Energy Conversion and Management 51 (2010) 235240

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Adsorption of phenol by activated carbon: Inuence of activation methods

and solution pH
Ulker Beker a,*, Batchimeg Ganbold b, Halil Dertli c, Dilek Duranoglu Glbayir a
a

Yildiz Technical University, Chemical Engineering Department, Davutpasa Campus, 34210 Esenler, Istanbul, Turkey
National University of Mongolia, Faculty of Organic Chemistry, Ikh Surguuliin Gudamj 1, P.O. Box 46a/523, 210646 Ulaanbaatar, Mongolia
c
Istanbul Technical University, Chemical Engineering Department, Maslak, Istanbul, Turkey
b

a r t i c l e

i n f o

Article history:
Received 31 January 2009
Received in revised form 9 May 2009
Accepted 21 August 2009
Available online 14 November 2009
Keywords:
Pyrolysis
Renewability
Activated carbon
Adsorption
Phenol

a b s t r a c t
Cherry stone based activated carbon derived from a canning industry was evaluated for its ability to
remove phenol from an aqueous solution in a batch process. A comparative adsorption on the uptake
of phenol by using commercial activated carbon (Chemviron CPG-LF), and two non-functional commercial polymeric adsorbents (MN-200 and XAD-2) containing a styrenedivinylbenzene macroporous hyperreticulated network have been also examined. Equilibrium studies were conducted in 25 mg L1 initial
phenol concentrations, 6.59 solution pH and at temperature of 30 C. The experimental data were analyzed by the Langmuir and Freundlich isotherm models. Besides, the cherry stone based activated carbons
were carried out by using zinc chloride and KOH activation agents at different chemical ratios (activating
agent/precursor), to develop carbons with well-developed porosity. The cherry stone activated carbon
prepared using KOH as a chemical agent showed a high surface area. According to the results, activated
carbons had excellent adsorptive characteristics in comparison with polymeric sorbents and commercial
activated carbon for the phenol removal from the aqueous solutions.
2009 Elsevier Ltd. All rights reserved.

Introduction
Industrialization and agricultural development together with
the population growth reduced the clean water resources. Petroleum and petrochemical, coal gasication and carbonization, pharmaceutical, wood preserving chemicals, plastic, pesticide, paper
and pulp industries generate highly toxic and carcinogenic phenolic compounds. Wastewaters containing phenolic compounds are
considered as priority serious problems since they are not only carcinogenic but also cause bad taste and odor even at low concentrations. For that reason, The US Environmental Protection Agency
(EPA) regulations call for lowering phenol content in the wastewater to less than 1 mg L1 [1]. Therefore, it is considered necessary to
remove the phenol from wastewaters before discharging into the
water stream.
Various removal technologies such as oxidation, precipitation,
adsorption, ion exchange and solvent extraction methods have
been developed for the removal phenol from wastewater. Generally, solvent extraction treatment for high levels of phenol (above
500 ppm), biological and physico-chemical treatments for intermediate levels of phenols (5500 ppm), adsorption treatments
such as ion exchange and biosorption methods for low level of phe* Corresponding author. Tel.: +90 212 383 4734; fax: +90 212 383 4725.
E-mail address: ubeker@gmail.com (U. Beker).
0196-8904/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2009.08.035

nol are the most widely used methods for the removal of phenol.
Adsorption method is well-established technique for treating
domestic and industrial efuents. The adsorption of phenol and related compounds from wastewater has been the subject of numerous studies by using novel adsorbents. A proper evaluation of
industrial byproducts is very important for the environment and
economy, since it would not only help assuage disposal problems,
but would also help reduce shortages of several materials [24].
Activated carbon is the most effectively used adsorbent since it
has a porous structure consisting of a network of interconnected
macropores, mesopores, and micropores due to the high surface
area and the surface chemistry such as polarity, ionic nature, functional groups.
Cherries are one of the most abundant fruits, with a world production of 1,896,522 metric tons (Mt) in 2004 [5]. Cherry stones
are obtained as a byproduct of the food industry and an inexpensive material that is available in large quantities, thus presenting
a promising application for the production of cheap and efcient
activated carbons. In Turkey, cherry stones are one of the main
byproducts of the food industry. The cherry production in Turkey
increased by 10% to 600,000 metric tons (Mt) in 2008/2009 [5].
There are very little studies in the literature relating to the preparation of activated carbons from cherry stone [6,7]. However, there
is no systematic study related to the preparation of adsorbents
from cherry stones and sorption experiments.

