Biochemical Engineering Journal 105 (2016) 420–427

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Biochemical Engineering Journal

journal homepage: www.elsevier.com/locate/bej

Regular article

Integrated process of fungal membrane bioreactor and photocatalytic

membrane reactor for the treatment of industrial textile wastewater
Ece Ümmü Deveci a,∗∗ , Nadir Dizge b , H. Cengiz Yatmaz c,∗ , Yasin Aytepe d
a
Nigde University, Department of Environmental Engineering, 51240 Nigde, Turkey
b
Mersin University, Department of Environmental Engineering, 33343 Yenisehir, Mersin, Turkey
c
Gebze Technical University, Department of Environmental Engineering, 41400 Gebze, Kocaeli, Turkey
d
Nigde University, Department of Chemistry, 51240 Nigde, Turkey

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

Article history: In this study, fungal membrane bioreactor (FMBR) and semiconductor photocatalytic membrane reactor
Received 29 July 2015 (PMR) were used in order to test the efficiency of integrated fungal biodegradation and photocatalytic
Received in revised form 7 October 2015 degradation of textile wastewater from reactive washing processes. It was found that color removal and
Accepted 19 October 2015
chemical oxygen demand (COD) reduction efficiencies were 88% and 53% for photocatalytic degradation,
Available online 27 October 2015
respectively. TiO2 and ZnO were tested as semiconductor catalysts in the PMR and TiO2 showed better effi-
ciencies than ZnO for both color and COD removal. However, it was attained that color removal and COD
Keywords:
reduction efficiencies were about 56% and 60% for fungal biodegradation using Phanerochaete chrysospo-
Membrane bioreactor
Heterogeneous biocatalysis
rium, respectively. Moreover, integrated system in which photocatalytic degradation was employed as
Biodegradation a post-treatment application after fungal biodegradation process achieved high removal efficiencies for
Integrated processing color and COD removal as 93% and 99%, respectively.
White-rot fungi © 2015 Elsevier B.V. All rights reserved.
Photocatalysis

1. Introduction Certain textile effluent contains dyes, salts, caustic, surfactants

chelating agents, by-products, precursors etc. [2].
Water is an essential substance in virtually each industry espe- Many processes which include physicochemical, biochemical,
cially for textile industry with direct and indirect utilization in the combined treatment processes and other advanced treatment tech-
different processes (cooling water, chilled water, washing water nologies have been studied to treat textile wastewater up to now.
etc.). Industry collects fresh water from water resources located However, the application of these processes in an industrial scale
near natural areas such as lake, river, underground etc. However, becomes difficult due to the operational problems, maintenance
these resources are rapidly depleting [1]. The textile industries con- and costs. Chemical oxidation via ozone, or a combination of ozone
sume large amount of fresh water and produce large volumes of and H2 O2 has great interest but their costs are quite high. In addi-
wastewater in different steps while dyeing and finishing processes. tion, biological treatment by activated sludge allows high efficiency
In textile industry, wastewater containing excessive color, COD, for COD removal, but it does not provide complete color removal
and complex chemicals is produced. These parameters are consid- and some potential problems such as bulking and foaming can
ered as critical contaminants. This kind of wastewater contains a occur [3].
large amount of dyes which are considerably toxic to living sys- Fungi which have broad range degradation capacity were found
tems. Therefore, textile wastewater has been considered an urgent to be most efficient in breaking down synthetic dyes. White-rot
need for protection and providing aquatic life cycle. fungi are the most promising biological agents which can be utilized
Due to the fact that extremely changing the content of textile for developing novel biological wastewater treatment processes
industry, its effluent contains complex chemicals. In this perspec- such as fungal membrane bioreactor. They are able to degrade a
tive, for effective decolorization of textile industry effluent requires wide range of recalcitrant pollutants including various types of
some kind of fungal assistance and suitable reactor conditions. dyes, lignocellulose compounds, organic pollutants such as poly
aromatic hydrocarbons (PAHs), chlorophenols and poly chlori-
nated biphenyls. These microorganisms finally break down the
compounds via their enzymatic reactions (such as manganese per-
∗ Corresponding author.
∗∗ Corresponding author.
oxidases, lignin peroxidases, laccase etc.) [4–6].
E-mail addresses: ecedeveci@gmail.com (E.Ü. Deveci), yatmaz@gtu.edu.tr
Blanquez et al. studied the operational conditions for the con-
(H.C. Yatmaz). tinuous treatment process of the metal complex dye in a fluidized

