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1 © IWA Publishing 2017 Water Science & Technology | in press | 2017

Reuse and recovery of raw hospital wastewater

containing ofloxacin after photocatalytic treatment with
nano graphene oxide magnetite
D. T. Sponza and P. Alicanoglu

ABSTRACT

Inadequate treatment of the hospital wastewater could result in considerable risk to public health D. T. Sponza (corresponding author)
Environmental Engineering, Engineering Faculty,
due to its macro and micropollutant content. In order to eliminate this problem, a new nano particle Dokuz Eylül University,
Kaynaklar Campus, Buca,
composite was produced under laboratory conditions and a photo-catalytic degradation approach Turkey
E-mail: delya.sponza@deu.edu.tr
was used. COD, BOD5 TSS, TKN, TP (macro) and OFL (micro) pollutant removals were investigated
with the nano graphene oxide magnetite (Nano-GO/M) particles by two different processes, namely P. Alicanoglu
Environmental Engineering, Engineering Faculty,
adsorption and photodegradation. Low removal efficiencies (21–60%) were obtained in the Pamukkale University,
Kınıklı Campus, Denizli,
adsorption process for the parameters given above, after a 90 min contact time at a pH of 7.8 and at Turkey

5 g/L Nano-GO/M composite. With the photodegradation process, higher removal efficiencies were
obtained at 2 g/L Nano-GO/M composite for COD (88%), TSS (82%), TKN (95%) and OFL (97%), at pH
7.8, after 60 min irradiation time at a UV power of 300 W. The synthesized nano particle was reused
and it was used for four sequential treatments of pharmaceutical wastewater with no significant
losses of removal efficiencies (for OFL 97%–90%). The quality of the treated hospital wastewater was
1st class according to the Turkish Water Pollution Control Regulations criteria. This water could also
be used for irrigation purposes.
Key words | micropollutant, nano graphene oxide magnetite composite, ofloxacin, photooxidation,
recovery, reuse, treatment

