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Comparative Study of the UV and UV/VUV

Photolysis of Phenol in Aqueous Solution by
Using Different Types of Low-pressure...

Article in Journal of Photochemistry and Photobiology A Chemistry · May 2007

DOI: 10.1016/j.jphotochem.2007.01.002

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International Conference Ozone and UV, April 3rd 2006

Comparative Study of the UV and UV/VUV Photolysis of Phenol

in Aqueous Solution by Using Different Types of Low-pressure
Mercury Lamps
Tünde Alapi, András Dombi

1
Department of Inorganic and Analytical Chemistry
University of Szeged, SZEGED, Hungary H-6701, P.O. Box 440
Phone: +36-62-544335, e-mail: dombia@chem.u-szeged.hu
Keywords: UV irradiation, 184.9 nm, hydroxyl radical, radical scavenger, phenol decomposition

Introduction
The pre-treatment and treatment of waters and wastewaters has a growing interest because of
the toxicity of the pollutants and high treatment cost of the available methods. The advanced
oxidation processes (AOPs) have been developed as emerging technologies for treatment of
waters containing hazardous pollutants. The potential of AOPs to remove both organic and
inorganic compounds from r waters or air are currently being intensively studied. The AOPs
include direct ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis, which are promising
methods for producing drinking or ultrapure water besides the disinfection without addition of
other reagents. These methods can be successfully applied to remove aromatic pollutants such
as phenol and phenol type compounds, which are widespread pollutants of waters.
The commercially available low-pressure mercury vapour lamp is a widely applied light source
in water purification and disinfection technologies. This light source has main output at 253.7
nm, with a small portion (6% of the total intensity of irradiation) at 184.9 nm. For utilizing the
184.9 nm VUV light a special quartz sleeve has to be applied because the commercial quartz
fully absorbs the VUV light. It is of interest to have a closer look at the efficiency and
mechanism of the direct photolysis of phenol by using low-pressure mercury lamps with
different types of sleeves [1].
The generally low quantum yield and the relatively small molar absorptivity of the target
compounds over the lamp’s emission range are the factors that limit the efficiency, and
therefore the applicability of direct photolysis process in water remediation [2].
The VUV light is able to generate •OH radicals from water [3]. As this is one of the most
reactive species among the oxygen containing radicals, several technologies are based on the
•OH radical initiated reactions for the removal of organic pollutants from aqueous solutions.
During the degradation of aromatic compounds generally the first step is a nucleophilic addition
of •OH radical to the aromatic ring [3].
In this work, the direct photolysis of phenol has been investigated in aqueous solutions by using
low-pressure mercury vapour lamps immersed in the irradiated solution. The aim of the present
work is the comparison of the efficiency of two different low-pressure mercury lamps in phenol
decomposition. The first lamp is covered with commercial quartz and emits at 253.7 nm (UV
lamp). The other lamp is covered with SUPRASIL and emits both at 253.7 and at 184.9 nm
(UV/VUV lamp). The geometric and electric parameters (hence the intensity of the 253.7 nm
light) were identical for the two lamps.

Materials and Methods

The low-pressure mercury vapour lamps applied were made by LightTech and have the same
geometry (the 307 nm long and 20.5 nm external diameter of the sleeve) and electric
parameters (15 W electric and 4.0 W UV output). The lamp emitting at 253.7 nm
(GCL307T5VH/CELL) was covered with commercial quartz sleeve (UV lamp). The lamp
emitting at both 253.7 and 184.9 nm (GCL307T5/CELL) was covered with SUPRASIL sleeve
(UV/VUV lamp). The emitted photon flux of the light sources was measured by potassium
ferrioxalate actinometry [4]. The photon flux of the 253.7 nm component of both lamps was
independent of the material of the sleeve, and it was found to be 1.57(±0.09)×10-4 molphotondm-
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International Conference Ozone and UV, April 3rd 2006

