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Bioresource Technology 99 (2008) 5595–5601

Biosorption of heavy metals from aqueous solutions with tobacco dust


B.C. Qi, C. Aldrich *

Department of Chemical Engineering, University of Stellenbosch, Stellenbosch, Private Bag X1, Matieland 7602, South Africa

Received 21 November 2006; received in revised form 19 October 2007; accepted 24 October 2007
Available online 21 December 2007

Abstract

A typical lignocellulosic agricultural residue, namely tobacco dust, was investigated for its heavy metal binding efficiency. The tobacco
dust exhibited a strong capacity for heavy metals, such as Pb(II), Cu(II), Cd(II), Zn(II) and Ni(II), with respective equilibrium loadings
of 39.6, 36.0, 29.6, 25.1 and 24.5 mg of metal per g of sorbent. Moreover, the heavy metals loaded onto the biosorbent could be released
easily with a dilute HCl solution. Zeta potential and surface acidity measurements showed that the tobacco dust was negatively charged
over a wide pH range (pH > 2), with a strong surface acidity and a high OH adsorption capacity. Changes in the surface morphology of
the tobacco dust as visualized by atomic force microscopy suggested that the sorption of heavy metal ions on the tobacco could be asso-
ciated with changes in the surface properties of the dust particles. These surface changes appeared to have resulted from a loss of some of
the structures on the surface of the particles, owing to leaching in the acid metal ion solution. However, Fourier transform infrared spec-
troscopy (FTIR) showed no substantial change in the chemical structure of the tobacco dust subjected to biosorption. The heavy metal
uptake by the tobacco dust may be interpreted as metal–H ion exchange or metal ion surface complexation adsorption or both.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Biosorption; Heavy metals; Lignocellulose; Tobacco

1. Introduction successive treatment cycles. Moreover, the end product is


usually a low volume, highly concentrated metalliferous
The increased attention on the harmful effects of heavy sludge that may be difficult to dewater and dispose of (San-
metal ions on human health and the environment over dau et al., 1996). Likewise, ion exchange and membrane
the past few decades has led to a concomitant focus on systems could be expensive, especially in small-scale pro-
improved water quality. Since industrial effluents in partic- cesses, with the resins or membranes prone to fouling or
ular are a major contributor to heavy metal contamination, oxidation. Similarly, activated carbon, the most widely
the removal of such metals from these effluents has been a used adsorbent in the treatment of waste water, is expen-
priority in the tightening and enforcement of environmen- sive and may also require complexing agents to improve
tal regulations. Removal of these contaminants can be its ability to remove inorganic matter (Babel and Kurnia-
accomplished by use of physical or chemical methods, wan, 2002).
including the use of chemical reagents, ion exchange, acti- Biosorption, which is the ability of certain biomaterials
vated carbon sorption and membrane technology. Most of to bind and concentrate heavy metals from even the most
these approaches have significant disadvantages. For dilute aqueous solutions, offers a technically feasible and
example, chemical reagents are costly (Kadiverlu et al., economically attractive alternative to the conventional
2001), as the active agents cannot be recovered for use in technologies for removal of heavy metal from the contam-
inated effluents (Davis et al., 2000; De Carvalho et al.,
2001; Esposito et al., 2001; Demir and Arisoy, 2007).
*
Corresponding author. Tel.: +27 21 808 4485; fax: +27 21 808 2059. Various biomaterials produced or harvested from natural
E-mail address: CA1@sun.ac.za (C. Aldrich). resources or agricultural products, mostly in metabolically

0960-8524/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.10.042
5596 B.C. Qi, C. Aldrich / Bioresource Technology 99 (2008) 5595–5601

