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Bioresource Technology 99 (2008) 18531860

COD and BOD reduction from coee processing wastewater


using Avacado peel carbon
Rani Devi
a

a,*

, Vijender Singh b, Ashok Kumar

Department of Energy and Environmental Science, Ch. Devi Lal University, Sirsa, Haryana, India
b
District Science Specialist, Hisar, Haryana, India
c
District Food and Supplies Ocer, Sirsa, Haryana, India
Received 22 February 2007; received in revised form 8 March 2007; accepted 19 March 2007
Available online 9 May 2007

Abstract
The aim of this study was the assessment of reduction of chemical oxygen demand (COD) and biological oxygen demand (BOD) of
wastewater from coee processing plant using activated carbon made up of Avacado Peels. The complete study was done in batch mode
to investigate the eect of operating parameters. The results of the COD and BOD concentration reduction with avocado peel carbon
(APC) and commercial activated carbon (CAC) were compared and optimum operating conditions were determined for maximum
reduction. Adsorption isotherm was also studied besides the calculation of optimum treatment parameters for maximum reduction of
COD and BOD concentration from euent of the coee processing plant. The maximum percentage reduction of COD and BOD concentration under optimum operating conditions using APC was 98.20% and 99.18% respectively and with CAC this reduction was
99.02% and 99.35% respectively. As the adsorption capacity of APC is comparable with that of CAC for reduction of COD and
BOD concentration, it could be a lucrative technique for treatment of domestic wastewater generated in decentralized sectors.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Avacado; BOD; COD; Coee processing wastewater/euent

1. Introduction
Ethiopia had been the origin of coee because rst coee
plant was initially found and cultivated by Oromo people
in the Kafa province of Ethiopia from which it got its name
(ITC, 2002). Ethiopia is worlds third largest coee exporter after Burundi and El Salvador (ITC, 2002). Jimma zone
is one of the areas in Ethiopia where coee processing
plants are cultivated in large numbers.
In this zone, wet coee processing method has been
adopted. Wet coee processing procedure requires mechanical removal of pulp with the help of water as a result of
which it produces considerable amount of wastewater
*

Corresponding author. Address: H. No. 1357, Sector 15, Faridabad,


Haryana 121007, India. Tel.: +91 1294006166; fax: +91 1294006167.
E-mail address: rani_sahu@yahoo.com (R. Devi).
0960-8524/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.03.039

(Adams and Dougan, 1987; Enden, 2002 and Murthy


et al., 2003, 2004). The water used for de-pulping of the
coee cherries is known as pulping water (GTZ-PPP,
2002) and it accounts for over half of the water used in this
process (Fresner and Schnitzer, 1996 and Enden and Calvert, 2002).
The wastewater generated from coee processing has
high concentration of organic pollutants (Chapman,
1996; Matos et al., 2001; INEP, 2001; MoEF, 2003) like
pectin, proteins and sugars (Adams, 1980; Calvert, 1997;
Mendoza and Rivera, 1998; Deepa et al., 2002). Due to
high pollutant concentration, its disposal without treatment in water bodies has became undesirable (Rolz,
1982; Betram and Balance, 1996; Tomar, 1999) because if
done so, it will be very dangerous for the water bodies
and human health. So, before its nal disposal in water
bodies, it needs a proper treatment.

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R. Devi et al. / Bioresource Technology 99 (2008) 18531860