3 -1
s . The actinometric measurements were carried out using the same volume as the irradiated
phenol solutions in the reactor. The emission spectrum of the low-pressure mercury lamps was
measured with a T3000-RT-UV-VIS photometer in the wavelength range of 200-890 nm. The
emission spectra of the light sources applied were found to be identical.
The scheme representing the experimental apparatus is shown on the Fig. 1.The low-pressure
mercury lamp (3) was centred in the water-cooled, glass tubular rector (4) with double wall
(length 340 mm, inner diameter 27 mm) and the irradiated aqueous solution (220 cm3) was
circulated (375 cm3 min-1) continuously around the lamp, which was immersed directly in the
solution. The phenol solution irradiated was thermostated to 25 °C. Oxygen or nitrogen was
bubbled (855 cm3 min-1) through the aqueous solution in the thermostated reservoir (6) and it
was continuously stirred with a magnetic stirrer bar (7) during the experiments. Prior to each
measurement the gas was bubbled through the phenol solution at least for 10 min and the
kinetic measurement was commenced by switching on the lamp.
The photolytic degradation of phenol was characterized by the initial rate of degradation
calculated on the basis of the time dependence of ln(c0/c), when c and c0 is the actual and initial
concentration of phenol, respectively.

PS 1

4
8

F
9

{ { { {
{ {
{ { {
6
10 T { { {

P
5
7

Fig. 1.: Experimental apparatus

1.: power supply 2.: Teflon packing ring 3.: UV or UV/VUV lamp 4.: reactor 5.: pump
6.: reservoir 7.: magnetic stirrer 8.: flow meter 9.: oxygen or nitrogen bottle 10.: thermostat

The concentration of phenol and the various aromatic intermediates (1.2- and 1,4-
dihydroxybenzene) were measured with an HPLC system consisting of a Merck-Hitachi L-7100
low-pressure gradient pump equipped with a Merck-Hitachi L-4250 UV-Vis detector (λ = 210
nm) applying a Lichrospher RP 18 column and methanol/water (28/72) mixture as eluent. The
concentration of organic acids formed during the irradiation were separated by using GROM-
RESIN ZH column and 0.01 M sulphuric acid as eluent by applying the same HPLC system (λ =
206 nm). The quantitative calibration was carried out by using standard solutions of known
concentration.
The sum of the hydrogen peroxide, methyl- and ethyl-hydroperoxide concentration was
measured by the method of Zhang and Wong [5] using enzyme (horseradish peroxidase from
Sigma) catalysed transformation of leuko crystal violet (Aldrich, Hungary) in tartarate buffer (pH

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International Conference Ozone and UV, April 3rd 2006

= 4.0). The absorbance of the solution was measured at 592 nm with Hewlett Packard
(HP8452A) diode array spectrophotometer. The molar absorptivity of the crystal violet formed
from the leuco crystal violet was 75 600 M-1cm-1 [6].
The total organic carbon (TOC) concentration of the solutions investigated was measured by
using Euroglass 1200 TOC apparatus with 100 µl sample volumes.
Decomposition and mineralization of phenol have been investigated under four different
conditions: irradiated with UV or UV/VUV light solutions saturated with oxygen or nitrogen. The
initial concentration of phenol solutions was adjusted in the range of 0.1-1.0×10-3 M. According
to control experiment performed without irradiation the concentration of phenol was found to
decrease by less than 2 %, which most likely to be due to the gas stripping.
The effect of methanol as hydroxyl radical scavenger was also investigated. Phenol (from
Sigma) was analytical grade, methanol (from Scharlau) was HPLC grade and in each
experiments ultrapure water obtained from Millipore purifier (Milli-Q) was applied.

Results and Discussion

The initial degradation rate of phenol was found to be systematically higher in the UV/VUV than
in the UV irradiated solutions both in oxygen saturated and in oxygen-free solutions (Table. I.
and Fig. 2.) It is likely to be due to the contribution of •OH radical based reactions to the
decomposition of phenol in the presence of VUV light. The •OH radical is originated from water
by the homolytic bound dissociation, which is caused by the 184.9 nm light.

