Solar Energy 135 (2016) 348–358

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Removal of volatile sulfur compounds by solar advanced oxidation

technologies and bioprocesses
F.A. Almomani a,⇑, R.R. Bhosale a, A. Kumar a, C. Kennes b
a
College of Engineering, Department of Chemical Engineering, Qatar University, P.O. Box 2713, Doha, Qatar
b
University of La Coruña, Department of Chemical Engineering and Center for Advanced Scientific Research (CICA), Faculty of Sciences, Rúa da Fraga 10, E – 15008 La Coruña, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The degradations of volatile sulfur compounds (VSCs) by advanced oxidation technology, solar advanced
Received 7 October 2015 oxidation technology, biological treatment, and the combination of solar advanced oxidation technology
Received in revised form 23 March 2016 and biological treatment were studied in a pilot plant. Three volatile sulfur compounds (methanethiol
Accepted 22 May 2016
(MeSH), dimethyl sulfide (Me2S), and hydrogen disulfide (H2S) were selected as model compounds.
Available online 13 June 2016
Solar advanced oxidation technologies (AOTs) processes eliminate more than 65% of VSCs at high resi-
dence time. VSCs were completely oxidized in less than 6.0 min by solar AOTs and ozone. Significant
Keywords:
VSCs elimination levels were achieved by solar advanced oxidation in combination with biological treat-
Biodegradation
Irradiation
ment. Total VSCs removal efficiencies of up to 87.2% and 91.2% for MeSH and Me2S respectively were
Solar oxidation achieved in combined processes at initial concentrations of 100 mg m
3, with HRTsolar of 10 min and
Mechanism HRTbio of 105 s. The results obtained from the combined processes (solar AOTs and bioprocess) confirm
the suitability of solar AOTs as pre-treatment for the removal of VSCs.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction As a result of the contribution of VSCs to odour pollution, their

The continuous increase in world population has raised the
environmental awareness of the public, and has seriously moti-
vated the search for a more suitable alternative method to reduce
and control the emission of odors generated by the disposal of
urban and industrial wastes (Zhang et al., 2003). It has been
reported that most residential developments near urban disposal
and waste treatment plants are exposed to high levels of odorous
gases (Iranpour et al., 2005), and that there are serious concerns
related to the elimination of these odors that affect the public
health (Iranpour et al., 2005). Of the many odorous gases, volatile
sulfur compounds (VSCs) are also the most predominant odorous
molecules associated with several processes used in the petroleum
or petrochemical industries. VSCs can also be generated in different
bioindustrial processes related to thermal sludge treatment and
the anaerobic degradation of wastewater, as well as sludge com-
posting of sulfur-containing amino acids (Smet and Langenhove,
1998). The liquefied petroleum gas (LPG) industry is also an impor-
tant source for the production of a wide variety of VSC, such as
methanethiol (MT), ethanethiol (ET), propanethiol, dimethylsulfide
(DMS), and dimethyldisulfide (Leerdam et al., 2006).
⇑ Corresponding author.
E-mail address: falmomani@qu.edu.qa (F.A. Almomani).
potential corrosive effects, and their dangerous effect on public
health, quite a number of chemical and biochemical treatment pro-
cesses have been proposed and developed to treat VSCs emissions
(Reij et al., 1998; Smet and Langenhove, 1998; Herrygers et al.,
2000). The proposed treatment alternatives include biofilters
(Smet and Langenhove, 1998; Omri et al., 2011), chemical reduc-
tion (Katoh et al., 1995; Kastner et al., 2003; Cellier et al., 2004;
Moreno et al., 2010; Omri et al., 2011), carbon adsorption
(Bashkova et al., 2002; Wang et al., 2011), and chemical scrubbing.
Nevertheless, when these treatment alternatives have been used
for the removal of VSCs, different technical problems have
appeared, such as low and variable removal efficiencies, the
requirement for large reactor volumes, and unstable operational
conditions (Smet and Langenhove, 1998; Herrygers et al., 2000;
Sipma et al., 2003; Wang et al., 2011). Biological treatment, which
is considered the cheapest alternative, has recently been used for
the treatment of sulfur compounds. In these biological processes,
inorganic VSCs are converted to elemental sulfur in a two-step pro-
cess, and organic VSCs are converted to elemental sulfur in a three
-step process (Castro et al., 2014). However, many questions
remain about the steady state performance of this process.
Advanced oxidation technologies (AOTs) have been considered
effective and promising for the treatment of different organic and
inorganic contaminants contained in water and air (Tekin et al.,