http://dx.doi.org/10.1016/j.bej.2015.10.016
1369-703X/© 2015 Elsevier B.V. All rights reserved.
 E.Ü. Deveci et al. / Biochemical Engineering Journal 105 (2016) 420–427 421

bed bioreactor using air pulses with retained pellets of the white rot Table 1
Properties of ultrafiltration membrane.
fungus, Trametes versicolor. It was reported that decolorization effi-
ciency was calculated as >80% for the different hydraulic retention MP 005 Membrane Properties
times (HRTs) ranging from 18 to 120 h, and the dye removal rates Membrane material PES (polyethersulfone)
ranged from 1.16 to 6.73 mg/L/h [7]. Therefore, HRTs and biomass Manufacturer Microdyn-Nadir GmbH
concentrations considered as significant parameters during decol- Membrane configuration Flat sheet
orization of real textile effluents. Blanquez et al. also investigated Pore size 0.05 ␮m
Pure Water Flux [L/m2 /h] >800
the decolorization of textile wastewater using white rot fungus
Module Properties
pellets, T. versicolor in the scale up of a 10 L air pulsed bioreactor. Module configuration Flat plate
Decolorization experiments of 150 mg/L Grey Lanaset G dye solu- Effective membrane area 30 cm2
tions showed that in both discontinuous and continuous treatment Module material Teflon
Module size (W × L cm) 3 × 20
with an HRT of 48 h, the decolorization efficiency was higher than
90% [8].
Photocatalytic processes for wastewater treatment are com- Table 2
monly studied in powder suspended and immobilized (fixed) Characteristic parameters of textile reactive washing bath wastewater.
semiconductor systems. Photocatalytic degradation efficiency is Parameters Value
affected by many parameters such as; pH, temperature, type of
Total COD (mg/L) 1125 ± 70
semiconductors, pollutant concentration, contact time and illumi-
Soluble COD (mg/L) 800 ± 100
nation intensity [9–14]. Photocatalytic membrane reactor (PMR), Suspended Solids (mg/L) 35 ± 2
in which photocatalysis is coupled with membrane separation Conductivity (␮S/cm) 2660 ± 16
process, is a new hybrid technology for water and wastewater pH 8.7 ± 0.5
treatment. With some unique advantages such as nontoxic and con- Color Very dark violet