Iabs at 254 nm UV/VUV UV

cphenol (M) oxygen nitrogen oxygen nitrogen
(×10-5 molphoton dm-3s-1)
v0 (×10-7 mol dm-3s-1)
1.0×10-4 0.25 6.87 3.38 0.72 0.30
-4
2.0×10 0.50 7.48 3.03 1.38 0.61
5.0×10-4 1.22 7.27 3.26 3.00 0.91
7.5×10-4 1.79 7.52 2.63 3.23 0.77
1.0×10-3 2.34 7.38 2.51 3.78 0.92
1.5×10-3 3.37 7.29 2.45 4.73 1.10
2.0×10-3 0.99 7.40 2.28 4.93 1.23

Table I.: The photon flux of 253.7 nm light absorbed by phenol, calculated according to the Beer-Lambert
low (εphenol(253,7 nm) = 460 dm3 mol-1 cm-1 l = 0.35 cm ) and the initial degradation rate of phenol at
different initial concentrations using UV or UV/VUV lamps in solutions saturated with oxygen or nitrogen

1.0 . 1.0
phenol concentration (×10 -3 M)
phenol concentration (×10 -4 M)

A B
0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 1 2 3 4 0 5 10 15
3
irradiation time (×10 s) irradiation time (×103 s)
Fig. 2.: Decomposition of phenol in UV/VUV and UV irradiated solutions at 1.0×10-4 M (A) and 1.0×10-3
M (B) initial phenol concentrations in solutions saturated with oxygen or nitrogen
(z: concentration of phenol in UV/VUV irradiated, oxygen saturated solution S: concentration of phenol
in UV irradiated, oxygen saturated solution: |: concentration of phenol in UV/VUV irradiated, oxygen free
solution: ∆: concentration of phenol in UV irradiated, oxygen free solution)

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International Conference Ozone and UV, April 3rd 2006

The relative contribution of the direct photolysis at 253.7 nm light and •OH radical based
reactions to the degradation of the target substance is likely to depend on the amount of the
absorbed light at different wavelengths by the irradiated solution. The radiation at 184.9 nm is
fully absorbed in 2 mm thick water layer therefore the •OH radical is formed at a stationary rate.
On the other hand, the amount of absorbed light at 253.7 nm depends on the phenol
concentration according to the Lambert-Beer law (Table I.).
The degradation rate of phenol was found to be independent of the initial concentration when
the UV/VUV lamp was applied and exceeded appropriate values that measured in UV irradiated
solutions at each initial concentration. At same time, by applying the UV lamp the degradation
rate dramatically increased with increasing the initial phenol concentration, and thus
proportionally to the 253.7 nm light absorbed (Table I.). This confirms that in UV irradiated
solutions the direct photolysis is the dominant initial step of the decomposition. Consequently,
the difference between the calculated degradation rates in UV and UV/VUV irradiated solutions
decreased strongly with increasing the initial phenol concentration (Table I. and Fig. 2.).
Based on these results, it can be supposed that, the initial step of phenol transformation
happens mainly via radical type reactions in UV/VUV irradiated solutions mainly at lower initial
concentrations. Nevertheless, we have to consider that, besides the •OH radical based
reactions the relative contribution of the direct photolysis of phenol at 253.7 nm must increasing
with increase of the initial concentration in UV/VUV irradiated solutions, similarly to the UV
irradiated ones.
The phenol decomposes with lower rate in oxygen free than solutions saturated with oxygen by
using either UV or UV/VUV light source. For UV/VUV irradiation, the concentration of •OH
radical strongly depends on the concentration of dissolved oxygen at a given light intensity. The
dissolved oxygen inhibits the recombination of •H and •OH radicals originated from water [3].
This can be one of the reasons of the higher degradation rate of phenol in solutions saturated
with oxygen. At same time, the HO2• radical resulted by the addition of oxygen molecule to the
hydrogen radical can also have an important role in the degradation of phenol and further
transformations of its byproducts.
The absorption of 253.7 nm UV light can lead to the formation of an excited state phenol.
Besides relaxing to the ground state, the excited state phenol can decompose by different ways.
In the presence of dissolved oxygen, the excited molecule can react with oxygen resulting a
transition complex. Consequently, due to the formation and further transformation of this
instable intermediate, the dissolved oxygen opens another pathway for the decomposition of
phenol.
Methanol was used as •OH radical scavenger [7] to study the role and the relative contribution
of •OH radical based reactions to the decomposition. Experiments were performed at two
different (1.0×10-4 and 1.0×10-3 M) initial phenol concentrations (Table II.). Addition of methanol
strongly decreased the degradation rate of phenol in UV/VUV irradiated solutions at 1.0×10-4 M
initial concentration both solutions saturated with oxygen or nitrogen. At same time methanol
was found to have no considerable inhibition effect at 1.0×10-3 M initial concentration. This
dependence of the inhibitory effect of methanol on the initial concentration confirmed that the
relative contribution of •OH radical based reactions to the degradation decreased with
increasing the initial phenol concentration in UV/VUV irradiated solutions. Contemporaneously
with it the relative contribution of direct photolysis at 253.7 nm must increased with increasing
the initial concentration and thus the absorbed 253.7 nm light. Addition of methanol has no
considerable effect on the degradation rate of phenol in UV light irradiated solutions, when the
phenol decomposes by direct photolysis.