The conventional wastewater treatment technologies


being adopted in industrialized nations are quite expensive
to build, operate and maintain (Piet et al., 1994; Mazumder
and Kumar, 1999; Mazumder and Roy, 2000). Moreover,
to comply with stringent environmental regulations and
for restoration of safe environment, it has become imperative to nd less costly and easily adaptable treatment technologies for the wastewater.
Research eorts are going on (Mohammed et al., 1998;
Wang et al., 2005) for development of such type of wastewater treatment technologies. Fly ash can be used as a
promising adsorbent for removal of various types of pollutants from wastewater (Patnaik et al., 1996; Wang and Wu,
2006). Low cost adsorbents of dierent origins like Industrial waste material, bagasse y ash and jute-processing
waste can also be used for removal of organic matter from
wastewater (Manju et al., 1998; Banerje and Dastidar,
2005; Srivastava et al., 2005; Bhatnagar, 2007). Removal
of organic matter from wastewaters with the help of activated carbons prepared from waste materials has also been
reported in the literature (Pala and Tokat, 2002). Various
low cost adsorbents like chitin, chitosan, corn stalks, peat,
rice husk and wood have been used for removal of organic
matter from industrial euent (Hall, 1975; Poots et al.,
1976; George, 1982; Mckay et al., 1980; Annadurai and
Krishan, 1996; Sharma and Sharma, 1994).
Adsorption-based innovative technology (Devi et al.,
2002; Devi and Dahiya, 2006) developed with low cost carbonaceous materials showed good potential, more so for
COD removal from such wastewater. Such adsorption
approach can oer an easy and economic solution to these
environmental challenges. Moreover, activated carbon is
considered very eective in reduction of color, absorbable
organic halides (AOX) and non-biodegradable pollutants
of such wastewater (Mall and Prasad, 1998; Mall and
Upadhyay, 1998) but this process has some additional costs
associated with the production of activated carbon
(Shawwa et al., 2001).
The aim of this study was to assess the potential of Avacado peel carbon in reduction of COD and BOD concentration from coee processing wastewater. For this
purpose, activated carbon prepared from Avacado peel
has been used in the present study to see the feasibility of
adsorbent under batch operation and accordingly, optimum operating conditions have been worked out for the
treatment of coee processing wastewater.
2. Methods
2.1. Materials
The wastewater generated in this coee processing plant
was discharged without treatment to the nearby stream.
For the river, it became a source of pollution as the decomposition of this waste required much of the available oxygen from water which created a high BOD and COD
load in water bodies. It created a lot of health problems

also due to discharge of euents with large volumes of


organic waste. Wastewater samples were taken from this
coee processing plant and these samples were stored at
23 C to avoid any change in their physico-chemical
characteristics.
Adsorbent used in the present study was prepared from
peels of Avacado fruits. The peels of these fruits were initially scraped with a knife to remove all bers present at
surface and then these were crushed using a crushing mill
(Model-BB 100 Rosrfrei, Retsch Germany). The resulting
product was washed several times with distilled water to
eliminate water soluble impurities and then oven-dried at
105 C for 24 h. 250 g small pieces of this oven-dried Avacado peels were mixed with 30 mL of concentrated sulphuric acid (H2SO4). The mixture was carbonized at 600 C for
12 h. Then sample was withdrawn from furnace and cooled
in a desiccator. After cooling, this sample was rinsed several times with distilled water till its pH became 67. The
wet sample was dried at 105 C for 24 h. It was further
crushed and ltered. The particles of size ranging from
0.75 mm to 0.25 mm were recovered and were used
throughout the study. Properties of activated carbon prepared in this way were; surface area of 750 m2/kg, bulk
density 165 kg/m3, porosity 75%, moisture content 8.5%
and carbon content 88%.
Since the raw discarded material was available free of
cost but its transportation and processing costs were to
be taken into account and thus the resulting adsorbent
was expected to be economically viable for the wastewater
treatment. This method was specically eective for removing the organic substances from wastewater. For standardization of the results, same types of experiments were
conducted with commercial activated carbon also. The
commercial activated carbon (Calgon Co-Filtrasorb 400)
was purchased from a local chemical supplier. Some of
its important characteristics prescribed by the manufacturer were; surface area 1000 m2/kg, bulk density 175 kg/
m3, porosity 90%, moisture content 5.8% and carbon content was 85%.
2.2. Methods
The pH and temperature of the wastewater samples
were measured on collection site. Electrical conductance,
turbidity, total solids, total suspended solids, total dissolved solids, BOD, COD and most probable number
(MPN) were analyzed in laboratory according to the methods prescribed by APHA (American Public Health Association, 1998) handbook. In this paper, we have studied the
removal of COD and BOD only. The COD and BOD of
the wastewater samples were measured in laboratory
before and after its treatment with adsorbents.
2.2.1. Batch mode treatment of wastewater samples
All the experiments were carried out at ambient temperature (25 C) in batch mode. The batch experiments were