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U. Beker et al. / Energy Conversion and Management 51 (2010) 235240

In this study, the adsorption capacity of the hypercrosslinked

polymeric ion exchangers (XAD-2 and MN-200), the commercial
(Chemviron CPG-LF) and cherry stone based activated carbons produced towards phenol was compared in order to investigate the effect of sorbent texture characteristics of the adsorbents, as well as
the chemical nature of the phenol.
The object of this study was to compare the mechanism of phenol adsorption on different adsorbents aimed towards use of cherry stone based activated carbons for phenol removal. Surface
acidity of adsorbents was determined in terms of their pH titration
(PZC values) and point of zero charges (electrophoretic mobility
IEP values). The IEP values and PZC have been considered as an
excellent reference index for correlating changes in the surface
acidity of carbons to the degree of surface oxidation. PZC is shifted
to lower pH values as the degree of activation increases due to the
introduction of acidic groups such as carboxyl, phenolic, carbonyl
and lactonic. The isotherm data for phenol removal were tted to
Langmuir and Freundlich models. Since the change from acidic
pH to alkaline pH reduces the adsorption capacity of adsorbents
drastically, experiments were performed at slightly acidic and basic pH values.
2. Materials and methods
Bituminous coal based commercial granular activated carbon
(Calgon CPG-LF) was provided by Calgon Carbon [8]. MN-200 (Purolite) and XAD-2 containing a styrene-divinyl benzene macroporous hyperreticulated network have essentially hydrophobic
matrix [9,10].
2.1. The production of the activated carbons from cherry stone
Cherry stones used as precursors were obtained from a canning
factory in Bursa, Turkey. They were washed with hot distilled
water to remove impurities like dust, and the material was then
dried and nally sieved to approximately 0.24 mm in diameter
particles. Initially the raw material was carbonized at 500 C under
nitrogen atmosphere for 2 h with the 5 C min1 heating rate in
an inert environment (400 ml min1 ow of nitrogen). A certain
amount of the char produced was then soaked with potassium
hydroxide (KOH) or zinc chloride (ZnCl2) pallets at impregnation
ratio of 1:1; 2:1; 3:1 (KOH/or ZnCl2 pallets (g):char (g)). These samples were designated as KK500-1, KK500-2, KK500-3, KK500-4 for
KOH series and KZ500-1, KZ500-2, KZ500-3, KZ500-4 for ZnCl2 series, respectively. The mixture was dehydrated in an oven overnight
at 105 C; then pyrolysed at a rate of 5 C min1 in a sealed ceramic
oven under high purity nitrogen (99.995%) ow of 150 cm3 min1
to a nal temperature of 500 C and activated for 2 h. Once the nal
temperature was reached, activation was continued for 2 h. The
activated product was then cooled to a room temperature under
nitrogen ow and washed with deionized water to remove the
remaining chemicals. Subsequently the sample was transferred
to a beaker containing a solution of 0.10 M hydrochloric acid, stirred for 1 h, and then washed with hot deionized water until the pH
of the washing solution reached 6.57 and dried at 105 C for 24 h.
The properties of the activated carbons were investigated.
2.2. Characterization of the adsorbents
Surface areas of the adsorbents were determined from nitrogen
adsorption isotherms at 77 K by using Micromeritics-Gemini III
surface area analyser. BET equation was used for calculating the
surface area of the sorbents. Pore volumes and pore radius of the
activated carbons were determined by using Quantachrome Autoscan-33 Mercury Porosimeter.