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International Conference Ozone and UV, April 3rd 2006

v0 (×10-7 mol dm-3s-1)

cphenol cmethanol
UV/VUV UV
(M) (M)
oxygen nitrogen oxygen
1.0×10-4 - 6.87 3.38 0.72
1.0×10-4 1.0×10-2 3.31 2.97 0.70
1.0×10-4 1.0 2.14 0.77 0.71
1.0×10-3 - 7.38 2.51 3.78
1.0×10-3 1.0×10-2 6.30
1.0×10-3 1.0 6.63 2.39 3.82

Table II.: The effect of methanol as •OH radical scavenger on the initial rate of degradation (v0) of phenol
at various initial concentrations

The effect of methanol depends on the concentration of dissolved oxygen. The inhibitory effect
of methanol was more remarkable solutions saturated with oxygen. This can be explained by
the higher •OH radical concentration due to the presence of oxygen.
Dihydroxybenzenes were measured as aromatic intermediates both for UV and UV/VUV
photolysis of phenol solutions saturated with oxygen. In oxygen-free solutions their
concentration was found to be lower by one magnitude. Their formation might be initiated by
•OH radical based reactions [3,8]. On the other hand, according to literature data they were
also detected in the absence of •OH radical due to the direct photolysis of phenol in UV range
[9] or via reaction with singlet oxygen.
In the absence of VUV photons the accumulation and degradation rate of 1,2-, and 1,4-
dihydroxybenzenes is lower than in their presence, but the sum of their concentrations as a
function of the amount of decomposed phenol concentration displays the same dependency
(Fig. 3.). This suggests that these compounds are formed along of a very similar reaction
pathway both during UV or UV/VUV photolysis. It can be noted, that the effect of methanol on
the conversion of dihydroxybenzenes is not considerable.