R. Devi et al. / Bioresource Technology 99 (2008) 18531860

conducted in dierent asks of 250 ml capacity using an


average speed shaker. Adsorption experiments were conducted in dierent batches for all the experimental conditions like adsorbent treatment time, adsorbent dose, pH
of the solution, initial COD and BOD concentrations, agitation speed and adsorbent particle size.
The inuence of various operating parameters were
studied by varying one parameter and keeping others constant. Stirring speed of the shaker was kept constant for
each run throughout the experiment thus ensuring equal
mixing, except for those, which were meant for investigating the eect of agitation speed. The desired pH was maintained using dilute NaOH (0.1 N)/HCl (0.1 N) solutions.
Each ask was lled with a known volume of sample having desired pH and stirring was initiated. The sample was
withdrawn from the shaker at predetermined time intervals, ltered through Whatmann No. 44 lter paper and
analysed for COD and BOD concentrations.
Eect of contact time of the adsorbents with wastewater
sample was investigated by agitating 100 ml sample and
adding 2 g adsorbent for dierent time-periods varying
from 10 to 100 min. Initial COD and BOD concentration
of the sample was 22,000 mg/l and 12,000 mg/l respectively, ph of 7.2, agitation speed 600 rpm and adsorbent
particle size: 60.75 mm. The treated samples were withdrawn from shaker at predetermined time intervals, ltered
and the residual COD and BOD concentrations were
measured.
To determine contribution of the adsorbent dose on
COD and BOD reduction, 100 ml of sample was treated
with dierent doses of adsorbent ranging from 0.1 to
10 g/100 ml, the other conditions were; treatment time of
70 min, ph 7.2, initial COD and BOD concentration of
the sample was 22,000 mg/l and 12,000 mg/l respectively,
agitation speed 600 rpm and adsorbent particle size:
60.75 mm. The samples were agitated for specic time
intervals, ltered and then analyzed for the residual COD
and BOD concentration.
The eect of pH was studied with constant initial concentration, adsorbent dose, and contact time but varying
the pH values from 1 to 12 using dilute NaOH or HCl solution. The samples were agitated for specic time, ltered
and then analyzed for residual COD and BOD concentration and data was tted into Freundlich adsorption isotherm (Faust and Aly, 1986).
The eect of initial COD and BOD concentration was
studied by keeping all other conditions constant except
changing the initial COD and BOD concentration ranging
from 15,000 mg/l to 30,000 mg/l and 3000 mg/l to
18,000 mg/l respectively.
The eect of agitation speed and adsorbent particle size
on the COD and BOD reduction was also studied. As
usual, one parameter is varied for one set of experiments.
Discrete values of the agitation speed kept from 100 rpm
(revolution per min) to 1000 rpm and adsorbent particle
size as category A (60.75 mm), B (60.55 mm), C
(60.35 mm) and D (60.25 mm) respectively.

1855

3. Results and discussions


The physico-chemical analysis of the wastewater collected from the coee processing plant was done as shown
in Table 1. It was evident that this wastewater was polluted
with organic load besides dissolved and suspended matter.
Organic load was presented in terms of COD, BOD and
most probable number (MPN). In this paper, study was
done only for reduction of COD and BOD concentrations
using discarded material-based carbon made up of Avacado peel.
The COD and BOD concentrations were very high compared to their permissible limits to discharge for irrigation
and horticultural uses as prescribed by WHO as shown in
Table 1. The wastewater was treated at 25 C under batch
mode operation with APC and its COD and BOD concentrations were measured before and after treatment with
adsorbent. The important operating parameters taken
under consideration for the present study were; adsorbent
treatment time, adsorbent dose, pH of the medium, initial
COD/BOD concentration of the wastewater, agitation
speed and adsorbent particle size.