http://dx.doi.org/10.1016/j.solener.2016.05.037
0038-092X/Ó 2016 Elsevier Ltd. All rights reserved.
 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358
2006; Alessandra et al., 2013; Castro et al., 2014). AOTs are effec-
tive treatment technologies which, if designed properly, could
eliminate many harmful contaminants from water and air. With
such technologies, problematic compounds can be partially or
totally oxidized into smaller by-products that can be easily
removed through conventional biological processes (Tekin et al.,
2006; MacAdam et al., 2012; Nawaz and Ahsan, 2014). AOTs are
advantageous because they can be used to oxidize a wide vari-
ety of contaminants in water and air (Nawaz and Ahsan, 2014;
Polo-Lopez et al., 2014). The hydroxyl radicals generated in AOTs
can oxidize organic contaminants in a short time and at ambient
temperatures (Tekin et al., 2006; MacAdam et al., 2012; Brienza
et al., 2014; Nawaz and Ahsan, 2014; Polo-Lopez et al., 2014).
These hydroxyl radicals can be produced in different ways in AOTs,
allowing better compliance with different treatment requirements
(Brienza et al., 2014; Castro et al., 2014; Liu et al., 2014; Tijani et al.,
2014).
Solar advanced oxidation processes were effectively used in the
treatment of water and air containing non-biodegradable and/or
toxic organic pollutant (Reeves et al., 1992; Lichtin et al., 1996;
Blanco et al., 1999; Sano et al., 2004; Amat et al., 2005; Nogueira
et al., 2005). Using solar energy as a light source reduces the cost
of AOTs and makes them suitable treatment alternatives. Different
previous works have addressed the treatment and abatement of
sulfur compounds in water using advanced photo-catalysis pro-
cesses (Antonopoulou et al., 2014; Vega et al., 2014) and ozonation
(Popiel et al., 2009; Bildsoe et al., 2012). However, to the best of our
knowledge, there is no work published so far dealing with solar
photo-catalytic oxidation and solar photo-catalytic ozonation of
volatile sulfur compounds at pilot-plant. Thus, this study aims at
exploring the application of advanced oxidation technology
(AOTs), solar advanced oxidation technology (solar AOTs), biologi-
cal treatment, and the combination of solar advanced oxidation
technology and biological treatment as alternative process for the
treatment of VSCs in pilot scale processes. This will be the first
pilot-scale investigation of the use of solar AOTs technology for
treatment of VSCs, and will generate the fundamental knowledge
that will be required to narrow down the operational conditions
and optimum operation of the pilot-scale system.
2. Materials and methods
2.1. Experimental set up
2.1.1. Pilot-scale solar reactor
The pilot solar reactor used in this study is a prototype designed
on the basis of a compound parabolic collector (CPC). CPC technol-
ogy allows all the received solar radiation to be utilized for oxida-
tion. The pilot-scale solar reactor setup used in this study is
presented in Fig. 1. The set up consists of: (1) an inlet VSC gas pipe,
(2) a dry air humidification line, (3) an inlet gas flow meter, (4) 20
quartz solar elements (ID = 1.6 cm, L = 80 cm), (5) an outlet gas
line, and (6) a solar irradiation intensity meter. The solar elements
were plated with a film of TiO2 using the modified sol–gel method
(Al Momani and Jarrah, 2009). The TiO2 photo-catalyst was
attached to the solar elements according to the following proce-
dure; a mixture of tetrabutylorthotitanate (Ti(OC4H9)4), acetyl ace-
tone (C5H8O), n-propanol(C3H8O) and deionized water with a
volumetric ratio of 1.0:0.5:5.0:0.5 was prepared at a controlled
temperature of 25 °C and a mixing speed of 500 rpm for
60 min. Acetyl acetone was used in this mixture as chelating agent
and to control the hydrolysis of tetrabutylorthotitanate. Then, the
mixture was mixed with carbon black powder (particle size
18 nm and surface area 265 m2 g
1) at a ratio of 1 mL Ti(OC4H9)4
to 2.4 mg carbon black. The resultant mixture was then kept
349
standing at controlled temperature of 25 °C for 2 h to complete
the hydrolysis reaction and produce stable TiO2 sol. After that,
the films are formed on the solar elements by dipping–withdraw-
ing in an ambient atmosphere. The solar elements coated with gel
films are heat-treated at 550 °C for 2.5 h in air using an electric
oven. The thickness of the TiO2 films is adjusted by repeating the
cycle from dipping to heat treatment for eight times.
2.1.2. Biological reactor
The experimental set-up used in the biodegradation of VSCs is
shown in Fig. 2. A suspended culture biological reactor with a
working volume of 2 L was equipped with dissolved oxygen level
and pH controllers. The reactor was filled with 2 L mineral medium
with suspended biomass. The temperature of the bioreactor was
held constant at 30 ± 0.5 °C by circulating water through a jacket
connected to the temperature controller; the mixer speed was
set at 300 rpm, and the oxygen saturation was held at 80 w/w%.
The pH of the biological culture was maintained at 7.0 ± 0.5 by
automatically adding 1 mol L
1 NaOH solution to neutralize the
H2SO4 formed during VSC biodegradation. The neutralization step
led to the accumulation of Na2SO4 inside the reactor. To control
the accumulation of Na2SO4 and to avoid the inhibition of micro-
bial activity, the conductivity of the media inside the reactor was
kept below 20 mS cm
2 by replacing part of the mineral medium
when needed. When required, the biomass recovered from the
mineral medium was recycled to the reactor to maintain a constant
biomass concentration. The polluted gas stream was generated by
mixing two different gas streams. A small stream of VSCs gas was
mixed with a large pure humid air stream in a mixing chamber.
Gas-phase concentrations ranging from 100 ± 1 to 300 ± 5 mg m
3
were obtained by changing the flow rate of the VSCs stream. The
total gas flow rate was kept in the range from (3.4 ± 0.21) 
10
2 m3 h
1 to (13.6 ± 0.20)  10
2 m3 h
1, and the gas residence
time was in the range 106 ± 2–53 ± 1 s. The gas flow rates were
adjusted by means of a flow meter. Air samples were regularly
taken from the inlet and outlet gas streams to determine the inlet
and outlet VSCs concentration.
2.2. Ozone generation
The ozone used in the oxidation of the VSCs was produced by
means of an ozone generator (Anseros COM-AD-01) using high-
purity oxygen. The ozonation step was combined with the solar
process.
2.3. Analytical procedures
The concentrations of VSCs were analyzed online in a Shimadzu
GC analyzer, which was equipped with a flame ionization detector
and a packed column (AT OV101) with a diameter of 3 mm and a
length of 2 m. The oven temperature of the gas chromatograph
was held constant at 190 °C and the detector temperature was
maintained constant at 250 °C.
The inlet and outlet gaseous ozone concentrations were deter-
mined using an ozone analyzer (Ozomat GM-60000-OEM). The
analyzer was calibrated using the indigo method and the detection
limit of ozone was found to be ±0.02 mg L
1. Residual ozone in the
water solution was determined by the indigo method according to
Standard Methods (APHA, 1985).
The relative humidity (RH) of the gaseous stream was measured
using a humidity analyser.
2.4. Bioreactor mineral medium
The mineral medium used in the biological reactor contained
per litre distilled water: 4.88 g Na2HPO412H2O, 1.83 g KH2PO4,
350 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358

Fig. 1. Solar setup.

Fig. 2. Schematic of biological reactor.

