ARTICLE IN PRESS

Water Research 38 (2004) 309–316

Radiation-induced degradation of polyvinyl alcohol in

aqueous solutions
Shu-Juan Zhang, Han-Qing Yu*
Laboratory of Environmental Engineering, Department of Chemistry, University of Science and Technology of China, Hefei,
Anhui 230026, PR China
Received 5 December 2002; received in revised form 12 June 2003; accepted 17 September 2003

Abstract

The degradation of polyvinyl alcohol (PVA) by g-ray irradiation was investigated. Degradation efficiency of PVA
was influenced by several factors, such as initial PVA concentration, dose rate, pH, and the addition of H2O2. The
degradation kinetics depended on initial PVA concentration and dose rate. At a relatively lower PVA concentration,
e.g., 180 mg/L, and a higher dose rate, e.g., 55.7 Gy/min, the degradation followed pseudo-first-order kinetics. On the
contrary, at a higher PVA concentration, e.g., 500 mg/L, but a lower dose rate, e.g., 12.1 Gy/min, a pseudo-zero-order
reaction occurred. The removal of PVA was more effective under acidic or alkaline conditions than that under neutral
conditions. At a certain dose rate there was an optimal dosage of H2O2 to facilitate the degradation of PVA. For
instance, at a dose rate of 17.2 Gy/min, the optimal H2O2 dosage was found to be about 2.5 mmol/L. Radical
scavenging experiments, total organic carbon determination, and FTIR analysis on the degradation products
demonstrated that PVA radiolysis was initiated by dOH and Hd, leading to chain scission and formation of ketones/
enols. Ultimately, complete mineralization of PVA was achieved.
r 2003 Elsevier Ltd. All rights reserved.

Keywords: PVA; g-ray; Degradation; Irradiation; Mechanisms

1. Introduction or even in some cases impossible, for the biological

Polyvinyl alcohol (PVA), a well-known water-soluble
polymer, is widely used as warp sizing and paper coating
agents, adhesives, and films. The global production of
PVA is about 650 000 tons/year, and the large amount of
discharged PVA from industrial effluents has become a
significant pollution problem [1]. Conventional biologi-
cal technologies are not efficient for the degradation of
PVA because the PVA-degrading capacity of most
microorganisms is very limited [1–5]. Using mixed
cultures acclimated by PVA, only about 40% of PVA
was mineralized after 48-day incubation [2]. Further-
more, much foam is formed when PVA-rich wastewater
is treated in biological reactors, making it very difficult,
*Corresponding author. Tel.: +86-551-3607592; fax: +86-
551-3601592.
E-mail address: hqyu@ustc.edu.cn (H.-Q. Yu).
processes to operate steadily and achieve satisfactory
results [6]. Therefore, effective methods for the removal
or pretreatment of PVA from wastewater need to be
pursued.
A considerable amount of research work on the
degradation of PVA has been carried out, most of which
has focused on photochemically initiated degradation
processes [7–9]. Those processes are often initiated by
dOH, which is generated during illumination with band-
gap radiation. At an iron (II)/PVA-unit mol ratio of
1:20 and a stoichiometric H2O2/PVA-unit ratio, ap-
proximately 90% of dissolved organic carbon with an
initial concentration of 200 mg/L was mineralized within
30 min under UV-irradiation at a temperature of
4072
C [7]. An investigation into TiO2 mediated
photocatalytic degradation of PVA showed that in the
presence of TiO2 and UV light, 55.3% of PVA with an
initial concentration of 30 mg/L was degraded after 1 h