INTRODUCTION

Hospital wastewaters (HWWs) are complex mixtures
capable of generating major environmental problems,
since they have been estimated to be between 5 and 15
times more toxic than classical urban effluents (Mendoza
et al. ). The micropollutants in the HWWs are directly
discharged into the sewage system without treatment since
the conventional sewage/urban treatment plants can only
remove macro-pollutants such as BOD5, COD, nitrogen
and phosphorus (Guney & Sponza ). Many of the phar-
maceuticals have low biodegradability and they cannot be
transformed into ultimate inorganics. In European countries
there are specific treatment methods for the direct discharge
of HWWs in surface waters. In Turkey, there are no regu-
lations yet for the discharge of HWW into sewage
channels. Among widely used antibiotics, FQs (ciprofloxa-
cin, norfloxacin, levofloxacin, ofloxacin, clinafloxacin, etc.)
are the most common ones. The selection of appropriate
treatment technologies influenced the effluent quality of
doi: 10.2166/wst.2017.531
HWW treatment. The quality of reclaimed water sources
for water reuse can also be determined based on the treated
effluent limits. The utilization of treated wastewater as a
water source should be highlighted for sustainable water
management. Hospital discharges can contain disinfectants,
detergents, contagious faeces/excreta, biological liquids,
drug residues, metal radioelements, and many other chemi-
cals (acids, alkalis, solvents, benzene, hydrocarbons,
colorants, etc.) (Fallis ). These substances may exhibit
different behavior in the wastewater treatment plants due
to their different solubility, volatility, molecular weight,
adsorbility and biodegradability. If they are not treated in
the wastewater treatment, they are released in surface
waters (Verlicchi et al. ). In İzmir/TURKEY, water
resources are not sufficient and the water demand has
increased due to the increase in the urban population and
expansion of industrial and agriculture activities. Therefore,
treated water should be used again in various industries.
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2 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
Certain advanced technologies should be used to improve
the quality of treated effluent for reusing the treated water
in the industrial sectors (Al Aukidy et al. 2014).
Some advanced treatment processes have been reported
about OFL removals from HWWs in the recent literature:
Peng et al. (), investigated the adsorption of OFL (initial
concentration was 10 mg/L) onto carbon nanotubes (CNTs-
200 mg/L) at different pHs (pH 2.0–12.0). 76% OFL
removal was obtained at pH ¼ 5 at 25  C after 7.0 d.
Wang et al. (), used a magnetic chitosan grafted with
graphene oxide (MCGO) for the removal of CIP water by
adsorption. The maximum adsorption capacity of OFL
was 282.9 mg g1 using Langmuir model.
Recent studies relevant to OFL removals via photode-
gradation from HWWs can be summarized as follows:
Titouhi & Belgaied (), investigated the heterogeneous
oxidation of OFL using a composite material synthesized
from sodium alginate and cyclohexane dinitrilo tetraacetic
acid (CDTA). The maximum removal yield was obtained
as 94% at an initial OFL concencentration of 10 mg/L at
pH 3, after 2 h of photooxidation. Zheng et al. (2017) used
a mesoporous silicon supported Fe-Cu bimetallic catalyst
(Fe-Cu@MPSi) for the photodegradation of 30 mg/L OFL.
85% OFL removal was obtained in 2 h at 1 g/L catalyst
and 2,000 mg/L H2O2. Ding et al. (), prepared a magne-
tite nanoparticle (MNP) throughout activation of persulfate
(PS) to degrade norfloxacin (NOR). 90% NOR was deter-
mined within 60 min at a NOR concentration OF 15 μM
and at a of MNP concentration of 0.3 g L1 at pH 4.0).
(Kong et al. ) and Nguyen et al. (2017) obtained
approximately 69–74% OFL removals using an aerobic acti-
vated sludge sequencing batch reactor (SBR) at 52 days of
HRT and a membrane reactor using FS-Sponge. Kong
et al. () studied the OFL removal from aqueous solution
using activated carbon (AC). 96% of OFL was adsorbed
(132 mg/g) at pH 6 at a temperature of 293 K and at a AC
dosage of 0.5 g/L.
Graphene exhibits an extremely high specific surface
area (2,600 m2 g1) (Shahriary & Athawale 2014). This
can serve as a good support to make the loaded nanoparti-
cles (NPs) achieve uniform distribution without aggregation
in the adsorption of pollutants. Graphene, is a single layer
of sp2 bonded carbon atoms, due to its mechanical, thermal,
optical, and electrical properties. The presence of oxygen
functionalities in graphene oxide (GO) allows interactions
with the cations and provides reactive sites for the nuclea-
tion and growth of NPs (Guria et al. ). Magnetite
(Fe3O4-M) NPs have promising applications in the treatment
of antibiotics (Mostofizadeh et al. 2011). Additionally,
Water Science & Technology | in press | 2017
Fe3O4 NPs are also known to have low cost and eco-friend-
liness when serving as a stabilizer (Dong et al. 2010).
Magnetic Fe3O4 (M) has an advantage for usage as a support
material for the Nano-GO/M composite because it can be
easily separated by an external magnetic field (Dong et al.
2010). Iron oxide (IO) nanomaterials binding with GO as
magnetic adsorbents were useful in the separation of treated
wastewater from the GO since they do not need extra fil-
tration or centrifugation (Mostofizadeh et al. 2011).
Recovery of nanocomposites constituted an eco-friendly
approach and this decreased the treatment cost of the pollu-
tants. On the other hand, HWW treatment with Nano-GO/M
has not been attended yet via adsorption and photooxida-
tion. The recovery of Nano-GO/M composite and reuse of
treated water have not been studied before for the removals
of macropollutants and OFL antibiotic in HWWs. For the
reasons given above, in this study, the photocatalytic treat-
ment and adsorption of pollutants in HWW was studied
with the Nano-GO/M composite.
In this study, the adsorption and photocatalytic treat-
ment of macro pollutants (BOD5, COD, TSS, TKN and
TP) and OFL antibiotic as a micropollutant from a real
raw HWW were investigated using graphene oxide magne-
tite (GO/M) composite produced under laboratory
conditions. The effects of increasing Nano-GO/M compo-
site concentrations (0.5, 2, 5 and 10 mg/L) both for
adsorption and photodegradation process was studied. The
effects of increasing irradiation times (30, 60, 90 and
120 min), increasing pH levels (4.0, 7.8 and 10.0) and UV
powers (100, 300, 400 and 600 W) on the photodegradation
of the macropollutants mentioned above and the OFL in the
raw HWW were investigated. For maximum adsorption and
photodegradation of both macro and micropollutants in the
HWW; the optimum Nano-GO/M composite dose,
irradiation time and pH were detected. In addition, a cost
analysis was performed for optimum operational conditions.
Moreover, the reusability of the treated HWW and recovery
of Nano-GO/M composite were investigated.
MATERIALS AND METHODS
Preparation of Nano-GO/M
In brief, 5.0 g of graphene was mixed with 2.5 g of NaNO3
and 200 mL of (180:20, 9:1) sulphuric acid and 15 g of
KMnO4 mixture at an initial temperature of 18  C and
then heated to 50  C for 12 h. After the reaction time,
1.5 mL of hydrogen peroxide was added to the ice cooled
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3 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
reaction mixture and washed successively using 30% HCl,
water, ethanol to remove other reactants with the help of
centrifugation. Finally the material was precipitated with
diethylether and dried to get Nano-GO (Ai et al. ). The
resulting material was washed with ultrapure water to
remove the ions in order to attain neutral pH and then cen-
trifuged at 10,000 rpm to obtain Graphene oxide-Sodium
borohydride (GO-NaBH4). Synthesis of nano GO-Fe3O4
(Nano-GO/M composite) was performed in two steps:
Initially, Nano-GO/M composite was prepared by using
the one step co-precipitation and reduction technique.
100 mL of an aqueous dispersion of GO (1 mg/mL) was sub-
jected to sonication for 30 min at 70% amplitude. Initially,
100 mL of GO suspension was taken in a reaction flask
with equal volumes of Fe3þand Fe2þ salts solution (molar
ratio of 2:1) and the mixture was stirred in N2 atmosphere
for 5 min. The pH of the reaction mixture was adjusted to
10–11 with ammonia solution. Furthermore, 10 mL of
hydrazine hydrate was added to the reaction mixture and
the temperature of the solution was increased to 85–90  C
with stirring at 1,500 rpm for 3 h. Then the reaction mixture
was cooled to room temperature and magnetically decanted
several times with milli-Q water to bring the pH to 7 (Ai
et al. ). In the second step, Nano-GO/M composite dis-
persion was mixed with ammonia solution to increase the
pH to 10 and heated at 80–85  C for 24 h. Synthesized
Nano-GO/M composite dispersion was purified by mag-
netic decantation and was stored at 4  C until further use
(Ye et al. ).
Reactors used in the studies
Adsorption studies
Adsorption isotherms were obtained by equilibrium of 1 L sol-
utions of raw HWW with the sorbing media (Nano-GO/M
composite). 0.5, 2, 5 and 10 g Nano-GO/M were added to 1
liter of raw HWW and were shaken in an incubator for
30 min, 60 min, 90 min and 120 min. The Nano-GO/M com-
posite particles were settled. Then, the BOD5, COD, TSS,
TKN and TP and OFL analyses were performed in the super-
natant samples. The most efficient doses used for different
pHs (4.0, 7.8, and 10.0) and different reaction times (30 min,
60 min, 90 min and 120 min) were investigated. Equation (1)
shows the maximum adsorption capacity;
(C0  Ce ):V
qe ¼
W (APHA/AWWA/WEF ). Total nitrogen and total
Water Science & Technology | in press | 2017
where C0 and Ce (mg/L) are the initial and the equilibrium con-
centrations of OFL, respectively. V (L) is the volume of the
solution and W (g) is the mass of the adsorbent. The maximum
OFL adsorption was investigated using an optimum amount of
Nano-GO/M composite and at optimum pH.
Photocatalytic studies
Photocatalytic experiments were conducted in an open
batch system at a room temperature of 20–25 C. Quartz
glass reactors (with dimensions of 38 cm × 3.5 cm) and
10 UV lamps with a power of 30 W were placed into the
closed stainless steel system for the photocatalytic exper-
iments. The effects of Nano-GO/M composite concentrations
(0.5, 2, 5 and 10 g/L) irradiation times (30 min, 60 min,
90 min and 120 min), pH (4.0, 7.8, 10.0) on the treatment
of the HWW were investigated. After experiments the
Nano-GO/M composite was separated magnetically, then
analyzed. All the experimental data were found from the dupli-
cates analysis and the results presented as the mean values of
the duplicates samples.
Analytical procedure
Measurement of OFL in HPLC
Aqueous OFL stock solution was prepared from the ofloxa-
cin standard (>98%, Bayer AG, Germany, HPLC). A HPLC
Degasser (Agilent 1100), a HPLC Pump (Agilent 1100), a
HPLC Auto-Sampler (Agilent 1100), a HPLC Column
Oven (Agilent 1100) and a HPLC Diode-Array-Detector
(DAD) (Agilent 1100) and C-18 (5 μm, 4.6 mm 250 mm,
Thermo Scientific) column were used. The analyte was sep-
arated at ambient temperature. The mobile phase consisted
of acetonitrile (18:82, v/v). The aqueous component of the
mobile phase was prepared by dissolving 1.0 g of
ammonium acetate and 1.75 g of potassium perchlorate by
ultrasonic treatment in 325 mL of water and the pH was
adjusted to 3.50 using 85% orthophosphoric acid. The
column was equilibrated to a stable baseline at a flow rate
of 1.0 mL min1, maintaining the temperature of the
column at 45  C. Detection was at 294 nm (Zivanovic
et al. ). Also, a C8 column was used for the analysis.
Macro-pollutant measurement methods
COD and BOD5 were measured according to Standard
Methods APHA 5220A, APHA 5210A, respectively
(1)
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4 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
phosphorus were measured with reagent kits in a Photo-
meter Nova 60/Spectroquant. pH was measured with
WTW probes. The concentrations of Na, K, Ca and Mg
ions were measured by an Atomic Absorption Spectropho-
tometer (APHA 3111B method). TDS, conductivity and
salinity measurements were performed by a portable Mettler
Toledo type conductivity meter (APHA 2540C). Bicarbonate
was determined by titration method (APHA 2310B method).
The total coliform number was enumerated using Standard
Methods (APHA 9222 A). The SAR, RSC, SSP and ESP
values were calculated with the following equations:
[Naþ ]
SAR ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
[Ca2þ þ½Mg2þ ]=2

