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Procedia Engineering 117 (2015) 337 – 344

International Scientific Conference Urban Civil Engineering and Municipal Facilities,

SPbUCEMF-2015

Modeling of H2O2 and UV Oxidation of Organic Pollutants at

Wastewater Post-treatment
Elizaveta Simonenko, Alexander Gomonov, Nikolay Rolle,
Ludmila Molodkina*
St. Petersburg State Polytechnical University, Politekhnicheskaya, 29, Saint-Petersburg, 195251, Russia

Abstract

For an efficient post-treatment of waste water from dissolved organic impurities drawing on the example of one of the three
model objects – BPhB dye, effectiveness of "Advanced Oxidation Methods" was experimentally verified. Individual impact of
hydrogen peroxide and UV radiation on BPhB aqueous solutions was also.
© 2015
© 2015The TheAuthors.
Authors. Published
Published by Elsevier
by Elsevier Ltd.
Ltd. This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of SPbUCEMF-2015.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of SPbUCEMF-2015
Keywords: Model systems; oily wastewater; oxidation; hydrogen peroxide (H2O2); ultraviolet (UV); OH-radicals

1. Introduction

The organic impurities are found in most wastewaters. Domestic wastewater organic contaminants are usually
accessible to biochemical oxidation, so traditional methods of water purification are applicable to these wastewaters.
Other wastewaters such as oil producing and oil refining industry effluents, may contain a wide variety of organic
impurities, including toxic and highly toxic.
Despite the fact that many methods were developed and implemented for wastewater purification form films,
coarsely dispersed and highly dispersed unstabilized and stabilized organic emulsions, dissolved organic substances,
including oil products [1–7], quite often, it is not possible to adjust the content of organic impurities up to the
required parameters to discharge of water into the sewage system or water sources using economically viable

* Corresponding author. Tel./fax: + 7(812) 552-60-80.

E-mail address: [email protected]

1877-7058 © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of SPbUCEMF-2015
doi:10.1016/j.proeng.2015.08.170
338 Elizaveta Simonenko et al. / Procedia Engineering 117 (2015) 337 – 344

technologies [8–10]. Therefore, the development of new technologies of oily and similar wastewaters post-treatment
and modification of existing once, allowing us to carry out authorized discharge or to use these waters in the
recirculating water supply systems are actual.
Quite often the research conducting directly on oily wastewaters is problematic due to their toxicity and the
difficulty of ensuring variation of concentration of individual components over a wide range. Therefore, the model
systems have been used for the research [11–13].
ɋhemical and physical methods of wastewaters post-treatment by oxidation of organic and mineral substances
have proved their worth, where chlorine, hydrogen peroxide, ozone and ultraviolet (UV) were used as oxidizing
agents [14–19].
Hydrogen peroxide exhibits properties of both the oxidant and reductant. In comparison with other oxidants used
in water purification technologies, hydrogen peroxide has a number of advantages, including the ability to use it in a
wide range of temperatures and pH values, high selectivity of oxidation of various wastewater impurities, good
solubility in water solutions, high stability of commodity solutions during storage, simplicity of hardware design of
water purification processes and ecological compatibility [15–18].
It is well known that hydrogen peroxide is used for oxidation of hydrogen sulfide and sulfides, thiosulfates, and
sulfites; nitrogen and chlorine compounds, cyanides. An important advantage of H2O2 use in water purification
processes is the fact that this compound does not cause secondary water pollution by decomposition products. The
substances, formed as a result of chemical processes, are less dangerous than their reactants.
Ultraviolet oxidation is a photochemical process in which chemical components almost instantly decompose into
harmless components in the ultraviolet radiation reactor. UV oxidation allows, for example, to deal effectively with
the decomposition of such toxic substances as nitrosodimetylamine (NDMA), hydrazine, 1,4-dioxane and
methylthrethylbutaneethyl (MTBE) [20–26].
Organic substances are generally more sensitive to light than inorganic once and therefore are subjected to
degradation by direct absorption of photons of hard UV radiation or by reaction with water photolysis products, i.e.
with OH-radicals. These radicals play a leading role in the mineralization of dissolved organic matter. Generation of
OH- radicals in aqueous solutions is more effective as a result of "Advanced Oxidation Methods". Several methods
(non-photochemical and photochemical) are available for generating OH-radicals [27]:

x Ozonation at elevated pH (>8.5);

x Ozone + hydrogen peroxide (O3/H2O2);
x Ozone + catalyst (O3/CAT);
x Fenton system (H2O2/Fe2+);
x O3/UV; H2O2/UV;
x O3/H2O2/UV;
x Photo-Fenton/Fenton-like systems;
x Photocatalytic oxidation (UV/TiO2).

