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Radiation Physics and Chemistry 59 (2000) 399404

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Radiolytic dechlorination of PCBs in presence of active


carbon, solid oxides, bentonite and zeolite
V. Mucka a,*, R. Silber a, M. Posp s il a, M. Camra b, B. Barton cek c
a

Faculty of Nuclear Sciences and Physical Engineering, Czech technical University, 115 19 Prague 1, Czech Republic
b
Tesla V. T. Mikroel Ltd, 180 72 Prague, Czech Republic
c
Nuclear Research Institute plc, 250 68 Rez, Czech Republic
Received 7 February 2000; accepted 8 May 2000

Abstract
The inuence of various solids on the radiation dechlorination of polychlorinated biphenyls using electron beam
radiation was investigated. Some of the promoters exhibited a positive eect on the radiation dechlorination with a
maximum at a determined amount of solids. Some of them exhibited a pronounced negative eect in dechlorination
reaction. 7 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Polychlorinated biphenyls; Dechlorination; Irradiation; Electron beam; Promoters

1. Introduction
All chloro-organic compounds, inclusive of polychlorinated biphenyls (PCBs), are hazardous compounds. Hence, the eective methods for their
destruction are desired (the conventional method
incineration at temperatures greater than 11008C
seems to be rather expensive and dangerous if the temperature is lower than the above mentioned values).
The radiation treatment of the PCBs seems to be one
of the most promising methods for this purpose. Hydroxyl radicals created during the radiolysis of water
may degrade the PCBs, which are only sparingly soluble in aqueous solutions, under the irradiation by oxidative attack. This method may be useful for a
remediation of groundwater slightly polluted (of the

* Corresponding author. Tel.: +420-2-231-5212; fax: +4202-232-0861.


E-mail address: mucka@br.fj.cvut.cz (V. Mucka).

order from ppm to ppb) with chlorinated organic compounds. But, as it was shown (Gehringer et al., 1992),
water radiolysis alone is not sucient for eective
degradation of chlorinated pollutants in water. Therefore, seeking for some apt promoters for the production of OH-radicals in irradiated aqueous solution
seems to be one of the most actual tasks. The ozone
dissolved in the polluted water was found (Gehringer
et al., 1992, 1995; He et al., 1997) to be a high eective
promoter for oxidative radiation destruction of the
chlorinated substances presented in water solution.
This is because all reducing species formed during irradiation lead to ozone decomposition into OH-radicals. The PCBs radiolysis in isooctane, proceeding by
reductive, rather than oxidative processes, was performed (Mincher et al., 1996) in the presence of ozone.
But, unlike the aqueous solutions, the PCBs decomposition in the alkane solution was inhibited by ozone
probably because of the ozoneelectron capture reaction. The OH-radicals resulting from this reaction are

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V. Mucka et al. / Radiation Physics and Chemistry 59 (2000) 399404

likely to be scavenged by the solvent before they can


react with the PCBs.
A degradation of chlorinated organic compounds
(2,3,7,8-tetrachlorodibenzo-p-dioxin TCDD) in a
water containing system may be protected (Hilarides et
al., 1994; Gray and Hilarides, 1995) by a non-ionic
surfactant. This method, suggested for remediation of
contaminated soil, appears to be not only technically
feasible but it may also be economically competitive. A
full dechlorination of PCBs after g-irradiation of aqueous micellar system, containing the Triton X-100 as a
surfactant, was observed (Schmelling et al., 1998) even
if the reaction rate was found to be lower than in the
homogeneous system. A greater fraction of solvated
electrons probably reacts with the surfactant than with
the PCBs. A signicant increases in both PCBs
dechlorination yields and degradation rates were found
(Schmelling et al., 1998) in an aqueousmethanol solution using the carbonate buer as a promoter of the
reaction which reduces concentrations of H3O+-ions
and, thereby, limits scavenging of solvated electrons by
H3O+-ions.
The PCBs dechlorination has been studied intensively in 2-propanol alkaline solution where the g-irradiation (Sawai et al., 1974; Singh et al., 1985) or the
accelerated electrons (Mucka et al., 1997) initiate a
chain reaction which does not occur in neutral 2-propanol (Mincher et al., 1996) solution. The Gi(Cl)values for tetrachloroethylene (PCE) and PCBs irradiated with accelerated electrons in a large volume
ow-through equipment were found to be (Mucka et
al., 1999) from about 250 to 850 and 100 [102eV1],
respectively. The G (Cl) values sharply decrease with
increasing dose of irradiation and so the eciency of
dechlorination was found to be lowered (Mucka et al.,
2000, 1999). This represents a serious problem from
the point of view of industrial utilization of the radiation method. One of the possible solutions of this
problem may be the application of suitable promoters
(Mucka et al., 1999). Yamamoto and Tagawa (1998)
found that dehalogenation of the CFC-113 is promoted by the molecular sieve and the reaction proceeds by a chain mechanism when 2-propanol is
adsorbed on the molecular sieve 13X together with the
CFC-13. Similarly, the radiation degradation of various pesticides followed by their adsorption on granular activated carbon proved to be better (Dessouki et
al., 1999) than the conventional methods of waste
water purication. Therefore, it is of interest to investigate the inuence of various solids (active carbon,
some solid oxides, bentonite and zeolite) on the radiation dechlorination of PCBs in alkaline 2-propanol
solution initiated by EB-irradiation.