tinuous running, PMR was developed rapidly in the past few years
[15]. Moreover, a low-cost and eco-friendly recovery of the pho-
conductor powders for PMR experiments. A flat plate membrane
tocatalysts and the separation of products and/or inter mediates
module with MP005 membrane type was used in both PMR and
simultaneously occur in PMR. In the meantime photocatalytic pro-
FMBR (Table 1). Textile wastewater was provided from a textile
cess improves membrane cleaning and delays membrane fouling
factory in Kayseri, Turkey. The characterization parameters of tex-
[16].
tile reactive washing bath wastewater were given in Table 2. The
In the past decades, various hybrid processes were being devel-
types of dyes that were utilized in this sort of textile industry were
oped for wastewater treatment. For example, Mozia et al., reported
supplied by the company as follows; sunfron red, sunfix blue, sunfix
that the results of the investigation on the possibility of coupling
deep red, sunfix red, sunfix navy blue, sunfix orange, sunfix yellow,
photocatalysis and membrane distillation (MD) for degradation
sunzol navy blue, sunfron blue, sunzol turquoise blue, sunfix scar-
of acid red 18 in aqueous solutions [17]. In other study, the suc-
let. The deionized water used in all the experiments was obtained
cessful operation of a hybrid photocatalysis–membrane separation
from Milli-Q ultrapure water system.
process (in a laboratory-scale pilot system) was demonstrated for
degradation of humic acids (HA). The photocatalytic membrane
reactor (PMR) employing an ultrafiltration (UF) submerged module 2.1.2. Potato Dextrose Agar (PDA)
was operated in continuous mode with TiO2 catalyst [18]. Potato Dextrose Agar (PDA) was growth medium of Phane-
In recent studies, fungal membrane bioreactor or photocatalytic rochaet echrysosporium and it was purchased from Merck and
membrane reactor processes have been investigated separately to prepared as indicated on the PDA package. This medium was
treat different and complex wastewater effluents [19–28]. PMR autoclaved at 121 ◦ C for 15 min. After cooling to atmospheric tem-
allows the separation characteristics of membrane in order to sep- perature (below 40 ◦ C) the media was poured into the test tubes
arate the treated effluent and to maintain constant semiconductor or Petri dishes for solidification in the laminar chamber and inocu-
suspension within the photoreactor. The membrane can act as a lated from the stock culture. Taking out from the chamber of these
barrier to confine the catalyst within the system. Also, FMBR pro- tubes or Petri dishes were incubated in a BOD incubator for fungi
vides constant fungi suspension within the bioreactor. Moreover, growth.
the membrane keeps the enzyme released from fungi in the reactor.
The aim of this study is to develop a novel integrated treatment 2.1.3. Fungus strain
process involving fungal biodegradation in FMBR and ultraviolet Phanerochaete chrysosporium was obtained from Environmental
assistedphotodegradation in PMR. Theseprocesses were used inte- Microbiology Laboratory of Environmental Engineering Depart-
grated in order to achieve high color and COD removal in industrial ment, University of Nigde, Turkey. It was white in color and had
textile wash water effluent. The primary objective of this study was a mycelia structure. The fungus was available on PDA slant in a test
to utilize the integrated feature of organic matter degradation by tube.
white-rot fungi and color removal by semiconductor photocatalytic
reduction sequentially. The integrated process performance was 2.2. Methods
followed up in bench-scale reactors in sequential process to evalu-
ate the long term performance of FMBR and PMR for high color and 2.2.1. Making sub-culture of fungus strain
COD removal from washing bath wastewater. P. chrysosporium was grown for 5 days at 30 ◦ C in PDA plate and
it was used to inoculate 250 mL erlenmeyer flasks with 50 mL of
2. Materials and methods stock basal media which was prepared by glucose (2 g/L) and other
nutrients into Milli-Q water. The other components of the stock
2.1. Materials basal media were as follows: 2 g/L peptone, 2 g/L KH2 PO4 , 0.1 g/L
CaCl2 , 0.5 g/L MgSO4 .7H2 O, 0.001 g/L thiamine and 1 mL/L trace
2.1.1. Chemicals elements. Stock trace elements solution was prepared by dissolv-
Commercially pure ZnO (particle size <1 ␮m, Sigma–Aldrich) ing 0.08 g CuSO4 .5H2 O, 0.05 g NaMoO4 .2H2 O, 0.07 g MnSO4 .4H2 O,
and TiO2 (particle size <1 ␮m, Evonik P-25) were used as semi- 0.043 g ZnSO4 , 0.05 g Fe(SO4 )3 in 1 L of ultrapure water. The solution
422 E.Ü. Deveci et al. / Biochemical Engineering Journal 105 (2016) 420–427