We consider only UV/H2O2 oxidation process.

To activate this process, hydrogen peroxide (H2O2) is added to the water prior to the UV-reactor.
The effect of the process is based on two principles: direct conversion by UV (photolysis) and conversion by
hydroxyl radicals.
The direct photolysis of hydrogen peroxide leads to the formation of OH-radicals [27–29]:

ଶ ଶ ൅ ŠȞ ฺ ʹx
(1)
Conversion of unwanted compounds can take place by absorption of UV light (photolysis) or reaction with •OH:

x
…‘’‘—† ൅ ฺ †‡‰”ƒ†ƒ–‹‘…‘’‘—†ሺ•ሻ ൅ ଶ ൅ ଶ 
ŠȞ
(2)
Some compounds may even be mineralized towards CO2 and H2O.
 Elizaveta Simonenko et al. / Procedia Engineering 117 (2015) 337 – 344 339

The aim of this work was the experimental confirmation of "Advanced Oxidation Methods" effectiveness on the
example of organic substances with different functional groups. To achieve the goal it was also necessary to choose
the appropriate methods of model substances analysis in various ranges of their concentration.

2. Results and discussion

Three dyestuffs – bromophenol blue, methyl violet and methyl orange – were chosen as model systems. The
choice of model objects was caused by the fact that they have various functional groups, can be analyzed by spectral
methods, and they are available.
Methyl orange (IUPAC name Sodium 4-[(4-dimethylamino)phenyldiazenyl]benzenesulfonate) is a well-known
acid-base indicator, its structural formula is shown in Fig.1a. Methyl orange is organic synthetic dyestuff from the
group of azo dyes.
Bromophenol blue (3',3",5',5"-tetrabromophenolsulfonphthalein, IUPAC name 4,4'-(1,1-dioxido-3H-2,1-
benzoxathiole-3,3-diyl)bis(2,6-dibromophenol)) is an acid-base indicator, belonging to the group of arylmethane
dyestuffs (triphenylmethane derivatives). The structural formula of bromophenol blue is shown in Fig. 1b.
Methyl violet (methylrosanilinium chloride, hexamethylparosanilinium chloride and other names) is a family of
organic compounds. Depending on the number of attached methyl groups, the color of the dye can be altered. The
structural formula of methyl violet 6B is shown in Fig. 1c.
The purity of hydrogen peroxide used in the work was qualified as "ultra high".
a b c

Fig. 1. Structural formulas of (a) Methyl orange, (b) bromophenol blue, (c) methyl violet 6B

Solutions of model substances were analyzed by spectrophotometric method on spectrophotometer SF-56

("LOMO – Spektr", Russia), as well as by spectrofluorometric method on Fluorat®-02-Panorama
Spectrofluorometer (LUMEX, Russia). Processing the luminescence spectra correction for the absorption of the
fluorescent light, were taken into account (in addition to correction on the lamp spectral characteristics and the
absorption of the incident light, which were accounted by the program).
We used the laboratory equipment with coaxial quartz flow cell (length 5 cm, thickness of treated layer 1 cm),
UV low-pressure (LP) lamp (Philips TUV 30 w / GTB, emission at 253.7 nm, length 100 cm) and the control unit.
In separate experiments quartz cells of 1 cm in thickness were used.
In this paper, we demonstrate the results obtained mainly by the example of the dye BFS. In the presented results
distilled water (pH 5.6–5.8) and 0.05–0.1 M phosphate buffer (pH 6.5–7.5) were used as solvents.
During experiments the light absorption spectra of the dye solutions in distilled water and buffers in the
wavelength range of 200 – 800 nm were obtained, the field of absorption and maxima in the visible range and near
UV were found. So for methyl orange (MO) the main maximum was observed at 460 nm, for bromophenol blue
(BPhB) – at 590 nm and for methyl violet (MV) – at 585 nm (Fig. 2).
340 Elizaveta Simonenko et al. / Procedia Engineering 117 (2015) 337 – 344

Fig. 2. Absorption spectra for water solutions of methyl orange, bromophenol blue and methyl violet at concentration of 5 mg/dm3