0043-1354/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2003.09.020
 ARTICLE IN PRESS
310 S.-J. Zhang, H.-Q. Yu / Water Research 38 (2004) 309–316
[9]. Other physico-chemical methods have been reported
for the degradation of PVA. For example, an investiga-
tion into ultrasonic depolymerization of PVA showed
that ultrasonication reduced the molecular weight of
PVA simply by splitting the most susceptible chemical
bonds without causing any changes in the chemical
nature of the polymer [10]. Direct oxidation of PVA by
KMnO4 in alkaline solutions resulted in the formation
of polyvinyl ketones as the final products [11].
From application point of view, the methods men-
tioned above have obvious disadvantages, either low
efficiency or high cost. Therefore, effective methods for
the treatment of PVA-rich wastewaters are still in need.
Ionizing radiation has proven to be promising for the
degradation of biorefractory substances [12–15]. As a
consequence of the interaction between ionizing radia-
tion and aqueous solutions, several primary species
(dOH, e aq ; Hd) are formed. These species, especially
dOH, are very reactive and can initiate the degradation
of many types of pollutants in wastewaters. Utilizing g-
ray irradiation to treat wastewaters has some advantages
over other methods: a complete degradation of pollu-
tants can be achieved without consumption of any
chemicals and resulting in no further pollution providing
that irradiation dose is sufficient [12].
The irradiation of PVA has been studied due to its
high hydrophilicity, stability, and biocompatibility
[12,16–19]. However, information about the effects of
irradiation parameters on the degradation of PVA in
aqueous solutions is still sparse. Therefore, radiation-
induced degradation of PVA under various conditions
was investigated in this work. The influences of several
factors, such as initial PVA concentration, dose rate,
pH, and addition of H2O2, on the degradation efficiency
were evaluated. In addition, the mechanisms behind the
radiolytic degradation of PVA were proposed.
2. Materials and methods
2.1. Materials
PVA (the average polymerization degree=1750750),
boric acid, iodine, potassium iodide, sodium hydroxide,
perchloric acid, hydroxy peroxide (H2O2), 2-propanol
(2-PrOH), and tert-butanol (t-BuOH), purchased from
Shanghai Chemical Reagent Company, were of the
highest purity commercially available and were used for
experiments without further purification. All samples
were prepared in doubly distilled water.
2.2. Irradiation experiments
A 60Co-g-source with an activity of about 30 kCi
(1.11  1015 Bq) was used for irradiation. All irradiation
experiments were carried out in a radiation field
Fig. 1. Schematic diagram of radiation field.
schematically shown in Fig. 1. The dose rates varied
with the distance between 60Co column and dose dots.
The dose rates of the dots in concentric circles to 60Co
column were even and were determined by means of a
Fricke-dosimeter using G (Fe3+)=15.6. G-value is
defined as the number of formed or decomposed
molecules per 100 eV absorbed energy. For conversion
into SI-units, multiplying the G-value by 0.10364 results
in GðxÞ value in mmol/J. The samples were irradiated in
100-mL Pyrex glass vessels at certain dose rates and
sampled at certain time intervals. All experiments were
performed at ambient temperatures.
2.3. Analytical methods
Quantitative determination of PVA in aqueous
solutions was carried out by a UV–Vis spectrophot-
ometer (UV751-GD, Shanghai Analytical Instrument
Co.) after addition of boric acid and iodine solutions
according to the procedure described by Finley [20].
Calibration curve was obtained by plotting the absor-
bance value at 690 nm against PVA concentration.
Absorption spectra were measured with another UV–
Vis spectrometer (UV-2401PC, Shimadzu Co.). The
average degree of polymerization of PVA before and
after irradiation was determined using an Ubblehode
meter according to the procedure described by Finch
[21]. The pH of the solutions was adjusted with
appropriate amount of sodium hydroxide or perchloric
acid solutions and was determined by a pH meter (pHS-
25, Shanghai Scientific Instrument Co.). The total
organic carbon (TOC) concentration was determined
using a TOC analyzer (TOC-VCPN, Shimadzu Co.).
Analysis of final products was carried out using an
EQUINOX-55 FTIR spectrometer (Brucker Co.). Pre-
treatment of the analysis samples prior to FTIR
measurement was carried out according to the following
procedure: PVA aqueous solutions before and after
irradiation were dried in an oven at 105
C. The residue
was grounded with KBr and was pressed at 40 MPa to
form a uniform disk.