solution was retained with the aid of blown air system. During the
experiments the removal of organic material was evaluated with
COD analyzes. The decolorization percent of dye chemicals was
monitored by measuring the absorbance values in a spectropho-
tometer. A flat plate membrane module with MP005 membrane
type was immersed into the reactor. Sampling was conducted by
applying a suction pressure (200 mbar) through membrane mod-
ule.
A laboratory scale column FMBR, made of Pyrex glass with a
working volume of 900 mL was used. Air was provided from the
bottom of the reactor by using a diffuser connected to air pump. This
air also keeps the fungi as suspended in the reactor which is nec-
essary for biosorption and biodegradation. The MP005 membrane
comprised module was placed inside the bioreactor. A peristaltic
pump was installed into the membrane module to withdraw the
treated effluent. Wastewater effluent was continuously fed with
same amount of membrane permeate flow. The pH of the bioreac-
Fig. 1. The experimental setup of the sequential photocatalytic membrane reactor
tor was monitored continuously. The system was first inoculated
(PMR) and fungal membrane bioreactor (FMBR) integrated process 1. Stock wastew- with fungi grown for two weeks in 1 L erlenmeyer flasks each con-
ater, 2. Pyrex glass reactor (FMBR), 3. Membrane module, 4. Fritz filter, 5. UVA lamps, taining 500 mL of the culture media and wash water effluent was
6. Lid for keeping the light in, 7. Pyrex glass reactor (PMR), 8. Ice vessel, 9. Peristaltic injected. The reactor was operated for 1 day in batch mode which
pump, 10,11. Air blower.
the hydraulic residence time (HRT) was 15 h.
Biodegradation and photodegradation experiments were car-
was taken into test tubes and plugged with cotton and autoclaved ried out separately in the respective reactors; this was then
in 121 ◦ C (1.2 atm pressure) for 15 min. Test tubes were cooled followed by an integration of two processes. In the integrated sys-
and inoculated in UV-Laminar chamber which provided sterilized tem, two processes were arranged in series such that, in the first
condition. Inoculated test tubes were kept in BOD incubator for case, the photodegradation process was followed by the FMBR pro-
incubation for 20 days and preserved in a refrigerator for further cess while in the second case, the fungal biodegradation process
use. In every one month the culture was refreshed. Initial cell con- was followed by the PMR. Photodegradation was carried out at
centration was 80 mg dry weight/L. original pH of wastewater and experiments were conducted using
Spore production was conducted at 30 ◦ C and for 5 days 500 mL effluent solution inside the tubular reactor irradiated with
growth on the PDA medium. The spores were prepared by sus- UVA lamps. Fungal biodegradation was performed at pH 4.5 since
pension in 0.09% NaCl solution and then they were harvested this was the optimum pH condition for the fungal growth [29,30].
without disturbing the mycelial growth using a loop and filtered. Membrane filtrate obtained from one process was fed to the other
Spore concentration was determined by measuring absorbance at process sequentially. The pH of the PMR effluent was adjusted to
650 nm (an absorbance value of 1.0 is approximately equivalent to about 4.5 before feeding to the FMBR. Although the pH of the fungi
2 × 106 spores/mL) by spectrophotometer. Spores were incubated biodegraded treated effluent was not adjusted before feeding the
at 30 ◦ C for 5 days at stock basal media, in 250 mL erlenmeyer PMR since photocatalytic processes proceeded in wide range of
with 100 mL working volume. After 5 days incubation, spores were pH [9,10]. Both of the FMBR and PMR effluent was obtained using
transformed to erlenmeyer 1.2–1.8 g pellets and then they were MP005 membrane comprised module immersed in reactors. The
harvested for use in bioreactor. membrane was regularly cleaned (off site manual cleaning with
distilled water) when membrane fouling was so severe that the
2.2.2. Operation of the FMBR and PMR integrated reactor pump could not control the flow rate.
Laboratory scale FMBR and PMR were used in this study. Experi-
ments were carried out in both single and sequential reactor set-up. 2.3. Analytical method
Process scheme is shown in Fig. 1. Photocatalytic degradation as a
single treated technique was studied for color and COD removal. The fungal and photocatalytic degradation efficiencies of
Two different catalyst types (ZnO and TiO2 ) and three different wastewater were measured by monitoring the COD and color
catalyst loading (1.0, 1.5, 2.0 g/L) were optimized in PMR. TiO2 removal. Color measurements were monitored using values of
and ZnO were selected as the most active and widely used semi- indexes of transparency parameter. Values of indexes = DFZ (Durch-
conductors [10]. Photocatalytic membrane reactor was performed sichtsFarbZahl) in accordance with the standards were obtained by
in a column-shaped batch of 900 mL capacity Pyrex glass column taking absorbance in three wavelengths as 436, 525 and 620 nm
photo-reactor, 50 cm in length and 5 cm in diameter. The effective using a visible spectrophotometer (WTW Photolab 6600 UV–vis
working volume of PMR was 500 mL while the membrane module Spectrophotometer) [31]. The color change of the solution was
in and the oxidation was continued for 2 h. Air was blown into the determined by measuring the absorbance values after the collec-
reactor at a flow rate of 100 mL/min to feed and accelerated the tion of effluent permeate in half an hour intervals. Percentage of
oxidation processes. The column photo-reactor was surrounded by color and COD removal was calculated.
six UVA type lamps (Philips TL 8W Actinic BL) emitting waves at COD was analyzed by closed reflux method with a thermo reac-
365 nm predominantly. Lamps were placed in hexagonal position tor (Giant QBH2) using potassium dichromate solution as oxidant
inside an aluminum foil coated cylinder for equal reflection. The according to the standard methods [32]. The analysis for COD was
light-intensity of the lamps was measured as 3.5 mW/cm2 using a performed in duplicates and average value was presented. pH and
UV-light meter (Lutron UVA-365) sensor inside the column reac- conductivity values were monitored by a multi meter (WTW 9430
tor. To obtain stability during the process, cooled air was blown Multiparameter).
between the lamp assembly and the column reactor to keep the Lignin peroxidase (LiP) activity was measured with the refer-
temperature around 25 ± 1 ◦ C. ZnO or TiO2 powders were poured ence of Tein and Kirk [33]. One unit of activity (U) represents
into the reactor and uniform distribution of catalyst particles in 1 ␮M veratryl alcohol oxidized to the aldehyde per min at room
 E.Ü. Deveci et al. / Biochemical Engineering Journal 105 (2016) 420–427 423

