6 H. A. AL-AOH ET AL.
Figure 3. The TEM spectrum of as-prepared (a) CuO and (b) NiO NPs.
et al. 2016; Rashad et al. 2013; Teoh and Li
2015), and the XRD patterns did not show any
peaks attributable to impurities. In order to
understand the phase symmetry of the prepared
CuO and NiO NPs, a systematic study of the
XRD results was performed. Sharp peaks were
obtained at angles corresponding to the planes
(110), (002), (111), (202), and (202), indicating
that CuO and NiO NPs have monoclinic nano-
crystalline structures (Yao et al. 2005). The space
group of CuO (Niggli 1922) and NiO (Cairns
and Ott 1933) are C62h–C2/c and Fm – 3 m,
respectively. They have the following parameters
a ¼ 4.18 ± 0.01 Å and a ¼ 4.67 Å, b ¼ 3.43 Å,
c ¼ 5.12 Å, respectively for CuO and NiO NPs.
The XRD pattern obtained from the product
(Figure 2b) was identical to that of the NiO NPs.
The mean average sizes of the nanocrystals were
estimated according to the Debye–Scherer equa-
tion (Rashad et al. 2013):
Kk
D¼ (11)
b cos h
where the constant, K, was taken to be 0.94, k
was the X-ray wavelength using CuK radiation
(k ¼ 1.5406 Å), and b was the full width of the
diffraction peak at half of the maximum corre-
sponding to 2h: Using Equation (11), the calcu-
lated crystallite sizes were found to range
 CHEMICAL ENGINEERING COMMUNICATIONS 7

Table 1. Characteristics of NiO and CuO NPs.

Type of adsorbent NiO NPs CuO NPs
Specific surface area (m2/g) 78.3733 6.1881
Total pore volume (cm3/g) 0.06842 0.0280
Average pore diameter (Å) 34.920 116.134
pHZPC 8.1 7.6