RSC ¼ ([CO2 2þ 2þ
3 ] þ [HCO3 ])  ([Ca ] þ [Mg ])
 
[Naþ ]
SSP ¼ 100
([Ca ] þ [Mg2þ ] þ [Kþ ] þ [Naþ ]
2þ
100( 0:0126 þ 0:01475SAR)
ESP ¼
1 þ ( 0:0126 þ :0:1475SAR)
Recovery of Nano-GO/M composite and reusability
of treated HWW
After the first use of the Nano-GOM composite, it was sep-
arated magnetically and then regenerated using ethanol
(adjusted to pH 2.0 with 0.1 mol/L HCl) as eluent (Chowdhury
& Balasubramanian ). Then the Nano-GO/M composite
was dried under vacuum and the Nano-GO/M reused was
used for the second treatment process of the HWW again.
For every new treatment step the same procedure was
applied to the same Nano-GO/M composite used.
In the investigation of the reusability of the treated
wastewater; the HWW was treated sequentially twice with
the new Nano-GO/M NP to reach irrigation standards or
to be used as cooling water, as process water and as cleaning
water for toilets and other dirty places.
Characterization of the photocatalytic properties of Nano-
GO/M composite
Fourier transform infrared (FT-IR). FT-IR spectra were car-
ried out to recognize the functional groups in the
synthesized composites and to confirm the chemical bond-
ing between Fe3O4 and graphene. The FT- IR spectra of
the Fe3O4, synthesized GO and Nano-GO/M were
Water Science & Technology | in press | 2017
measured with Perkin Elmer FTIR Spectrum System using
BX and KBr method.
SEM. The morphological and structural observation of
the raw Nano-GO/M composite was made on a scanning
electron microscope VegaII/LMU (Tescan, Czech Republic).
Scanning Probe Microscopy (SPM). The particle size of
the Nano-GO/M was measured using SPM.
Statistical analysis
Regression analysis is widely used for prediction and fore-
casting, where its use has a substantial overlap with the
field of machine learning. Regression analysis is used to
understand which among the independent variables are
related to the dependent variable, and to explore the forms
of these relationships. Alpha (α) level is the significance of
the Analysis of Variance (ANOVA) statistic. In the study α
was accepted as 0.05. F value of the analysis was performed
using MS Office 2010 Excell program.
RESULTS AND DISCUSSIONS
Physicochemical properties of Nano-GO/M composite
during adsorption process
FTIR analysis of Nano-GO/M composite
FT-IR is a powerful tool to verify the vibrational stretching
frequency of GO sheets, Fe3O4 particles and Nano-GO/M
composites and the peaks plotted between wavenumber
(cm1) and percentage of transmittance (T-%) (Figure 1).
In the FT-IR spectra of GO sample, two peaks at
1734.86 cm1 were observed, which were derived from the
C ¼ O stretching vibration of carboxylates and conjugated
carbonyls. A peak at 118.79 cm1 suggested the C-O stretch-
ing vibration of epoxy rings in the as-prepared GO. Note
that the characteristic peak at 996.36 cm1 was often attrib-
uted to the C-O stretching of alcohols. The peak at
590.32 cm1 was the typical Fe-O stretching vibration of
Fe3O4 (Zhou et al. ).
SEM analysis of Nano-GO/M composite
The SEM images of synthesized GO, Fe3O4 NPs and raw
Nano-GO/M composites are shown in Figures 2–4. Figure 2,
shows the GO structure which was in a sheet form. Fe3O4
NPs are shown as small dots on GO sheets (Figure 3). The
Fe3O4 sample was composed of spherical particles with a
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5 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater Water Science & Technology | in press | 2017

1
Figure 1 | FTIR analysis of raw Nano-GO/M (cm : wavenumber and T-%: percent transmittance).

size of approximately 20 nm and GO was composed of microspheres were firmly anchored on both sides of the
wrinkled sheets (Zhang et al. ). Many Fe3O4 wrinkled graphene sheets with a size of 48 nm (Figure 4).

Figure 2 | SEM image of GO. Figure 3 | SEM image of Nano Fe3O4.


