Water Air Soil Pollut (2017) 228:320

DOI 10.1007/s11270-017-3499-x

Graphene as an Efficient and Reusable Adsorbent Compared

to Activated Carbons for the Removal of Phenol from Aqueous
Solutions
Dina Gaber & Mohammad Abu Haija & Asma Eskhan &
Fawzi Banat

Received: 17 April 2017 / Accepted: 31 July 2017

# Springer International Publishing AG 2017

Abstract The adsorption capacity of graphene for re- exothermic process. Regeneration of graphene was
moving phenol from aqueous solutions was evaluated found to be possible using sodium hydroxide or meth-
and compared to those obtained for three different com- anol as eluents over five adsorption-desorption cycles.
mercial activated carbons. In this study, graphene, W-35
activated carbon, RB2H2 activated carbon, and Nuchar Keywords Graphene . Activated carbon . Adsorbent .
granular activated carbon were investigated. Various Phenol . Isotherms
techniques such as X-ray diffraction, BET surface anal-
ysis, and scanning electron microscopy were used to
characterize the adsorbents. The adsorption of phenol
1 Introduction
onto graphene was investigated under different experi-
mental conditions including temperature, solution pH,
Phenol is one of the organic pollutants found in the
adsorbent dosage, and initial concentration of phenol.
effluents of petrochemical, chemical, steel, pharmaceu-
For comparison, adsorption experiments of phenol onto
tical, and numerous industrial plants (Kulkarni et al.
the activated carbons were also conducted. The adsorp-
2013). Due to its prominent harmful effects on the aquat-
tion of phenol onto graphene and activated carbons
ic environments and its toxicity towards organisms (Abd
could be described by the pseudo-second-order kinetic
Gami et al. 2014; Bazrafshan et al. 2013), phenol levels
model and the Langmuir equilibrium isotherm. The
in the industrial effluents have been monitored and reg-
maximum adsorption capacities predicted by the Lang-
ulated by the different governments. In UAE, for in-
muir isotherm for graphene, W-35, RB2H2, and Nuchar
stance, the permissible level of phenol at the point of
granular activated carbons were found to be 233, 200,
discharge into the sea should not exceed 0.1 ppm (Al
91, and 167 mg/g, respectively. The thermodynamic
Zarooni and Elshorbagy 2006). Therefore, development
study demonstrated that the adsorption of phenol onto
of efficient methods for the removal of phenol from the
graphene and activated carbons is a spontaneous and
industrial effluents is essential.
Several methods have been proposed in the literature
D. Gaber : M. Abu Haija (*)
to treat wastewater from phenol. Phenol can be removed
Department of Chemistry, Petroleum Institute, Khalifa University by solvent extraction (Yang et al. 2006), biological
of Science and Technology, PO Box 2533, Abu Dhabi, UAE treatment (Chakraborty et al. 2010), or filtration methods
e-mail: mabuhaija@pi.ac.ae (Mukherjee and De 2014). Although these methods are
A. Eskhan : F. Banat
used for removing phenol from wastewater, they have
Department of Chemical Engineering, Petroleum Institute, Khalifa some serious limitations such as high cost, consuming
University of Science and Technology, PO Box 2533, Abu Dhabi, long periods of time, generation of secondary pollutants,
UAE and poor removal efficiency. An alternative, simple, and
320 Page 2 of 14
efficient method is adsorption in which a low-cost ma-
terial can act as an adsorbent to adsorb phenol and
separate it from wastewater. Adsorption method is af-
fected by different parameters such as the adsorbent
nature, surface area, porosity, pH of the media, and the
contact time (Singh and Srivastava 2002). Among vari-
ous adsorbents, carbon-based materials have increasing-
ly attracted the attention of researchers and scientists
over the last few years mainly because of their relatively
high surface area and widely distributed pore sizes. They
have been found to have high sorption capacities towards
many pollutants such as aniline, benzoic acid, toxic
gases, and heavy metals (Moreno-Castilla 2004; Girods
et al. 2009; Wang et al. 2013). Carbon-based materials
have also been utilized to remove phenol from wastewa-
ter (El-Naas et al. 2010; Tancredi et al. 2004; Zhang et al.
2014).
Graphene is a carbon-based material which has re-
cently been recognized as one of the most promising
adsorbents for the removal of organic pollutants from
wastewater. It is characterized by a large theoretical
surface area (up to 2600 m2/g) (Hu et al. 2015) which
makes it an ideal choice for adsorption studies. To date,
numerous studies have investigated the adsorption char-
acteristics of graphene. For example, Liu et al. have
investigated the adsorption of methylene blue onto
graphene and obtained a maximum adsorption capacity
of 153.85 mg/g, indicating its good adsorption proper-
ties (Liu et al. 2012). Similarly, Wu et al. have found that
the maximum adsorption capacities of p-toluenesulfonic
acid, 1-naphthalenesulfonic acid, and methylene blue
onto graphene to be 1.43, 1.46, and 1.52 g/g, respec-
tively (Wu et al. 2011). They have concluded that
graphene is a promising adsorbent for the removal of
chemicals containing benzene rings from wastewater
(Wu et al. 2011). However, a limited number of studies
have explored the adsorption of phenol onto graphene-
based materials in the literature (Li et al. 2012, 2017).
Considering the potential properties of graphene such as
its high surface area and thermal stability, it would be of
interest to study the adsorption efficiency of graphene
samples prepared from graphite nanoplatelet and to
compare its uptake with other commercial activated
carbons under similar experimental conditions. More-
over, the desorption characteristics of phenol from
graphene are still missing in the literature.
The purpose of the current study is to investigate the
merit of conventionally synthesized graphene as an effi-
cient and potential reusable adsorbent for removing
Water Air Soil Pollut (2017) 228:320
phenol from aqueous solutions and compare its adsorp-
tion capacity with commercial activated carbons. The
adsorption of phenol onto graphene was investigated
under different operating conditions such as graphene
dosage, initial concentration of phenol, solution pH, and
temperature. Furthermore, the physicochemical proper-
ties of graphene and activated carbons were character-
ized and compared in connection with their adsorption
capacities. Adsorption kinetic, adsorption isotherms, and
thermodynamic studies were performed on graphene
and commercial activated carbons. Reusability is an
essential feature of the adsorbent and was tested in this
study for graphene by thermal and chemical regeneration
methods.
2 Materials and Methods
2.1 Materials
In a preliminary study, four samples of graphene were
tested. Three samples (G1, G2, and G3) were prepared
from graphite nanoplatelet while another sample
thermally reduced graphene (TRG) was prepared by
thermal reduction method. G1 graphene sample showed
the highest surface area (according to BET surface anal-
ysis), the least oxygen functionalities (according to ele-
mental analysis), the most amorphous structure (accord-
ing to XRD patterns), and achieved the highest percent-
age removal of phenol from aqueous solution. There-
fore, G1 graphene was selected for further studies of
phenol adsorption. To compare the adsorption capacity
of phenol onto graphene, three commercial activated
carbons (NORIT W-35, NORIT RB2H2, and Nuchar
Table 1 List of the commercial activated carbon samples used in
this study
Activated Activation method Source
carbon
NORIT Steam activation of MWV Specialty
W-35 vegetable raw material Chemicals—USA
NORIT Steam activation of coal Cabot
RB2H2 Corporation—Netherl-
and
Nuchar Chemical activation of MWV Specialty
granu- wood Chemicals—USA
lar
Water Air Soil Pollut (2017) 228:320
granular activated carbon) were selected and their
source and method of activation are shown in Table 1.
The TRG (Thermally reduced graphene) sample was
prepared by mixing H3PO4 and H2SO4 in a 2-L glass
beaker with a molar ratio of 1:9, followed by adding
graphite flakes into this mixture with continuous stir-
ring. KMnO4 was then added gradually to this mixture
and stirring was continued for 72 h. H2O2 was added
gradually until the color of mixture turned into yellow.
The product was washed with 2 M HCl and with deion-
ized water to remove chloride ions from the product.
Then, it was placed in Teflon petri dish under lyophili-
zation process for 5 days under vacuum. The dried
product was annealed for 30 s at 1000 °C under inert
atmosphere to obtain the TRG sample. The preparation
of G1 sample followed the same procedure for preparing
the TRG sample except that the last annealing process
was not performed. Instead of the annealing process,
100 mg of the dried product was added to 100 mL of
deionized water in a round-bottom flask. This mixture
was kept under sonication process until forming a uni-
form mixture. The mixture was then heated at 100 °C,
followed by gradual addition of 1.0 mL hydrazine hy-
drate. The heating of the mixture was continued until the
formation of a black powder. Subsequently, the powder
was filtered and washed with deionized water and ace-
tone. The obtained product was then dried in an oven at
70 °C. G2 and G3 samples were prepared according to
the same procedure for preparing the G1 sample but the
treatment temperatures were 80 or 60 °C for G2 or G3
samples, respectively.
2.2 Characterization of Adsorbents
The graphene and activated carbon samples (adsorbents)
were characterized by X-ray diffractometer (X’Pet Pro
Panalytical Powder diffractometer) operating at 40 kV
and 40 mA with Cu Kα radiation (λ = 1.5406 Å). BET
surface analyzer (Quantachrome, Autosorb 06) was used
to determine the specific surface area, pore size, and pore
volume of the adsorbents. The surface area was deter-
mined by relating the amount of nitrogen adsorbed to the
surface by van der Waals forces to the pressure of the
nitrogen. N2 physisorption was carried out at liquid N2
temperature (77 K) and the surface area was calculated
using the BET method. The texture and the morphology
of the adsorbents were examined using scanning elec-
tron microscopy (Quanta 200-Oxiford XTREAM/
MICS).
Page 3 of 14 320
2.3 Batch Adsorption Experiments
A stock solution of phenol (200 ppm) was prepared and
further diluted to the required concentration by adding
deionized water. Adsorption experiments were per-
formed in glass vials containing 10.0 mg of adsorbent
dosage and 20 mL of phenol solution. The solution pH
was adjusted (if needed) to the required value using
0.1 M NaOH or 0.1 M HCL. The flasks were then
placed in a water bath shaker at a shaking speed of
140 rpm and at the required temperature (20, 40, or
60 °C). Afterwards, aliquots were taken from the vials
at predetermined time intervals and filtered using
0.2-μm syringe filters. The concentration of phenol in
the filtrate was measured by UV-Vis spectrometer
(Agilent 8453 UV-vis) at the maximum phenol absor-
bance wavelength of 270 nm (Srivastava et al. 2006).
The percentage removal of phenol was calculated as
follows:
ðC 0 −C f Þ
Removal ð%Þ ¼ x 100 ð1Þ
C0
where C0 is the initial concentration of phenol solution
(ppm) and Cf is the final phenol concentration (ppm).
The adsorption capacity of the phenol at time t, qt
(mg/g), was calculated by (Mehrizad and Gharbani
2014):
ðC 0 −C t Þ
qt ¼ V ð2Þ
m
where C0 is the initial concentration of phenol solution
(ppm), Ct is the phenol concentration (ppm) at time t, m
is the mass of adsorbent (g), and V is the volume of
phenol solution (L).
Similarly, the adsorption capacity of the phenol at
equilibrium, qe (mg/g), was calculated:
ðC 0 −C e Þ
qe ¼ V ð3Þ
m
where C0 is the initial concentration of phenol solution
(ppm), Ce is the equilibrium phenol concentration
(ppm), m is the mass of adsorbent (g), and V is the
volume of phenol solution (L).
2.4 Adsorption Kinetics
Adsorption kinetics is significant for identifying the
efficiencies of adsorbents and for understanding the
320 Page 4 of 14 Water Air Soil Pollut (2017) 228:320