0.17 g MgSO47H2O, 0.45 g (NH4)2SO4, 0.5 mL of trace minerals, and
1 mL of vitamin solution. The trace mineral solution was prepared
by mixing 5.5 mg CaCl2, 0.15 mg MnSO45H2O, 1.5 mg FeSO47H2O,
0.2 mg ZnSO47H2O, 0.2 mg CuSO45H2O, 0.02 mg H3BO3 and 3 mg
Na2MoO42H2O in 1 L distilled water. The vitamin solution
contained per litre of distilled water: 0.15 mg folic acid, 0.15 mg
biotin, 0.25 mg thiamine, 0.25 mg riboflavin, 0.25 mg nicotinic
acid, 0.001 mg vitamin B12, 0.26 mg p-aminobenzoic acid, 0.7 mg
pyridoxamine, and 0.25 mg lipoic acid. The pH of the medium
was adjusted to 7.
 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358
3. Experimental procedure
3.1. Determination of the mass transfer coefficient
The mass transfer coefficient for the VSCs in the biological reac-
tor medium was measured by passing a mixture of gas streams
(VSCs, air, and water) through the biological reactor medium in
the absence of the activated sludge. The VSCs concentration in
the gas stream was set to 100 mg m
3. The gas flow rates were kept
in the range from (3.4 ± 0.20)  10
2 m3 h
1 to (13.6 ± 0.20) 
10
2 m3 h
1. Gas samples of 250 lL were periodically taken using
Gas Tight Hamilton syringes to monitor inlet gas concentration
(Cin,g) and outlet gas concentration (Cout,g) until the saturation of
the liquid phase was reached (Cout,g/Cin,g  0.99).
3.2. Solar oxidation
Gaseous VSC compounds were obtained by mixing stock gases
with clean air. Humidity was added to the gaseous mixture by bub-
bling the dry air stream though deionized water. The gas stream
(containing VSCs, air, and water vapor) was then pumped through
the solar reactor at a flow rate ranging from 0.22 ± 0.01 to
1.66 ± 0.03 L min
1. The gas was circulated through the solar reac-
tor at different residence times (2–15 min). The outlet gas samples
were analyzed online by GC. Humidity meters were installed at the
entrance and exit of the solar reactor to measure the humidity of
the inlet and outlet streams. The solar irradiation intensity was
measured during the experiment using the solar intensity meter.
The ozonation/solar oxidation experiments were carried out by
mixing ozone with the VSC stream in the mixing chamber. The
mixture was then introduced into the solar reactor and left to react
and reach a steady state. The solar reactor outlet stream was con-
nected to an ozone analyzer (UVAD-1000, Shimadzu) to continu-
ously monitor the outlet concentration of gaseous ozone, and to
a gas chromatograph to measure the outlet VSC concentration.
3.3. Biooxidation
A mixture of gas streams (VSCs, air, and water) with VSC con-
centrations ranging from 0.1 to 0.3 g m
3 was passed through the
biological reactor. The total gas flow rate was maintained in the
range (6.8 ± 0.65)  10
2 m3 h
1 to (13.6 ± 0.20)  10
2 m3 h
1,
for which the gas residence times was in the range 106–53 s. The
gas flow rates were adjusted by means of flow meters. Air samples
were regularly taken from the inlet and outlet gas streams to
determine the inlet and outlet VSCs concentrations.
4. Results and discussion
4.1. Solar oxidation of volatile sulfur compounds (VSCs)
Before testing the oxidation of VSCs through solar photocat-
alytic oxidation, experiments were carried out in order to measure
the adsorption constants of MeSH, Me2S, and H2S in the solar reac-
tor. Experiments were carried out in the dark, and the inlet and
outlet concentrations were measured. After measuring the inlet
and outlet concentrations, the amount of VSCs adsorbed on the
TiO2 catalyst was determined using Eq. (1):
ðC 0
C e ÞV
Qe ¼ ð1Þ
M TiO2
where C0 and Ce are the initial and equilibrium concentrations of the
adsorbate, respectively (mg L
1). V is the total volume of the reactor
(L), and Mcat is the mass of the TiO2 catalyst (mg). The Langmuir
351
isotherm model, Eq. (2), was used to determine the adsorption con-
stant, Ki for all the VSCs:
Q max K i C o
Qe ¼ ð2Þ
ð1 þ K i C 0 Þ
where Qe (mg/gcat) and C0 (mg L
1) are the amounts of VSCs
adsorbed per unit weight of adsorbent and the concentration in
the gas phase at equilibrium, respectively. Qmax (mg/gcat) is the
maximum VSC adsorbed and Ki (mg
1 L) is the adsorption constant.
Table 1 shows the obtained adsorption constants for MeSH, Me2S,
and H2S. The results in Table 1 are reported as the average of three
repeated experiment at 95% confidence level. The adsorption ten-
dency of the three VSCs are different; the adsorption rate constants,
arranged from the highest to the lowest, are K Me2 S > K MeSH > K H2 S .
The differences in adsorption rate constants between the three
model VSCs are expected to affect the solar oxidation, as will be
explained next.
The results of solar oxidation of different VSC compounds
(MeSH, Me2S and H2S) at different residence times are presented
in Fig. 3. Each point in Fig. 3 represents the main of three repeated
samples (see error bars). The solar experiments were carried out in
June under clear sky conditions. The experimental results obtained
in Fig. 3 correspond to an initial VSCs concentration of
100 ± 1 mg m
3, an average light intensity of 8.5 ± 0.2 kW h m
2,
and a relative humidity (RH) of 40%. Solar oxidation can be used
effectively to reduce the concentration of VSCs in gas streams.
The oxidation removal efficiencies were observed to be directly
proportional to the residence time. For all the studied residence
times the solar oxidation of dimethyl sulfide (Me2S) was most
effective. Limited VSCs elimination efficiencies were observed in
the experiments carried out at low residence times (s = 2 and
5 min), in comparison with the experiments carried out at higher
residence times (s = 10 and 15 min). The average removal efficien-
cies achieved at s = 2 and 5 min ranged from 18% to 56% and 32% to
60%, respectively (see Fig. 3). At s = 5 min, the average removal effi-
ciencies were 60%, 46.7%, and 32%, for Me2S, MeSH, and H2S,
respectively. Higher average removal efficiencies (>65%) were
observed for higher residence times (s = 10 and 15 min). The
removal efficiencies at s = 10 min were 90%, 76.7%, and 64.7%,
and at s = 15 min the average removal efficiencies reached 91%,
79%, and 68%, for Me2S, MeSH and H2S, respectively. Similar results
were reported by Goswami et al., 1997 regarding the effect of the
hydraulic retention time (HRT) on the rate of oxidation. The previ-
ous study and the present study concluded that at low HRT it is
possible that the contaminants did not have sufficient time in
the reactor to achieve complete photo-oxidation. Thus, the average
removal efficiency is low. The principle mechanism of photocat-
alytic oxidation by solar energy is shown in Fig. 4. Solar photons
with an energy level (hm) equal to or greater than the catalyst band
gap energy (Eb) can excite the electrons and transfer them from the
valance band (VB) to the conduction band (CB), creating holes in the
Table 1
Adsorption constants for different VSCs on TiO2 film.
Compound Maximum organic compound Adsorption constant, Ki
adsorbed, Qmax (mg/gcat)

x  CIa (L/mg)

x  CI (Std. Dev.)
(Std. Dev.)
MeSH (23.1 ± 0.92)  10
3 (1  10
3) (13.5 ± 0.54)  10
4
(5.9  10
5)
Me2S (33.1 ± 1.32)  10
3 (1.4  10
3) (23.2 ± 0.9)  10
4
(1.0  10
4)
H2S (15.6 ± 1.32)  10
3 (0.62  10
3) (8.9 ± 0.01)  10
4
(3.8  10
5)
a
CI: confidence interval at 95% confidence level.
b
Std. Dev.: Standard Deviation.
352 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358

1.25 1.25
Residence time= 2 min Residence time= 5 min
[VOSC]/[VOSC] i 1.00 (τ) 1.00 (τ)

[VOSC]/[VOSC] i
0.75 0.75

0.50 0.50
MESH MESH
0.25 Me2S 0.25 Me2S
H2S H2S
0.00 0.00
0 50 100 150 200 0 50 100 150 200

1.25 MESH 1.25

Residence time= 10 min MESH
Residence time= 15 min
(τ) Me2S Me2S
(τ)
[VOSC]/[VOSC] i

1.00

[VOSC]/[VOSC] i
1.00
H2S H2S
0.75 0.75

0.50 0.50

0.25 0.25

0.00 0.00
0 50 100 150 200 0 50 100 150 200
Reaction time (min)

Fig. 3. Degradation of different VSCs by mean of solar irradiation. [VSC]i = 100 mg m
3, RH = 40%, solar intensity = 8.5 ± 0.2 kW h m
2 and temperature range 25–27 °C.