3.1. Adsorbent treatment time


The percentage COD and BOD reduction as a function
of treatment time with APC was shown in Fig. 1. Commercial activated carbon (CAC) was taken for comparing the
results. The percentage reduction of COD and BOD with
APC was 83.82% and 85.95% after a treatment time of
70 min whereas the maximum reduction of COD and
BOD concentrations with commercial activated carbon
was 88.5% and 92.52% respectively after a treatment time
of 70 min. As the treatment time progressed, the adsorbent
sites had the tendency towards saturation. Dierence
between the adsorption capacities could be attributed due
Table 1
Physicalchemical properties of euent of coee processing plant along
with WHO permissible limits (1995) for the discharge of treated euent to
irrigation channel
Parameters

Characteristics of
euent

WHO permissible
limits

pH
Electrical conductance (mho/
cm)
Temperature (C)
Turbidity (Nephalometer
Turbidity Unit)
Total solids (mg/l)
Total suspended solids (mg/l)
Total dissolved solids (mg/l)
Chemical oxygen demand
(mg/l)
Biochemical oxygen demand
(mg/l)
MPN (coliform cells/100 ml)

4.5
3.1 104

6.8  8.5
1 103

25
430

20
510

2050
700
1350
22,000

650
200
450
300

12,000

100

1 109

1.5 107

1856

R. Devi et al. / Bioresource Technology 99 (2008) 18531860

95

100

90

90

85

80

% reduction

110

% reduction

100

80
75

70
60
% COD by CAC
% COD by APC

70

% BOD by CAC
% BOD by APC

50

65

% COD by CAC

% BOD by CAC

% COD by APC

% BOD by APC

40

60
0

20

40

60

80

100

30

120

Treatment Time (min)


Fig. 1. Eect of treatment time on % COD and BOD reduction using
APC and CAC adsorbents. Initial COD and BOD concentrations: 22,000/
12,000 mg/l, adsorbent dose: 2 g/100 ml of wastewater, pH: 7, agitation
speed: 600 rpm and particle size of adsorbent: 60.75 mm.

10

11

12

Fig. 2. Eect of adsorbent dose on % COD and BOD reduction using


APC and CAC adsorbents. Initial COD and BOD concentrations: 22,000/
12,000 mg/l, treatment time: 70 min, pH: 7, agitation speed: 600 rpm and
particle size of adsorbent: 60.75 mm.

5.5

Freundlich adsorption isotherm for COD concentration reduction by APC

log x/m

3.2. Adsorbent dose

where, x/m (mg/g) was the amount of COD and BOD removed (x) per unit mass of adsorbent (m), Ce (mg/l) was
residual COD and BOD concentration of aqueous solution, k and 1/n were Freundlich constants and measure
of adsorption capacity and adsorption intensity
respectively.
The Freundlich isotherm corresponding to the experimental measurements for APC and CAC were plotted on
log scales as shown in Figs. 3 and 4 respectively. Values
of regression coecient (r2) had been calculated from the
linear t and based on the t, the respective values of the
slope 1/n and intercept on y-axis taken as k were also calculated. Values of 1/n, k and regression coecient r2 for
APC were 0.2401, 4.7786 and 0.8636 corresponding to

Adsorbent dose (g/l)

to the dierence in number of carbonaceous adsorption


sites in the dierent adsorbents.

y = -0.2401x + 4.7786
2
R = 0.8636

4.5
4
3.5

COD by APC

3
2.5

Linear (COD by APC)

log Ce
Freundlich adsorption isotherm for BOD concentration reduction by ApC

log x/m

The eect of adsorbent dose on percent reduction of


COD and BOD concentrations with APC and CAC was
shown in Fig. 2. Here the treatment time was kept constant
at 70 min. Equilibrium was reached corresponding to 4 g/
100 ml of adsorbent dose for both APC as well as CAC.
Percent reduction of BOD concentration was greater than
that of COD concentration for all the adsorbent doses and
was also comparable to CAC.
The adsorption studies conducted at xed initial COD
and BOD concentration and varying adsorbent dose were
tted to Freundlich isotherm (Faust and Aly, 1986) of
the form:
x
kC 1=n
e
m

5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0

y = -0.2497x + 4.5886
2
R = 0.8645

BOD by APC
Linear (BOD by APC)

log Ce
Fig. 3. Freundlich plot for COD and BOD reduction using APC
adsorbent. Initial COD and BOD concentrations: 22,000/12,000 mg/l,
treatment time: 70 min, pH: 7, agitation speed: 600 rpm and adsorbent
particle size: 60.75 mm.