6 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
Figure 4 | SEM imagine of raw Nano-GO/M (1 μm).
The graphene layers might play a part in hindering the
Fe3O4 microspheres from forming aggregation as reported
by (Tang et al. ). The Fe3O4 particles were dispersed
on GO and there were some interspaces among them.
Characterization of raw HWWs
The characterization of the raw HWW taken from the influ-
ent of the Dokuz Eylül University HWW is illustrated in
Table 1 with mean and standard deviation values. The
COD and BOD5 concentrations were not high (625 ±
12.3 mg/L and 259 ± 10.1 mg/L, respectively) while the
OFL concentration varied between 7 and 10 mg/L. The
mean TKN and TP concentrations were 13.5 ± 2.4 mg/L
and 2.8 ± 1.1 mg/L, respectively, with a low TSS concen-
tration of 197 ± 10.1 mg/L.
Effects of Nano-GO/M composite concentrations on the
treatment of HWWs by adsorption process
In order to determine the effects of increasing Nano-GO/M
composite concentrations (0.5, 2, 5 and 10 g/L) on the
adsorption process of some pollutants in the raw HWWs,
the adsorption studies were performed at a pH of 7.8 and
at a temperature of 21  C. Preliminary experiments showed
that among the adsorption times that were tested, the maxi-
mum removal yields were obtained after 90 min adsorption
time (data not shown). Therefore, all experiments were
Table 1 | Characterization of HWW
Macro/Micro Pollutant pHa
Raw HWW 7.8 ± 0.2
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Water Science & Technology | in press | 2017
performed at 90 min adsorption time. Increasing the
Nano-GO/M concentration from 0.5 g/L up to 5 g/L signifi-
cantly increased the OFL and COD adsorption yields from
20% and from 40% up to 39% and to 60% at a temperature
of 21  C and a pH of 7.8 (Figure 5). For the other pollutant
parameters in the HWWs (BOD5, TSS, TKN and TP) the
adsorption yields increased from 30%, 17%, 30%, 32% and
10% up to 42%, 29%, 42% and to 19% as the Nano-GO/M
was increased from 0.5 g/L up to 5 g/L. A multiple linear
regression between maximum adsorption efficiencies of all
pollutant parameters and Nano-GO/M composite concen-
trations was obtained (R ¼ 0.99) and this regression was
significant (ANOVA p ¼ 0.06 < α (0.05) and F ¼ 100.92) as
the Nano-GO/M was increased from 0.5 g/L to 5 g/L. Any
further increase of Nano-GO/M from 5 g/L up to 10 g/L
did not significantly affect the adsorption yields of all pollu-
tants (Figure 5). The multiple regression analysis between all
pollutant adsorptions and 10 g/L Nano-GO/M concen-
tration showed no linear regression (R ¼ 0.09) and the
correlation was not significant (ANOVA, p ¼ 0.71>α (0.05)
and F ¼ 65.07). The results reveal that the removal of pollu-
tants by adsorption from HWW increases up to a certain
Nano-GO/M limit (5 g/L) and then it remains almost con-
stant. An increase in the adsorption efficiency with an
increasing adsorbent (Nano-GO/M) concentration up to
5 g/L can be attributed to an increase in the surface area
and the availability of more adsorption sites up to this
Nano-GO/M concentration as reported by Hameed ().
Figure 5 | The comparison of the efficiencies of COD, BOD5, TSS, TKN, TP and OFL
according to Nano-GO/M concentration (T: 21  C, pH: 7.0, contacting time:
90 min) by adsorption process.
BODa5 (mg/L) CODa (mg/L) TSSa (mg/L) TKNa (mg/L) TPa (mg/L) OFL concentration (μg/L)
259 ± 101 625 ± 123 197 ± 101 13.5 ± 2.4 2.8 ± 1.1 7–10
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7 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
The reason for the same adsorption yields at high Nano-
GO/M (10 g/L) levels compared to 5 g/L can be attributed
to limited numbers of active sites on the surface of adsorbent
in contact with the pollutants in the HWW. A limited active
surface area on the Nano-GO/M did not increase the
adsorption yield although the Nano-GO/M concentration
was doubled (Li et al. ). As a result, the optimum
Nano-GO/M concentration was chosen as 5 g/L for maxi-
mum adsorption of COD, BOD5, TSS, TKN, TP and OFL
in order to reduce the operational cost of the adsorption pro-
cess. The optimum amount of Nano-GO/M increases the
number of active sites on the adsorbent surface, which
causes the adsorption of the pollutants increase (COD,
OFL, TSS). Excess catalyst cause turbidity, prevents the
adsorption of pollutants onto the surface of Nano-GO/M.
At a high catalyst concentration the active sites on the sur-
face of the Nano-GO/M were low and partially exposed to
COD and OFL. Therefore, low adsorption yields were
obtained at high Nano-GO/M concentrations as reported
by Li et al. (). The proposed mechanisms for the adsorp-
tion of COD, OFL and of the other pollutants in HWW on
Nano-GO/M materials mainly involve van der Waals forces
(permanent dipole–induced dipole forces and London dis-
persion forces), hydrophobic interaction, π–π interaction
(π was considered as one of the predominant driving
forces due to the aromatic rings of OFL), electrostatic inter-
action and hydrogen bond (Chen et al. ). The π  π
interaction has always been applied to explain the binding
mechanism of OFL with C ¼ C double bonds adsorbed on
the surface of graphene. On the other hand, graphene also
contains π electrons and may interact with the π electrons
of benzene rings of OFL by means of π  π electron coupling
(Chen et al. ). Generally, the intensity of van der Waals
forces between an adsorbed OFL and Nano-GO/M compo-
site is related to the contacted surface area of them and to
the van der Waals index, which is specific to the adsorbent
surface (Teixidó et al. ). The graphene surface of carbon-
aceous adsorbents has a very high van der Waals index, and
the OFL molecule has a planar ring. However, no significant
adsorption yields were obtained between the Nano-GO/M
composite and OFL since no strong van der Waals forces
occurred between OFL and the Nano-GO/M composite
(Chen et al. ).
The maximum adsorption yields with this Nano-GO/M
concentration were 39%, 42%, 30%, 45%, 21% and 60% for
COD, BOD5 TSS, TKN, TP and OFL after 90 min contact
time at a pH of 7.8 and at a temperature of 21  C (Figure 5).
The effluent concentrations of COD, BOD5 TSS, TKN, TP
and OFL were obtained as 384.3 mg/L, 150.8 mg/L,
Water Science & Technology | in press | 2017
140 mg/L, 7.645 mg/L, 2.291 mg/L and 3.28 μg/L, respect-
ively, after the adsorption process. Since low adsorption
yields were obtained for all the pollutant parameters in the
HWW, the effects of some operational conditions such as
pH, temperature and pollutant concentrations on the
adsorption were not studied.
Effects of Nano-GO/M composite concentrations on the
treatment of HWWs by photocatalytic process
In this step of this study the HWW containing COD, BOD5
TSS, TKN, TP and OFL was treated via photodegradation
under UV light power in the presence of a nano composite
(Nano-GO/M) generated under laboratory conditions.
Nano particle concentration is an important parameter
for the photo-treatment of pollutants. In order to determine
the effects of increasing Nano-GO/M concentrations on the
photocatalytic treatment of COD, BOD5 TSS, TKN, TP and
OFL; the effects of 0.5 g/L, 2 g/L, 5 g/L and 10 g/L Nano-
GO/M composite concentrations were researched. Prelimi-
nary experiments showed that among the irradiation times
tested, the maximum OFL removal was obtained after
60 min irradiation time (data not shown). Figure 6 summar-
izes the photocatalytic treatment efficiencies of COD, BOD5
TSS, TKN, TP and OFL at increasing Nano-GO/M concen-
trations (0.5, 2, 5 and 10 g/L) at an UV power of 300 W. The
photodegradation removals of each pollutant (COD, BOD5,
TSS, TKN, TP and OFL) increased significantly with an
increase of the Nano-GO/M concentration from 0.5 g/L to
2 g/L. The photo-removals of the pollutants mentioned
above increased from 80–90% up to 88–98%, respectively.
These yields were also the maximum photodegradation effi-
ciencies. The photocatalytic treatment efficiencies of COD,
BOD5 TSS, TKN, TP and OFL (89%, 91%, 84%, 97%,
Figure 6 | The comparison of the efficiencies of COD, BOD5, TSS, TKN, TP and OFL
according to Nano-GO/M concentration (T: 21  C, pH: 7.0, irradiation time:
60 min, UV Power: 300 W) by photocatalytic process.
 Uncorrected Proof
8 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
81%, and 99%, respectively) increased slightly as the Nano-
GO/M concentration was increased to 5 g/L. Any further
increase of Nano-GO/M from 5 g/L to 10 g/L slightly
decreased the photo-removals of all pollutants (Figure 6).
At the optimum catalyst concentration (2 g/L) more active
sites and hydroxyl radicals in its surface lead to increase in
the photo-degradation extent of the pollutant. But, excessive
dosage of the catalyst led to an increase in the suspension
turbidity and light scattering (Arabpour & Nezamzadeh-
Ejhieh ). Consequently, a screening effect of excess par-
ticles occurs which can mask a part of the photosensitive
surface and hence, the obstruction in the penetration of pho-
tons in the solid phase decreases in the activated
semiconductors (Arabpour & Nezamzadeh-Ejhieh ).
Finally, the number of hydroxyl radicals generated and con-
sequently the photodegradation rate tend to decrease. Our
results showed that, by increasing of the Nano-GO/M con-
centration from 0.5 to 2 g/L, the surface area of the Nano-
GO/M particle was increased, leading to an increase in
the production of reactive species as reported by Pelaez
et al. (). Further increasing of the Nano-GO/M compo-
site concentration from 2 to 5 and to 10 g/L, resulted in a
slight decrease of the photodegradation efficiencies of the
pollutant parameters (COD, BOD5 TSS, TKN, TP and
OFL) in the HWW. A high concentration of the catalyst
led to a more turbid solution, thus obstructing the pen-
etration of incident UV radiation and impairing the
effectiveness of the photocatalytic process (Bhatia et al.
). Therefore, 2 g/L Nano-GO/M composite was used
as optimum nano-composite to maintain maximum photo-
degradatıon yields for all pollutants in the HWW.
Furthermore, this optimum Nano-GO/M concentration
was used in all experimental studies to reduce the oper-
ational cost of the photooxidation process.
The photocatalytic process is initiated by the illumina-
tion of a semiconductor catalyst with radiation of energy
higher than the band gap energy of the semiconductor.
This irradiation generates electrons (e–) and holes (hþ) in
the conduction band (CB) and valence band (VB) respect-
ively and is as given by Equation (1) (Rajamanickam &
Shanthi )
hv þ
Nano  GO=M → e
(CB) þ h(VB)
The electron-hole pair formed may recombine in the
bulk lattice (or) migrate to the surface where its can react
with the adsorbents (Rajamanickam & Shanthi ). The
trapping reaction in the holes proceeds with the formation
Water Science & Technology | in press | 2017
of hydroxyl radicals as given by Equation (2).
hþ þ OH ! OH (2)
hþ þ H2 O ! OH þ Hþ (3)
The electrons are trapped by dissolved oxygen resulting
in the formation of superoxide ion.
e þ O2 ! O
2 (4)
The photocatalytic degradability by Nano-GO/M
involved the hydroxy radical and holes for oxidation of
organic molecules (OM) like COD and BOD5. The reactions
are given below.
hþ þ OM ! OMþ (5)
OMþ þ O2 ! Products (6)