Fig. 4. Mechanism of photocatalytic oxidation.

þ
valance band (h+) and free electrons (e
) in the conduction band, Formation of hydroxyl radicals : H2 O þ h ! HO
þ Hþ
and starting a series of reactions (Reactions (1)–(8)) that form ðReaction7Þ
hydroxyl radicals (Ireland et al., 1995; Konstantinou and
Triantafyllos, 2003) which mainly attack the VSC leading to
degradation: Organic matter oxidation : HO
þ R
H ! R
þ H2 O ðReaction8Þ

Photoexcitation : TiO2 þ hm ! e
þ h
þ
ðReaction1Þ The and e
h+VB
are defined as the surface trapped conduction
TR
band electron and valence band hole, respectively. In the absence
Charge—carrier trapping of e : e
CB ! e
TR


ðReaction2Þ of electron acceptors, the e
+
TR/hVB recombination is highly expected.
Therefore, the presence of electron scavengers is very important to
þ þ þ avoid this undesirable reaction (Malato et al., 2002).
Charge—carrier trapping of h : hVB ! hTR ! heat ðReaction3Þ
The degradation efficiencies trends of the three VSCs were com-
þ pared. The highest degradation efficiencies were obtained for
Electron—hole recombination : e
TR þ hVB ! heat ðReaction4Þ
Me2S, followed by MeSH, and finally H2S. This trend shows that

advanced oxidation processes can be used to attack chemical
Photoexcited e scavenging : ðO2 Þads þ e
! O


2 ðReaction5Þ
bonds in VSCs and achieve a high degradation rate. It is known that
þ the main power of AOT comes from the production of hydroxyl
Formation of hydroxyl radicals : OH
þ h ! HO
ðReaction6Þ radicals (
OH) which can effectively destroy all organic
 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358 353

contaminants and mineralize them into CO2 and H2O. These hydro-
xyl radicals (
OH) are nonselective and will attack a wide variety of
chemical bonds. However, AOTs are more powerful in attacking
organic compounds than inorganic compounds. Thus, it is expected
that the organic VSCs are more vulnerable to AOTs than are inor-
ganic VSCs, as was verified in the present work. The efficiency of
heterogeneous oxidation by TiO2 improves by increasing the
amount of organic compounds adsorbed on the catalysis surface,
which initiates a series of oxidation reactions that lead to high oxi-
dation rate and consequently greater removal of VSC.
The relative humidity (RH) plays an important role in the oxida-
tion of organic matter through advanced oxidation processes by
enhancing the generation of hydroxyl radicals and reducing the
chance of catalyst deactivation (Konstantinou and Triantafyllos,
2003). The effect of relative humidity on the percentage removal
of VSCs by solar oxidation was examined. Relative humidity values
in the range of 10–60% were tested for the removal of VSCs. The
removal efficiency of VSCs first increased with increasing humidity
up to 40%; after that, the percentage removal efficiency of VSCs lev-
elled off at higher humidities, suggesting that a relative humidity
of around 40% was optimum. The highest percentage removal effi-
ciencies reached 79% for MeSH and 91% for Me2S, and were
obtained at a relative humidity value of 40%. Similar oxidation
trends were previously reported by Goswami et al., 1995 and
Goswami et al., 1997 in their study of photo-catalytic oxidation
using titanium dioxide for disinfecting indoor air. The study indi-
cated that at low humidity (630%) no significant difference was
observed between photolysis and photo-catalysis due to insuffi-
cient water to produce hydroxyl radicals. Increasing the relative
humidity up to 50% showed significant improvement in the
photo-catalytic process performance in comparison with photoly-
sis. However, when the relative humidity increased more than
85% no increase on the performance of the photo-catalytic process
was reported.
The effect of seasonal solar irradiation on the performance of
AOT was tested by repeating the same experiments in March and
September of the same year. Because of space limitations, only
the results for the experiment carried out in March will be
presented and discussed. The average removal of VSCs during the
solar oxidation experiments carried out in March is presented in
Fig. 5. Experiments were repeated 3 time and carried out with an
initial VSCs concentration of 100 ± 1 mg m
3 and RH of 40%. The
degradation efficiency of VSCs is highly dependent on the solar
intensity, decreasing in March and September compared to the val-
ues reported for June. The obtained results are related to the
monthly average local solar radiation. The monthly solar irradia-
tion intensity was found to be 6.1 ± 0.1 kW h m
2 for the month
of March and 8.5 ± 0.2 kW h m
2 for the month of June. The aver-
age removal efficiencies achieved at s = 2 and 5 min ranged from
9.8% to 49% and 25.2% to 52%, respectively (see Fig. 5). At
s = 5 min, the average removal efficiencies were 52%, 41.3%, and
25.21% for Me2S, MeSH, and H2S, respectively. At higher residence
times, the removal efficiencies increased to 85.7%, 70.8%, and 55.8%
at s = 10 min, and 88.75%, 73.75%, and 60.25% at s = 15 min for
Me2S, MeSH, and H2S, respectively. However, the oxidation effi-
ciencies in March and September were still acceptable and
effective.
It is worth mentioning that due to the low ambient temperature
(maximum 24 °C), low heat capacity of the gases stream and the
short residence time inside the solar reactor (maximum
15 min) the maximum change in gaseous mixture temperature
for the experiments carried out on March and September did not
exceed 3 °C. However, for the experiment carried out on June the
temperature of gaseous mixture increased from 25 °C (typical ini-
tial value) up to 32 °C. The increase in gas temperature has likely a
positive effect on VSCs degradation therefore it was decided not to
interfere with the reaction by using any cooling process.
4.2. Treatment of volatile sulfur compounds (VSCs) by an aerobic
bioprocess
4.2.1. Mass balance
The mass transfer coefficients of VSC gases were determined in
the bioreactor medium to verify whether the mass transfer
between the gas and the liquid limits the removal efficiency. Mass
balances can be used to determine the mass transfer coefficients of