adsorption mechanisms. Several kinetic models have 1

RL ¼ ð7Þ
been developed by the researchers to describe the ad- ½1 þ ð1 þ k L C 0 Þ
sorption reactions and the diffusion processes (Qiu et al.
2009). Lagergren’s pseudo-first-order model and Ho’s The value of RL indicates the type of isotherm to be
pseudo-second-order models are the most commonly irreversible adsorption (RL = 0), favorable adsorption
used adsorption reaction models in the literature. The (0 < RL < 1), unfavorable adsorption (RL > 1), and linear
pseudo-first-order model is expressed as (Ho and adsorption (RL = 1).
McKay 1999): The Freundlich model is based on multilayer adsorp-

tion on a heterogeneous surface (Freundlich 1906) and
qt ¼ qe 1−e−k 1 t ð4Þ can be expressed as:

where qt and qe are the adsorbed amounts of phenol at 1

lnqe ¼ lnk F þ lnC e ð8Þ
equilibrium and at time t, respectively, and k1 is the n
pseudo-first-order rate constant of adsorption (min−1). where kF is Freundlich isotherm constant [mg(1 – 1 /
The pseudo-second-order model (Ho and McKay n)
· L(1 / n) / g] and n is the adsorption intensity and the
2000) is given as: degree of heterogeneity of the adsorbent surface.