S.-J. Zhang, H.-Q. Yu / Water Research 38 (2004) 309–316
3. Results and discussion
3.1. Radiolytic degradation of PVA aqueous solution
A PVA solution with an initial concentration of
200 mg/L was irradiated at a dose rate of 19.6 Gy/min.
Fig. 2 illustrates the evolution of the absorption spectra
of PVA–iodine complex as a function of irradiation
time. A significant decrease of the optical density of
PVA–iodine complex was observed, and the absorption
peak gradually shifted to shorter wavelength with
irradiation time, which was attributed to the dependence
of the molar extinction coefficient of PVA–iodine
complex on the molecular weight [3]. This result
indicates that the molecular weight of PVA effectively
reduced through endocleavage of polymer chains during
g-ray irradiation. Viscosity determination of PVA
aqueous solutions showed that the average degree of
polymerization of PVA was reduced from 1793 to 102
after 117-min irradiation at a dose rate of 66.3 Gy/min,
providing further support for the chain scission.
Fig. 3 illustrates the TOC reduction of PVA aqueous
solutions as a function of irradiation time. Within the
initial 10-h irradiation, no TOC reduction was observed,
whereas nearly 40% and 80% TOC reduction were,
respectively, achieved after 1- and 2-day irradiation. On
the other hand, the irradiated solutions presented a
strong optical absorption in the region of around 280 nm
due to n-p transitions of carbonyl groups. A yellow
color increased gradually with irradiation time in the
initial 10 h, and then weakened until the solutions
became non-colored again. This result, together with
TOC analysis, demonstrates that complete mineraliza-
tion of PVA can be achieved by g-ray irradiation after
chain scission and formation of ketones, and that the
efficiency of PVA radiation degradation is much higher
than that of biodegradation. Furthermore, the chain
0.8
initial
15 min
30 min
0.6
60 min
Absorbance
90 min
150 min
0.4
0.2
0.0
450 500 550 600 650 700
Wavelength (nm)
Fig. 2. Absorption spectra of PVA–iodine complex evolution
versus irradiation time (initial PVA concentration: 200 mg/L;
dose rate: 19.6 Gy/min).
ARTICLE IN PRESS
311
100
80
TOC reduction (%)
60
40
20
0
0 1 2 3 4 5
Irradiation time (days)
Fig. 3. TOC reduction of PVA aqueous solutions versus
irradiation time (initial PVA concentration: 250 mg/L; dose
rate: 100.0 Gy/min).
scission rate of PVA induced by g-ray irradiation was
significantly faster than that by biodegradation. In
biological processes, the PVA degradation pathways
were proven to be oxidation by oxidative-type enzymatic
systems with formation of carbonyl groups along the
polymer chain [2]. Activated b-diketones or a-keto
groups are subsequently hydrolyzed with fission of the
polymer carbon backbone. The fission of main chain
seems to be the rate-limiting step in PVA biodegrada-
tion. Therefore, a two-step system, utilizing ionizing
radiation to convert the long-chain PVA into small
fragments with ketones group followed by biological
processes, should be a promising method for the
treatment of PVA-rich wastewaters.
3.2. Effect of initial PVA concentration and dose rate on
PVA degradation
Both initial PVA concentration and dose rate are
critical factors determining the degradation of PVA
during g-ray irradiation. The effects of these two factors
on the PVA degradation kinetics are, respectively,
illustrated in Figs. 4 and 5. The PVA degradation
kinetics at a certain dose rate was dependent upon the
initial PVA concentration, and vice versa. As presented
in Table 1, at a higher initial concentration, e.g., 246 mg/
L or higher, the PVA degradation at a dose rate of
12.1 Gy/min followed pseudo-zero-order reaction within
the initial 60 min irradiation, but thereafter reaction
occurred with an order between 0 and 1. At a lower
750 800
initial concentration, e.g., 43 mg/L, the degradation of
PVA followed pseudo-first-order kinetics. Moreover,
PVA degradation was faster at lower concentrations.
The effects of dose rate on PVA degradation are
summarized in Table 2. At a fixed PVA concentration,
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480 is evaluated based on the determination of iodometric

absorption values. The removal of PVA was more
400 effective under acidic or alkaline conditions than that
under neutral conditions. The pH effect on PVA
PVA (mg/L)

320
degradation, on the one hand, was attributed to the
240 different removal pathways under acidic or alkaline
conditions. On the other hand, the acid or base in
160 aqueous solutions altered the G-values of primary
species generated from water radiolysis as discussed
80
below. As a result, the degradation efficiency was
200
affected.

