCl and HNO
3
(metal-free) were supplied by J.T. Baker and Merck & Co. Inc.
and used without any further purification. Whatman No. 42 filter papers (blue band ashless,
110 mm) were used without the addition of any adsorbent material.
Preparation of standard solutions
Stock solutions of Fe
2+
, Co
2+
, Mn
2+
, Cd
2+
, Cu
2+
, Pb
2+
and Zn
2+
ions were prepared at 1000 mg/
concentration in 1 flasks. Standard working solutions of 1, 2, 3, 5, 10, 20, 50 and 100 mg/
concentrations were then prepared at 100 m volumes from the stock solutions by successive
dilution. These were used in the construction of the calibration graphs and the filter paper adsorption
experiments. All solutions were prepared using demineralised or doubly distilled water and all stock
solutions were stored in the dark. Solutions > 10 mg/ concentrations were diluted for FAAS
measurements in order to obtain linear calibration graphs over the higher concentration range.
Filter paper experiments
All filter papers were washed with a 1:1000 (v/v) metal ion-free HCl solution and dried at 70 C in
an oven for 2 h prior to use. When used, such filter papers were folded according to analytical practice
and carefully placed in quantitative funnels; they were then soaked with demineralised water squirted
from a wash bottle. In each case, a prepared standard solution of 100 m volume was taken and its
absorbance measured by FAAS for 20 s to obtain a calibration point (first response), the remaining
solution being then passed through a filter paper by filling the paper to three-quarters of its volume.
The absorbance of the resulting filtrate was then measured again by FAAS after a single filtration
(second response), both to compare and to calculate the difference between the first and second
responses of the solution. Additional experiments were also carried out with Cu
2+
and Co
2+
ions to see
the effect of using dry and soaked filter paper on the degree of heavy metal ion adsorption.
pH Studies
All the measured pH values of the original standard solutions were found to be below 7 due to
hydrolysis. To examine the effect of the solution pH on the metal ion adsorption capacity of filter
papers, experiments were carried out at three different pH values, viz. 3, 5 and 7. The pH of the
standard solutions was adjusted by the addition of 0.1 M HCl or 0.1 M NaOH as necessary. The
concentration employed for each metal ion in all the pH experiments was 5 mg/.
Effect of Adsorptive Character of Filter Papers in Studies Involving Heavy Metal Ions 839
Spiked activated carbon samples
The commercially available 2060 mesh untreated granular activated carbon (Sigma Catalogue
No. C-3014) was used in the experiments. Approximately 10 g of granulated activated carbon was
pre-conditioned by washing with 5 M HCl, then thoroughly rinsed with de-ionised water, dried in
an oven at 105 C and stored in a desiccator until used. The nitrogen BET surface area of the dried
activated carbon was measured as 325 m
2
/g. In each experiment, 0.1 g activated carbon was added
to a 100 m volume of a 10 mg/ standard solution of each metal ion and shaken for 60 min at
room temperature (19 5 C). The following procedures were then undertaken: (1) following the
adsorption step, a 10 m portion of the aqueous phase was taken, any solid adsorbent separated
by centrifugation and the metal ion content measured for 20 s by FAAS; (2) the original and
remaining solutions were then combined and filtered by filter paper, and resulting metal ion
content of the filtrate measured once more by FAAS. Any adsorption arising from the use of filter
paper could then be deduced from the measurements obtained before and after the filtering steps.
This procedure was repeated three times for each metal ion studied.
Spiked soil samples
A soil sample of ca. 1 kg weight was taken from the traffic-free and relatively clean part of the
university campus. Two 10 g soil samples were taken each time from the homogenised bulk and
digested with hot conc. HNO
3
/HCl (1:3) mixture. One of the digested parts was then directly
diluted with demineralised water to a volume of 100 m, while the other part was spiked with 10 m
of a 50 mg/ solution of the metal ion and then diluted to a volume of 100 m (giving a final
concentration of 5 mg/). Both solutions were centrifuged and their metal ion content measured
for 20 s by FAAS. Following the measurement step, both solutions were filtered using filter paper
and the concentrations of the resulting filtrates again measured by FAAS. Adsorption by the filter
paper was deduced from the measurements obtained before and after the filtering steps. This
procedure was repeated for each metal ion studied.
Recovery experiments
The extent of adsorption was deduced from the FAAS measurements of the standard solutions
before and after the filtering steps. In particular, in the activated carbon and soil experiments,
to prove that adsorption had occurred on the filter papers, the latter were also treated with 10 m
of 0.1 M HCl following the experiments and the amounts of metal ions adsorbed calculated
from measurements of the metal ion concentrations of the resulting solutions by FAAS
methods.
Statistical evaluation
The results given throughout this paper are the average of at least three measurements.
Regression analysis was applied to the calibration graphs through the use of MS Excel