q2e k 2 t 2.6 Adsorption Thermodynamics

qt ¼ ð5Þ
1 þ k 2 qe t
To further understand the nature of the adsorption pro-
where qt and qe are the adsorbed amounts of phenol at
cess and the effect of temperature on the adsorption rate,
equilibrium and at time t, respectively, and k2 is the
thermodynamic parameters can be calculated according
pseudo-second-order rate constant of adsorption
to the following equations (Mehrizad and Gharbani
(g/mg min).
2014; Xu et al. 2012):
   
2.5 Adsorption Isotherms ΔS- ΔH-
lnK 0 ¼ − ð9Þ
R RT
Adsorption isotherms describe the relationship between
the amount of the adsorbate remained in the solution and qe
kd ¼ ð10Þ
the amount adsorbed on the adsorbent when the process Ce
reaches equilibrium (Roostaei and Tezel 2004). The where K0 is the unitless equilibrium constant which can
most used adsorption isotherm models in the literature be approximated by Langmuir calculated from the
are Langmuir isotherm and Freundlich isotherm. Lang-
muir isotherm assumes homogeneous monolayer cover-
age on the adsorbent surface and negligible interaction
forces between the adsorbed species. The linear form
can be written as (Langmuir 1916):

Ce Ce 1
¼ þ ð6Þ
qe qmax k L qmax

where Ce is the equilibrium concentration of the adsor-

bate (ppm), qe is the amount adsorbed per gram of the
adsorbent (mg/g), qmax is the maximum adsorption ca-
pacity (mg/g), and kL is Langmuir isotherm constant
(L/mg) which relates to the adsorption capacity and
the affinity of the adsorbate with the adsorbent. Further
analysis of the Langmuir equation can be done in terms
of the dimensionless separation factor, RL, which is Fig. 1 XRD patterns of graphene and activated carbon samples:
determined by: W-35, RB2H2, and Nuchar granular
Water Air Soil Pollut (2017) 228:320
distribution coefficient (kd) by plotting ln(qe/Ce) versus Ce
and extrapolating Ce to zero (Moradi et al. 2010). The
distribution coefficient (kd, L/g) can be converted to the
equilibrium constant (K0, as dimensionless) by multiplying
kd to a factor of 1000 (Tran et al. 2016). ΔS° and ΔH° are
the entropy change and the enthalpy change during the
adsorption process, R is universal gas con-
stant = 8.314 J mol−1 K−1, and T is temperature in Kelvin.
The enthalpy (ΔH°) and entropy (ΔS°) changes of process
can be determined from the slope and intercept of the plot
of ln K0 versus 1/T.
The change in the Gibbs free energy, ΔG, can be
calculated by (Xu et al. 2012):
ΔG- ¼ −RTlnK 0 ð11Þ
2.7 Regeneration Experiments
Graphene regeneration experiments were carried out to
investigate its feasibility and reusability as an adsorbent
for the removal of phenol. In this study, different feasible
recovery methods and regenerating solvents were tested
for the regeneration of graphene. Adsorption experiments
were first performed by mixing 10.0 mg of graphene with
20 mL of 50 ppm phenol. The solution was then placed in
a water bath shaker at 140 rpm and 295 K. After 2 h, the
solution was centrifuged and the supernatant was tested by
the UV-Vis spectrometer to determine the concentration of
phenol. The remaining graphene was regenerated using
two methods: either by washing with a solvent or by
heating. In the heating method, the graphene was placed
on a petri dish in an oven at 100 °C for overnight drying. In
Fig. 2 Nitrogen adsorption-desorption isotherms of graphene
Page 5 of 14 320
the washing method, the graphene was washed with
20 mL of one of the following solutions: 1 M hydrochloric
acid, methanol, 1 M sodium hydroxide, acetone, or pure
acetic acid for 2 h at 140 rpm. The mixture was then
centrifuged and the collected graphene pellets were
washed with 20 mL deionized water by shaking for
15 min. The washing process with water was repeated
twice. The graphene sample was then placed in an oven
for overnight drying. The regenerated graphene was used
again for the adsorption of phenol, and the whole process
was repeated up to five adsorption cycles.
3 Results and Discussion
3.1 Characterization of Graphene and Activated Carbon
X-ray diffraction patterns of graphene and the three sam-
ples of activated carbon are shown in Fig. 1. Commonly,
XRD patterns of high quality monolayer graphene should
not contain any diffraction peaks due to its 2-D structure
(Lian et al. 2010). However, weak diffraction peaks are
typically observed for the synthesized graphene (Bianco
et al. 2013). The angles of diffraction and the correspond-
ing interlayer distances of these typical peaks depend on
the presence of residual functional groups that may remain
during the production process (Xu et al. 2012). In this
study, the XRD pattern of graphene shows a week diffrac-
tion peak at 26.5° corresponding to the (002) planes of
graphene layers as reported elsewhere (Liu et al. 2012;
Bradder et al. 2011; Wang et al. 2008). Another weak peak
is observed at 42.5° which corresponds to the (100) planes
(Bradder et al. 2011; Wang et al. 2008). For the three
activated carbon samples, XRD patterns show a broad
peak at 20–30° which is attributed to the (002) plane of
carbon (Shang et al. 2015). The peaks at 40–45° corre-
spond to the (100) planes (Shang et al. 2015). These broad
peaks indicate the amorphous structure of the activated
carbon samples (Shang et al. 2015).
The nitrogen adsorption-desorption isotherm of
graphene is shown in Fig. 2. According to the IUPAC
classification, graphene isotherm is classified as type IVa
indicating that it is a mesoporous adsorbent where capil-
lary condensation is accompanied by hysteresis (Li et al.
2012; Worsley et al. 2010; Thommes et al. 2015). Fur-
thermore, the type H2 (a) hysteresis loop typically occurs
in systems with networked pores. The sharp decline of the
desorption branch is attributed to pore blocking, percola-
tion in a narrow range of pore necks, or to cavitation-
320 Page 6 of 14 Water Air Soil Pollut (2017) 228:320