between 14 ± 1 nm and 14.5 ± 1.3 nm for CuO

and NiO NPs, respectively.
Transmitted electron microscopy was used to
investigate the morphology and size of the syn-
thesized NPs. Figure 3(a,b) show that the pre-
pared CuO and NiO NPs appeared to be mostly
spherical in shape in the TEM images, with aver-
age sizes ranging from 10 ± 2 nm and 13 ± 2 nm, Figure 4. Effect of initial concentration and solution tempera-
respectively. Al-Aoh (2018) also noted that TEM ture on the adsorption of methylene blue on NiO NPs.
micrographs of NiO NPs revealed that they were
spherical in shape and averaged 13 nm in size.
Furthermore, Dhananasekaran et al. (2015)
observed that the chitin NPs in TEM images
were spherical and 49 nm in size. Hernandez
et al. (2015) noted that the scanning electron
microscopy (SEM) images of synthesized Fe3O4
NPs were acicular in shape, with an average size
of 42 nm.
Table 1 presents the results of surface analyses
and the pHZPC of both NiO and CuO NPs. These
results suggest that the total pore volumes and
surface areas of NiO NPs were higher than those
of CuO NPs. Additionally, the average pore
diameter of CuO NPs was also higher than that
of NiO NPs. The BET surface analyzer results Figure 5. Effect of initial concentration and solution tempera-
ture on the adsorption of methylene blue on CuO NPs.
indicate that NiO NPs had higher adsorption
capacities and lower adsorption rates when com-
pared to CuO NPs. both of the adsorbents were greater at higher initial
concentrations of MB. This can be explained in
terms of the higher adsorbate concentration offer-
Effects of adsorption experimental conditions
ing a substantial driving force to overcome the
The effects of the initial concentration of MB and mass transfer resistance of the dye between aque-
of temperature on the adsorption uptake at equi- ous and solid phases. However, at concentrations
librium on the surfaces of NiO and CuO NPs are over 200 mg/L, the amount of MB adsorbed (qe
shown in Figures 4 and 5, respectively. It can be mg/g) was almost constant. This is due to the fact
seen from these figures that increasing MB con- that all active adsorption sites were saturated after
centrations from 10 mg/L to 200 mg/L resulted in 200 mg/L.
an increase in the solute uptake on the surface of Figures 4 and 5 illustrate that the adsorption
both adsorbents. The results obtained in this study of MB on the surface of NiO NPs decreased,
agree well with the reported results for the adsorp- while it increased in the case of CuO NPs, when
tion of MB on commercial activated and activated the solution temperature was raised from 30
C
carbon fibers (Al-Aoh et al. 2014). Moreover, these to 60
C. These results indicate that the adsorp-
findings demonstrate that the adsorption rates for tion processes were exothermic for NiO NPs but
8 H. A. AL-AOH ET AL.
Figure 6. Effect of the contact time on the adsorption capacity
of MB on the NiO NPs.
endothermic for the CuO NPs. The decreasing of
MB uptake to the surface of NiO NPs can be
explained by the fact that an increase in the tem-
perature of the liquid phase will increase the
solubility of the adsorbate molecules, as well as
their diffusion inside the adsorbent pores
(Cotoruelo et al. 2012). It has been reported that
the adsorptions of 4-nitrophenol (Al-Aoh et al.
2013a) and acid red (27) dye (Al-Aoh et al.
2013b) on activated coconut husks, as well as
commercial activated carbon, are exothermic in
nature. The increase of MB adsorption by raising
the temperature was due to the increase in the
mobility of MB (Hameed and Ahmad 2009). A
minimum amount of energy may be also needed
for further molecules of MB to interact with the
sites of active adsorption (Hameed and Ahmad
2009). Similar observations were noted for MB
adsorption on coconut husk-activated carbon and
commercial activated carbon (Al-Aoh et al. 2014)
and garlic peels and agricultural waste biomass
(Oyelude and Applat-Takyi 2012).
Effects of agitation time
Plots of the amounts of MB adsorbed (qt mg/g)
at variable initial concentrations (20 mg/L, 30 mg/
L, 50 mg/L, and 100 mg/L) versus adsorption con-
tact time were shown for NiO and CuO NPs
(Figures 6 and 7). It is evident from Figure 6 that
the adsorption of the dye on the surface of NiO
NPs increased with increasing agitation time,
reaching equilibrium after 6 h for each concentra-
tion. Similarly, Figure 7 reveals that the amount
Figure 7. Effect of the contact time on the adsorption capacity
of MB on the CuO NPs.
of MB adsorbed by CuO NPs was also enhanced
with increasing contact time; equilibrium was
achieved after 1 h for lower initial concentrations
(20 mg/L and 30 mg/L) and after 6 h for higher
initial concentrations (50 mg/L and 100 mg/L) of
adsorbate. The results obtained in this study
agree with those reported for the adsorption of
MB on activated carbon prepared from coconut
husk fibers (Al-Aoh et al. 2014) and graphene
(Liu et al. 2012).
Effects of solution pH on adsorption
Solution pH has a substantial effect on the degree
of ionization of adsorbates and the charges of
adsorbent surfaces (Wu et al. 2016). The adsorb-
ate presents as ions in the solution when the
solution pH is higher than the corresponding
value of pKa. Additionally, the adsorbent surface
will be positively and negatively charged when
the solution pH is respectively lower and higher
than the pHZPC of the adsorbent. The relation-
ship between the amount of MB adsorbed (qe
mg/L) on NiO and CuO NPs and the initial pH
of the solution is shown in Figure 8. This figure
shows that the adsorption capacity of MB (pKa ¼
3.8) slightly increases with increasing solution
pH, ranging from 2 to 8 and from 2 to 6 in the
cases of NiO (pHZPC ¼ 8.1) and CuO (pHZPC ¼
7.6), respectively. These slight changes may be
attributed to the competitive adsorption between
the positive ions of MB and hydrogen ions at
low pH.