OH þ OM ! Products (7)
Small molecules such as water and carbon dioxide are
eliminated by OFL when this compound is subjected to
photocatalysis, as reported by Calza et al. (2008). Sub-
sequent attacks of hydroxyl radicals can lead to the
formation of bi- or tri-hydroxylated products or dimerization
of the ofloxacin molecule, resulting in by-products (data not
shown). Peres et al. () suggested that there are two main
routes for the generation of OFL by-products by photocata-
lytic reactions: dealkylation of the piperazine ring and
decarboxylation (removal of the carboxyl group, –COOH)
(Peres et al. ). Studies have shown that the principal
photolytic reactions that occur are that FQs lose fluoride
(F), followed by decarboxylation (Peres et al. ).
Photocatalytic removal of dissolved organic TN and TP
compounds release inorganic nutrient compounds such as
nitrite, ammonia and phosphate as well as CO2 in the pres-
ence of Nano-TiO2 and Nano-Fe2O3 (Helbling & Horacio
2003). Photocatalytic oxidation proposed for the conversion
of ammonia and N-organic into nitrogen gas or nitrate while
it was reported that free hydroxyl radicals generated during
(1)
photodegradation create the possibility of ammonia oxi-
dation to N2 (Maroneze et al. ).
Bhatia et al. (), studied the photodegradation of
25 mg/L OFL antibiotic using TiO2 (0.5–2 g/L) as a catalyst.
After 6 h irradiation the maximum OFL photodegradatıon
yield was found to be 72% with 1.5 g/L TiO2 NP
 Uncorrected Proof
9 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
concentration. A further increase of TiO2 concentration to
2 g/L, decreased the photo-removal efficiency to 56%. This
can be explained as follows: the increase in the turbidity
of the solution, decreased the degree of light penetration
through which the solution takes place. Arabpour &
Nezamzadeh-Ejhieh (), studied the photodegradation
of cotrimaxazole antibiotic using IO supported clinoptilolite
NPs and an Hg-lamp as radiation source. They found that
increasing the catalyst concentration from 0.25 to 0.5 g/L
increased the removal efficiencies slightly from 50% to
55%. A further increase in the catalyst dosage from 0.5 g/L
to 4 g/L decreased the removal efficiency of cotrimaxazole
antibiotic from 55% to almost 35%. Our results were compa-
tible with the studies mentioned above (Nezamzadeh-Ejhieh
& Moazzeni ; Arabpour & Nezamzadeh-Ejhieh ;
Bhatia et al. ). Rodriguez et al. (), found 76% photo-
degradation yields for 1 mg/L OFL with 4 g/L TiO2 at
360 W UV power after 120 min (Rodriguez et al. ).
A multiple linear relationship between maximum COD,
BOD5 TSS, TKN, TP and OFL photodegradation efficien-
cies and Nano-GO/M composite concentration (from
0.5 g/L to 2 g/L Nano-GO/M) was obtained (R ¼ 0.89) and
this regression was significant (ANOVA p ¼ 0.0009 < α
(0.05) and F ¼ 1.10). However, the multiple linear relation-
ship between the maximum photodegradation efficiencies
of all pollutants and the Nano-GO/M composite concen-
tration at between 5 and 10 g/L was not obtained (R ¼
0.16) and this regression was not significant (ANOVA p ¼
0.21 > α (0.05) and F ¼ 19.08).
Effects of UV powers on the treatment of HWWs by
photocatalytic process
UV power is an important parameter for the yield of the
photocatalytic process in order to degrade the pollutants.
To investigate the effect of large range UV powers, COD,
BOD5 TSS, TKN, TP and OFL removals were studied
under increasing UV powers (100 W, 300 W, 400 W and
600 W) at a pH of 7.8 at a temperature of 21  C after
60 min irradiation. For maximum removal efficiencies of
each pollutant the optimum Nano-GO/M concentration
(2 g/L) and the optimum irradiation time (60 min) were
determined in previous stages of the study as mentioned
above. As the UV power increased from 100 W to 600 W,
the removal yields also increased (Figure 7). However, this
increase was not significant in the range of 300–400 W.
The removal efficiencies were in the range of 81%–88%
and 83%–89% for COD and BOD5, respectively as the UV
powers were increased from 100 W to 300 W. TSS and
Water Science & Technology | in press | 2017
Figure 7 | The comparison of the efficiencies of COD, BOD5, TSS, TKN, TP and OFL
according to UW powers (T: 21  C, irradiation time: 60 min, Nano-GO/M
concentration: 2 g/L) by photocatalytic process.
TKN removal efficiencies varied between 72%–82% and
89%–95%, respectively, for UV powers between 100 W
and 300 W (Figure 7). The TP and OFL the photo-removal
efficiencies were obtained as 71%–79% and 88%–97%,
respectively, for the same UV powers. In the present study,
300 W UV light power was determined as the optimum
UV level for the maximum photooxidation yield of the pol-
lutants in the HWW. The UV power determines the
amount of photons absorbed by the catalyst. In the photoca-
talytic treatment process with Nano-GO/M, at increased
light power electron-hole pair separation competes with
recombination, causing less of an effect on the reaction effi-
ciency (Konstantinou & Albanis ). With the increase of
the UV power to the optimum, the catalyst absorbs more
photons, producing more electron-hole pairs in the catalyst
surface, and this increases the concentration of hydroxyl
radicals and consequently increases the removal percentage.
Earlier studies on the effect of UV light power on the photo-
degradation of different pollutants such as dye, have shown
almost the same results. Muruganandham & Swaminathan
() researched the influence of UV power on the deco-
lourisation of reactive yellow 14 (RY14) at varying UV
powers (from 16 W to 62 and 97 W). An increase of UV
power from 16 W to 62 W increased the decolourisation effi-
ciency from 35.9% to 87.9% at 20 min irradiation for initial
RY14 concentration of 5 × 104 M. A further increase of UV
power decreased the dye photodegradation yield. The solar
TiO2 process, yielded 65% degradation of the examined sub-
strate and DOC reduction of about 50% in 120 min of the
photocatalytic treatment. Michael et al. () found 78%
OFL photo-degradation yield for 12 mg/L OFL concen-
tration after 89 min irradiation time at an UV power of
445 W using 12 g/L TİO2. A further increase of UV power
to 167 W did not significantly affect the OFL oxidation
 Uncorrected Proof
10 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
under UV. In our study the OFL yields were higher and the
irradiation time and the UV power used was lower than in
the study of Michael et al. (Michael et al. ). This can
be attributed to the high activity of Nano-GO/M, to the
type of HWW and to some operational conditions like temp-
erature and pH.
A multiple linear regression between maximum COD,
BOD5 TSS, TKN, TP and OFL photodegradation efficien-
cies and increasing UV powers was obtained up to 400 W
(R ¼ 0.99) and this regression was significant (ANOVA