Table 2 Results of BET analysis performed on graphene and the three samples of commercial activated carbon

Activated carbon sample Specific surface area (m2/g) Average pore size (nm)

Graphene 1410 1.4

NORIT-W35 753 1.5
NORIT-RB2H2 886 1.3
Nuchar granular 2355 1.4

induced evaporation (Thommes et al. 2015). The BET-
specific surface area and average pore size of graphene
and activated carbon samples are listed in Table 2. The
difference between the measured surface area of graphene
which is used in this study (1140 m2/g) and the theoretical
surface area of monolayer graphene (2600 m2/g) can be
attributed to the aggregation of graphene layers during the
reduction process. This is due to the unavoidable van der
Waals forces between the layers of graphene (Liu et al.
2012; Worsley et al. 2010).
Scanning electron microscopy (SEM) images at dif-
ferent magnifications of the graphene and activated
carbon samples are shown in Fig. 3. The image of
graphene reveals that it consists of plate-like particles,
with an approximate length of 11.7 μm. The image of
W-35 activated carbon indicates its relatively higher

Fig. 3 SEM images of a graphene, b W-35 AC, c RB2H2 AC, and d Nuchar granular AC
Water Air Soil Pollut (2017) 228:320
Fig. 4 Effect of the initial concentration of phenol on the adsorp-
tion uptake of phenol at equilibrium (qe) at three different temper-
atures (10.0 mg of graphene and 20 mL of phenol at 230 rpm after
24 h)
porosity compared to RB2H2 and Nuchar activated
granular samples. The average particle size is less than
2 μm for W-35, 50 μm for RB2H2, and 60 μm for
Nuchar granular activated. Moreover, at high magnifi-
cations, the SEM image of Nuchar granular shows
cracks on the particle surface.
3.2 Effect of Phenol Initial Concentration
and Temperature
The adsorption capacity of phenol onto graphene at
equilibrium (qe) is plotted against the initial concentra-
tion of phenol (C0) at three different temperatures (22,
40, and 60 °C) as shown in Fig. 4. The concentration
Fig. 5 Effect of graphene dosage on the adsorption uptake (qe)
and the phenol percentage removal (%) (20 mL of 50 ppm phenol
at 295 K and 230 rpm after 24 h). The error bars represent the
standard errors of the mean (n = 3)
Page 7 of 14 320
Fig. 6 Effect of the solution pH on the percentage removal of
phenol (%) (10.0 mg of graphene and 20 mL of 50 ppm phenol at
295 K and 230 rpm after 24 h). The data labels show the exact pH
values of the prepared solutions. The error bars represent the
standard errors of the mean (n = 3)
range of phenol was chosen according to its typical
levels in refinery wastewaters (20–200 mg/L) (Al
Zarooni and Elshorbagy 2006). Similarly, the tested
temperatures were chosen within the common range of
refinery wastewater’s temperature in the literature
(Bustillo-Lecompte et al. 2015). Increasing the initial
concentration of phenol in the solution increases the
driving force necessary to overcome the mass transfer
Fig. 7 Effect of contact time on the adsorption uptake of phenol
(qt) (10.0 mg of adsorbent and 20 mL of 50 ppm phenol at 295 K
and 230 rpm). The circles represent the data points of graphene,
the triangles are for W-35 AC, the diamonds for RB2H2 AC, and
the crosses for Nuchar granular AC. The solid lines represent the
pseudo-first-order models fits, while the dashed lines are the
pseudo-second-order model fits. The error bars represent the
standard errors of the mean (n = 3)
320 Page 8 of 14
Table 3 Kinetic parameters for the adsorption of phenol
Adsorbent Pseudo-first-order
k1 (min−1) qe (mg/g)
Graphene 113.90 72.20
W-35 119.99 60.01
RB2H2 132.58 34.84
Nuchar granular 147.30 5.40
resistances against phenol diffusion through the bound-
ary layer to the adsorbent surface. Above a certain level,
the adsorption capacity reaches a constant value. This
can be attributed to the rapid occupation of the adsorp-
tion sites on the graphene surface (Zhang 2013; Saha
et al. 2013). In addition, Fig. 4 shows that at a given
initial concentration of phenol (50–135 mg/L), the ad-
sorption capacity of phenol at equilibrium (qe) decreases
with increasing the temperature. This indicates that the
adsorption process in this range is exothermic, as will be
discussed in Section 3.7.
3.3 Effect of Graphene Dosage
The effect of graphene dosage on the adsorption capac-
ity (qe) and on the percentage removal is shown in Fig.
5. As the graphene dosage increases from 2 to 15 mg,
the adsorption capacity decreases from 131 to 60 mg/g,
while the percentage removal increases from 30 to 92%.
The addition of graphene provides more absolute sur-
face area and more adsorption sites for phenol to interact
with, and therefore more phenol is removed from water
(Liu et al. 2012). Above a certain graphene amount, the
percentage removal (%) reaches a constant value. This
can be attributed to the agglomeration of graphene par-
ticles and hence the increase in the diffusion path length
of phenol molecules (Li et al. 2012; Mehrizad and
Gharbani 2014). On the contrary, the higher the
graphene dosage, the more unsaturated adsorption sites
will be left on the adsorbent surface resulting in a
decrease in its adsorption capacity. Based on Fig. 5,
the optimum graphene dosage of 10 mg (or 0.5 g/L)
was selected for the adsorption studies.
3.4 Effect of Solution pH
Solution pH is a significant parameter of the adsorption
process as it affects both the surface charge of the
Water Air Soil Pollut (2017) 228:320
Pseudo-second-order
R2 k2 (g/mg min) qe (mg/g) R2
0.9989 0.30 72.46 0.999
0.9898 0.12 60.66 0.9903
0.9975 0.80 34.84 0.9975
0.204 2.57 × 10−5 97.58 0.9895
adsorbent and the degree of ionization of the adsorbate
(Li et al. 2012). The percentage removal of phenol
versus the solution pH is illustrated in Fig. 6. It can be
observed that the percentage removal of phenol remains
almost unchanged in the pH range of 2.75 to 9.3, while it
decreases sharply at pH greater than 9.3. It is proposed
that, at higher pH values, phenol (pKa 9.89) dissociates
into phenolate anions (Li et al. 2012). Therefore, the
decline in the percentage removal of phenol can be
attributed to the electrostatic repulsion between the neg-
atively charged surface of graphene and the phenolate
anions and also to the competition between hydroxyl
anions and phenolate anions on the surface adsorption
sites (Li et al. 2011, 2012; Xu et al. 2012).
3.5 Effect of Contact Time and Adsorption Kinetics
The adsorption capacity of phenol (qt) onto graphene
and the three activated carbons was measured at differ-
ent time intervals as shown in Fig. 7. Except for Nuchar
granular activated carbon, the adsorption rate is very
fast in the first 5 min and then it starts to decrease
slowly until the process reaches equilibrium within
60 min. The fast adsorption rate in the beginning is
due to the availability of several adsorption sites on the
adsorbent surface as well as the large concentration
gradient necessary for the mass transfer of phenol. In
contrast, the adsorption capacity onto Nuchar granular
activated carbon increases slowly until it reaches equi-
librium after 1 h. This indicates the weak interactions
between phenol and Nuchar granular activated carbon.
Another reason could be its relatively large particle size
(~ 60 μm) which means longer pore diffusion paths to
reach the adsorption sites compared to the other
adsorbents.
Furthermore, the kinetic pseudo-first-order and
pseudo-second-order models were used to fit the adsorp-
tion data in Fig. 7. The pseudo-first-order model gave
Water Air Soil Pollut (2017) 228:320 Page 9 of 14 320