(a) 100 (a)100

436 nm TiO2
525 nm
80 620 nm 80

Color removal (%)

Color removal (%)

60
60

40
40

20 436 nm
525 nm
20
620 nm
0
0 30 60 90 120
0
Time (min)
TiO2 ZnO
Catalyst type
(b) 100
(b) 100 TiO2

80

80

COD removal (%) 60

COD removal (%)

60

40

40

20

20
0
0 30 60 90 120
0 Time (min)
TiO2 ZnO
Fig. 3. The effect of reaction time on the (a) color and (b) COD removal efficiency in
Catalyst type
PMR (catalyst loading: 1 g/L, catalyst type: TiO2 , pH = 8.7).

Fig. 2. The effect of catalyst type on the (a) color and (b) COD removal efficiency in
PMR (catalyst loading: 1 g/L, pH = 8.7, reaction time: 120 min).
investigated decoloring methylorange under sunlight conducted in
a photocatalytic membrane reactor (PMR). For the PMR with ZnO
temperature (25 ± 1 ◦ C). Manganese peroxidase (MnP) activity was particles in suspension, the photocatalytic decolorization percent
measured by spectrophotometry in presence of Mn2+ as a substrate was over 98% after 40 min. These results demonstrated that PMR
[34]. based on ZnO particles and polypropylene macroporous membrane
could be applied in decoloring dyes [38].
3. Results and discussion In other work, photocatalysis of an actual textile dye house
wastewater with TiO2 was investigated. It was reported that COD
3.1. Photodegradation in the photocatalytic membrane reactor reduction was generally varied between about 40% and 90%
depending on the operating conditions after 4 h of treatment [39].
Color and COD removal efficiencies of two catalysts (TiO2 and The possible explanation of the low COD removal is that, the indus-
ZnO, 1 g/L) were compared. Photocatalytic degradation of the trial textile effluent wastewater is more complex and it can contain
industrial textile washing bath wastewater at its original pH (8.7) some recalcitrant inorganic and organic additives [11,39]
was shown in Fig. 2. The percentage color removal in the pres- Degradation results in time for photocatalytic degradation of the
ence of TiO2 was observed to be 81%, 83%, 88% at 436, 525, 620 nm, textile effluent wastewater at their original pH (8.7) and with TiO2
respectively. On the other hand, ZnO shows lower percentage color (1.0 g/L) were shown in Fig. 3a. Reaction time increased from 30
removal than TiO2 catalyst and it was observed to be 53%, 57%, to 120 min, the decolorization efficiency also increased from 19%,
67% at 436, 525, 620 nm, respectively (Fig. 2a). COD removal effi- 20%, 14% to 81%, 83%, 88% at 436, 525, 620 nm, respectively. The
ciency was 21% and 53% for ZnO and TiO2 catalyst, respectively observed reduction in color during photocatalytic degradation can
(Fig. 2b). It can be clearly seen that TiO2 catalyst was more effective be explained by increasing photogenerated hydroxyl radicals with
than ZnO catalyst. TiO2 semiconductor is more stable on wide pH time [40]. However, a lower COD reduction was observed for wash-
range and performs better for different effluent sources [35]. On the ing bath wastewater with time (Fig. 3b). Reaction time increased
other hand, color removal was improved for synthetic dye solutions from 30 to 120 min, the COD removal efficiency also increased from
when ZnO was used as semiconductor powder compare to TiO2 but 12% to 53%, respectively. The possible reason is that, the change in
COD removal was better when TiO2 was used [36,37]. Hu et al. [38] the structure of organic molecules during photocatalytic degrada-
424 E.Ü. Deveci et al. / Biochemical Engineering Journal 105 (2016) 420–427

100 (a) 100

436 nm
525 nm
80 620 nm 80

Color removal (%)

Color removal (%)

60 60

40 40
436 nm
525 nm
620 nm
20 20

0 0
0 1 2 3 4 5
1 1,5 2 3
Time (days)
Catalyst dose (g/L)

Fig. 4. The effect of TiO2 dose based on the absorbance values for the color removal (b) 100
efficiency in PMR (catalyst type: TiO2 , pH = 8.7, reaction time: 120 min).