Figure 8. Effect of initial pH on the adsorption of methylene
blue on NiO and CuO NPs.
The concentration of hydrogen ions rapidly
decreased as the pH of the solution increased,
resulting in less competition between the ions of
MB and hydrogen adsorbed on the active sites of
the absorbent. Figure 8 also shows that the
adsorbed amount of this dye sharply increased
when the pH of the solutions was raised over 8 or
6 in the cases of NiO and CuO NPs, respectively.
These observations may be explained by the fact
that the adsorption of MB at higher pH occurred
as a result of the electrostatic attraction between
the positively charged MB ions and the negatively
charged adsorbent surfaces (pH > pHZPC), as
increasing the solution pH also increases the num-
ber of negatively charged ions on the surfaces of
the adsorbents, leading to an enhancement in the
number of MB ions adsorbed on the active sites.
Similar results were previously observed for the
adsorption of MB on commercial activated carbon
and chemically activated coconut husk-carbon
fibers (Al-Aoh et al. 2014). The results obtained in
this study confirm that the MB adsorption capacity
can be maximized at higher values of solution pH.
These results agree well with those reported in the
literature for the adsorption of MB on cotton stalks
and on Fe3O4-graphene@mesoporous SiO2 nano-
composite (Deng et al. 2011; Wu et al. 2016).
Adsorption isotherms
The plots of Ce/qe against Ce (i.e. the Langmuir
isotherm model) for adsorption of MB on the
CHEMICAL ENGINEERING COMMUNICATIONS 9
NiO and CuO NPs are shown in Figures 9 and
10, respectively. The lnqe versus lnCe (i.e.the
Freundlich isotherm model) for adsorption of the
dye on NiO and CuO NPs are similarly shown in
Figures 11 and 12. The isotherm parameter val-
ues of the Langmuir (qmax and KL) and
Freundlich (KF and n) models were calculated
from the slopes and intercepts and summarized
along with their corresponding correlation coeffi-
cients (R2) in Table 2. The values of RL were also
computed using Equation (4) and also listed in
Table 2.
The values of RL and 1/n presented in Table 2
were between 0 and 1, indicating that the
adsorption of MB on both NiO and CuO NPs
was favorable under the experimental conditions
in this study. The correlation coefficients (R2) of
the Langmuir model were higher than those of
the Freundlich model in the case of NiO NPs.
This suggests that the Langmuir isotherm model
is applicable for studying the adsorption of MB
on the surface of NiO NPs, assuming monolayer
coverage and uniform active adsorption sites
over the adsorbent surface. These results also
agreed well with those reported for the adsorp-
tion of MB on activated carbon derived from
Ficus carica bast (Pathania et al. 2017).
Significant linear relationships, as evident from
the correlation coefficients (R2) (Table 2), con-
firmed the applicability of both the Langmuir
and Freundlich models for describing the adsorp-
tion of MB on the CuO NPs. Similar trends have
been observed for the adsorption of MB on vari-
ous types of carbon (Kannan and
Sundaram 2001).
The values of qmax for the NiO NPs presented
in Table 2 were found to be higher than those of
the CuO NPs at each of the different experimen-
tal temperatures. These findings indicate that the
adsorption performance of the former is better
than that of the latter. The higher surface area
and total pore volume of NiO NPs are believed
to be the reason that NiO NPs served as more
effective adsorbents than the CuO NPs. The
higher adsorption capacities of the NiO NPs
observed in this study also suggest that this
adsorbent will attract more attention in the future
for wastewater purification.
10 H. A. AL-AOH ET AL.
Figure 9. Langmuir isotherm models for adsorption of MB on NiO NPs at different temperatures.
Figure 10. Langmuir isotherm models for adsorption of MB on
CuO NPs at different temperatures.
Figure 11. Freundlich isotherm model for the adsorption of
MB on NiO NPs at different temperatures.
Figure 12. Freundlich isotherm model for the adsorption of
MB on CuO NPs at different temperatures.
Kinetic studies
The experimental kinetic data at four initial MB
concentrations (20 mg/L, 30 mg/L, 50 mg/L, and
100 mg/L) for adsorption on the NiO and CuO
NPs were analyzed using the linearized integral
forms of pseudo-first-order (Equation 8), pseudo-
second-order (Equation 9), and intraparticle dif-
fusion models (Equation 10) in that order. This
was carried out to determine the kinetic parame-
ters for adsorption of this dye on these selected
adsorbents. The values of pseudo-first-order kin-
etic model parameters (K1 and qe) were calcu-
lated from the slopes and intercepts of the plots
of log(qeqt) versus t, which are illustrated in
 CHEMICAL ENGINEERING COMMUNICATIONS 11

Table 2. Langmuir, Freundlich parameters and separation factors (RL) for the adsorption of MB on NiO and CuO NPs at three dif-
ferent temperatures.
Langmuir isotherm Freundlich isotherm