inactive states, have been used in disposal of heavy metal Batch equilibrium sorption was performed in 1 L screw
effluents by biosorption. These include microorganisms, capped plastic bottles on a roller at a speed of 58–60 rpm at
such as bacteria, fungi, yeast and algae and lignocellulose ambient temperatures (23–25 C) for 24 h. The pH values
biomaterials, such as peat moss, raw rice bran, rice straw, of the final suspensions were measured at equilibrium sorp-
coconut husks, waste coffee powder, dried plant leaves, tion conditions. The suspension was then filtrated and the
etc. (Oliveira et al., 2005; Orhan and Buyukgungor, 1993; individual metal ion concentrations of the filtrate were ana-
Zouboulis et al., 1999; Feng and Aldrich, 2004). Among lyzed as the equilibrium concentrations of each metal ion
these biomaterials, marine algae and peat moss have been species. Metal ion loadings on the biosorbent were deter-
studied extensively to sequester heavy metals from contam- mined from the difference of metal ion concentrations in
inated effluents (Zümriye, 1997; Brown et al., 2000). the initial and final suspensions. The capacity of the biosor-
However, among others, owing to the heterogeneous com- bent for the single species sorption system was estimated
position and complex chemical structures of various bioma- from the equilibrium metal ion loading values, which
terials, as well as a wide spectrum of heavy metals, standard showed no obvious change with an increase in the metal
criteria through which biosorption can be industrialized are ion loading. However, for the multi-species sorption sys-
still lacking at present. For lignocellulosic biomaterial (e.g., tem, the equilibrium metal ion loading values were not
peat moss and black liquor), it is especially the lignin and observed over the concentration ranges of the multiple
humic acids that are involved in the chemical bonding of metal ions under the investigation. Thus no sorption capac-
heavy metals during biosorption (Brown et al., 2000; Babel ity values could be obtained for the multi-species sorption
and Kurniawan, 2002). system. For both sorption systems, the biosorbent load was
Furthermore, besides a strong metallic affinity, the 1.0 g/L metal solution.
search for a low-cost and easily available adsorbent has Batch kinetic tests were performed at 25 C using an
led to the investigation of materials of agricultural origin overhead stirrer with a baffle attachment at stirring speeds
as potential metal adsorbents (Pagnanelli et al., 2001; Sheth of 800–1000 rpm. The biosorbent load was 1.0 g/L metal
and Soni, 2004). These low cost materials have not been solution.
studied as extensively as other biosorbents, owing to their Desorption experiments were carried out under the same
local, rather than global availability (Babel and Kurnia- conditions as the batch sorption experiments, except that
wan, 2002) and therefore, in this investigation, the biosorp- both the biosorbent and heavy metal ion loadings were
tion capacity of a typical lignocellulosic plant biomass and doubled in the sorption stage. After 24 h of contacting,
a waste product from the tobacco industry, namely tobacco reaction suspensions were filtrated and the filtrated cakes
dust, is considered. were washed three times using the same volumes of distilled
water as the sorption suspensions. This was done in order
2. Experimental work to remove the physically attached metal ions from the
loaded tobacco dust. The washed solids were oven dried
2.1. Materials overnight at 105 C for subsequent desorption tests.
Desorption tests were carried out by magnetically suspen-
The heavy metal ions tested in this study included ding the loaded biosorbents in a series of HCl solutions
Pb(II), Cu(II), Cd(II), Zn(II) and Ni(II). The metal ion at varied concentrations (the suspension contained 1%
solutions were made up of atomic absorption standard weight of the metal loaded biosorbent). After the required
metal solution (Merck, 1000 mg/L) by diluting with dis- contact time, the reaction mixture was filtrated and the
tilled water to the required concentrations. Analytical metal ion content of the filtrate was analyzed. Desorption
grades of HCl and NaOH (Merck) solutions were used efficiency was calculated as a percentage of the amount of
for pH adjustment. The air-dried tobacco dust was the released metal ions relating to the total amount of
obtained in ground form from the British American metal ions which were previously adsorbed on the
Tobacco Company in Paarl, South Africa, with a particle biosorbent.
size of 1–2 mm. The metal ion content in the solution was measured
using an atomic absorption spectrophotometer (AA 250
2.2. Methodology plus) and ICP spectrometry (Varian Liberty Series II
Sequential ICP AES).
The tobacco dust was protonated with 0.1 M HCl at 1:5 The morphological microstructures of the tobacco dust
(w/v) for 1 h, followed by washing with distilled water until were examined by atomic force microscopy (AFM) using
the pH of the suspensions reached 4.5–5.0, and dried at a TMX 2000 Explorer (Topometrix, American, force con-
105 C. The tobacco dust had the following mass-based stant of probe, 35–65 N/m). The surface roughness was
composition: 30% lignin, 94.2% total solids, 72.0% volatile estimated from the AFM images and calculated with the
solids, 28.0% ash, 43.0% carbon and 2.37% nitrogen, 1.70% AFM surface analysis software (SPMLab V3.0 6.0).
potassium, 4.29% calcium and 0.70% magnesium. It also The surface acidity of the biosorbent was investigated
contained 26, 57, 0.57, 761 and 288 mg/kg of B, Cu, Fe, using alkalimetric titration (Huang, 1981). To prepare the
Zn and Na, respectively. samples for titration, 140 mL of biosorbent suspension
B.C. Qi, C. Aldrich / Bioresource Technology 99 (2008) 5595–5601 5597