and the
limits of detection (LODs) given by the graphs calculated as three-times the values of the
standard deviations of the intercepts. The paired t-test was used ( = 0.05) in the statistical
evaluation of the results to point out the significant differences between (1) the dry and wet
filtering results for Cu
2+
and Co
2+
ions, (2) the non-filtered and filtered results for each metal
ion solution and (3) the results for the non-filtered (centrifuged) and filtered spiked activated
840 M.S. Engin et al./Adsorption Science & Technology Vol. 28 No. 10 2010
carbon and soil samples by employing the data analysis tools of MS Excel

(Miller and Miller

2005).
RESULTS AND DISCUSSION
Adsorption of metal ions on filter paper
The superimposed results of the non-filtered and filtered standard solutions, together with the
calculated percentage error due to adsorption plus the calculated standard deviations at each
point, are presented in Figures 1(a)(g) for Cu
2+
, Cd
2+
, Co
2+
, Fe
3+
, Mn
2+
, Pb
2+
and Zn
2+
ions,
respectively. The error bars associated with the data points on the graphs were smaller than the
symbols employed. The experimental results clearly show that using filter paper in any step to
separate adsorbent materials from the final solutions, particularly at lower metal ion
concentrations, causes constant systematic errors. The broad arc-like curves superimposed on the
plots provide valuable information regarding the degree of adsorption of each metal ion studied.
The broader the curve on a given plot, the greater the adsorption. The adsorption observed from
the curves for 5 mg/ concentrations followed the order Pb
2+
> Cu
2+
> Zn
2+
> Fe
3+
> Cd
2+
> Co
2+
> Mn
2+
(see the corresponding values listed in Table 1). However, at relatively higher
concentrations, the amount of adsorption onto the filter papers decreased, probably due to the
occupation of the active sites on the cellulose surface. The effect of solution temperature on the
adsorption process was not studied because the filtering process is generally practised at room
temperature.
It may be seen from Table 1 that filtering using a filter paper resulted in remarkably different
values from those obtained from non-filtered measurements. Using the paired t-test, significant
differences (P < 0.05) were observed between the filtered and non-filtered results for each metal
ion studied, as listed in the last column of Table 1. Soaked filter papers were used throughout the
experiments, but a set of standard Cu
2+
and Co
2+
ion solutions in the 1100 mg/ range was
filtered using wet and dry filters before commencing the experiments and the differences assessed
via the paired t-test. The results indicated that there were no significant differences between both
filtering processes for Cu
2+
ions (P = 0.3473 > 0.05) or for Co
2+
ions (P = 0.2123 > 0.05) at their
respective 95% confidence levels.
Activated carbon and soil experiments
The adsorption order onto filter paper observed as the arc-like curves for Pb
2+
> Cu
2+
> Zn
2+
>
Fe
3+
> Cd
2+
> Co
2+
> Mn
2+
in Figures 1(a)(g) was also obtained from the activated carbon
experiments (see Table 2). However, in the soil experiments, the adsorption degrees onto filter
paper for the metal ions were lower than those obtained from the activated carbon experiments,
since the soil itself contained all the studied metal ions at remarkable high levels (particularly Fe
3+
and Mn
2+
) and all the metal ions competed with the spiked metal ions in each case. Hence, the
adsorption order Cd
2+
> Zn
2+
> Co
2+
> Mn
2+
> Pb
2+
> Cu
2+
> Fe
3+
was also representative of the
competitive adsorption of the spiked metal species in the presence of other metal ions in the soil
experiments (Table 3). Paired t-tests for the spiked activated carbon and the spiked soil (excluding
Fe
3+
and Mn
2+
ions) indicated significant differences between the centrifuged and filtered results
(P = 0.0002 < 0.05) and (P = 0.001 < 0.05) at 95% confidence level, respectively.
Effect of Adsorptive Character of Filter Papers in Studies Involving Heavy Metal Ions 841
842 M.S. Engin et al./Adsorption Science & Technology Vol. 28 No. 10 2010
Figure 1. Calibration graphs for standard solutions of (a) Cu
2+
ions, (b) Cd
2+
ions, (c) Co
2+
ions, (d) Fe
3+
ions, (e) Mn
2+
ions, (f) Pb
2+
ions and (g) Zn
2+
ions. Data points relate to the following: () centrifuged; () filtered; () percentage error.
0 20 40 60 80 100
Concentration (mg/ ) Concentration (mg/ )
0 20 40 60 80 100
0
1
2
3
4
5
6
7
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)
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b
s
o
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a
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c
e