1.25 1.25
Residence time= 2 min Residence time= 5 min
(τ) (τ)
[VOSC]/[VOSC] i

1.00
[VOSC]/[VOSC] i

1.00

0.75 0.75

0.50 0.50
MESH
MESH
0.25 Me2S 0.25 Me2S
H2S
0.00 H2S
0.00
0 50 100 150 200 0 50 100 150 200

1.25 MESH 1.25

Residence time= 10 min Residence time= 15 min MESH
(τ) (τ)
Me2S Me2S
[VOSC]/[VOSC] i

1.00
[VOSC]/[VOSC] i

1.00
H2S H2S
0.75 0.75

0.50 0.50

0.25 0.25

0.00 0.00
0 50 100 150 200 0 50 100 150 200
Reaction time (min)

Fig. 5. Degradation of different VSCs by mean of solar irradiation; [VSC]i = 100 mg m
3, RH = 40%, solar intensity = 6.1 ± 0.1 kW h m
2 and temperature range 22–25 °C.
354 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358

VSCs in the CSTR. For the present work, it can be assumed that the experimental results and Equation (8), with the coefficient of deter-
reactor is well mixed in the liquid phase, that the gas bubbles mination (R2) being greater than 70, demonstrating goodness of fit.
through the reactor are uniform, that the bubbles have constant Table 2 presents the average mass transfer coefficients of three
volumes (Vb) and surface areas (Ab), that the transferred com- repeated experiments and the coefficients of determination (R2)
pounds (e.g., VSCs) have a low gas molar fraction as they are for the aerobic biological CSTR operated at gas flow rates in the
diluted in the air stream, and that the pressure difference between range of (3.4 ± 0.20)  10
2 m3 h
1 to (13.6 ± 0.20)  10
2 m3 h
1.
the top and bottom of the reactor is negligible. With these assump- The values of Kmass for the liquid medium ranged from
tions, the VSCs mass flow from the bubble to the liquid phase is (6.5 ± 0.4)  10
2 [Std. Dev = 2  10
3] to (15.6 ± 0.01)  10
2
proportional to the bubble’s area and the concentration gradient, [Std. Dev = 6.4  10
3]. These results confirmed that the CSTR
as in Eq. (3): exhibited good mass transfer where the VSCs move from gas bub-
  bles to the liquid media. The significant mass transfer coefficients
dC g Cg
Vb ¼ kLG Ab
Cw ; ð3Þ for the present CSTR configuration suggests a high interfacial area
dt Hw
between the liquid media and the gas phase established by uniform
where Hw and kLG are the dimensionless Henry’s constant in water gas bubbling through the liquid phase. In particular cases (e.g., at
and the liquid mass transfer coefficient, respectively, and Cg and Cw flow rate of (13.6 ± 0.8)  10
2) m3 h
1), the poor mass transfer of
are the VSCs concentration in the gas and the water phase, respec- the VSCs could be attributed to limited dispersion, as a result of
tively. Hernández et al., 2011 in their study of mass transfer coeffi- the relatively high gas-flow rate. The experimental results also
cient of VSCs in liquid phase CSTR, employed the ratio Ab/Vb of the showed that, for the reactor configuration tested here, the gas flow
specific area and the gas hold-up in the stirred tank (H = Vg/Vr). The rate has the highest impact on the mass transfer coefficient.
calculation of this ratio assumes that the volume of the reactor (Vr)
equals the sum of the total volume of the gas phase in contact with 4.2.2. Biological removal of VSCs
the liquid phase (VL) and the gas phase, (VG). Eq. (3) can thus be The efficiency of the CSTR bioreactor in removing VSCs from
rewritten as follows: gaseous streams was tested. Although biofilters and biotrickling
  filters are the most common bioprocesses nowadays for waste
dC g a Cg
¼ kLG
Cw : ð4Þ gas and odour treatment (Kennes and Veiga, 2013), suspended-
dt H Hw
growth bioreactors such activated sludge systems have also
Integrating Eq. (4) leads to Eq. (5): successfully been used already for decades, among others for
  hydrogen sulfide removal (Bielefeldt, 2001). Those systems can
C out;G
Hw C w a
Ln ¼ kLG t; ð5Þ advantageously be used when both wastewaters and waste gases
C in;G
Hw C w mwH need to be treated on a same site, as one same bioreactor can then
where Cin,G and Cout,G are the initial and the final VSCs concentra- be used for the treatment of both types of effluents, which allows
tions in the rising gas bubbles, respectively, and t is the bubble cost savings. This avoids costs associated with the installation of an
retention time in the bioreactor ðt ¼ HVF r Þ, where F is the gas flow additional bioreactor such as a bio-filter or a bio-trickling filter.
rate. Eq. (5) can be rewritten in the form of Eq. (6)
  4.2.2.1. Start up. The start-up stage of the biological reactor was
kLG aV r performed by feeding the reactor with glucose as an easy
C out;G ¼ Hw C w þ ðC in;G
Hw C w ÞExp
: ð6Þ
Hw F biodegradable source of organic carbon—for a period of 45 days.
The biomass used in the inoculation of the bioreactor was collected
Eq. (6) can be written for measured quantities by assuming that the
from an activated sludge process of a local wastewater treatment
amount of VSCs transferred from the gas to the liquid per unit time
plant. Daily feeding of the reactor with glucose allows for stable
and reactor volume is given by Eq. (7):
biomass build-up, produces a high concentration of biomass,
F F reduces the effects of any toxic material, and improves the stability
K mass ðC in;G
Hw C w Þ ¼ R ¼ ðC in;G
C out;G Þ; ð7Þ
Vr Vr of the bioreactor. A similar approach was followed in other studies
that used biological processes for the treatment of toxic organic
where Kmass is the dimensionless mass transfer coefficient
  chemicals (e.g., 4-chlorophenol, 3-nitrobenzoic acid, and 4-
expressed as K mass ¼ 1
exp
kLG aV r
Hw F
. nitrophenol) (Bielefeldt, 2001). The start-up stage was considered
By combining Eqs. (7) and (5), the following expression for mass to be complete when the bioreactor reached constant performance,
transfer can be obtained: as evidenced by the complete biodegradation of glucose, by stable
  biomass (VSS), and by neutral pH conditions.
C in;G
C out;G F
Ln ¼ LnK mass
K mass t: ð8Þ
C in;G Vr
4.2.2.2. Treatment of volatile sulfur compounds (VSCs). Following the
The experimental results obtained in the bioreactor were fitted start-up period, VSCs were fed to the bioreactor at three different
to Eq. (8). Good agreement was obtained between the concentrations (100 ± 1, 200 ± 2 and 300 ± 5 mg m
3) and two

Table 2
Mass transfer coefficient and coefficient of determination (R2) for aerobic biological CSTR for flow rates ranging from 0.034 to 0.136 m3 h
1.