(1.0 g/L) was transferred into each of four beakers. Two their sorption equilibria within approximately 90 min at
were directly titrated, one with acid (0.1 N HClO4) and an equilibrium pH of 6.34. Dynamic biosorption selectivity
the other with base (0.1 N NaOH) (sample titration). The of the tobacco dust for heavy metals was approximately in
other two were titrated after removing the biosorbent solid the order: Zn(II) ffi Cu(II) > Cd(II) > Pb(II) > Ni(II).
by passing through a 0.45 lm filter (blank titration). The
initial pH value was measured, followed by titration of
the solutions under continuous mixing using 0.1 N HClO4 3.2. Equilibrium experiments
to pH 3.0 or 0.1 N NaOH to pH 11.0. The volumes of the
acid or base added and the corresponding equilibrium pH Equilibrium experiments were performed for both sin-
values were recorded. The pH values were taken every gle-ion sorption systems and multi-species sorption sys-
30 min after each addition of acid or base. Pure N2 gas tems. The solution pH was presumed to be an important
was continuously purged to exclude CO2 during titration. factor influencing the heavy metal distributions in the
The change of pH after each acid or base addition was liquid phase, as well as the interactions between the metal
ensured not to exceed 0.3 units. ions and the biosorbent. Fig. 2 indicates that the influence
The surface charging characteristics of the biosorbent of the pH on the biosorption of the heavy metals generally
were examined by zeta potential measurements (Malvern followed the expected metal sorption behaviour, with the
Zetasizer 4) on a multi-species sorption system. Under removal efficiency increasing with an increase in the pH
the same pH conditions, the biosorbent suspensions in of the solution, but decreasing under high equilibrium
the absence of heavy metals were used as the blank pH (pH > 9) conditions.
samples. Sorption started at a pH of 4–5 and began to decline at a
Changes in the surface structures of the tobacco dust pH of 9–10 for most of the heavy metal ions. This suggests
subjected to metal sorption and desorption were examined that sorption from dilute hydrolysable metal ion solutions
using FTIR spectra. The KBr pellets were prepared with a (such as that of a heavy metal) usually occurs at a pH
mixture of 1.0 mg oven-dried tobacco dust with 300.0 mg below the region where hydrolysis occurs. This is where
KBr (both were dried at 105 C for 48 h). The FTIR spec- sorption may be driven either by ion exchange or surface
tra of the pellets were recorded on a Perkin Elmer 1600 Ser- complexation, in which metal ions replace surface protons,
ies FTIR spectrometer. or as the preferential sorption of the hydrolyzed species
(James, 1981). FTIR analysis has suggested the presence
of aromatic structures, nonaromatic double bonds, H-
3. Results and discussion bonded C@O of conjugated ketones and quinines and sym-
metric COO- groups (Sparks, 1999) in the tobacco dust
3.1. Kinetic experiments biomass. At a pH of 4–5, the ionic state of ligands of func-
tional groups, such as carboxyl, phosphate and amino-
The changes in solution pH and heavy metal removal groups, which are mostly the chemical structures of the sur-
efficiency in a multi-species sorption system with sorption face cell walls of the tobacco dust, would promote a reac-
time are shown in Fig. 1. The pH of the sorption system tion with metal ions. This reaction would occur through
decreased steadily during the first 370 min, then stabilized electrostatic attraction between positively charged metal
throughout the sorption process. This implies that the cations and negatively charged binding sites on the tobacco
metal binding to the biosorbent was associated with H+– dust (detailed surface charge conditions will be discussed
metal ion exchange. Almost all the heavy metals achieved later). This would result in a rapid rise in the metal removal