(
a
.
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.
)
%

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r
r
o
r

d
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o

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%

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i
n
g
0
10
20
30
40
50
60
70
80
y = 0.0618x + 0.0146
R
2
= 0.9996
LOD = 0.62 mg/
0
2
6
4
8
10
12
14
16
18
0
10
20
30
40
50
60
70
(a) (b)
y = 0.1601x + 0.0558
R
2
= 0.9999
LOD = 0.04 mg/
0 20 40 60 80 100
Concentration (mg/ ) Concentration (mg/ )
0 20 40 60 80 100
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)
A
b
s
o
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b
a
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e

(
a
.
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.
)
%

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r
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r

d
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t
o

f
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r
i
n
g
1
3
2
0
(c)
1
3
4
2
0
0
10
20
30
40
50
60
70
(d)
0
5
10
15
20
25
30
35
40
45
50
y = 0.0244x + 0.0176
R
2
= 0.9998
LOD = 0.19 mg/
y = 0.0298x + 0.0276
R
2
= 0.9996
LOD = 0.02 mg/
Concentration (mg/ )
Concentration (mg/ )
0 20 40 60 80 100
0 20 40 60 80 100
Concentration (mg/ )
0 20 40 60 80 100
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)
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r
i
n
g
0
1
2
3
4
5
6
7
8
(e) (f)
(g)
0
5
10
15
20
25
30
35
40
0
1
1
2
2
3
y = 0.021x + 0.008
R
2
= 0.9997
LOD = 0.43 mg/
0
10
20
30
40
50
60
70
80
90
100
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)
0
2
4
6
8
10
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14
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%

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d
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t
o