2. Experimental
All dechlorinations were performed with the solutions of commercial mixture of polychlorinated biphenyls (DELOR 103) in 2-propanol of technical purity or
of analytical grade (0.5 vol. %) saturated with kalium
hydroxide (0.8 mol l1). The solutions of PCBs (100
ml) were introduced into the at polyethylene vials (c.
100 ml), in the most cases leached with the alkaline 2propanol for 24 h before use. The solutions were deaerated by means of bubbling with nitrogen gas (10
min) and irradiated with 4.5 MeV electrons (Mucka et
al., 1997) with the dose of 8 kGy under intense magnetic stirring. The solid modiers (Table 1) were introduced into the deaerated solutions before irradiation.
The samples containing the modiers were irradiated
simultaneously with those without modiers. Some of
the modiers were, before their use, heat-treated at
2008C for 4 h in air or at 1038C under vacuum for 1
h. The X-ray diraction method was used for determination of the crystal structure of some modiers and
the nitrogen-adsorption at low temperature (N2 (l)) was
used for estimation of their surface area values. Determination of Cl ions in irradiated samples was performed by argentometric as well as by mercurymetric
titration in aqueous solutions after evaporating of organic liquid phase. A degree of dechlorination was calculated as a ratio 100 mKCl/a mKCl; mKClPis the
experimentally measured amount of KCl and
mKCl
is theoretically presumed total amount of KCl which
would be created after total dechlorination of PCBs
containing on the average three Cl-atoms in each molecule of PCB (Mucka et al., 1997). The following expression was used for description of the eect D of
modiers: D% 100m m0 =m0 where m and m0
are the measured amounts of KCl in the irradiated solutions with and without modier, respectively.

Table 1
The purity and specic surface area values S (m2 g1) of the
solids used as promoters in radiation dechlorination of PCBs
Promoter

Purity

S (m2 g1)

Active carbon
Active carbon
Cu2O
PbO
PbO
TiO2
NiO
Bentonite
Zeolite

Analytical grade
Technical purity
Analytical grade
Analytical grade
Technical purity
Technical purity
99.7 wt.%
Technical purity
Technical purity

381.5
865.8
0.4
0.3
0.4
49.1
13.0
153.1
9.0

V. Mucka et al. / Radiation Physics and Chemistry 59 (2000) 399404

Fig. 1. Dependence of degree of dechlorination a (%) of


PCBs solutions on the dose of irradiation D (kGy) for the
undeaerated samples stored for 2 (a ) or 7 (b ) days and for
the deaerated samples (c ) previously stored for 7 days.

3. Results and discussion


Fig. 1 gives evidence that deaeration of the samples
(containing again the 2-propanol of technical purity)
for 10 min with nitrogen gas increases the degree of
dechlorination of PCBs similarly as it was found earlier (Mucka et al., 1997). Further experiments (performed with the 2-propanol of analytical grade)
showed with the relative standard deviation of 2 3.5%
that the degree of dechlorination did not depend on
the time of deaeration (Table 2, column a). The irradiation of PCBs in alkaline 2-propanol solution deaerated for 10 min was performed in the polyethylene
vials which were earlier leached with alkaline 2-propanol for various time. A comparison of the values
obtained in these experiments (Table 2, column b) with