Adsorbent Temperature, C qmax (mg/g) KL (L/mg) RL R2
KF (mg/g)(L/mg)
1/n
1/n n R2
NiO 30 166.67 0.0930 0.021 0.995 25.063 0.413 2.421 0.693
45 156.25 0.0159 0.112 0.973 5.753 0.599 1.669 0.904
60 111.11 0.0059 0.253 0.948 1.947 0.643 1.555 0.957
CuO 30 28.66 0.0233 0.079 0.997 4.704 0.294 3.398 0.932
45 34.47 0.0679 0.029 0.997 15.506 0.131 7.646 0.975
60 50.25 0.1146 0.017 0.997 24.723 0.122 8.224 0.954

this study cannot be described well by a pseudo-

Figure 13. Pseudo-first-order kinetics model for the adsorption
of MB on NiO NPs at 30 ± 1
C.
first-order kinetic model. Similar results have also
been observed by Soares et al. (2017).
Figures 15 and 16 show the pseudo-second-
order kinetic model plots of t/qt versus t for NiO
and CuO NPs, respectively. The vales of qe and K2
were determined from the slopes and intercepts of
these plots. These values were listed along with
their correlation coefficients (R2) in Table 3. It can
be seen in Table 3 that the values of R2  1 for
both adsorbents. Furthermore, there was conform-
ance between the experimental and calculated qe.
This indicates that the pseudo-second-order model
is applicable for describing the adsorptions of MB
on the NiO and CuO NPs, and the adsorption of
this dye on the NiO and CuO NPs is chemisorp-
tion. The chemical reaction between the adsorbate
and adsorbents would be occurred by transfer,
exchange, or sharing of electrons (Wang et al.
2017). It was also reported previously by Li et al.
(2009) that the metals oxides and MB in the aque-
ous solution exist as anionic (MO–) and cationic
([C16H18 N3S]þ) forms, respectively. Therefore,
the adsorption mechanism of MB by NiO and
CuO NPs can be represented by the following
chemical reaction equations:

1. NiO– þ [C16H18 N3S]þ ! NiO[C16H18 N3S]

Figure 14. Pseudo-first-order kinetics model for the adsorption
of MB on CuO NPs at 30 ± 1
C.
Figures 13 and 14 for the NiO and CuO NPs,
respectively. These values, together with their
correlation coefficients, are reported in Table 3.
It is evident from Table 3 that the correlation
coefficients (R2) were quite low and the calcu-
lated values of qe did not agree well with the
experimental data of qe for each adsorbent. This
suggests that the experimental data obtained in
2. CuO– þ [C16H18 N3S]þ ! CuO[C16H18 N3S]
Additionally, it can be shown in Table 3 that
the adsorption rates of MB on CuO NPs are
higher than that of NiO NPS; this is due to the
fact that the average pore diameter of the CuO
NPs is greater than that of the NiO NPs.
The slopes and intercepts of the plots of qt versus
t1/2 (Figures 17 and 18 for NiO and CuO NPs,
respectively) were used to determine the parame-
ters of the intraparticle diffusion models (Kdif
and C). The correlation coefficients (R2) and
12 H. A. AL-AOH ET AL.

Table 3. Comparison of pseudo-first and pseudo-second-order models for the adsorption of MB on NiO and CuO NPs at Four ini-
tial dye concentrations and 30 ± 1
C.
Pseudo-first-order kinetic model Pseudo-second-order kinetic model
1
Adsorbent C0 (mg/L) qe,exp (mg/g) qe,cal (mg/g) K1 (h ) R 2
qe,cal (mg/g ) K2 (g/mg min) R2 Rate
NiO 20 8.569 3.93 0.0046 0.921 8.42 0.0053 0.996 0.045
30 11.313 5.52 0.0055 0.869 11.36 0.0037 0.998 0.042
50 16.169 8.69 0.0037 0.938 15.41 0.0023 0.997 0.035
100 22.091 15.64 0.0058 0.956 23.20 0.0008 0.996 0.019
CuO 20 4.168 1.39 0.0021 0.930 3.62 0.0552 0.999 0.200
30 5.442 2.19 0.0028 0.948 4.16 0.0326 0.997 0.136
50 9.847 5.73 0.0016 0.977 5.48 0.0308 0.998 0.169
100 11.813 7.51 0.0032 0.988 9.78 0.0115 0.973 0.112

Figure 15. Pseudo-second-order kinetics for the adsorption of Figure 17. Intraparticle diffusion model for the adsorption of
MB on NiO NPs at 30 ± 1
C. MB on NiO NPs at 30 ± 1
C.