p ¼ 0.007 < α (0.05) and F ¼ 68.48).
Effects of irradiation time on the treatment of HWWs by
photocatalytic process
Although in the previous section it was mentioned that
60 min irradiation was found to be optimum for maximum
photodegradation of all pollutants in HWW, in this step a
large irradiation interval (30, 60, 90 and 120 min) was
studied to determine maximum pollutant yields. The concen-
tration of Nano-GO/M composite was selected as 2 g/L
as mentioned in the upper section. The irradiation time
experiments were performed at a pH of 7.8 and at 21  C
under 300 W UV light. The maximum removal efficiencies
of COD, BOD5 TSS, TKN, TP and OFL were obtained as
88%, 89%, 82%, 95%, 79%, and 97% respectively, after
60 min irradiation time (Figure 8). As the irradiation time
was increased from 30 min to 60 min and then to 90 min
the removal efficiencies of each pollutant increased.
A further increase in the irradiation time from 90 min to
120 min did not affect the removal efficiencies and a satur-
ation plateau was reached. A plausible explanation would
be the generation of oxidation products, which would com-
pete with the parent compound for the oxidizing species and
Figure 8 | The comparison of the efficiencies of COD, BOD5, TSS, TKN, TP and OFL
according to irradiation time (T: 21  C, pH: 7.0, Nano-GO/M concentration:
2 g/L, UV Power: 300 W) by photocatalytic process.
Water Science & Technology | in press | 2017
for the available radiation, and thus, the photodegradation
yield after 120 min remained as it was at 60 min. The
removals of pollutants were found to increase linearly with
an increase in the retention time from 30 min up to
90 min. The removal efficiencies of pollutant parameters
decreased for photooxidation time >90 min since at long
irradiation times the surface energy of Nano/GO-M
decreases (Upadhyay et al. ). The photooxidation can
form small molecules such as H2O, CO2 and benzene etc.
after long irradiation; it will lead to the decrease of the
polar groups and the oxygen content of the pollutant sur-
face. Therefore the dispersivity decreaeses resulting in low
photooxidation yields. The dispersive component of the sur-
face energy, and the density of GO surface has a great
influence on the dispersivity of pollutants in the HWW (Li
et al. ). Aromatic metabolites of OFL which would
adsorb strongly on the Nano/GO-M surface block a signifi-
cant part of photo-reactive sites (Li et al. ). Kaur et al.
() found that the irradiation time did not significantly
increase the OFL photodegradation using 0.25 g/L silver
modified ZnO after 150 min irradiation at pH 7 (Kaur
et al. ).
A linear relationship between maximum COD, BOD5
TSS, TKN, TP and OFL photodegradation efficiencies and
irradiation time was obtained (R ¼ 0.95) and this regression
was significant (ANOVA p ¼ 0.007 < α (0.05) and F ¼ 4.5).
Effects of pH on the treatment of HWWs
by photocatalytic process
The pH of HWW is an important parameter for the treat-
ment mechanism. In this study, the effect of acidic, neutral
and alkaline pH levels (4.0, 7.8 and 10.0) were investigated
on the treatment efficiency of the HWW with the Nano-GO/M
composite. All experiments were performed with 2 g/L
Nano-GO/M composite at 60 min retention times at 21  C
and under 300 W UV light. The photo-removal efficiencies
of COD and BOD5 were obtained as 70%, 88%, 65% and
72%, 89%, 68%, respectively at pH 4.0, 7.8 and 10.0. The
TSS and TKN removal efficiencies were obtained as 67%,
82%, 60% and 90%, 95%, 88%, respectively at pH levels of
4.0, 7.8 and 10.0 (Figure 9). The TP photo-degradation
yields were 70%, 79%, 63% while the OFL removal efficien-
cies were 89%, 97%, 80% at pH 4.0, 7.8 and 10.0,
respectively. Maximum pollutant photo-degradation yields
were obtained at neutral pH levels (7.8). This decreases
the treatment cost of the HWW since no chemical was
added to adjust the pH for maximum pollutant removals.
As a result, it can be seen that as the pH increased from
 Uncorrected Proof
11 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
Figure 9 | The comparison of the efficiencies of COD, BOD5, TSS, TKN, TP and OFL
according to pH levels (T: 21  C, irradiation time: 60 min, Nano-GO/M con-
centration: 2 g/L, UV Power: 300 W) by photocatalytic process.
4.0 to 7.8, the photodegradation yields of all pollutants
increased while under alkaline conditions (pH ¼ 10.0) the
photo-removals of each pollutant decreased. The zero
charge point of (pHpzc) Nano-GO/M is at pH ≈ 5.5 (Liu
et al. ). Thus, the surface of Nano-GO/M was positively
charged when pH < pHpzc, and become negatively charged
when pH > pHpzc. OFL was positively charged at pH
values lower than the pKa1 (6.05) while it was negatively
charged at pH values above the pKa2 (8.11), and neutral
at pH values between pKa1 and pKa2 (Peres et al. ).
The low photo-degradation efficiency at more acidic pH
(for example, at 4) may be related to the decomposition
and corrosion of the catalyst in the acidic medium. By
increasing the pH levels, both Nano-GO/M and OFL, and
other organic (BOD5, COD) and inorganic (TSS, TKN and
TN) molecules, are becoming negatively charged and elec-
tronic repulsion occurs between them. The decrease in the
photo-degradation after a certain pH value can also be
explained by both the surface chemical state of Nano-GO/M
and the ionization state of ionizable organic molecules at
this pH. It is very well-known that for pH values higher
than the point of zero charge (pzc) which is pH 6.8 for
Nano-GO/M, the surface becomes neutral and it is the
opposite for pH < pH pzc. OFL molecule ionizes easily in
neutral media and becomes a soluble OFL anion. Therefore,
in the neutral solutions, OFL anions are easily adsorbed to
Nano-GO/M particles with a positive surface charge.
These OFL anions can be oxidized directly by oxygen
under visible radiation (Li et al. ). That is why high
degradation ratios were achieved in neutral pH regions.
However, at higher pH values, OFL anions are generally
excluded away from the negatively charged surface
of Nano-GO/M particles, so photo-degradation ratio
decreases. The reason for the decrease in photo-degradation
Water Science & Technology | in press | 2017
ratio in the alkaline medium may be the occurrence of par-
tial radical oxidation degradation (Kaur et al. ). Lower
degradation rates at acidic pH have also been reported for
Nano-GO/M because of an inefficient electron transfer pro-
cess due to low surface complex bond formation (Kaur et al.
). As a consequence, photo-degradation yields decreased
at acidic and basic conditions. Kaur et al. () investigated
the photo-degradation efficiency of OFL in the reaction time
of 80 min under acidic and alkaline conditions. For maxi-
mum OFL (79%) photodegradation efficiency the optimum
pH was found to be 7.9 (Kaur et al. ).