Methanethiol (MeSH), Dimethyl sulfide (Me2S) Hydrogen disulfide H2S

Flow rate (m3/h)

x  CIa (Std. Dev.) Kmass

x  CIa (Std. Dev.) R2

x  CIa Kmass

x  CIa (Std. Dev.) R2

x  CIa Kmass

x  CIa (Std. Dev.) R2

x  CIa
(3.4 ± 0.216)  10
2 (15.6 ± 0.01)  10
2 90 ± 3 (21.0 ± 0.01)  10
2 89 ± 2 (14.4 ± 0. 01)  10
2 (0.0091) 83 ± 1
(0.1388  10
2) (0.0064) (0.0086)
(6.8 ± 0.65)  10
2 (0.0027) 12.0 ± 1.14  10
2 (0.0048) 88 ± 1.5 (16.0 ± 1.52)  10
2 86 ± 1.5 11.0 ± 1.05)  10
2 (0.0044) 81 ± 1.5
(0.0064)

2
2
(10.03 ± 1.2)  10 (0.0052) (8.9 ± 1.0)  10 (0.0045) 85 ± 2 (12.2 ± 1.4)  10
2 (0.0062) 77 ± 1
2
(8.7 ± 1.0)  10 (0.0044) 73 ± 3
(13.6 ± 0.8)  10
2 (0.003) (6.5 ± 0. 4)  10
2 (0.002) 77 ± 3 (10.0 ± 0.6)  10
2 (0.003) 76 ± 2 (5.5 ± 1.2)  10
2 (0.001) 1
a
CI: confidence interval at 95% confidence level.
b
Std. Dev.: Standard Deviation.
 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358 355

different hydraulic retention times (HRT) of 96 s and 50 s (see Eq.
(10)). The performance of the suspended culture bioreactor at dif-
ferent hydraulic residence times (HRT) is described by the average
removal efficiencies (RE) and the average elimination capacity (EC),
as shown in Table 3. The three parameters are defined in Eqs. (9)–
(11):
V
HRT ðsÞ ¼
F elemental sulfur and then to H2SO4 in a two-stage process, the
ðC i
C 0 Þ
RE ð%Þ ¼
Ci

1 FðC i
C 0 Þ
EC ðg m
3 h Þ¼
V S0 þ H2 O þ 1:5O2 ! H2 SO4
3
where V is the active volume (m ) of the reactor, F is the gas flow
rate (m3 h
1), and Ci and Co are the inlet and outlet concentrations
(g m
3) of the pollutant, respectively.
Figs. 6 and 7 illustrate the evolution of inlet concentration, out-
let concentration, and the percentage removal efficiency (RE) of
MeSH and Me2S over 55 days of operation with an initial VSCs con-
centration of 100 mg.m
3. The maximum RE for MeSH and Me2S
was no more than (65 ± 2.3)% and (68 ± 0.9)%, and the elimination
capacity, EC, was 2.21 ± 0.6 and 2.3 ± 0.3 g m
3 h
1, respectively.
Table 3 shows the performance of the suspended culture bioreac-
tor in treating VSCs at different initial concentrations and different
HRTs.
The removal efficiencies of VSCs were affected by the initial
concentration of VSCs, the biological reactor hydraulic retention
time (HRT), and the VSCs fed to the reactor. Me2S showed the high-
est removal efficiencies in comparison with MeSH and H2S. The
high initial concentration of VSCs and the short HRT were found
to negatively affect the VSCs removal efficiencies. Values in Table 3
are the average of 3 repeated experiments at 95% confidence level.
The removal efficiencies for Me2S, MeSH, and H2S at an initial con-
centration of 100 ± 1 mg m
3 and HRT of 105 s were 65 ± 2.5,
68 ± 0.9, and 45 ± 0.8%, respectively. Increasing the initial concen-
trations of VSCs to 300 ± 5 mg m
3 reduced the removal efficien-
cies at the same HRT for the previous VSCs to (18.0 ± 1.1)%,
(19 ± 1)%, and (9 ± 1)%, respectively. The elimination capacity of
the VSCs ranged from (1.9 ± 0.) to (2.3 ± 0.) g m
3 h
1 for Me2S,
(1.8 ± 0.7) to (2.21 ± 0.6) g m
3 h
1 for MeSH, and (1.4 ± 0.2) to
(1.5 ± 0.2) g m
3 h
1 for H2S.
ð9Þ Kennes and Veiga, 2013 have shown that H2S is converted to
mechanism of this conversion is summarized in Reaction (9) and
(10)
ð10Þ
H2 S þ 0:5O2 ! S0 þ H2 O ðReaction9Þ
ð11Þ
ðReaction10Þ
Organic sulfur compounds, on other hand, are converted to
H2SO4 usually in more than 2 stages. The mechanism of the conver-
sion of Me2S and MeSH can be written as Reactions 11 and 12
Me2 S ! MeSH ! H2 S ! S ! H2 SO4 ðReaction11Þ
MeSH ! H2 S ! S ! H2 SO4 ðReaction12Þ
4.3. Treatment of volatile sulfur compounds (VSCs) by solar AOT and
ozone
Fig. 8 illustrates the average evolution of VSCs and the removal
efficiencies during the process of solar advanced oxidation and
ozone. The initial concentration of VSCs used in this experiment
was 100 ± 1 mg m
3. Experiments were carried out with an initial
ozone concentration of 0.5 mg L
1. VSCs were oxidized to a very
low level by solar advanced oxidation and ozone in less than
10 min. Moreover, during the oxidation reaction, it was observed
that the half-lives of the VSCs were less than 3.0 min, which indi-
cated fast advanced oxidation, due to the contribution of both solar
oxidation and ozone.

Table 3
Performance of the suspended culture bioreactor at VSC initial concentration and different hydraulic residence times.