150 3.4. Effect of added H2O2 on PVA degradation

PVA (mg/L)

100 Without irradiation, the optical density of PVA–

iodine complex was directly reduced by the addition of
50 0.5 mol/L H2O2 into PVA solutions, but the maximum
absorption peak did not shift to shorter wavelength as
0 that in the irradiated solutions. This result suggests that
0 30 60 90 120 150 no chain scission occurred during the direct oxidation of
Irradiation time (min) PVA by H2O2. When added H2O2 concentration was in
Fig. 4. Effect of initial PVA concentration on its degradation mmol/L order of magnitude, no direct oxidation was
(initial PVA concentration: 436–43 mg/L; dose rate: 12.1 Gy/ observed. However, positive or negative effects on PVA
min). radiation degradation were observed in the presence of
H2O2.
180 Further experiments were carried out to study the
effect of H2O2 on PVA degradation efficiency as a
1
150 function of H2O2 dosage. As shown in Fig. 7, there was
an optimal H2O2 dosage at a certain dose rate for PVA
120 degradation. At higher dose rates, e.g., 55.7 Gy/min, the
2
PVA degradation efficiency was enhanced with H2O2
PVA (mg/L)

90 dosage from 2 to 10 mmol/L. Further increase of H2O2

dosage reduced the degradation efficiency. At lower
60 3 concentration, e.g., 17.2 and 30.6 Gy/min, the optimal
4 H2O2 dosage was about 2.5 mmol/L. Moreover, the
30 5 optimal H2O2 dosage was independent of initial PVA
6 concentration.
0
0 30 60 90 120 150 3.5. Mechanisms of PVA degradation
Irradiation time (min)
Fig. 5. Effect of dose rate on PVA degradation (initial PVA When dilute PVA aqueous solutions are irradiated,
concentration: 180 mg/L; dose rates from line 1 to 6: 5.0, 8.5, the energy of the ionizing radiation is principally
12.1, 19.6, 27.6, and 55.7 Gy/min, respectively). absorbed by water, resulting in the formation of several
primary reactive species, dOH, e aq ; Hd, and molecular
PVA degradation followed pseudo-zero-order kinetics at products, H2 and H2O2. This is illustrated in reaction
a lower dose rate, e.g., 5.0 Gy/min, whereas that at a (1). The values in brackets are the radiation-chemical
higher dose rate, e.g., 55.7 Gy/min, a pseudo-first-order yields of these species, i.e. G-values, at pH 7. These G-
reaction occurred. The reaction order for PVA degrada- values are affected by several factors, including the
tion at dose rates ranging from 8.5 to 55.7 Gy/min was nature of solvents, additives, atmosphere, etc. In the
between 0 and 1. presence of oxygen, the reducing species e aq and Hd are
converted into oxidizing species, peroxyl radicals
ðHO2 d; Od2 Þ; as shown in reactions (2) and (3);
3.3. Effect of pH on PVA degradation reactions (4) and (5) indicate that in acidic or alkaline
solutions eaq and Hd are converted into each other;
The influences of pH on the degradation efficiency of when a considerable amount of H2O2 is present,
PVA are illustrated in Fig. 6. The degradation efficiency reactions between H2O2 and e aq =dOH occur readily
 ARTICLE IN PRESS
S.-J. Zhang, H.-Q. Yu / Water Research 38 (2004) 309–316 313

Table 1
Kinetic data of the radiation-induced degradation of PVA at various initial PVA concentrations (dose rate: 12.1 Gy/min, pH=6.8, air
saturated)

PVA (mg/L) Reaction order Kinetic model Rate constant t1=2 a (min)

436 n ¼ 0b c ¼ c0  k0 t k0 ¼ 0:577 mg/(L min) 377.82

345 n ¼ 0b c ¼ c0  k0 t k0 ¼ 0:585 mg/(L min) 294.87
246 n ¼ 0b c ¼ c0  k0 t k0 ¼ 0:600 mg/(L min) 250.00
180 0ono1 — — —
87 0ono1 — — —
43 n¼1 c ¼ c0 ek1 t k1 ¼ 0:0516 min1 13.43
a
Half-life.
b
Within the initial 60 min irradiation.

Table 2
Kinetic data of the radiation-induced degradation of PVA at various dose rates (initial PVA concentration: 180 mg/L, pH=6.8, air
saturated)

Dose rate (Gy/min) Reaction order Rate constant t1=2 a (min)

5.0 n¼0 k0 ¼ 0:272 mg/(L min) 330.88

8.5 0ono1 — —
12.1 0ono1 — —
19.6 0ono1 — —
27.6 0ono1 — —
55.7 n¼1 k1 ¼ 0:0664 min1 10.44
a
Half-life.