100 100
90 90
80
80
Ion removal (%)

70
Ion removal (%)

70
60
60
50
50
40
40
30
30 Cd Cu Cd Cu
Ni Pb 20 Ni Pb
20 Zn
10 Zn
10 0
0 1 2 3 4 5 6 7 8 9 10 11 12
0 2 4 6 8 10 12 14 16 18 20 22 24 pH
Contact time (hour)
Fig. 2. Changes in heavy metal removal efficiency of the tobacco dust with
Fig. 1. Heavy metal adsorption kinetics of the tobacco dust (pH = 6.34). equilibrium solution pH for single-species sorption.
5598 B.C. Qi, C. Aldrich / Bioresource Technology 99 (2008) 5595–5601

efficiency at a pH of 4–5. As the pH is lowered, the mea- the whole, the metal loadings of Pb(II) and Zn(II) appeared
sured surface charge on the tobacco would become more similar in both multi-species and single species sorption
positive, leading to a weakening of the electrostatic interac- systems. Therefore, synergism (for Cu(II)), antagonism
tion of metal ions with the tobacco dust. (for Cd(II) and Ni(II)) and non-interaction (for Pb(II)
Both the single and multiple species sorption isotherms of and Zn(II)) were present simultaneously in the multi-spe-
the tobacco dust are presented in Fig. 3. The sorption capac- cies sorption system, depending on the species of heavy
ities for Pb(II), Cu(II), Cd(II), Zn(II) and Ni(II) of the metals. When the combined effects of more than one metal
tobacco dust were approximately 39.6, 36.0, 29.6, 25.1 and ion on the same biomass were found to be antagonistic,
24.5 mg/g sorbent, respectively, in a single species sorption such as the interactions between Cd(II) and Cu(II) or Ni(ii)
system. In contrast, under the same equilibrium metal con- and Cu(II), it can be postulated that the effective number of
centrations, the heavy metal sorption isotherms in multi- binding sites available for the uptake of a single metal spe-
species sorption system were different from those in a single cies was reduced, depending on the sorption equilibria of
species sorption system. The selectivity of the metal binding the other cations. The extent of this reduction for the indi-
capacities of the tobacco dust also differed in the single and vidual species is possibly related to the electro-negativities
multiple species systems. In a multi-species sorption system of the cations. In contrast, screening or competition for
it was in the order of Cu(II) > Pb(II) > Zn(II) > Cd(II) > the binding sites on the biomass surface could result in
Ni(II), while in the single species sorption system it was in the metal ions mutually improving their individual affinity
the order of Pb(II) > Cu(II) > Cd(II) > Ni(II) ffi Zn(II). for the biomass, leading to a synergistic effect. A thermo-
In general, three types of interactive sorption behaviour dynamic model could be developed by extracting the active
could be displayed by a mixture of heavy metals, viz. syn- metal ion absorption sites on the surfaces of the tobacco
ergism, antagonism or non-interaction. With synergism, dust to prove this postulation. However, such a develop-
the effect of the mixture is greater than the sum of each ment falls beyond the scope of this paper.
of the individual effects of the constituents in the mixture.
With antagonism, the effect of the mixture is less than that 3.3. Desorption experiments
of the sum of the individual effects of the constituents in the
mixture. With non-interaction, the effect of the mixture is Desorption of heavy metal ions from the loaded tobacco
equivalent to the sum of each of the individual effects of dust with different concentrations of HCl solutions
the constituents in the mixture (Zümriye, 1997). (desorption time 6 h) is shown in Fig. 4. The changes of
The sorption competition among these heavy metal ions, desorption efficiency with time is given in Fig. 5, for a
especially among Cu(II), Cd(II) and Ni(II), was evident 0.09 mol/L HCl solution.
from comparison of the metal uptake in the single and mul- Fig. 4 shows that except for the Pb(II), almost all of
tiple species systems. Under the same initial metal concen- the heavy metals adsorbed on the tobacco dust could
trations, the metal loading of Cu(II) was generally higher in be desorbed easily by a dilute HCl solution (less than
the multi-species sorption system than in the single species 0.01 mol/L). The desorption efficiency was in the order:
sorption system. Conversely, the metal loadings of Cd(II) Ni(II) > Zn(II) > Cd(II) > Cu(II) > Pb(II). This confirmed
and Ni(II) were generally lower in the multi-species sorp- that the tobacco dust had higher binding capacities for
tion system than in the single species sorption system. On Pb(II) and Cu(II) than for Ni(II) in particular, which could