In the wavelength range of 200–700 nm with the excitation wavelengths step of 5–40 nm registration
luminescence spectra for the studied dyes were obtained. The examples of BPhB spectra are shown in Fig. 3a. The
resulting spectra contained bands of Rayleigh light scattering by colloidal particles [30] (at excitation wavelength of
luminescence, as well as to twice the length), the band of Raman light scattering by water molecules and the
luminescence bands. The excitation wavelengths of detected registration luminescence bands have been clarified
when analyzing the excitation spectra (Fig. 3b). So for BPhB dye the distinct maximum of bandwidth of the
registration luminescence observed at wavelengths 430–440 nm was caused by the excitation of luminescence in the
region of 250–260 nm.
a)
 Elizaveta Simonenko et al. / Procedia Engineering 117 (2015) 337 – 344 341

b)

Fig. 3. Spectra of luminescence registration (a) and luminescence excitation (b) for BPhB

From the data of Fig. 2 it is seen that all dyes absorb radiation in the range of emission of low-pressure mercury
lamp (257.3 nm [31]). Figure 4 shows the spectrum of its radiation [31], and also the absorption spectra at different
hydrogen peroxide concentrations which demonstrate that a significant amount of OH-radicals may formed at
hydrogen peroxide concentrations of 1–3 g/dm3. Figure 3 shows that the main band of BPhB luminescence
registration corresponds to the excitation band (250–260 nm), which coincides with the emission spectrum of the
lamp. Thus, we can expect an effect on the studied dyes as UV radiation and OH-radicals formed under the
combined action of hydrogen peroxide and UV radiation.
The linear dependences of signal (absorbance D at 590 nm and fluorescence signal Flu) on the concentration of
the dye (Fig. 5,a,b, for BPhB) were obtained for two methods of analysis. The curves shown in Fig. 5 demonstrate
that both methods of analysis allow to work in differing concentration ranges of BPhB.

Fig. 4. The absorptions of H2O2 – solutions (1–4 g/dm3) and emission spectrum of a LP-lamp (from [31])
342 Elizaveta Simonenko et al. / Procedia Engineering 117 (2015) 337 – 344

a) b)

Fig. 5. Dependences of absorbtion D at 590 nm (a) and fluorescence signal Flu (b) on the concentration of BPhB

Dependences of the decrease of relative BPhB optical density at 590 nm (main absorption maximum) on the
concentration of acting hydrogen peroxide, as well as on the time of exposure of UV radiation are shown in Fig. 6
(a, b), respectively. It can be seen that the most sharp dependence is observed up to a concentration of hydrogen
peroxide 0.1 g/dm 3 (Fig. 6). Under the action of only UV – emission on BFS solution in the time interval 10–60
seconds a negligible effect is observed. It reaches only 30% at the exposure time of 60 seconds.
Figure 7 shows the absorption spectra in the entire range (200–800 nm) and it is seen that in the band of the lamp
emission (253.7 nm) spectra are practically indistinguishable, i.e. considerable effect of the photolysis could not be
expected for these time intervals.
The results of the combined action of hydrogen peroxide and UV radiation are shown in Fig. 8 (a, b). Figure 8a
shows the relative decrease of optical density on the concentration of hydrogen peroxide under the action of UV for
30 seconds. Figure 8b shows the relative decrease of optical density on the time of UV-radiation at a hydrogen
peroxide concentration of 1 g/dm3 (except zero point).
When comparing the data obtained with the results shown in Fig. 6 (a, b), we can conclude that the effect of OH-
radicals formation with the short duration of exposure of LP UV lamp (at used technique and procedure) is not
observed. Noticeable impact of the combined action of both factors on the BPhB is observed in irradiation time of
100 seconds and more.
a) b)

Fig. 6. Dependencies of relative absorption decrease, %, on the hydrogen peroxide concentration (no action of UV) (a) and on UV treatment
time (without hydrogen peroxide) (b). The initial concentration of BPhB 5 mg/dm3.
 Elizaveta Simonenko et al. / Procedia Engineering 117 (2015) 337 – 344 343

Fig. 7. Absorption spectra for water solutions of bromophenol blue after UV treatment of various durations. The initial concentration of BPhB
5 mg/dm3.

a) b)

Fig. 8. Dependencies of absorption relative decrease, %, on the hydrogen peroxide concentration (30s action of UV) (a) and on UV treatment
time (1g/dm3 hydrogen peroxide except zero point) (b). The initial concentration of BPhB 5 mg/dm3.

3. Conclusions

Thus, in terms of one of the three model objects as the example, the possibility of study the individual and
combined effects of hydrogen peroxide and UV by use of spectrophotometry and spectrofluorometry methods was
shown. The results of the action of hydrogen peroxide, direct photolysis and OH-radicals on the aqueous BPhB
solutions were obtained and analyzed.

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