2.0 2.0
dihydroxibenzenes (×10 -4 M )

dihydroxibenzenes (×10 -4 M )

A B
1.5
concentration of

1.5
concentration of

1.0 1.0

0.5 0.5

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
concentration of decomposed phenol (×10-3 M) -3
concentration of decomposed phenol (×10 M)

Figure 3.: The sum of the concentrations of 1,2- and 1,4-dihydroxibenzene versus concentration of
decomposed phenol in UV/VUV (A) and UV (B) light irradiated solutions at different initial concentrations
(±: 1.0×10-4 M z: 2.0×10-4 M S: 5.0×10-4 M ‘: 7.5×10-4 M  :1.0×10-3 M ) in oxygen saturated solutions

The total organic carbon contents (TOC), the concentration of oxalic acid and the sum of the
concentration of hydroperoxides (hydrogen peroxide and alkylhydroperoxides) were measured
during the decomposition of phenol at 1.5×10-3 M initial concentration both in UV and UV/VUV
irradiated aqueous solutions saturated with oxygen. Although the phenol was decomposed
totally

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International Conference Ozone and UV, April 3rd 2006

1.5 120 1.5 120

A B
concentration (×10 -3 M)

concentration (×10 -3 M)
Total Organic Carbon

Total Organic Carbon

100 100

conc. (ppm)
1.0 80

conc. (ppm)
1.0 80

60 60

0.5 40 0.5 40

20 20

0.0 0 0.0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Figure 4.: The time dependence
irradiation time (×103of
s) the phenol concentration (z), sum ofiradiation time (×103 s) of 1,2- and
the concentrations
1,4-dihydroxibenzene (‹), oxalic acide concentration (S), sum of hydroperoxide concentration (†) and
total organic carbon concentration (±) in UV/VUV (A) and UV (B) irradiated solutions at 1.5×10-3 M initial
concentration in solutions saturated with oxygen

within 103 s by both lamps, rather great difference was found in the variation of the total organic
carbon content depending on the light source (Fig. 4.).
The rate of accumulation and decomposition of oxalic acid and hydroperoxids is much higher in
UV/VUV irradiated solutions (Fig. 4.). Thus it can be stated that the 184.9 nm light, in spite of its
relatively small intensity, causes not only considerably higher degradation rate of phenol but it
plays an important role in the fragmentation and thus the complete oxidation of the formed
intermediates. The very similar time dependence of the oxalic acid and hydroperoxid
accumulation and decomposition (Fig. 4.) suggests that hydroperoxides are important
intermediates in the oxidation process. The oxalic acid and hydroperoxide accumulation
commences when the phenol and dihydroxibenzenes disappears from the solution (Fig. 4.),
suggesting that the fragmentation becomes significant after the disappearance of aromatic
compounds. It is very important to denote that the total mineralization rate of phenol is much
higher when UV/VUV lamp is used, as it was demonstrated by the change of the TOC content
(Fig. 4.).

Conclusions
The photolysis of phenol was investigated and compared in aqueous solutions irradiated both
with UV and UV/VUV lamp. The presence of VUV (184.9 nm) light component plays an
important role not only in the faster decomposition of phenol, but also in the opening of the
aromatic ring, fragmentation and decomposition of intermediates and thus reaching the total
oxidation of phenol, although its intensity is rather small comparing to the intensity of 254 nm
light. Thus, the decrease in the total organic carbon content was found to be much faster for the
UV/VUV irradiated solutions. The relative contribution of •OH radical based reactions and the
direct photolysis was found to depend strongly on the initial phenol concentration. At lower initial
concentrations the •OH radical based reactions seem to be the dominant by using UV/VUV
lamp, but at higher initial concentrations the phenol decomposed mainly by direct photolysis at
253.7 nm. It was confirmed by the investigation of the inhibitory effect of methanol, as •OH
radical scavenger.

Acknowledgement
This work was financially supported by grants from the National Science Foundation of Hungary
(OTKA T/04355 and T/15 043273), the National Development Plan (NFT, NKFP 3A/089/2004)
and the Economic Competitiveness Operative Programme (GVOP, AKF 3.1.1.-2004-05-
0259/3.0)

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 International Conference Ozone and UV, April 3rd 2006

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[8] Sonntag; C.V., Schuchmann; H.-P. Peroxyl Radicals in aqueous Solutions, John Wiley & Sons LtD.
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[9] Roig; B., Gonzalez; C., Thomas; O. Monitoring of phenol photodegradation by ultraviolet
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