100 100
1
1
1
95 80
2
Degradation (%)
Degradation (%)

2
90 60

3 2
85 40

3
80 20 3

0 2 4 6 8 10 12 14 (a) (b) (c)

pH
Fig. 6. Effect of pH on PVA degradation (initial PVA
concentration: 200 mg/L; dose rate: 12.1 Gy/min; irradiation
time: 90 min).
(reactions (6) and (7)); in the presence of 2-PrOH or t-
BuOH, dOH is scavenged quickly (reactions (8) and (9));
2-PrOH can also remove Hd (reaction (10)). The
reactive species generated from the primary and
secondary reactions of water radiolysis react with
PVA, leading to the degradation. According to the
principles of competitive reaction kinetics, which reac-
0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
H2O2 (mM)
Fig. 7. Effect of H2O2 concentration on PVA degradation
(dose rates from line 1–3: 55.7 Gy/min, 30.6 Gy/min, 17.2 Gy/
min, irradiation time: 30 min, initial PVA concentation: (a)
100 mg/L, (b) 200 mg/L, (c) 300 mg/L).
tion predominates depends on the values of the rate
constants and the concentrations of competitive com-
ponents. The influences of irradiation parameters and
additives on PVA degradation efficiency are derived
from those competitive behaviors, e.g., the effect of
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314 S.-J. Zhang, H.-Q. Yu / Water Research 38 (2004) 309–316

Table 3
Degradation efficiency of PVA under various conditions (initial PVA concentration: 200 mg/L; dose rate: 12.1 Gy/min; irradiation
time: 102 min)

Scavengera pH Air saturated N2 saturated

Primary species Degradation (%) Primary species Degradation (%)

2-PrOH 6.8 Od

2 3.07 e
aq 3.01
t-BuOH 6.8 Od
2 ; HO2 d 3.03 e
aq ; H 7.65
t-BuOH 1.0 HO2 d 51.52 H 77.03
t-BuOH 12.5 Od
2 22.21 e
aq 22.21
— 6.8 dOH; Od
2 ; HO2 d  82.20 dOH; e aq ; Hd 83.05
a
The concentration of these scavengers is 0.1 mol/L.

added H2O2 on the degradation of PVA. At an

appropriate level, H2O2 would accelerate the degrada-
A
tion of PVA by supplying more dOH (reaction (6)). On
the contrary, when the dosage of H2O2 exceeded the
optimal concentration, it would compete dOH with B
PVA (reaction (7)). As a result, the PVA degradation Transmittance (%)
efficiency was reduced. The rate constants listed in this C
paper are reported by Buxton et al. [22]:
H2 O*dOHð2:8Þ; e
aq ð2:7Þ;
Hdð0:6Þ; H2 ð0:45Þ; H2 O2 ð0:72Þ; ð1Þ

HdþO2 -HO2 d ðk ¼ 1:2  1010 L=ðmol sÞÞ; ð2Þ

aq þ O2 -O2
e ðk ¼ 1:9  1010 L=ðmol sÞÞ;
d
ð3Þ 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
aq þ H -Hd ðk ¼ 2:3  10 L=ðmol sÞÞ;
e þ 10
ð4Þ
Fig. 8. FTIR spectra of PVA (spectrum A) and its degradation

products (spectra B and C) (initial PVA concentration: 500 mg/
Hd þ OH -e
aq ðk ¼ 2:2  107 L=ðmol sÞÞ; ð5Þ L; dose rate: 60.9 Gy/min; irradiation time: spectrum B, 2.5 h;
spectrum C, 25 h).
aq - dOH þ OH