Compound Waste air composition (mg/m3) HRT (s) Average RE (%)

x  CIa Loading rate (g m
3 h

1
) Average EC (g m
3 h

1
) Operational


x  CIa (Std. Dev.)

x  error b (Std. Dev.)

x  CIa (Std. Dev.)

x  CIa (Std. Dev.) time (day)

MeSH 100 ± 1.5 (0.34) 105.0 ± 1.0 65.0 ± 2.3 (0.76) 3.4 ± 0.7 (0.89) 2.21 ± 0.6 (0.67) 55
100 ± 1.0 (0.27) 52.0 ± 1.0 28.0 ± 1.2 (0.55) 6.8 ± 0.6 (0.9) 1.90 ± 0.8 (1.1) 20
200 ± 0.5 (0.33) 105.0 ± 1.0 29.0 ± 1.0 (1.1) 6.8 ± 0.4 (1.3) 2.00 ± 0.6 (2.1) 25
200 ± 1.1 (0.17) 52.0 ± 1.0 13.0 ± 1.2 (0.89) 13.6 ± 0.5 (1.8) 1.8 ± 0.7 (1.6) 20
300 ± 3.5 (1.8) 105.0 ± 1.1 18.0 ± 1.1 (0.65) 10.2 ± 0.2 (0.6) 1.8 ± 0. (0.5) 20
(1.6)
300 ± 2.5 (0.89) 52.0 ± 1.1 9.0 ± 0.5 (0.23) 20.4 ± 0.3 (2.3) 1.8 ± 0.7 (1.7) 20
Me2S 100 ± 1.0 (0.34) 105.0 ± 1.0 68.0 ± 0.9 (0.78) 3.4 ± 0.6 (3.3) 2.3 ± 0.3 20
(1.5)
100 ± 0.9 (0.21) 52.0 ± 1.0 33.0 ± 0.9 (0.98) 6.8 ± 0.5 (1.2) 2.2 ± 0. (2.1) 20
200 ± 1.5 (0.5) 105.0 ± 1.0 30.0 ± 1.4 (0.99) 6.8 ± 0.6 (2.1) 2.0 ± 0.2 20
(0.45)
200 ± 2.5 (1.3) 52.0 ± 1.0 14.0 ± 0.4 (0.67) 13.6 ± 0.5 (1.1) 1.9 ± 0.3 (0.90) 20
(0.35)
300 ± 5 (2.5) 105.0 ± 1.0 19.0 ± 1.0 (1.2) 10.2 ± 0.1 (1.9) 1.9 ± 0.5 ± 4.2 20
300 ± 5 (2.1) 52.0 ± 1.0 9.2 ± 1.0 (1.1) 20.4 ± 0.3 (1.5) 1.9 ± 0.5 (1.6) 20
(1.5)
H2S 100 ± 1.1 (0.89) 105.0 ± 1.0 45.0 ± 0.8 (1.0) 3.4 ± 0.2 (0.89) 1.5 ± 0.2 (2.1) 20
(1.2)
100 ± 1.5 (3.2) 52.0 ± 1.0 20.0 ± 0.3 (0.45) 6.8 ± 0.3 (1.5) 1.4 ± 0.5 (1.5) 20
200 ± 3.5 (0.56) 105.0 ± 1.0 19.0 ± 0.9 (2.3) 6.8 ± 0.4 (2.1) 1.3 ± 0.2 (0.88) 20
200 ± 1.5 (0.45) 52.0 ± 1.0 11.0 ± 1.1 (3.2) 13.6 ± 0.4 (2.1) 1.5 ± 0.6 (1.6) 20
300 ± 7 (1.3) 105.0 ± 1.0 9.0 ± 1.0 (1.2) 10.2 ± 0.1 (2.1) 0.9 ± 0.1 (0.89) 20
300 ± 8 (3.1) 52.0 ± 1.0 7.0 ± 1.5 (1.7) 20.4 ± 0.1 (1.3) 1.4 ± 0.2 (1.7) 20
a
CI: confidence interval at 95% confidence level.
b
Error at 95% confidence level.
c
Std. Dev.: Standard Deviation.
356 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358

Initial concentration of MESH (mg/m 3) 150 80

60

% RE of MESH
100

40

50
20
Inlet
Outlet
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (day) time (day)

Fig. 6. Evaluation of inlet, outlet, and percentage removal of MeSH inlet in aerobic biological CSTR reactor.

150 80
Initial concentration of Me2S (ppbv)

60
100 % RE of Me2S
40

50
20

Inlet
Outlet % removal
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (day) time (day)

Fig. 7. Evaluation of inlet, outlet, and percentage removal of Me2S inlet in aerobic biological CSTR reactor.

15.0 100

12.5
80

MSH
10.0
[VOSC] PPbv

Me2S
% Removal

60
H2S
7.5 % MSH
% Me2S
40
% H2S
5.0

20
2.5

0.0 0
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0
Time (min)

Fig. 8. Evaluation of VSCs and the percentage removal efficiency during solar advanced oxidation and ozone processes; [VSC]i = 100 mg/m3, [O3]i = 0.5 mg/L, and solar
irradiation in June.

Measuring the inlet and outlet ozone concentrations allows to outlet gas. The amounts of ozone used for the degradation of MeSH,
calculate the amount of ozone used in oxidizing the VSCs. The used Me2S, and H2S were 0.3, 0.38 and 0.32 mg L
1, respectively.
ozone dose was calculated with the following equation: The oxidation mechanism of the TiO2/hm-solar/O3 system involve
r ¼ F  ð½O3 gas; in
½O3 gas;out Þ ð12Þ the absorption of photons by TiO2 promoting electrons from the
valence to the conduction band and generating electronic
where r is the ozone dose used, [O3]gas,in is the ozone concentration vacancies at the valence band. The promoted electrons participate
in the inlet gas, and [O3]gas,out is the ozone concentration in the in reduction–oxidation reactions producing a free radicals
 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358 357

Table 4
Removal of VSCs by combined advanced oxidation processes and biological treatment.

Waste air composition (mg m
3) HRT

x  CI RE

x  CI ECbio (g m
3 h
1)