f
i
l
t
e
r
i
n
g
0
10
20
30
40
50
60
y = 0.154x + 0.005
R
2
= 0.9998
LOD = 0.66 mg/
y = 0.0702x + 0.1317
R
2
= 0.9962
LOD = 1.19 mg/
Effect of Adsorptive Character of Filter Papers in Studies Involving Heavy Metal Ions 843
T
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Effect of pH values on the adsorption process
The original pH values of the solutions were measured as 4.5, 5.8, 5.8, 1.5, 6.5, 4.6 and 5.9 for
Cu
2+
, Co
2+
, Cd
2+
, Fe
3+
, Mn
2+
, Pb
2+
and Zn
2+
ions, respectively. Hence, since the solution pH is an
important parameter in the adsorption of heavy metal ions, its effect was investigated at three
different values, viz. 3.0, 5.0 and 7.0. It may be seen from the pH plots depicted in Figure 2 that
the degree of adsorption onto filter paper increased with increasing pH of the solutions, indicating
that an ion-exchange mechanism is likely to have an important part in the adsorption process. In
order to prevent metal ions from undergoing hydrolysis and hence lowering the degree of
adsorption, the pH values of the solutions were adjusted to the lowest value studied (pH = 3.0) in
all the experiments except those for the Fe
3+
ion (pH = 1.5).
Recovery results
For the recovery of the ions adsorbed in the spiked activated carbon and soil experiments, all the
filter papers employed were treated with 10 m of 0.1 M HCl after use. Tiny activated carbon and
soil particles containing adsorbed metal ions tend to fill the pores of the filter papers and
subsequently release their retained metal ions on treatment with 0.1 M HCl, thereby producing
844 M.S. Engin et al./Adsorption Science & Technology Vol. 28 No. 10 2010
TABLE 2. Effect of Filter Papers on the Determined Concentrations of Spiked Heavy Metal Ions
Adsorbed onto Activated Carbon Samples from Aqueous Solutions at the 10 mg/ Concentration Level
Metal Amt. of metal ion Amt. of metal ion present Amt. of metal ion present % Difference
ion added initially (mg/) after centrifugation (mg/) CV after filtration (mg/) CV
Pb
2+
10.0 4.29 0.13 1.98 0.03 53.85
Cu
2+
10.0 7.19 0.02 4.75 0.04 33.94
Zn
2+
10.0 6.31 0.07 4.17 0.02 33.91
Fe
3+
10.0 8.29 0.03 5.85 0.05 29.43
Cd
2+
10.0 6.77 0.07 5.37 0.06 20.67
Co
2+
10.0 8.56 0.11 7.09 0.09 17.20
Mn
2+
10.0 6.69 0.03 5.79 0.06 13.45
TABLE 3. Effect of Filter Papers on the Determined Concentrations of Spiked Heavy Metal Ions
from Soil Samples at the 5 mg/ Concentration Level
Metal Soil metal ion Added metal Metal ion conc. after Metal ion conc. % Difference
ion content ion conc. centrifugation after filtration
(mg/) CV (mg/) (mg/) CV (mg/) CV
Cd
2+
0.01 0.90 5.00 4.96 0.21 3.63 0.41 26.81
Zn
2+
2.97 0.07 5.00 7.82 0.11 5.78 0.06 26.09
Co
2+
1.32 0.08 5.00 6.29 0.04 4.67 0.15 25.75
Mn
2+
10.6 0.24 5.00 15.2 0.12 12.13 0.15 21.59
Pb
2+
0.79 0.13 5.00 5.65 0.04 4.54 0.04 19.64
Cu
2+
2.20 0.09 5.00 7.13 0.09 5.94 0.10 16.69
Fe
3+
115.3 0.04 5.00 121.1 0.01 108.62 0.02 15.41
higher amounts of metal ions than predicted. For this reason, any such trivial recovery results were
not included in the relevant tables.
CONCLUSIONS
It should be remembered that the filtration of metal ion solutions is the easiest way of separating
unwanted particles and exhausted adsorbents. However, as shown in the present study, this may
also cause inconvenient results particularly in the development of new methods of analysis. To
eliminate this apparent source of systematic error, filter papers should not be employed
whatsoever in adsorption experiments. In real situations, however, processed waste solutions
contain solid particles and a separation step is usually necessary prior to the adsorption and
pre-concentration stage. If filter papers are used in this stage, quantitative adsorption checks
should be performed on the used filter papers before commencing the experiments or the filter
papers should be digested together with the solid residue after filtration. Generally, no remarkable
systematic errors are observed due to the loss metal ions following such digestion unless the filter
papers are used in subsequent steps. However, a digestion step may not be suitable in adsorbent-
containing experiments since tiny adsorbent materials may block the pores of the filter paper and
then be released to produce higher and trivial results. In conclusion, centrifugation or a filtering
process employing methods other than filter papers is to be recommended as a more convenient
approach in studies of heavy metal ions, where the separation of solid particles and/or adsorbent
materials from the final solutions is necessary.
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