Figure 16. Pseudo-second-order kinetics for the adsorption of Figure 18. Intraparticle diffusion model for the adsorption of
MB on CuO NPs at 30 ± 1
C. MB on CuO NPs at 30 ± 1
C.

parameters of this model are listed in Table 4. The

results indicated that intraparticle diffusion was not
an important factor in the adsorption of MB by
NiO and/or CuO NPs. Al-Aoh et al. (2014) found a
similar observation in the case of MB adsorption
on commercial activated carbon and activated car-
bon fibers produced from coconut husks.
Adsorption thermodynamics
The plots of lnKc vs. 1/T are shown in Figures 19
and 20 for the NiO and CuO NPS, respectively.
The values of DH0 and DS0 were estimated from
the slopes and intercepts of these plots (based on
Equation 6) and were used to determine the
 CHEMICAL ENGINEERING COMMUNICATIONS 13

Table 4. Parameter values of an intraparticle diffusion model while it is endothermic in the case of CuO NPs.
for the adsorption of MB on NiO and CuO NPs at Four initial These observations agree well with the previous
dye concentrations and 30 ± 1
C.
Intraparticle diffusion kinetic model
results that related to the effects of solution tem-
peratures and adsorption isotherms. Moreover,
Adsorbent C0 (mg/L) qe,exp (mg/g) Kdif (mg/h1/2 g) C R2
NiO 20 8.569 0.205 3.852 0.889
the lower values of DH0 (Table 5) are over the
30 11.313 0.328 4.300 0.859 adsorption enthalpy range (2.1–20.9 KJ/mol) that
50 16.169 0.461 5.283 0.836
100 22.091 0.829 3.948 0.926 correspond to physisorption processes, as
CuO 20 4.168 0.057 2.494 0.940 reported in the literature (Kurniawan and Ismadji
30 5.442 0.099 2.817 0.973
50 9.847 0.172 3.389 0.993 2011; Theydan and Ahmed 2012). Thus, the val-
100 11.813 0.343 2.957 0.953 ues of DH0 observed in this study confirmed that
the adsorption of this dye on both of these two
adsorbents can be classified as chemisorption.
Additionally, it was observed in the case of kin-
etic adsorption that the experimental data were
well described by applying the pseudo-second-
order model, which also indicates that the
adsorption was not physical adsorption but rather
was chemical in nature.
The negative values of DS0 in the case of NiO
NPs indicate that the randomness at the adsorb-
ent-solution interface increased during the
adsorption process, while the reverse was
observed for CuO NPs. The negative and positive
values of DG0 suggest that the adsorptions of MB
on these two adsorbents are correspondingly
Figure 19. Plots of LnKc versus 1/T for the adsorption of MB
on NiO NPs at different dye concentrations. spontaneous and non-spontaneous processes. It
can also be seen in Table 4 that the values of
DG0 became less negative in the case of NiO NPs
and more negative with CuO NPs as the solution
temperature increased for each concentration.
This suggests that a higher temperature is the
most important factor in the higher adsorption
capacity of CuO NPs, while the opposite is true
for the NiO NPS. It has been reported that the
adsorption of MB on Fe3O4-graphene@mesopo-
rous SiO2 nanocomposite was endothermic (Wu
et al. 2016), whereas adsorption of this dye by
graphene oxide occurred as an exothermic pro-
cess (Yang et al. 2011).

Figure 20. Plots of LnKc versus 1/T for the adsorption of MB
on CuO NPs at different dye concentrations.
values of DG0. The estimated thermodynamic
parameters are given in Table 5. The values of
DH0 were negative in the case of NiO and posi-
tive for CuO NPs, indicating that the adsorption
of MB on NiO NPs is exothermic in nature,
Comparison of performance of NiO NPs with
reported metallic oxides NPs
The maximum adsorption capacities of MB on
NiO NPs and the other metallic oxides NPs have
been used in the literature for adsorption of MB
from aqueous solutions were summarized in
Table 6. This is to illustrate the significance of
NiO NPs used in this work comparing to others.
14 H. A. AL-AOH ET AL.