80
tion, did not reach to total mineralization of the organic molecules
in 120 min final time thus resulting in the low COD reduction.

COD removal (%)

The similar results for low COD reduction were observed in pre- 60
vious studies [39–42]. Anaerobic up-flow fixed bed reactor and
annular photocatalytic reactor were used to study the efficiency
of integrated anaerobic digestion and UV photodegradation of real 40
distillery effluent and raw molasses wastewater. It was found that
UV photodegradation as a stand-alone technique achieved COD
reduction of <20% and a negligible BOD reduction [40]. 20
During photocatalytic process, one of the most important
parameters in operation was catalyst loading. The effect of differ-
ent TiO2 between 1 and 3 g/L. loading on photocatalytic oxidation of 0
0 1 2 3 4 5
textile washing bath wastewater was then studied According to the
data obtained from the COD results, TiO2 catalyst was used to deter- Time (days)
mine the effect of the catalyst loadings on color removal. To make
Fig. 5. The effect of reaction time on the (a) color and (b) COD removal efficiency in
a clear comparison of color removal at different TiO2 loadings, the FMBR (pH = 4.5, fungi concentration: 1.2–1.8 g/L).
absorbance of textile washing bath wastewater at 436, 595, 620 nm
was measured during the experimental run, which was presented
in Fig. 4. It can be clearly seen that the catalyst loading increased enzymatic activity degraded the dye in the remaining incubation
from 1 to 3 g/L, the color removal efficiency increased significantly time. A similar color removal results for Coriolus versicolour, T. ver-
from 19%, 20%, 14% to 74%, 75%, 76% at 436, 525, 620 nm, respec- sicolor and P. chrysosporium was also obtained in previous studies
tively. Since intensity of light and irradiation time is constant, an [7,8,44].
increase in catalyst loading can enhance the active site for adsorp- Meanwhile the effect of time on COD removal of the washing
tion and degradation of dye on catalyst surfaces and the generation bath wastewater was investigated and indicated in Fig. 5b. With
of hydroxyl radicals will get increased [24]. However, increase in increase in time from 1 day to 5 days, the percentage COD removal
catalyst loading prevents light penetration throughout the reactor was increased from 2% to 53%. The COD reduction between the first
and diminishes the semiconductor light interaction [43]. There- and fifth days was probably related to the activity of the lignin and
fore, the extent of photocatalytic degradation was found to increase mangan peroxidaseenzymes in the medium (Fig. 6). It can be seen
with increasing TiO2 concentration up to 2.0 g/L TiO2 , above this from the Fig. 6 that increasing in the enzyme activity had an impor-
value degradation was remained practically constant, reaching a tant role on the degradation of recalcitrant compounds as well
plateau. as decolorization. LiP and MnP were considered as the principal
decolorizing enzyme in cultures of P. chrysosporium [6].
3.2. Fungal biodegradation in the fungal membrane bioreactor Similar results were also obtained when P. chrysosporium and T.
versicolor were used as fungi [25,27,28].
Fungal biodegradation as a single treated technique was studied
for color and COD removal. Fig. 5a presented the effect of time on 3.3. Overall performance of the integrated biological and
color removal of the textile washing bath wastewater during 5 days photocatalytic process
of treatment. Color removal of textile washing bath wastewater by
adsorption in P. chrysosporium mycelium was about 40% after one 3.3.1. Color removal
day. The color removal until the first day was probably because The photodegradation and fungal biodegradation processes
of adsorption in the fungus mycelium (Fig. 5a). With increase in were integrated in two ways: in the first case, photodegradation
time during 5 days, the color removal efficiency increased to 57%, (carried out in PMR) was performed before fungal biodegradation
63%, 62% at 436, 525, 620 nm, respectively. Hai et al. [26] also indi- (carried out in FMBR) while in the second case fungal biodegrada-
cated that adsorption occurred in mycelia in the first 24 h and tion was conducted before photocatalytic degradation. The overall
 E.Ü. Deveci et al. / Biochemical Engineering Journal 105 (2016) 420–427 425