Fig. 8 Adsorption isotherms of phenol adsorbed onto a graphene, phenol at 140 rpm after 24 h). The error bars represent the
b W-35 AC, c RB2H2 AC, and d Nuchar granular AC at three standard errors of the mean (n = 3)
different temperatures (dosage = 2.0–20.0 mg, 20 mL of 50 ppm

poor fitting with low R2 values, while the pseudo-
second-order R2 values were all above 0.99. As a result,
the kinetic experimental data were better fitted by the
pseudo-second-order model. It can be seen in Table 3
that the experimental capacity values show good agree-
ment with the calculated ones. The applicability of the
second order indicates that the adsorption of phenol
molecules might be a process of a chemisorption nature.
3.6 Adsorption Isotherms
The adsorption isotherms of phenol onto graphene and
the three samples of activated carbons were generated
by changing the adsorbent dosage and allowing the
system to reach equilibrium as shown in Fig. 8. The
Langmuir and Freundlich isotherms were applied to fit
the data and the corresponding calculated parameters are

Table 4 Langmuir and Freundlich isotherm constants calculated at 295 K for the adsorption of phenol

Adsorbent Langmuir isotherm Freundlich isotherm

qmax (mg/g) kL (L/mg) RL R2 1/n n kF ((mg/g)·(L/mg)1/n) R2

Graphene 233 0.0278 0.2948 0.952 0.6524 1.5328 11.426 0.910

W-35 200 0.0714 0.1795 0.893 0.6637 1.5067 18.010 0.846
RB2H2 91 0.0387 0.2542 0.821 0.5957 1.6786 6.562 0.833
Nuchar granular 167 0.0277 0.2956 0.909 0.7496 1.3340 6.258 0.893
320 Page 10 of 14 Water Air Soil Pollut (2017) 228:320

Table 5 Examples of different adsorbents used for phenol onto graphene has reported a maximum adsorption ca-
removal
pacity of 182 mg/L at 302 K and with BET surface area
Sorbent qe Reference of 327 m2/g. Some examples of adsorbents used for
(mg/g) phenol adsorption are provided in Table 5 (Akgerman
and Zardkoohi 1996; Ahmaruzzaman 2008; Dursun and
Fly ash 67 Akgerman and Zardkoohi
(1996)
Kalayci 2005; Pigatto et al. 2013; Lin et al. 2009;
Djebbar et al. 2012; Păcurariu et al. 2013; Huang et al.
Chitin 21 Ahmaruzzaman (2008),
Dursun and Kalayci (2005), 2012; Kazmi et al. 2013; Sulaymon and Ahmed 2008;
Pigatto et al. (2013) Alhamed 2009; Ekpete and Horsfall 2011; Gundogdu
Hydroxyapatite 10 Lin et al. (2009) et al. 2012; Khalid et al. 2004; Tor et al. 2006; Gupta
nanopowders et al. 2004; Qin et al. 2013; Alshehri et al. 2014). By
Natural clay 11 Djebbar et al. (2012) comparing the capacities achieved by the various adsor-
Poly(styrene-co-divinyl 55 Păcurariu et al. (2013) bents, graphene appears to be a promising adsorbent that
benzene)
can be reused over multiple cycles as will be discussed
functionalized with
amino-phosphinic in Section 3.8.
acid groups
N-methylacetamide- 160 Huang et al. (2012) 3.7 Adsorption Thermodynamics
modified
hypercrosslinked
resin The thermodynamic parameters of phenol adsorption
Activated Commercial 76 Kazmi et al. (2013), Sulaymon onto graphene were calculated using Eqs. (9–11) and
carbon Waste 78 and Ahmed (2008), compared to those of activated carbons. The parameters
Alhamed (2009), Ekpete
are summarized in Table 6. The negative values of ΔG°
and Horsfall (2011),
Gundogdu et al. (2012) calculated at the three temperatures demonstrate the
Zeolites 160 Khalid et al. (2004)
spontaneous nature of the adsorption process. The de-
crease in the ΔG° values as the temperature increases
Red mud 42–59 Tor et al. (2006), Gupta et al.
(2004) from 295 to 333 K indicates that the adsorption of
Granular silica aerogels 142 Qin et al. (2013)
phenol is more spontaneous at lower temperatures.
The negative values of ΔH° reveal that the adsorption
Curcumin formaldehyde 357 Alshehri et al. (2014)
resin BCFR^ reaction of phenol is an exothermic process. The posi-
Graphene 233 This study tive values of (ΔS°) indicate an increase in the freedom
of the adsorbed phenol molecules. The thermodynamic
parameters calculated in this study are of the same order
listed in Table 4. Based on the values of the determina- of magnitude as the published results for the adsorption
tion coefficient (R2), Langmuir isotherm was more suit- of phenolic compounds onto graphene and activated
able to fit the equilibrium data confirming the monolay- carbons (Li et al. 2012; Xu et al. 2012; Zhao et al.
er coverage of phenol onto the adsorbent particles and 2011; Ma et al. 2013). The relatively low values of
the homogeneous distribution of active sites on the ΔH° indicate that the adsorption is most likely a
adsorbent. The dimensionless separation factor (RL) physisorption process involving interactions such as
was found to be less than 1 for all investigated adsor- van der Waals forces (4–10 kJ/mol), hydrogen bond
bents, indicating that the adsorption of phenol is favor- forces (2–40 kJ/mol), and dipole bond forces (2–29 kJ/
able. The maximum adsorption capacity of graphene mol) and is less likely a chemisorption process where a
predicted by Langmuir isotherm (233 mg/g) can be chemical bond (> 60 kJ/mol) forms between the adsor-
attributed to its larger specific surface area compared bate molecule and adsorbent surface (Ma et al. 2013).
to W-35 and RB2H2 activated carbons. Our results are
comparable with the published ones. For example, the 3.8 Regeneration of Graphene
maximum adsorption capacity of phenol onto graphene
with a BET surface area of 305.78 m2/g was found to be Graphene regeneration experiments were carried out for
27.17 mg/g at 285 K and pH 6.3 (Li et al. 2012). five cycles using different methods including washing
Another study conducted on the adsorption of bisphenol with different solvents and a heating method. The
Water Air Soil Pollut (2017) 228:320 Page 11 of 14 320