The FTIR (Fourier transform infrared spectroscopy) spectrometry was applied in the characterization of the surface functional
groups of the sorbents. The spectra were measured and recorded
(2500500 cm1) on a Mattson 1000 spectrometer.
Potentiometric titration data for the samples were carried out
using a method described by Helfferich [11]. The obtained proton-binding isotherms are positive for the proton-binding process
and negative for proton dissociation.
The electrophoretic mobilities of the equilibrated samples were
measured using a Malvern Instruments Zetasizer 3000HSA.
2.3. Batch sorption studies and analytical procedure
Phenol solution was prepared by diluting 1 g L1 of stock phenol
solution. Stock phenol solution was obtained by dissolving an exact
quantity of phenol (Merck) in distilled water. In adsorption equilibrium, experiments were conducted in a set of 250 mL Erlenmeyer
asks, in which solutions of phenol (100 mL) with initial concentration (25 mg L1) were added. Different masses of samples between 0.01 and 0.1 g were added to the phenol solutions and
each sample was kept in an isothermal shaker of 120 rpm at
30 1 C for 24 h to reach equilibrium of the solidsolution mixture. The pH of the solutions was adjusted by adding a few drops
of diluted 0.1 N NaOH or 0.1 N HCl. The nal concentration of phenol in the solution was analyzed using a UVvis spectrophotometer
(Analytic Jena Specord 40) at 270 nm wavelength. The samples
were ltered prior to analysis in order to minimize interference
of the carbon nes with the analysis. The amount of uptake capacity at equilibrium, qe (mg/g), was calculated by

qe

VC 0  C e
M

where C0 and Ce (mg L1) are the liquid-phase concentrations of

phenol at initial and equilibrium, respectively. V (L) is the volume
of the solution, and M (g) is the mass of dry adsorbent used.
3. Results and discussions
3.1. Characterization of the adsorbents
The main characteristics of the adsorbents are listed in Table 1.
As it can be seen in Table 1, activation with ZnCl2 reduced the surface area of the carbon samples activated with the increasing ZnCl2
ratios. It was observed that the surface areas decreased 300 and
170 m2 g1 for the KZ500-1 and KZ500-4 samples, respectively.
The lower surface areas and meanpore radius were found for the
ZnCl2 activated samples, compared with those for the KOH treated
samples. Both activation chemicals (ZnCl2 and KOH) promote bond
cleavage reactions and formation of acidic functional group cross-

Table 1
Properties of adsorbents.
0

Sample

Surface area
(m2 g1)

Mean pore radius (

A)

Pore volume
(cc/g)

K-500
KK-1
KK-2
KK-3
KK-4
KZ-1
KZ-2
KZ-3
KZ-4
CPG-LF
MN-200
XAD-2

360
456
465
431.3
261.9
298.2
333.6
287.4
170.3
648.5
8001000
300

565
589
621
830
1250
147
183
406
646
4450
850950
90

0.2157
0.3018
0.3258
0.3133
0.3047
0.0758
0.1836
0.2788
0.2151
0.1767
11.1
0.9345