401

those performed after just a storage of the samples for


various time periods (Table 2, column a) showed a
slight increase in dechlorination degree (the average
degree of dechlorination of 43:8%25:8%). Moreover,
as it can be seen from Table 2, column b, a time
period of leaching had no measurable eect on the
degree of dechlorination.
The degrees of radiation dechlorination of deaerated
alkaline 2-propanol (analytical grade) solutions of
PCBs at presence of various amount of untreated or
heat treated active carbon (analytical grade) performed
in unleached and standardly leached polyethylene vials
are presented in Fig. 2. It seems to be clear that, similarly as in the case of homogeneous system (without
modier), the leaching of the polyethylene vials led to
higher dechlorination degrees at all amounts of active
carbon used (i.e. from 0 to 1 g). Therefore, all further
irradiations were performed in polyethylene vials leached (24 h) before used with the alkaline 2-propanol
solution owing to eliminate possible inuence of some
foreign substances on the radiation reaction under
study.
A comparison of the curves a and A as well as b
and B in Fig. 2 gives evidence that the heat treatment
of the active carbon did not lead to measurable eect.
As it can be seen from Fig. 2, all dependences presented here (inclusive the dependence A' for the active
carbon of chemical purity) possess an unmonotonous

Table 2
Degrees of dechlorination a (%) (0 a, b ); (1) in the samples
deaerated for various time periods t (min) (a ); (2) in the vials
earlier leached with alkaline 2-propanol solution (b ) for various time intervals t (h)
t (min)

a (%)

10
20
30
40
50
60

32.0
32.7
34.4
33.1
31.4
32.0

t (h)
6
12
48
120

b (%)
41.8
43.8
45.9
43.8

Fig. 2. Dependence of degree of dechlorination a (%) on the


amount of untreated (a, b ) and heat treated in vacuum (A, B )
analytical grade active carbon mC (g). a, A and b, B process performed in leached and unleached vials, respectively.
A ' the same as A but for the active carbon of chemical
purity.

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V. Mucka et al. / Radiation Physics and Chemistry 59 (2000) 399404

feature with a reproducible maximum at about 0.1 g of


active carbon. The positive eect D on the dechlorination reaction at this amount of active carbon reached
the values from 20 to 30% (Fig. 3). The unmonotonous character of the dependences presented here gives
evidence that at least two antagonistic processes occur
on the surface of the active carbon. The rst one, leading to increasing D-values, may be connected with a
higher eciency of dechlorination of PCBs adsorbed
on the surface of the promoter. This process is probably due to the energy transfer from accelerated electrons to the adsorbed molecules via the solid phase
(Yamamoto and Tagawa, 1998). The second one,
observed at higher amount of promoter, causes an inhibition of the radiation dechlorination. The inhibition
of the reaction may be due to the recombination of the
radicals, taking place in the reaction mechanism, on
the surface of the solid phase. As it also can be seen
from Fig. 3, the heat treatment of the active carbon at
2008C in nitrogen atmosphere led to a slight decrease
in the positive eect D (Fig. 3, point 1). The same
eect was found with the sample earlier impregnated
with the solution of hexachloroplatinic(IV) acid (2 vol.
%) and subsequently heat-treated at 2008C in hydrogen atmosphere (Fig. 3, point 3). The heat treatment
of the unimpregnated sample at 2008C in hydrogen atmosphere sharply decreased the positive eect D
(Fig. 3, point 2).
The same unmonotonous feature of the dependence

Fig. 3. As in Fig. 2 but for the quantity D (%); designation of


the separate points: 1 and 2 promoters heat treated at
2008C in N2-and H2-atmosphere, respectively, 3 as the
point 2 but for the active carbon previously treated with
H2PtCl6 acid.