Table 5. Thermodynamic parameters of MB adsorption on NiO and CuO NPs (T ¼ 303,318,333 K).
DG
(KJ/mol)
Adsorbent Concentration (mg/L) DH
(kJ/mol) DS
(KJ/mol K) 303 K 318 K 333 K R2
NiO 20 43.096 0.128 4.312 2.392 0.472 0.978
30 78.310 0.242 4.984 1.354 2.276 0.952
50 36.570 0.112 2.634 0.954 0.726 0.992
100 71.516 0.221 4.553 1.238 2.077 0.983
200 84.828 0.263 5.139 1.194 2.751 0.974
300 115.398 0.357 7.227 1.872 3.483 0.975
20 88.004 0.286 1.346 2.944 7.234 0.976
30 82.325 0.270 0.515 3.535 7.585 0.905
CuO 50 104.781 0.338 2.367 2.703 7.773 0.985
100 57.175 0.176 3.847 1.207 1.433 0.988
200 26.131 0.070 4.921 3.871 2.821 0.969
300 23.529 0.058 5.955 5.085 4.215 0.967

Table 6. Comparison of adsorption capacity of NiO NPs used as adsorbent in this study with
other metallic oxides NPs towards MB.
Adsorbent qmax (mg/g) Sources
Ni0.5Zn0.5Fe2O4 nanoparticles 54.70 (Hoseini et al. 2013)
CuO-Al2O3 nano-materials 97.04 (Zhang, Su, et al. 2015)
CuO-NPs 4.11E þ 01 30
C (Mustafa et al. 2013)
9.66E þ 00 35
C
2.34E þ 02 40
C
1.18E þ 01 45
C
Gd0.5Sr0.5FeO3 1.45 (Tavakkoli and Hamedi 2016)
Fe2O3 NPs 0.56 20
C (Li et al. 2009)
0.85 40
C
Silica nano-sheets 12.66 (Zhao et al. 2008)
NiO NPs 166.67 30
C Present study
156.25 45
C
111.11 60
C
CuO NPs 28.66 30
C Present study
34.47 45
C
50.25 60
C

This table demonstrates that NiO NPs have
adsorption capacity higher than that of other
metallic oxides NPs. This confirms that this
adsorbent NPs will meet a significant interesting
in the case of water purification activities.
Conclusions
NPs of NiO and CuO were prepared and charac-
terized, and adsorption performances of these
adsorbents with respect to MB were also investi-
gated. The results suggest that the adsorptive
properties of NiO NPs (e.g. 78.37 m2/g ¼ surface
area and 0.068 cm3/g ¼ total pore volume) are
more effective than those of CuO NPs (6.19 m2/
g ¼ surface area and 0.028 cm3/g ¼ total pore vol-
ume). The factors affecting the adsorption cap-
acity, such as the initial concentration of MB,
contact time, solution pH, and temperature were
studied. It was found that all of these factors
have positive effects, except for temperature,
which negatively affects the adsorption capacity
of NiO NPs. Isotherm experimental data were
analyzed using the models of Langmuir and
Freundlich at three different solution tempera-
tures. It was observed that the experimental iso-
therm data could be expressed well by the
Langmuir model.
The adsorption capacities of MB on NiO NPs
(111.11 mg/L, 156.25 mg/L, and 166.67 mg/L) are
higher than those of MB dye on CuO NPs
(28.66 mg/L, 34.47 mg/L, and 50.25 mg/L). Pseudo-
first-order, pseudo-second-order, and intraparticle
diffusion kinetic models were applied to investi-
gate the kinetic experimental data. The results
obtained indicate that the pseudo-second-order
kinetic model is the most applicable. It was also
found that the rates of MB adsorption on CuO
NPs are higher than those of NiO NPs.
Thermodynamic parameters (DH0, DS0, and DG0)
were estimated and the obtained values demon-
strate that the removal of MB from synthesized
wastewater is exothermic and endothermic for the
NiO and CuO NPs, respectively. The results

obtained in this study further confirm that NiO
NPs are well suited for application in the purifica-
tion of industrial wastewater.
Disclosure statement
The authors declare that there is no conflict of interest.
Funding
The authors extend their appreciation to the Deanship of
Scientific Research at Tabuk University for funding the
work through the research group (Project No. S-90-1437H).
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