U. Beker et al. / Energy Conversion and Management 51 (2010) 235240

237

links within the precursor structure. This provides an explanation

for the low level of porosity where progressively increasing
amount of activation chemical takes place as more oxygen
functional group is incorporated into the impregnated char
samples.
The FTIR spectrums of the carbon samples have peaks between
650900, 9001000, 15501750 and 28003000 cm1. The band at
about 3435 cm1 is attributed to (OH) vibrations in the hydroxyl
groups. The location of the hydrogen-bonded OH groups is usually
in the range of 32003650 cm1 for alcohols and phenols. The band
appearing at 1736 cm1 is attributed to the carbonyl (C@O) groups.
The appearance of bands between 1300 and 900 cm1 could be assigned to CO stretching vibrations. The bands at 1252 cm1 and
the subsequent small rise at 1164 cm1 could be attributed to esters, ethers, or the phenol groups. The bands located at about
1614 and 1401 cm1 are attributed to the carbonyl and carboxylate
ion (COO) groups, respectively. Compared to study of surface
chemistry of the activated carbon, very few articles have been published about the carbonization and activation of cherry stones,
especially when (where) ZnCl2 and KOH are used as activating
agents. The FTIR results demonstrated that for cherry stone activation of ZnCl2 and KOH at 523 K for 1 h in inert environment is helpful for formation of oxygen structures.
The FTIR spectrum obtained for the MN-200 and XAD-2 resins
displayed the following bands:
450900 cm1:CH vibrations,
28003000 cm1: aromatic and aliphatic CH groups stretching
vibrations,
1706 cm1: C@O carbonyl functional group,
1300 cm1: CCC and CCOC bending,
14351405 cm1: methylene scissoring vibration of the CH2
CO.
An important parameter used to characterize the electrokinetic
behavior of a solidliquid interface is the electrophoretic mobility.
The pH value at this point is called the isoelectric point (IEP) of the
interface. The proton binding curve which crosses the pH axis is
called the point of zero charge (PZC) and dened as the pH value
at which the net surface charge of adsorbent is zero and changes
depending on the type and number of functional groups present
on the adsorbent. The results for the pH titration (PZC values)
and the electrophoretic mobility (IEP values) vs. pH plots for samples can be seen in Figs. 1 and 2, respectively. As it can be seen
from Fig. 1, KZ and KK samples have the lower pH values as a result
of a higher number of the acidic functional groups such as carboxylic, phenolic, carbonyl, and lactonic groups onto the surface and
this implies that acidic properties are more dominant in those activated carbons produced from cherry stone than the coal based
commercial activated carbon namely CPG-LF, depending on the
activation processes. Although the shapes of the proton binding
curves of the KK and KZ series samples are nearly the same, the
PZC value for the KK samples is around pH 3.25, whereas it is
shifted to pH 2.7 for the KZ samples. This is an indication of differences between the amount of the surface oxygen groups created in
samples KZ and KK. These weakly acidic functional groups are
known to dissociate over a wide range of pH. The proton binding
capacities for carbon samples produced are negative. Therefore,
they were classied as L-carbons.
It is well known that sorption of phenol ions on the activated
carbon strongly depend on the chemistry of the carbon surface. It
is clear from the PZC results that carboxyl groups are introduced
in the highest concentration, which will perform activated carbon
more efcient in the treatment of wastewater since they are completely dissociated at near-neutral pH. Hence, PZC values of polymeric adsorbents were determined as 6.96 and 6.67 for XAD and

Fig. 1. Proton binding curves of activated carbons: (a) KK series, (b) KZ series and
(c) polymeric adsorbents and commercial activated carbon.

MN-200, respectively. Although the polymeric adsorbents and

CPG-LF samples show a smooth curve, the KK and KZ activated carbon samples show inection points that are typical of the behavior
of polyfunctional ion exchangers. From the pH titration curves it
can be seen that the dissociation of the acidic functional groups
on the KK, KZ and CPG-LF samples to produce H+ ions starts at
an equilibrium solution pH of approximately 3.15, 2.7 and 7.2,
respectively. Therefore, one of the types of acidic functional groups
on the surface of the KK and KZ samples are likely to be carboxylic
groups, while that on the surface of the CPG-LF sample is likely to
be hydroxyl groups.
The IEP depends on the nature of the solid surface and the surrounding medium at different pHs. IEP values of the adsorbant
samples are given in Fig. 2. The IEP values for the KK and KZ activated carbon samples are around pH 1.3 and 1.8, respectively,
whereas it is pH 4.2 for the commercial CPG-LF, at 4.2 for the
XAD-2 and at 4.5 for the MN-200. The PZC relates to the internal

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U. Beker et al. / Energy Conversion and Management 51 (2010) 235240

Fig. 3. Phenol adsorption capacity of KK series activated carbon, CPG-LF and

polymeric adsorbents (a) @ pH 6.5 and (b) @ pH 9.0.