x  CI Time of operation (day)
AOT (min) Bio (s) AOT (%) Bio (%) Total (%)
MeSH 100 ± 1 2.0 ± 0.5 105 ± 3 50 ± 1.3 75 ± 0.3 87.5 ± 0.2 2.55 ± 0.20 15
100 ± 1 2 ± 0.5 52 ± 3 50 ± 1.0 48 ± 0.4 74 ± 1.1 3.26 ± 0.13 15
200 ± 2 2 ± 0.4 105 ± 2 33 ± 1.3 44 ± 0.4 62.5 ± 1.1 2.99 ± 0.06 15
200 ± 2 2 ± 0.4 52 ± 2 33 ± 0.8 33 ± 0.5 55.1 ± 1.0 4.49 ± 0.03 15
300 ± 5 2.0 ± 0.5 105 ± 3 27 ± 0.7 38 ± 0.3 54.7 ± 0.9 3.88 ± 0.02 15
300 ± 5 2.0 ± 0.5 52 ± 4 26 ± 0.9 29 ± 0.2 47.5 ± 1.1 5.92 ± 0.01 15
Me2S 100 ± 1 2.0 ± 0.5 105 ± 5 60 ± 0.7 78 ± 0.1 91.2 ± 1.3 2.65 ± 0.03 15
100 ± 1 2.0 ± 0.5 52 ± 4 60 ± 0.8 53 ± 0.6 81.2 ± 1.5 3.60 ± 0.01 15
200 ± 2 2.0 ± 0.6 105 ± 5 55 ± 1.0 45 ± 0.5 75.3 ± 1.1 3.06 ± 0.02 15
200 ± 2 2.0 ± 0.5 52 ± 3 55 ± 0.5 33 ± 0.7 69.9 ± 1.5 4.49 ± 0.04 15
300 ± 5 2.0 ± 0.6 105 ± 2 40 ± 0.4 45 ± 0.4 67 ± 1.0 4.59 ± 0.05 15
300 ± 5 2.0 ± 0.6 52 ± 2 40 ± 0.6 23 ± 0.3 53.8 ± 0.3 4.69 ± 0.04 15
H2S 100 ± 1 2.0 ± 0.5 105 ± 2 65 ± 0.5 66 ± 0.5 88.1 ± 0.4 2.24 ± 0.03 15
100 ± 1 2.0 ± 0.5 52 ± 2 65 ± 0.4 45 ± 0.7 80.8 ± 0.6 3.06 ± 0.02 15
200 ± 2 2.0 ± 0.6 105 ± 3 55 ± 0.7 35 ± 0.3 70.8 ± 0.6 2.38 ± 0.04 15
200 ± 2 2.0 ± 0.6 52 ± 3 55 ± 0.9 30 ± 0.3 68.5 ± 1.0 4.08 ± 0.03 15
300 ± 5 2.0 ± 0.5 105 ± 2 50 ± 0.3 27 ± 0.2 63.5 ± 1.1 2.75 ± 0.03 15
300 ± 5 2.0 ± 0.5 52 ± 1 50 ± 0.2 22 ± 0.1 61 ± 1.0 4.49 ± 0.04 15

(see Reactions (5) and (6)). Ozone molecule, on the other hand, adjusted to 2.5 ± 0.2 mg L
1 when necessary. Table 4 shows a sum-
accepts electrons from the surface of TiO2 to produce ozonide ion mary of the results obtained for each of the tested conditions, once
radical (Reaction (13)), which, in turn, forms hydroxyl radicals the reactors were assumed to be running at steady-state.
according to Reactions (14) and (15). Thus, the oxidation rate of The results presented in Table 4 correspond to experiments car-
VSCs increased. ried out with initial VSCs concentrations of 100 ± 1, 200 ± 2, and
300 ± 5 mg m
3, an AOT hydraulic retention time of 2 min, and a
O3 þ e
! O


3 ðReaction13Þ biological reactor retention time of either 105 s or 52 s.
For all operational conditions, the overall removal efficiencies of
O

þ

3 þ H ! HO3 ðReaction14Þ VSCs (MeSH, Me2S, and H2S) were >53%. Removal efficiencies of
(87.5 ± 0.2)%, (91.2 ± 1.5)%, and (88.1 ± 0.4)% were achieved at an
HO
3 ! O2 þ HO
ðReaction15Þ initial VSCs concentration of 100 ± 1 mg m
3, HRTAOT of 2 min
and HRTbio of 105 s for MeSH, Me2S, and H2S, respectively. In com-
The effect of RH on the performance of the combined processes
parison with a single aerobic bioprocess, solar oxidation increased
of solar oxidation and ozone on the degradation of VSCs was also
the VSCs removal efficiency by a factor of two. The results obtained
investigated. RH values in the range of 10–60% were tested for
from the combined process of solar AOTs and bioprocess confirm
their effects on VSCs degradation. Experiments were carried out
the suitability of solar AOTs as pre-treatment for VSCs followed
with an initial VSCs concentration of 100 mg m
3 and an initial
by a biological treatment.
ozone dose of 0.25 mg L
1. For the experiments carried out with
The high VSCs removal efficiencies in the combined processes
H2S, there was no effect of the variation of RH on the degradation
were related to the effect of both solar oxidation and biological
efficiency. For MeSH and Me2S, it was observed that the degrada-
process on degradation VSCs. The solar oxidation process involve
tion efficiency increased with increasing RH up to 35%; after that,
both degradation and partial mineralization of the studied com-
the RH effect is minimal. This tendency suggests that low RH
pounds. The remaining VSCS and their degradation by-products
enhances the generation of hydroxyl radicals and consequently
can be then completely oxidize in the biological process. Different
improves VSCs decomposition. However, excessive water vapor
studies have shown that during the oxidation of VSCs carbon diox-
may interfere with the surface activity of the TiO2 catalyst or
ide and sulfur dioxide were detected as gas phase, and different
occupy the adsorption sites on the photocatalyst, leading to ‘‘com-
organic by products (.g. dimethyl sulfoxide (CH3S(O)CH3, dimethyl
petitive adsorption” which results in a reduction in the rate of rad-
sulfone (CH3S(O)2CH3) methanesulfenic acid (CH3SOH), and sul-
ical generation and VSCs elimination. In addition, it is believed that
fate were detected as water soluble (Tevault et al., 1981;
high water vapor in the gas stream can act as a hydroxyl radical
Sahle-Demessie and Devulapelli, 2008; Devulapelli and Sahle-
scavenger or ozone inhibitor. Goswami et al., 1997 during the
Demessie, 2008). Based on the results obtained in this study it
study of photo-catalytic disinfection of indoor air using titanium
can be concluded that VSCs and their degradation by-products
dioxide as photo-catalysis suggested that high water vapor
are likely to be reduced from the gaseous stream by biological pro-
(humidity) may hinder the photoreaction and/or water can com-
cesses. Further future studies will be devoted to determine the
pete with the organic matter for the active titanium oxide sites
degradation by-product of the studied VSCs and relate these by-
thus the rate of oxidation reaction decrease. Similar effect were
product to the biological process efficiency.
reported in our previous work (Al Momani and Jarrah, 2009).
Further investigation of this phenomenon is required.
5. Conclusions
4.4. Treatment of volatile sulfur compounds (VSCs) by combined solar
oxidation and an aerobic bioprocess Volatile sulfur compounds (VSCs) can be reduced from air by
the use of advanced oxidation technology, solar advanced oxida-
In this part, partial oxidation of VSCs was performed by solar tion technology, biological treatment, and a combination of solar
radiation followed by aerobic oxidation. To guarantee uniform con- advanced oxidation technology and biological treatment. More
ditions on the bioreactor operation, the biomass concentration was than 65% of three VSC model compounds (methanethiol (MeSH),
358 F.A. Almomani et al. / Solar Energy 135 (2016) 348–358
dimethyl sulfide (Me2S), and (H2S) were eliminated by solar
advanced oxidation technologies (AOTs). High removals of VSCs
were achieved by solar AOTs and ozone, and significant VSCs elim-
ination was achieved by solar advanced oxidation and biological
treatment. The results indicate that solar AOTs and the combined
process (solar AOTs and bioprocess) can efficiently be used for
the treatment of VOSCs.
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