COD concentration reduction and 0.2497, 4.5886 and


0.8645 corresponding to BOD concentration reduction
respectively and those for CAC were 0.02658, 4.9472
and 0.8435 corresponding to COD concentration reduction
and 0.2698, 4.7302 and 0.8599 corresponding to BOD
concentration reduction respectively. CAC and APC had
the comparable values of 1/n and k. So APC showed the

R. Devi et al. / Bioresource Technology 99 (2008) 18531860

1857

Freundlich adsorption isotherm of COD concentration reduction by CAC


5
y = -0.2658x + 4.9472
2
R = 0.8435

90

3.5
COD by CAC
Linear (COD by CAC)

3
2.5
2

log Ce

% reduction

log x /m

4.5

70

Freundlich adsorption isotherm of BOD concentration reduction by CAC


5

50

log x /m

4.5

y = - 0.2698x + 4.7302
2
R = 0. 8599

% COD by CAC

% BOD by CAC

% COD by APC

% BOD by APC

3.5

30

2.5
2
1.5

BOD by CAC
Linear (BOD by CAC)

log Ce

pH

10

12

14

Fig. 5. Eect of pH on % COD and BOD reduction using APC and CAC
adsorbents. Initial COD and BOD concentrations: 22,000/12,000 mg/l,
treatment time: 70 min, adsorbent dose 4 g/100 ml, agitation speed:
600 rpm and particle size of adsorbent: 60.75 mm.

Fig. 4. Freundlich plot for COD and BOD reduction using CAC
adsorbent. Initial COD and BOD concentrations: 22,000/12,000 mg/l,
treatment time: 70 min, pH: 7, agitation speed: 600 rpm and particle size
of adsorbent: 60.75 mm.
100

3.3. pH
The eect of pH on the adsorption capacity of CAC and
APC and hence COD concentration and BOD concentration reduction from wastewater was shown in Fig. 5. The
optimum pH for maximum adsorption of organic impurities and COD concentration and BOD concentration
reduction from wastewater of coee processing plant by
CAC and APC was 7.
3.4. Initial COD concentration and BOD concentration
The eect of initial COD and BOD concentration of the
wastewater solution on the percent COD and BOD reduction by CAC and APC was shown in Fig. 6. The percent
COD concentration and BOD concentration reduction
with APC and CAC was found to increase with increase
in the initial COD concentration and BOD concentration
and after reaching to saturation levels, it started decreasing. The rate of adsorption increased because of the
increasing driving force. But at 24,000 mg/l of initial

90
80

% reduction

comparable adsorption capacity and adsorption intensity


with CAC.
The constant 1/n and k are of denite importance in
determining the adsorption capacity of organic pollutants
from wastewater and reduction of COD and BOD concentrations by adsorbents. The slope 1/n is dependent on the
order of the change of reduction in COD and BOD concentrations with the adsorbent dose, while k is dependent on
the extent of removal of COD by the adsorbents.

70
60
50
40
30
2000

7000

12000

% COD by CAC

% BOD by CAC

% COD by APC

% BOD by APC

17000

22000

27000

32000

Initial COD and BOD Concentration


Fig. 6. Eect of initial COD and BOD concentration on % COD and
BOD reduction using APC and CAC adsorbents. Treatment time: 70 min,
adsorbent dose 4 g/100 ml, pH: 7, agitation speed: 600 rpm and particle
size of adsorbent: 60.75 mm.

COD concentration and 12,000 mg/l of initial BOD concentration, the curves reached their saturation points. It
was because of saturation of adsorbent sites and hence
the ratios of the initial number of adsorbate molecules to
the available adsorption sites of the adsorbent diminished
accordingly.
3.5. Agitation speed
To investigate the eect of agitation speed on % COD
and BOD reduction with APC and CAC, the agitation
speed was kept from 100 rpm to 1000 rpm. Fig. 7 showed

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R. Devi et al. / Bioresource Technology 99 (2008) 18531860

110

Table 2
Eect of adsorbent particle size on % COD and BOD reduction by APC
and CAC

100

Adsorbent
particle size

APC
% COD
reduction

% BOD
reduction

% COD
reduction

% BOD
reduction

A (60.75 mm)
B (60.55 mm)
C (60.35 mm)
D (60.25 mm)