3.2. Sorption studies

Fig. 2. Electrophoretic mobility curves of activated carbons: (a) KK series, (b) KZ

series and (c) polymeric adsorbents and commercial activated carbon.

and external surface, and the IEP refers only to the external surface
of the adsorbent. It can be deduced that the distribution of acidic
surface groups is not homogeneous since the IEP is located at lower
pH values. This indicates that the concentration of acidic groups is
higher at the external surface as compared to the interior of the
activated carbon samples produced from cherry stones. The zeta
potential curves for the KZ and KK samples fall steeply with
increasing pH until pH 6 and then start to level off. Dissociation
of relatively strong carboxylic surface groups is probably responsible for this effect. Indeed, the dissociation of this type of group occurs at pH values between 2 and 6, thereby enhancing the
negativity of the surface. In those carbons produced, weaker surface functional groups are more prevalent than in the CPG-LF.
Therefore, it is zeta potential curve that changes more gradually
in comparison to those of the KZ and KK samples. The IEP for the
two non-functional polymeric adsorbents (MN-200 and XAD-2)
are close to 5. This value is somewhat high when compared with
the IEP for carbon samples.

The effect of solution pH on phenol removal by different adsorbents was examined and the results are presented in Figs. 3 and 4.
Phenol was better adsorbed to carbon adsorbents at the pH 6.5.
This behavior can be explained considering the nature of the adsorbent at different pH in phenol adsorption.
The surface of the activated carbon contains a large number of
functional groups. The pH dependence of phenol adsorption can
largely be related to the type and ionic state of these functional
groups and also on the phenol chemistry in solution. This might
have resulted from neutralization negative charges at the surface
of carbons with increasing hydrogen ion concentration, thereby
reducing hindrance to diffusion and making available more active
surface of carbons. The isoelectric point of activated carbon samples are between pH 1and 3; as the pH was lowered, the overall
surface charge became positive, and this led to donoracceptor
interactions between the aromatic ring of phenol activated by
the OH and the groups of the activated carbon. As the pH increased, however, the overall surface charge became negative
and sorption decreased. Phenols are adsorbed at the carbonyl oxygens on the activated carbon surface according to a donoracceptor
complexation mechanism. As seen in Figs. 3 and 4, the activated
carbons showed a better sorption capacity at pH 6.5 for phenol
since the undissociated species of the adsorbate is preferred by
the negatively charged surface groups. Such specic interaction
may play a positive role in phenol adsorption from aqueous solution; however, it will be effectively weakened in aqueous solution
due to the competitive effect of water.

U. Beker et al. / Energy Conversion and Management 51 (2010) 235240

Fig. 4. Phenol adsorption capacity of KZ series activated carbon, CPG-LF and

polymeric adsorbents (a) @ pH 6.5 and (b) @ pH 9.0.

The pKa value of phenol is 9.89 at 298 K, the pH-dependent nature may be explained by the fact that only the phenol molecules
adsorb effectively onto the adsorbents through van der Waals
interaction, while the phenolate anions do not, due to their hydrophilic nature. The pH at which this decrease occurs depended on
the difference between the external and internal surface charge

239

density determined by electrophoretic and titration measurements, respectively.