Table 6 Thermodynamic parameters for the adsorption of phenol

Adsorbent Parameter Temperature (K)

295 313 333

Graphene ln K0 8.85 8.49 8.61

ΔG° (J/mol) −21,703.70 −22,093.00 −23,845.22
ΔH° (J/mol) −5105.96
ΔS° (J/mol K) 55.60
W-35 ln K0 9.30 8.11 8.60
ΔG° (J/mol) −22,815.24 −21,096.06 −23,813.94
ΔH° (J/mol) −15,157.25
ΔS° (J/mol K) 23.64
RB2H2 ln K0 7.31 6.95 7.21
ΔG (J/mol)
°
−17,934.01 −18,097.71 −19,961.76
ΔH° (J/mol) −2226.90
ΔS° (J/mol. K) 52.40
Nuchar granular ln K0 8.18 7.87 7.76
ΔG° (J/mol) −20,062.65 −20,467.61 −21,490.28
ΔH° (J/mol) −8991.59
ΔS° (J/mol K) 37.24

adsorption-desorption cycles of phenol onto graphene
for both heating and washing methods are illustrated in
Fig. 9. It can be observed that washing with solvents
over the cycles was more efficient and resulted in higher
removal percentages of phenol compared to the heating
method. Among the used solvents, sodium hydroxide
and methanol were found to be the most effective
regenerating solvents where high removal percentages
could be maintained even after the fifth cycle. When
washed with hydrochloric acid, graphene efficiency was
reduced by more than 20% in the second cycle. Hence,
washing with hydrochloric acid was stopped after the
third cycle where the percentage removal reduced to
50%.
In the heating or thermal method, the adsorbed phe-
nol on the graphene surface is expected to be degraded
by means of volatilization and oxidation at high temper-
atures. However, heating to high temperatures increases