40 30
28
36
26
32 24
Metal loading (mg/g)

22
28
20
24 18
16
20
14
16 12
10
12 Cd
8
Cu
8 6 Ni
Cd Cu
Ni Pb 4 Pb
4 Zn
Zn 2
0 0
0 2 4 6 8 10 12 14 16 18 0 1 2 3 4 5 6 7 8 9 10
Equilibrium concentration of heavy metals (mg/l) Equilibrium concentrations of heavy metals (mg/l)

Fig. 3. Heavy metal sorption isotherms of the tobacco dust at pH 6.5–7.2 (left: single-species sorption, right: multi-species sorption).
B.C. Qi, C. Aldrich / Bioresource Technology 99 (2008) 5595–5601 5599

100 3.5. Surface acidity of tobacco


90
Desorption effitiency (%)

80 Surface acidity is an important property of hydrous sol-


70 ids which are closely related to the mode and extent of
60 interfacial reactions such as adsorption and coagulation.
50 As mentioned previously, surface adsorption was consid-
40 ered to be an important mechanism by which heavy metal
30 Pb Zn Cd
ions may be bound to the tobacco dust.
20
Cu Ni As a typical natural lignocellulosic biomass, tobacco
10 dust is a complex material with lignin, cellulose and hemi-
0 cellulose as its major constituents. These constituents gen-
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 erally have polar functional groups, such as alcohols,
HCl concentration (mol/l) carboxylic acids and phenolic hydroxides. The hetero-
geneous functional groups on the surface structure of the
Fig. 4. Desorption of heavy metal ions from the tobacco dust with
different concentrations of HCl solution. tobacco dust make it difficult to distinguish, by conven-
tional analytical means, between dissociation of protons
from the surface and adsorption of OH ions onto the sur-
100 face. However, simply recording the pH values during the
course of titration of a suspension is sufficient to interpret
Desorption efficiency (%)

the surface sorption property of the biomass in terms of


adsorption of hydrogen or hydroxide ions or their com-
plexes (Huang, 1981).
Titration analysis has shown that the pH of the suspen-
sion (supernatant) decreased or increased sharply corre-
Pb Zn Cd sponding to the acid or base added, since the free H+ or
Cu Ni OH ions released from the biomass surface were initially
neutralized by the added base or acid. In contrast, the
90
0 2 4 6 8 10 12 14 16 18 20 22 24 pH plateau on the titration curves resulting from further
Time (hour) addition of base or acid, represents a surface adsorption
or complexation of H+ and or OH with the soluble
Fig. 5. Desorption of heavy metal ions from the tobacco dust with
0.09 mol/L HCl solution.
organic components of the tobacco dust, which were previ-
ously leached into the solution.
Operationally, the amount of adsorption is related to
even be desorbed partially by distilled water (data not the number of appropriate ions that cannot be accounted
shown). for in a mass balance between the titration curve of sus-
Fig. 5 shows that desorption of heavy metals with HCl pension and that of the supernatant. Ions not in solution
solutions (pH < 2) from the tobacco dust is a rapid process, have to be on the surface of the biomass, so that a
which can be accomplished in less than 60 min. This sug- decreased rate of increase in the pH of the suspension
gests that H+ has a higher competitive capacity than the compared to that of supernatant with the same dosage
heavy metal ions under low pH condition (pH < 2). of the base indicates the adsorption or complexation
(neutralization) of OH on the solid surface of the
3.4. Surface morphology changes of the tobacco dust owing tobacco dust, possibly accompanied by proton release.
to biosorption and desorption Conversely, an increased rate of increase in the pH of
the suspension compared to that of the supernatant with
Atomic force microscopic images have shown that the the same dosage of the acid indicates the adsorption or
surfaces of the tobacco dust changed from fine homoge- complexation of H+ on the solid surface of the tobacco
neous particulate textures to structures dominated by dust. This also confirms the amphoteric property of the
bump-like aggregates, with some areas being significantly tobacco dust, which can adsorb both OH and H+.
smoother than others, following the sorption of heavy met- The dosage of base or acid that cannot be accounted
als and the desorption of hydrochloric acid. The presence for by the change of the pH of the supernatant, suggests
of smooth surface areas and channel-like configurations the complexation of H+ and or OH with the organic
indicated that certain components of the tobacco dust compounds in the supernatant, confirming the leachabil-
could be leached off the surface by the HCl or heavy metal ity of the organic component of the tobacco dust.
solutions. This also suggests that the sorption of heavy In addition, titration analysis has shown that a larger
metal ions on the tobacco dust could be associated with amount of base was needed for the suspension than for
changes in the local surface properties owing to the loss the supernatant to reach an equilibrium pH value of 11.
of some of the structural components of the tobacco dust. This indicated that the solid surface of the tobacco dust
5600 B.C. Qi, C. Aldrich / Bioresource Technology 99 (2008) 5595–5601