A multiple linear relationship between maximum COD,
BOD5 TSS, TKN, TP and OFL photodegradation efficien-
cies and pH levels was not obtained (R ¼ 0.53) and this
regression was not significant (ANOVA p ¼ 0.11 > α (0.05)
and F ¼ 0.39).
Effect of temperature on the treatment of HWWs by
photocatalytic process
Temperature is an important parameter for the photocataly-
tic process. To investigate the effect of temperature, HWWs
photodegradation was studied under different temperatures
(20  C, 40  C, 60  C and 120  C). For maximum HWWs
photodegradation the optimum Nano-GO/M concentration
(2 g/L) and optimum irradiation time (60 min) were deter-
mined in the preliminary studies as mentioned above. The
photocatalytic treatment efficiency of HWWs increased
(from 56% to 96% for OFL) with an increase in the tempera-
ture from 20  C up to 60  C (data not shown). Increasing the
temperature from 60  C to 120  C did not increase the
photocatalytic treatment efficiency as reported by Titouhi
& Belgaied (). At 20  C, photo-oxidation of the antibiotic
was not complete. The free radical concentration usually
increases with increasing reaction temperature, as reported
by Bautista et al. (), allowing an improvement of mol-
ecule degradation. Kondru et al. (), observed similar
results in their research. It’s established that increasing the
working temperature allows reactant molecules to over-
come the activation energy barrier by providing more
energy which makes the oxidative reaction easy (Hassan
& Hameed ). The OFL concentration did not decrease
at higher temperature (120  C) but reached a minimum at
60  C. At high temperature a photochemical disaggregation
of OFL was not recorded due to binding sites of Nano GO/M
on OFL are destroyed and insoluble hydrolysis products
were documented by Porcal et al. ().
 Uncorrected Proof
12 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater
Recovery of Nano-GO/M NPs for their Re-utilization
Nano-GO/M NPs could be reused to create a cost-effective
process. Magnetic separation of this nano composite pro-
vides a very convenient approach for removing and
recycling magnetic particles (such as magnetite) by applying
external magnetic fields. Most water or wastewater treat-
ment systems require settling, filtration or centrifuge
processes to separate the solids from the treated water. How-
ever, the magnetic NPs used in our study can be separated
and recovered with an external magnetic field due to the
intrinsic magnetic characteristic of the Nano-GO/M NPs,
helping to achieve a significant recovery of the NPs without
a filtration process (Tang & Lo ). Catalyst cost usually
dominates the photocatalytic processes. As a consequence,
the reusability of the catalyst becomes important. In this
study, two sequential photo-treatment step were applied in
order to determine the reusability of the Nano-GO/M com-
posite, the same 2 g/L Nano-GO/M composite that was
used for two sequential treatments. The photo-reactor was
operated under the same operational conditions mentioned
above (irradiation time: 60 min, UV power: 300 Watt, pH:
7.8 at room temperature). During each sequential new
photo-treatment step the Nano-GO/M composite was
cleaned and used again. From Figure 10, it can be clearly
seen that with the utilization of the Nano-GO/M composite
after the 2nd sequential treatment, the photo-removal effi-
ciencies of COD and BOD5 decreased slightly from 88%
and 89% to 82% and 83%. After the 2nd sequential treat-
ment the photo-removal efficiencies of TSS and TKN
decreased to 82%–75% and 95%–90%, respectively, while
the photodegradation yields of TP and OFL decreased
from 79% to 71% and from 97% to 94%, respectively
(Figure 10). As shown, the yields were not decreased
Figure 10 | COD, BOD5, TSS, TKN, TP and OFL measurement by recovery of Nano-GO/M
composite (T: room temperature, Nano-GO/M composite concentration:
2 g/L, UV irradiation time: 60 min, UV power: 300 Watt, pH: 7.0).
Water Science & Technology | in press | 2017
significantly (ANOVA R ¼ 0.98 p ¼ 0.008 < α (0.05) and
F ¼ 96.33). Slightly lower decreases in pollutant yields are
not important since only 2 g/L Nano-GO/M can be used
during the two sequential treatment steps with high pollu-
tant yields (in the range of 97%–71%) to treat the HWW.
This decreases the cost of producing the nano composite.
Reusing of treated HWW: water quality evaluation
Treated wastewater resources can be effectively used for
many useful urban, agriculture and industrial applications
as long as they are treated adequately. The treated water
can be used for irrigation, landscaping and recreational irri-
gation purposes where significant savings can be achieved
by reducing the purchase of utilized water. The water quality
requirement of each end-user determines the type of waste-
water and its degree of treatment (Vergine et al. ;
Rekik et al. ; Urbano et al. ). The treated water
can be utilized in various sectors. It can be used in urban
areas for irrigation and landscaping of public parks, rec-
reational fields, school yards, golf courses, highway
medians and residential areas, fire protection, toilet flushing
in commercial and industrial buildings and vehicle washing
(Vergine et al. ; Rekik et al. ; Urbano et al. ).
Treated water can be used as agricultural reuse for the irriga-
tion of non-food crops (seed crops, industrial crops,
processed food crops, fodder crops, orchard crops, etc.)
and commercial nurseries and as irrigation for food crops
and for the watering of livestock. Treated HWW can be
used as recreational impoundments like artificial lakes and
ponds by creating artificial wetlands and enhancing natural
wetlands, sustaining and augmenting river or stream flows
and as Non Potable Reuse like Groundwater recharge/
recovery of treated water for subsequent reuse or discharge
and recharge of adjacent surface streams (Vergine et al.
; Rekik et al. ; Urbano et al. ). Furthermore, it
can be used as industrial reuse, for example for process cool-
ing, cooling towers and boiler water make-ups.
In this study, in order to reuse the treated wastewater;
the HWW was sequentially treated twice with new Nano-
GO/M NPs. After the first and second sequential treatments
of the HWW with 2 g/L Nano-GO/M composite, high
removal efficiencies were obtained for COD, BOD5, TSS,
TKN, TP and OFL. Table 2 shows the removals and effluent
concentrations of the aforementioned pollutants after the first
and two sequential treatment steps. The initial 8.2 mg/L OFL;
reduced to 0.246 and 0.00246 mg/L after 1st and 2nd sequen-
tial treatments.630 and 260 mg/L COD and BOD5 reduced
to 75.6 and 28.6 mg/L after first treatment while their
 Uncorrected Proof
13 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater Water Science & Technology | in press | 2017