50.34
67.89
89.25
98.20

58.22
73.76
91.45
99.18

57.89
72.54
93.56
99.02

63.78
79.89
94.05
99.35

% reduction

90

80

CAC

70

60

50
50

250

% COD by CAC

% BOD by CAC

% COD by APC

% BOD by APC

450

650

850

Table 3
Residual COD and BOD concentration after treatment with APC and
CAC under batch mode operation
Adsorbents

Residual COD
concentration

Residual BOD
concentration

APC
CAC

296
215.6

98.4
78.0

1050

Agitation speed (rpm)


Fig. 7. Eect of agitation speed on % COD and BOD concentration using
APC and CAC adsorbents. Initial COD and BOD concentrations: 22,000/
12,000 mg/l, Treatment time: 70 min, adsorbent dose 4 g/100 ml, pH: 7
and particle size of adsorbent: 60.75 mm.

that there was a good trend for the percent COD and BOD
concentration reduction with the agitation speed for CAC
and APC. Maximum COD concentration and BOD concentration reduction were observed around 600 rpm for
both the adsorbents. But at higher agitation speeds, the
loosely attached molecules might re-enter into the adsorbate, hence lowering the % COD concentration and %
BOD concentration reduction. Therefore, we kept the agitation speed at 600 rpm to see the eect of percent COD
and BOD concentration reduction by both the adsorbents.
3.6. Adsorbent particle size
For observing the eect of adsorbent particle size on %
COD concentration and % BOD concentration reduction
of wastewater, they have been segregated in four categories
starting with A as A (60.75 mm), B (60.55 mm), C
(60.35 mm) and D (60.25 mm). From the study, it was
found that adsorbent particle size had signicant inuence
on percent reduction of COD and BOD concentration with
APC and CAC. The percent COD and BOD concentration
reduction for both the adsorbents were maximum for particle size of category D and the minimum reductions in
COD and BOD was obtained corresponding to particles
of category A for both the adsorbents as shown in Table
2. The values for maximum % COD concentration and %
BOD concentration reduction with APC and CAC were
98.20% and 99.18% and 99.02% and 99.35% respectively
corresponding to category D. It was observed that smaller
particles showed better adsorption than the larger ones
because surface area is directly related with adsorption
capacity. This could be explained on the basis of net surface area as smaller particles in a given quantity of powder

The optimum operating conditions were; treatment time: 70 min, adsorbent dose: 4 g/100 ml of euent, pH: 7, Initial COD and BOD concentrations: 24,000/12,000, agitation speed: 600 rpm and adsorbent particle
size: 60.25 mm.

would have larger surface area than the case when bigger
particles are taken.
3.7. Optimum operating conditions for maximum COD and
BOD reduction
We tried to obtain conditions for the maximum reduction of COD and BOD concentration for both the adsorbents. The optimum operating conditions for getting
maximum COD/BOD concentration reduction from coee
processing euent with APC and CAC were same and
these conditions were; treatment time: 70 min, adsorbent
dose: 4 g/l00 ml, pH: 7, initial COD/BOD concentration:
22,000/12,000 mg/l, agitation speed: 600 rpm and adsorbent particle size: 60.25 mm. It could be inferred from
the experimental results presented in this paper that residual concentrations of COD and BOD after treatment with
APC under optimum operating conditions were 396 mg/l
and 98.4 mg/l respectively and were well within the permissible limits of WHO standards as shown in Table 3. These
results could be utilized for working out the design parameters of an adsorption based industrial wastewater treatment system. Moreover, if APC was added in secondary
treatment tank for the euent treatment, there would be
a good saving of energy, which otherwise could hence been
consumed in aeration process.
4. Conclusion
Present study showed that APC is eective for reduction
of COD and BOD concentration from euent of coee
processing plant. Adsorption of COD and BOD was found

R. Devi et al. / Bioresource Technology 99 (2008) 18531860

to be dependent on treatment time, adsorbent dose, pH,


initial COD and BOD concentration, agitation speed and
adsorbent particle size. The studied adsorption data tted
well to Freundlich Adsorption Model. This adsorbent
made up of Avacado peel could be a good alternative to
expensive activated carbon and hence wastewater treatment process can become very economical. The quality of
water after treatment was found to be suitable for irrigation use and for direct discharge into the streams.
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