possessed a strong OH adsorption or complexation 4. Conclusions


capacity, i.e., the tobacco dust surface is a highly proton-
ated surface with a high proton releasing potential. There- In this investigation, the heavy metal binding efficiency
fore, in terms of surface acidity, the tobacco dust could be of tobacco dust was considered and the following conclu-
interpreted as S–H (‘‘S’’ stands for the solid surface of the sions can be made.
tobacco dust, while ‘‘H’’ stands for functional groups of
the protonated surface of the tobacco dust). The high sur- • The tobacco dust exhibited a strong capacity for the
face acidity of the tobacco dust explains its high heavy heavy metals considered in the study, viz. Pb(II), Cu(II),
metal binding capacity by proton replacement. Cd(II), Zn(II) and Ni(II), with respective equilibrium
loadings of 39.6, 36.0, 29.6, 25.1 and 24.5 mg of metal
3.6. Electrokinetic properties of the tobacco dust per g of sorbent.
• Titration and zeta potential measurements both sug-
Polar functional groups, such as alcohols, carboxylic gested that the heavy metal sorption by the tobacco dust
acids and phenolic hydroxides may contribute to the occur- was governed mainly by metal–H ion exchange or sur-
rence of charged sites on the surfaces of biomass (Matis face metal complexation adsorption or both. However,
et al., 1996). This partially accounts for the ability of the this could not be confirmed with FTIR spectral analysis
biomaterial to retain cations in non-leachable forms by of the tobacco dust after heavy metal sorption and
coulombic and electrostatic forces or partly covalent bond- desorption.
ing forces for some polyvalent cations. The surface charge • The tobacco dust had a strong surface acidity, with a
(zeta potential) of the biomaterial plays an important role high OH adsorption (neutralization) capacity. It could
in electrostatic adsorption on the biomaterial. The zeta be characterized as an amphoteric biosorbent, which
potentials of the tobacco dust under different pH and metal could form complexes with both H+ and OH ions.
ion concentrations are shown in Fig. 6. • The surface of the tobacco dust was strongly negatively
Fig. 6 shows that the tobacco dust was negatively charged over a wide pH range (pH > 2). The sorption of
charged over a wide pH range (pH > 2), indicating the heavy metals on the biomass surface and the increase in
affinity of tobacco dust for positively charged heavy metal ionic strength by increasing the heavy metal concentra-
ions. The negative charge of the tobacco dust increased tions in the sorption solution had little effect on the sur-
with an increase in the pH of the solution, despite increases face charge and properties of the tobacco dust,
in the heavy metal ion concentrations. This suggests that suggesting that electrostatic attraction was also one of
deprotonation or ionization of acidic functional groups the sorption mechanisms.
of the tobacco dust (or both) prevailed under higher pH
conditions, despite the increase in cationic strength, owing
to the increased concentrations of heavy metal ions. Acknowledgements
From the surface acidity and electrokinetic property
measurements, it can be presumed that the mechanism of The authors appreciate the financial support of the
biosorption of the heavy metals onto the tobacco dust is Water Research Commission of South Africa and helpful
principally governed by metal-proton ion exchange and suggestions from the Project Steering Committee during
electrostatic attraction under general sorption pH condi- this investigation.
tions (pH 4–7). Under higher pH conditions, hydroxide
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