Fig. 9 The removal percentage

of phenol versus graphene
regeneration cycle. The zero cycle
number indicates the removal
percentages of phenol achieved
by fresh graphene (10.0 mg
graphene and 20 mL of 50 ppm
phenol at 295 K and 230 rpm left
for 2 h)
320 Page 12 of 14
the operational cost and may change the characteristics
of the adsorbent after repeated cycles (El-Naas et al.
2010). The chemical regeneration or solvent washing
on the other hand establishes interaction forces between
the adsorbed phenol and the solvent molecules causing
the phenol molecules to leave the adsorption sites of the
adsorbent and dissolve in the solvent. The highest re-
covery of loaded graphene achieved by washing with
sodium hydroxide along the cycles may be attributed to
the reaction of phenol with sodium hydroxide forming
sodium phenolate which is readily desorbed and dis-
solved in the solvent solution (Singh and Srivastava
2002). When washing with methanol, the formation of
hydrogen bonds between phenol and methanol mole-
cules can be responsible for the relatively high achieved
recoveries of graphene. Phenol is less soluble in acetone
compared to methanol, and the acidity of the hydrochlo-
ric acid solution prevents phenol molecules from disso-
ciation hindering the desorption process.
Regeneration of the loaded graphene by sodium hy-
droxide or methanol solvents was possible with minimal
losses in its adsorption capacities up to five adsorption-
desorption cycles. The adsorption capacity of phenol
onto graphene decreased by 20% from the first cycle
to the fifth cycle.
3.9 Adsorption Mechanism of Phenol onto Graphene
The interaction of phenol molecule with graphene struc-
tures is dependent on several factors. The following
three mechanisms have been proposed in the literature
to interpret the interactions between carbon adsorbents
and organic adsorbates: the π-π dispersion interaction
mechanism, the hydrogen bonding formation mecha-
nism, and the electron donor-acceptor mechanism
(Moreno-Castilla 2004). The first two mechanisms were
proposed by Coughlin and Ezra (1968) in 1968 and the
third mechanism was proposed by Mattson et al. (1969)
in 1969. Usually, aromatic compounds such as phenol
are physisorbed on carbon materials. The π electrons in
the aromatic ring of phenol can interact with the π
electrons in the aromatic structure of graphene. In addi-
tion, the presence of oxygen functionalities on the sur-
face of graphene may initiate hydrogen bonds with the
non-dissociated phenol molecules (Moreno-Castilla
2004). Moreover, the strongly adsorbed phenol mole-
cules which could not be removed during the regenera-
tion cycles can be attributed to the electron donor-
acceptor mechanism (Moreno-Castilla 2004). A
Water Air Soil Pollut (2017) 228:320
hydrogen bonding can be established through the
shifting of π electrons of the aromatic ring leading to
an effective chemisorption of phenol molecules.
4 Conclusions
The results obtained in this study clearly demonstrated
that graphene is more effective and can be used as a
reusable adsorbent compared to the commercially avail-
able activated carbons for the removal of phenol from
aqueous solutions. The adsorption of phenol onto
graphene at high temperatures and alkaline pH solutions
was found to be unfavorable. The removal efficiency of
phenol achieved by graphene (72%) was higher than the
removal efficiency achieved by the commercial W-35
activated carbon (65%). The adsorption data of
graphene and W-35 activated carbon could be described
by the pseudo-second-order kinetic model and the Lang-
muir equilibrium isotherm. In addition, the adsorption of
phenol onto graphene and/or W-35 activated carbon was
exothermic and spontaneous in nature. Phenol
adsorption-desorption experiments onto graphene
showed that sodium hydroxide was the most effective
solvent to regenerate the loaded graphene and achieve a
removal efficiency of 62%.
Acknowledgements The authors are grateful to the Research
Office at The Petroleum Institute, Abu Dhabi for funding project
[no. 14513]. The contribution of Dr. Pal Priyabrata is appreciated.
References
Abd Gami, A., et al. (2014). Phenol and phenolic compounds
toxicity. Journal of Environmental Microbiology and
Toxicology, 2(1), 11–23.
Ahmaruzzaman, M. (2008). Adsorption of phenolic compounds
on low-cost adsorbents: a review. Advances in Colloid and
Interface Science, 143(1–2), 48–67.
Akgerman, A., & Zardkoohi, M. (1996). Adsorption of phenolic
compounds on fly ash. Journal of Chemical & Engineering
Data, 41(2), 185–187.
Al Zarooni, M., & Elshorbagy, W. (2006). Characterization and
assessment of Al Ruwais refinery wastewater. Journal of
Hazardous Materials, 136(3), 398–405.
Alhamed, Y. A. (2009). Adsorption kinetics and performance of
packed bed adsorber for phenol removal using activated
carbon from dates’ stones. Journal of Hazardous Materials,
170(2–3), 763–770.
Alshehri, S. M., et al. (2014). Synthesis, characterization of
curcumin based ecofriendly antimicrobial bio-adsorbent for
Water Air Soil Pollut (2017) 228:320
the removal of phenol from aqueous medium. Chemical
Engineering Journal, 254, 181–189.
Bazrafshan, E., Kord Mostafapour, F., & Jafari Mansourian, H.
(2013). Phenolic compounds: health effects and its removal
from aqueous environments by low cost adsorbents. Health
Scope, 2(2), 65–66.
Bianco, A., et al. (2013). All in the graphene family—a recom-
mended nomenclature for two-dimensional carbon materials.
Carbon, 65, 1–6.
Bradder, P., et al. (2011). Dye adsorption on layered graphite
oxide. Journal of Chemical & Engineering Data, 56(1),
138–141.
Bustillo-Lecompte, C. F., Knight, M., & Mehrvar, M. (2015).
Assessing the performance of UV/H2O2 as a pretreatment
process in toc removal of an actual petroleum refinery waste-
water and its inhibitory effects on activated sludge. The
Canadian Journal of Chemical Engineering, 93(5), 798–
807.
Chakraborty, S., et al. (2010). Biodegradation of phenol by native
microorganisms isolated from coke processing wastewater.
Journal of Environmental Biology, 31(3), 293.
Coughlin, R. W., & Ezra, F. S. (1968). Role of surface acidity in
the adsorption of organic pollutants on the surface of carbon.
Environmental Science & Technology, 2(4), 291–297.
Djebbar, M., et al. (2012). Adsorption of phenol on natural clay.
Applied Water Science, 2(2), 77–86.
Dursun, A. Y., & Kalayci, Ç. S. (2005). Equilibrium, kinetic and
thermodynamic studies on the adsorption of phenol onto
chitin. Journal of Hazardous Materials, 123(1–3), 151–157.
Ekpete, O., & Horsfall, M. J. (2011). Column removal of phenol
and chlorophenol using a commercial activated carbon.
Advances in Environmental Biology, 5(1), 194–200.
El-Naas, M. H., Al-Zuhair, S., & Alhaija, M. A. (2010). Removal
of phenol from petroleum refinery wastewater through ad-
sorption on date-pit activated carbon. Chemical Engineering
Journal, 162(3), 997–1005.
Freundlich, H. M. F. (1906). Uber die adsorption in losungen.
Zeitschrift für Physikalische Chemie, 57(A), 385.
Girods, P., et al. (2009). Activated carbons prepared from wood
particleboard wastes: characterisation and phenol adsorption
capacities. Journal of Hazardous Materials, 166(1), 491–
501.
Gundogdu, A., et al. (2012). Adsorption of phenol from aqueous
solution on a low-cost activated carbon produced from tea
industry waste: equilibrium, kinetic, and thermodynamic
study. Journal of Chemical & Engineering Data, 57(10),
2733–2743.
Gupta, V., Ali, I., & Saini, V. (2004). Removal of chlorophenols
from wastewater using red mud: an aluminum industry