H2 O2 þ e
ðk ¼ 1:2  1010 L=ðmol sÞÞ; ð6Þ
PVA degradation, and peroxyl radicals played a minor
H2 O2 þ dOH- H2 O þ HO2 d role.
Fig. 8 shows the FTIR spectra of original PVA and its
ðk ¼ 2:7  107 L=ðmol sÞÞ; ð7Þ
degradation products. With increasing irradiation time,
bands at 3440–3420 cm1 (vO–H), 2922 cm1 (vC–H), and
OH þ 2-PrOH- ðCH3 Þ2 dCOH þ H2 O
1096 cm1 (vC–O) decayed. Meanwhile, new transmit-
ðk ¼ 1:9  109 L=ðmol sÞÞ; ð8Þ tance bands at 1707–1712 cm1 (vC=O) and 1624–
1652 cm1 (vC=C) appeared. This observation demon-
dOH þ t-BuOH- dCH2 CðCH3 Þ2 OH þ H2 O strates the destruction of C–OH and C–H bonds and the
ðk ¼ 6:0  108 L=ðmol sÞÞ; ð9Þ formation of ketones and/or enols.
The evolution of FTIR spectra shown in Fig. 8
Hd þ 2-PrOH- ðCH3 Þ2 dCOH þ H2 suggests the hydrogen abstraction initiated by dOH and
Hd either from a-position to the OH-group or from the
ðk ¼ 7:4  107 L=ðmol sÞÞ: ð10Þ
neighboring methylene group (b-position). The a-hydro-
In order to clarify which species played the key role in gen was activated. Therefore, hydrogen abstraction at
PVA degradation, experiments were performed with 2- this position predominated, which has been proven by
PrOH or t-BuOH as scavengers and being saturated the reaction between tetranitromethane and the inter-
with air or nitrogen. The results are presented in Table 3. mediates from hydrogen abstraction [16]. The hydrogen
As shown in Table 3, both dOH and Hd played roles in abstraction resulted in the formation of ketones/enols
 ARTICLE IN PRESS
S.-J. Zhang, H.-Q. Yu / Water Research 38 (2004) 309–316 315

H
OH
C C chain scission CO2 + H2O
H H
OH (H ) H OH
C C
H2O (H2) H
H OH
C C disproportionation/crosslinking

H OH

OH (H )
C C
H2O (H2)
H H OH
OH
C C CO2 + H2O

H OH H O O H
(predominates) O2 HO2
C C C C

H OH H O
Scheme 1. Possible pathways of radiation-induced PVA degradation.

(vC=C) was not observed when H2O2 was present. In

A such a case, H2O2, as an oxidative reagent, might
directly oxidize PVA at –OH position, leading to the
formation of polyvinyl ketones but no chain scission.
Transmittance (%)

This result suggests that the degradation pathways of

B PVA were influenced by the addition of H2O2. There-
fore, it is of great significance to control the H2O2
dosage at an appropriate level to enhance the degrada-
tion of PVA.

4. Conclusions

4000 3500 3000 2500 2000 1500
Wavenumber (cm-1)
Fig. 9. FTIR spectra of PVA degradation products (initial
PVA concentration: 200 mg/L; dose rate: 12.1 Gy/min; irradia-
tion time: 60 min; spectrum A: in the absence of H2O2; spectrum
B: with the addition of 0.1 mol/L H2O2).
and the chain scission. Further oxidation of these
fragments led to complete mineralization. Based on the
analysis above, possible pathways of the radiation-
induced PVA degradation are proposed in Scheme 1.
The FTIR spectra of the degradation products of
PVA solutions with and without the addition of H2O2
were significantly different. As shown in Fig. 9, the peak
at 1724 cm1 (vC=O) derived from the irradiated PVA
solutions in the presence of 0.1 mol/L H2O2 was much
stronger than that in the absence of H2O2. On the other
hand, the peak that should have appeared at 1640 cm1
1000 500 The investigation into PVA degradation induced by g-
ray irradiation under various conditions demonstrated
that g-ray irradiation was an effective method for the
pretreatment of PVA-laden wastewaters. The efficiency
of PVA radiolytic degradation was influenced by initial
PVA concentration, dose rate, pH, and the addition of
H2O2. The degradation kinetics was dependent upon
initial PVA concentration and dose rate. At a relatively
lower PVA concentration, e.g., 180 mg/L, and a higher
dose rate, e.g., 55.7 Gy/min, the PVA degradation
followed pseudo-first-order kinetics. On the contrary,
at a higher PVA concentration, e.g., 500 mg/L, but a
lower dose rate, e.g., 12.1 Gy/min, a pseudo-zero-order
reaction occurred. Acidic or alkaline conditions were
more favorable for the removal of PVA than neutral
conditions. At a certain dose rate, there was an optimal
H2O2 dosage to facilitate the degradation of PVA.
Results from radical scavenging tests demonstrated that
PVA radiolysis was initiated by dOH and Hd. The TOC
 ARTICLE IN PRESS
316 S.-J. Zhang, H.-Q. Yu / Water Research 38 (2004) 309–316
determination and FTIR analysis on the degradation
products suggested that through chain scission and
formation of ketones/enol, complete mineralization of
PVA was achieved by g-ray irradiation.
Acknowledgements
The authors wish to thank the China Academy of
Sciences for the financial support of this study through
‘‘Bairen Project’’.
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