of degree of dechlorination on the amount of promoter


was found also for the cuprous oxide containing a
small amount of copper detected by X-ray diraction.
The maximum was found at about 0.4 0.8 g of
cuprous oxide (Fig. 4, curve 1). The quantity D
reached in this case, analogously as with active carbon,
values of about 30% (Fig. 4, curve 2). Owing to about
of three orders lower surface area value of the Cu2O
oxide than the surface area values of active carbons
(Table 1), it can be assumed that the surface area
values of the modiers do not inuence their promoting eect.
As it can be seen from Fig. 5a, the degree of
dechlorination a in presence of 0.1 g of active carbon
rises up linearly with increasing a0-values (straight line
1 with regression factor of 0.9114. The a0-value represents the degree of dechlorination in liquid homogeneous phase, i.e. in the system without any
modier). The straight line 1, described by equation
a 0:99a0 8:61, is parallelly shifted to higher avalues owing to the straight line 0 a a0 representing
a zero eect of the promoter. The constant mutual
shift of the straight lines 0 and 1 (+ 8.61%) leads to
linear decrease in D-values (with regression factor of
0.8140) with increasing a0-values (Fig. 5a, curve 2).
This constant shift represents the invariable inuence
of 0.1 g of promoter on the radiation dechlorination
process. An analogous situation was found for the
Cu2O-promoter (Fig. 5b) where the regression factors
0.9054 and 0.8917 were found for the straight lines 1
and 2, respectively, and the shift of the straight line 1
vs straight line 0 was found to be about of 13.18%.

Fig. 4. Dependence of the degree of dechlorination a (%) (1)


and the D-values (%) (2) on the amount of cuprous oxide
mCu2O (g).

V. Mucka et al. / Radiation Physics and Chemistry 59 (2000) 399404

403

Fig. 5. (a) Dependence of degree of dechlorination a (%) (1) and the D-values (%) (2) in presence of 0.1 g of active carbon on the
degree of dechlorination a0 (%) for the homogeneous system; 0 straight line a a0 corresponds to the zero eect of the promoter. (b) As in (a) but for 1 g of Cu2O promoter.

The inuence of various other solids (Table 1) on


the radiation dechlorination of PCBs under the standard conditions was investigated. The TiO2-oxide as
well as the bentonite had no pronounced eect on the

Fig. 6. Dependence of the D-values (%) on the amount mP (g)


of following promoters: TiO2-oxide (1), bentonite (2), zeolite
(3) and NiO-oxide (4).

radiation dechlorination at any amount of promoters


(Fig. 6, curves 1, 2). Because the specic surface area
value for bentonite was about three times higher than
that for the TiO2-oxide (Table 1), here it can be also
assumed that the surface area value of the modier is
not directly connected with the ability of the solid to
aect the radiation dechlorination process. The zeolite
showed a negative eect of about 25% (Fig. 6, curve
3) and the NiO-oxide monotonously decreased the
degree of dechlorination of PCBs (Fig. 6, curve 4) with
increasing amount of the oxide D 45% at about
3 g of the NiO-oxide). An extremely high negative
eect was found for the PbO-oxide (Fig. 7A) of analytical grade as well as of technical purity which was
able to stop the radiation process at very low amount
of the oxide (about 0.1 g). A pronounced negative
eect on the reaction under study was also found
using the water as an additive component. Its inhibiting eect at low concentrations (up to about 2 vol. %)
was found to be negligible (Mucka et al., 1997). The
negative eect rises up with increasing content of
water so that at about 8 and 50 vol. % H2O the Dvalues reached about 50 and 95%, respectively
(Fig. 7B). It might be possible that the electrons are
scavenged by the water. Simultaneously, an oxidative
mechanism of dechlorination with much lower Gvalues takes place (Mincher et al., 1996) at a high content of water in the system instead of reductive one
proposed for radiation dechlorination in alcoholic solution (Singh et al., 1985).

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V. Mucka et al. / Radiation Physics and Chemistry 59 (2000) 399404

References

Fig. 7. (A). Dependence of degree of dechlorination a (%) (1,


1') and the D-quantity (%) (2, 2 ') on the amount of the PbOoxide mPbO (g) of analytical grade (1, 2) and of technical
purity (1', 2'). (B) As in (A) but for the water added to the
system before irradiation.

4. Conclusions
1. A signicant positive inuence of active carbon and
Cu2O oxide on the radiation dechlorination of
PCBs in alkaline 2-propanol solution was proved.
2. Pronounced negative eects of PbO and NiO oxides
as well as partially of zeolite were found in the reaction under study.
3. The eect of solids depends on the amount of promoters presented in irradiated system. This dependence may be monotonous or unmonotonous
possessing a signicant maximum at a determined
amount of the promoter.

Acknowledgements
This work was performed under the auspices of the
Grant Agency of the Czech Republic, Contract No.
104/98/0466.

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