waste. Environmental Science & Technology, 38(14), 4012–
4018.
Ho, Y. S., & McKay, G. (1999). Pseudo-second order model for
sorption processes. Process Biochemistry, 34(5), 451–465.
Ho, Y. S., & McKay, G. (2000). The kinetics of sorption of
divalent metal ions onto sphagnum moss peat. Water
Research, 34(3), 735–742.
Hu, H., et al. (2015). Metal-free graphene-based catalyst—insight
into the catalytic activity: a short review. Applied Catalysis,
A: General, 492, 1–9.
Huang, J., Jin, X., & Deng, S. (2012). Phenol adsorption on an n-
methylacetamide-modified hypercrosslinked resin from
Page 13 of 14 320
aqueous solutions. Chemical Engineering Journal, 192,
192–200.
Kazmi, M., et al. (2013). Removal of phenol from wastewater
using activated waste tea leaves. Polish Journal of Chemical
Technology, 15(2), 1–6.
Khalid, M., et al. (2004). Removal of phenol from water by
adsorption using zeolites. Industrial & Engineering
Chemistry Research, 43(17), 5275–5280.
Kulkarni, S. J., et al. (2013). Adsorption of phenol from wastewa-
ter in fluidized bed using coconut shell activated carbon.
Procedia Engineering, 51, 300–307.
Langmuir, I. (1916). The constitution and fundamental properties
of solids and liquids. Journal of the American Chemical
Society, 38(11), 2221–2295.
Li, Y., et al. (2011). Adsorption of fluoride from aqueous solution
by graphene. Journal of Colloid and Interface Science,
363(1), 348–354.
Li, Y., et al. (2012). Equilibrium, kinetic and thermodynamic
studies on the adsorption of phenol onto graphene.
Materials Research Bulletin, 47(8), 1898–1904.
Li, C., et al. (2017). Synergy of adsorption and photosensitization
of graphene oxide for improved removal of organic pollut-
ants. RSC Advances, 7(26), 16204–16209.
Lian, P., et al. (2010). Large reversible capacity of high quality
graphene sheets as an anode material for lithium-ion batte-
ries. Electrochimica Acta, 55(12), 3909–3914.
Lin, K., et al. (2009). Study the adsorption of phenol from aqueous
solution on hydroxyapatite nanopowders. Journal of
Hazardous Materials, 161(1), 231–240.
Liu, T., et al. (2012). Adsorption of methylene blue from aqueous
solution by graphene. Colloids and Surfaces. B,
Biointerfaces, 90, 197–203.
Ma, Y., et al. (2013). Removal of phenol by powdered activated
carbon adsorption. Frontiers of Environmental Science &
Engineering, 7(2), 158–165.
Mattson, J., et al. (1969). Surface chemistry of active carbon:
specific adsorption of phenols. Journal of Colloid and
Interface Science, 31, 116–130.
Mehrizad, A. & Gharbani, P. (2014). Decontamination of 4-chloro-
2-nitrophenol from aqueous solution by graphene adsorption:
equilibrium, kinetic, and thermodynamic studies. Polish
Journal of Environmental Studies, 23(26), 2111–2116.
Moradi, O., et al. (2010). The studies of equilibrium and thermo-
dynamic adsorption of Pb(II), Cd(II) and Cu(II) ions from
aqueous solution onto SWCNTs and SWCNT–COOH sur-
faces. Fullerenes, Nanotubes, and Carbon Nanostructures,
18(3), 285–302.
Moreno-Castilla, C. (2004). Adsorption of organic molecules from
aqueous solutions on carbon materials. Carbon, 42(1), 83–
94.
Mukherjee, R., & De, S. (2014). Adsorptive removal of phenolic
compounds using cellulose acetate phthalate–alumina nano-
particle mixed matrix membrane. Journal of Hazardous
Materials, 265, 8–19.
Păcurariu, C., et al. (2013). Adsorption of phenol and p-
chlorophenol from aqueous solutions on poly (styrene-co-
divinylbenzene) functionalized materials. Chemical
Engineering Journal, 222, 218–227.
Pigatto, G., et al. (2013). Chitin as biosorbent for phenol removal from
aqueous solution: equilibrium, kinetic and thermodynamic
320 Page 14 of 14
studies. Chemical Engineering and Processing: Process
Intensification, 70, 131–139.
Qin, G., et al. (2013). Preparation of hydrophobic granular silica
aerogels and adsorption of phenol from water. Applied
Surface Science, 280, 806–811.
Qiu, H., et al. (2009). Critical review in adsorption kinetic models.
Journal of Zhejiang University. Science. A, 10(5), 716–724.
Roostaei, N., & Tezel, F. H. (2004). Removal of phenol from
aqueous solutions by adsorption. Journal of Environmental
Management, 70(2), 157–164.
Saha, P. D., Srivastava, J., & Chowdhury, S. (2013). Removal of
phenol from aqueous solution by adsorption onto seashells:
equilibrium, kinetic and thermodynamic studies. J Water
Reuse Desal, 3(2), 119–127.
Shang, H., et al. (2015). Preparing high surface area porous carbon
from biomass by carbonization in a molten salt medium. RSC
Advances, 5(92), 75728–75734.
Singh, D. K., & Srivastava, B. (2002). Removal of phenol pollut-
ants from aqueous solutions using various adsorbents.
Journal of Scientific and Industrial Research, 61, 208–218.
Srivastava, V. C., et al. (2006). Adsorptive removal of phenol by
bagasse fly ash and activated carbon: equilibrium, kinetics
and thermodynamics. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 272(1–2), 89–
104.
Sulaymon, A. H., & Ahmed, K. W. (2008). Competitive adsorp-
tion of furfural and phenolic compounds onto activated car-
bon in fixed bed column. Environmental Science &
Technology, 42(2), 392–397.
Tancredi, N., et al. (2004). Phenol adsorption onto powdered and
granular activated carbon, prepared from eucalyptus wood.
Journal of Colloid and Interface Science, 279(2), 357–363.
Thommes, M., et al. (2015). Physisorption of gases, with special
reference to the evaluation of surface area and pore size
distribution (IUPAC technical report). Pure and Applied
Chemistry, 87(9–10), 1051–1069.
Tor, A., et al. (2006). Removal of phenol from aqueous phase by
using neutralized red mud. Journal of Colloid and Interface
Science, 300(2), 498–503.
Water Air Soil Pollut (2017) 228:320
Tran, H. N., You, S.-J., & Chao, H.-P. (2016). Thermodynamic
parameters of cadmium adsorption onto orange peel calcu-
lated from various methods: a comparison study. Journal of
Environmental Chemical Engineering, 4(3), 2671–2682.
Wang, G., et al. (2008). Facile synthesis and characterization of
graphene nanosheets. Journal of Physical Chemistry C,
112(22), 8192–8195.
Wang, S., et al. (2013). Adsorptive remediation of environmental
pollutants using novel graphene-based nanomaterials.
Chemical Engineering Journal, 226, 336–347.
Worsley, M. A., et al. (2010). Synthesis of graphene aerogel with high
electrical conductivity. Journal of the American Chemical
Society, 132(40), 14067–14069.
Wu, T., et al. (2011). Adsorption characteristics of acrylonitrile, p-
toluenesulfonic acid, 1-naphthalenesulfonic acid and methyl
blue on graphene in aqueous solutions. Chemical Engineering
Journal, 173(1), 144–149.
Xu, J., Wang, L., & Zhu, Y. (2012). Decontamination of bisphenol
A from aqueous solution by graphene adsorption. Langmuir,
28(22), 8418–8425.
Yang, C., et al. (2006). Solvent extraction process development and
on-site trial-plant for phenol removal from industrial coal-
gasification wastewater. Chemical Engineering Journal,
117(2), 179–185.
Zhang, J. (2013). Phenol removal from water with potassium
permanganate modified granular activated carbon. Journal
of Environmental Protection, 04(05), 7.
Zhang, Y., et al. (2014). Recyclable removal of bisphenol a from
aqueous solution by reduced graphene oxide–magnetic nano-
particles: adsorption and desorption. Journal of Colloid and
Interface Science, 421, 85–92.
Zhao, G., Li, J., & Wang, X. (2011). Kinetic and thermodynamic
study of 1-naphthol adsorption from aqueous solution to
sulfonated graphene nanosheets. Chemical Engineering
Journal, 173(1), 185–190.