In general, adsorption of undissociated form of the phenol is
much higher at low pH values than dissociated form of the phenol
at high pH values. Above pH 9, phenol is converted into negatively
charged phenoxide. Reduction in adsorption at 9 is possible due to
increased solubility of phenol and abundance of hydroxyl ions
thereby increasing hindrance to diffusion of phenol ions. Increased
negative surface charges at high pH values may be caused by physical adsorption of hydroxyl ions or by dissociation of very weakly
acidic surface functional groups on the surface of the activated carbon. A reduction in pH can be expected to improve adsorption,
since the protonation of both the organics in solution and the surface functional groups on the GAC surface reduce electrostatic
repulsive forces, therefore promoting a greater degree of adsorption. Similar pH effects have been observed by other researchers
and have attributed to (a) increased negative repulsive forces between adjacent adsorbed ionic species, (b) increased negative
repulsive forces between the adsorbed anionic species and anionic
surface functional groups of the GAC and (c) competitive adsorption between OH and anionic adsorbate [12,13]. The researchers
concluded that the extent of the changes depended on the physico-chemical properties of individual organic solutes.
The results of phenol removal percentage at different pH values
are shown in Fig. 5. The tendency for phenol uptake is also reected in the proton binding curves and electrophoretic mobility
measurements. When the pH is increased the concentration of
the ionized phenol and the number of negatively charged sites
on the adsorbent also increase. For that reason, there was a fall
in the uptake of phenol at pH 9. This can be attributed to the
dependency of phenol ionization on the pH value and PZC. At
pH < PZC, the carbon surface is positively charged and as there is
no electrostatic repulsion between the unionized phenol species
and the positively charged surface. But at pH > PZC the carbon surface is negatively charged resulting in reduced adsorption due to
the repulsive force between the phenolate ion and negative charge
of the carbon surface.
The adsorption of phenol occurs in ultramicropores (d < 0.7 nm)
and micropores (d < 2 nm), which are smaller in size than the
molecular diameter of phenol (molecular diameter of phenol is
0.62 nm). Both polymeric adsorbents (MN-200 and XAD-2) with
this surface area are entirely suitable for phenol removal from
water. The sorbents used in this study are potentially useful for

Fig. 5. Phenol removal percentage of the activated carbons and polymeric adsorbents at pH 6.5 and 9.0.

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U. Beker et al. / Energy Conversion and Management 51 (2010) 235240

water treatment since they possess satisfactory capacities for

organics and have a distinct economic advantage. However, it is
shown that MN-200 has more phenol sorption capacity than
XAD-2.
Correlation of isotherm data by theoretical or empirical equations is thus desired for practical operation. The Freundlich and
the Langmuir adsorption equations were applied to isotherm data
for phenol for all sorbents. The results showed that the Freundlich
model ts better than the Langmuir model to the experimental
data. This suggests the presence of homogeneous surface sites
and that doublelayer adsorption is occurring for phenol adsorption.
4. Conclusion
Phenol can be removed by using two types of neutral polymeric
resins, i.e. XAD-4 and MN-200 and activated carbons. It was observed that activated carbon provides higher removal capacity
than that of the resins. The adsorption capacity is strongly dependent on the aqueous phase pH. Reduction in adsorption at pH 9 is
possibly due to the increased solubility of phenol, the abundance of
OH ions thereby increasing hinderance to diffusion of phenol ions
and also increasing electrostatic repulsion between the negatively
charged surface sites of the sorbent and phenolic ions. Both Langmuir and Freundlich models represent well the adsorption isotherm, the Freundlich model giving a better t of the data. XAD2 has a very little phenol sorption capacity due to the pore size.
The highest adsorption of phenols occurred at pH 6.5 and 9.0 for
KZ500-4 and CPG-LF. However, there was a similar behavior for
the removal percentage for KK500-4, KZ500-1, KZ500-2, KZ500-3,
KZ500-4 and CPG-LF at pH of 6.5 and 9.0. The data thus obtained
using different adsorbents may be helpful. The experimental results indicated that the activated carbon prepared by using agricultural byproduct was economically promising twofold. It would be

utilized and the production of activated carbon for the treatment

of wastewaters would be achieved at low cost.
Acknowledgements
This study was sponsored by Yildiz Technical University Scientic Research Projects Coordinating Department under the Project
No. 23-07-01-03.
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