200 200

180 180
MnP
160 LiP 160

140 140

MnP activity (Ul )

LiP activity (Ul )

-1
120 120

100 100

80 80

-1
60 60

40 40

20 20

0 0
1 2 3 4 5

Time (days)

Fig. 6. Lignin peroxidase and manganese peroxidase activity in FMBR during the treatment with P. chrysosporium.

performance of this set-up (integrated PMR followed by FMBR) was (a) 436 nm
then presented as the performance of integrated photocatalytic- 100 525 nm
biological process. This was then compared to the performance of 620 nm
the arrangement in which fungal biodegradation wasused as the
first treatment step and the FMBR effluent wasfed into the PMR 80
Color removal (%)

(integrated FMBR followed by PMR).

It could be seen that in Fig. 7a, the FMBR process was followed
60
by the PMR process in sequence. In this case, it was observed that
the photocatalytic degradation step further removed about 99% of
the original color. It could further be seen (Fig 7a) that the inte- 40
gration of the PMR was followed by FMBR achieved color removal
of around 90% for the textile washing bath wastewater. Apollo
et al. [40] found that UV photodegradation as a stand-alone tech- 20

nique achieved color removal of 54% and 69% for the distillery and
raw molasses wastewater, respectively. On the other hand, anaer-
0
obic digestion(AD) achieved low color removal efficiency, with an
FMBR-PMR PMR-FMBR
increase in color intensity of 13% recorded when treating molasses
wastewater while a color removal of 51% was achieved for the
distillery effluent [38].
(b) 100
3.3.2. COD reduction
In Fig. 7b, the overall COD reduction for integrated biological-
photocatalyticdegradation process was 93%. On the other hand, 80
the integrated photocatalytic degradation-biological process was
COD removal (%)

attained an overall COD reduction efficiency of 88%. Apollo et al.

[40] also reported that UV photodegradation reached a COD reduc- 60
tion of <20%. On the other hand, anaerobic digestion was found to
be effective in COD and BOD reduction with efficiencies of above
75% and 85%, respectively, for both wastewater samples. The appli- 40
cation of UV photodegradation as a pre-treatment method to the
AD process reduced the COD removal and biogas production effi-
ciency. However, an integration in which UV photodegradation was
20
employed as a post-treatment to the AD process achieved high
COD removal of above 85% for both wastewater samples, and color
removal of 88% for the distillery effluent. Thus, photodegradation
0
was employed as a post-treatment technique to an AD system treat-
FMBR-PMR PMR-FMBR
ing distillery effluent for complete removal of the biorecalcitrant
and color imparting compounds [40]. Fig. 7. Overall (a) color and (b) COD removal for the PMR and FMBR integrated
Examples of integrated processes were listed in Table 3 for system (catalyst type: TiO2 , catalyst loading: 2 g/L, pH = 4.5, fungi concentration:
the different kind of wastewater treatment. In most of the cases, 1.2–1.8 g/L).

advanced oxidation processes are used as post-treatments, fol-

lowed by biological process [40,44–46].
426 E.Ü. Deveci et al. / Biochemical Engineering Journal 105 (2016) 420–427

Table 3
Comparison of integrated process.

Integrated process Wastewater Efficiency (%) Reference

Fungal membrane bioreactor + Photocatalytic Textile reactive washing bath wastewater • 93% COD removal This study
membrane reactor • 99% color removal

Anaerobic up-flow fixed bed reactor + Annular Real distillery effluent, raw molasses wastewater • 85.4% and 85.7% COD removal for the [39]
photocatalytic reactor distillery wastewater and MWW,
respectively.
• 79% and 49% color removal for the distillery
wastewater and MWW, respectively.

Phanerochaete chrysosporium + Ozone Textile effluent • 40% color reduction [43]

• 55% phenol removal

Fungal + Photo-degradation Benzophenone (BP3), benzophenone-1 (BP1) • 100% BP1 degradation [44]

Anaerobic biofilm process + Photo-Fenton Textile azo dye • >90% COD removal [45]
oxidation
Trametes versicolor + pilot-scale bioreactor Textile waste water • >90% color removal [8]

4. Conclusions [9] M. Kaneko, I. Okura, Photocatalysis: Science and Technology, Springer,

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