Table 2 | Raw HWW and effluent concentrations of each pollutant in HWW at maximum suitable for agricultural irrigation. Also, electrical conduc-
tivity (ECw) and its specific ion toxicities, Naþ, Ca2þ and
removal efficiencies after 2nd sequential treatment (T: room temperature,
Nano-GO/M composite concentration: 2 g/L, UV irradiation time: 60 min, UV
power: 300 Watt, pH: 7.0) Mg2þ which impact on the SAR values were compared to
the irrigation water guidelines. The treated hospital water
Raw HWW After 2nd Removal
Parameters Conc. Treatment Conc. Efficiency (%)
gives a SAR value of 4.68 with an ECw 0.43708 dS/m.
Tables 2 and 3 show the limits for SAR and ECw were 3–6
COD (mg/L) 630 7.56 98.8
and >1.2, respectively). These results exhibited a good
BOD5 (mg/L) 260 2.288 99
water quality effluent suitable for agricultural irrigation.
TSS (mg/L) 200 5.4 97 The water quality assessment based on SAR, SSP, ESP and
TKN (mg/L) 13.9 0.02085 100 Naþ concentration in the above suggested blending ratio
TP (mg/L) 2.9 0.10353 96 results in the reduction of sodium hazard and specific
OFL (μg/L) 8.2 0.00246 99 ionic toxicity and miscellaneous hazards (Tables 2 and 3).
Ca (mg/L) 269 3.497 98 The sodium hazard related to RSC is completely resolved
Mg (mg/L) 174 3.8976 98 by this blending strategy. RSC values become negative
ECw 15.61 0.43708 97 which is required for agricultural irrigation water (Tables 2
TDS (mg/L) 3,985 135.49 97 and 3).
SAR – 4.68 –
The limits for Conductivity and Total Dissolved Solid
were <0.7 dS/cm and <450 mg/L while for Sodium Adsorp-
Na (mg/L) 1,213 9.704 99
tion Rate and Sodium they were >0.7 meq/L <3 mg/L,
K (mg/L) 92.3 2.98129 97
respectively (Table 3). For Chlorine and Boron, the limit
Bicarbonate 421 8.2095 98
values were <140 mg/L, <0.7 mg/L, respectively (Table 3,
RSC 3.2 0.00352 99
WPCF, 2010, official gazette, number: 27527). Limit values
SSP 48.32695797 of reuse for pH, BOD5 and Coliform were 6–9, <30 mg/L,
ESP 5.341574927 <200 number/100 mL, respectively. According to the
pH 7.8 ± 0.2 7.8 ± 0.2 7.8 ± 0.2 limits given above pH, salt, conductivity, ions (Caþ2 and
Coliform (Colony 0 Mgþ2), oil and grease, pathogen microorganism, heavy
number/100 mL) metal concentration in the HWW were measured before
being used for irrigation water (Table 2). After the 2nd
sequential treatment the effluent concentrations of the par-
concentrations decreased to 7.76 and 2.28 mg/L after the ameters given above were suitable for the limits given by
second treatment. Electrical conductivity (ECw) and RSC the irrigation parameters (Tables 2 and 3). Table 4 shows
levels decreased from and initial 15.61 and 3.2 to 3.12 and the limits given for the chemical quality of the treated
0.34, respectively. Their concentrations were recorded as water and the class of the wastewater. Table 5 shows the
0.43 and 0.00352 after the second treatment. All the pollutant maximum allowable limits for heavy metals and toxic
parameters given in Table 2 were removed with yields varying element concentrations necessary in the irrigation of treated
between 80% and 97%. water and the treatment results of HWW after 1st and 2nd
Tables 3–6 show the guidelines for interpretations of irri- treatments. Table 6 illustrated the Quality criteria according
gation water quality, limits for chemical quality of treated to the class of continuous water resources and the quality of
wastewater for utilization as irrigation purpose, limits for the treated HWW after 1st and 2nd treatments. According to
maximum allowable heavy metal and toxic element concen- Turkish Water Pollution Control Regulations after 2nd treat-
trations in irrigation and quality criteria according to the ment of the HWW, the effluent values of treated HWW
class of continuous water resources, respectively (WPCF could be classified as first class quality according to the par-
2010, official gazette, number: 27527 and SWQMR 2012, ameters studied in this work (Tables 2–6 (SWQMR, 2012,
official gazette, number: 28483). Table 3 shows the limits official gazette, number: 28483). Furthermore, the treated
given for irrigation of the treated HWW. In other words, HWW could be used as cooling water, and also for cleaning
the effluent of second treatment (Table 2) was evaluated water for toilets and other dirty places after disinfection as
for irrigation purposes. Based on the evaluation of salinity, mentioned in the above section. The use of wastewater for
infiltration, toxicity and miscellaneous hazards for the suit- irrigation is regarded as a way to address the imbalance
ability of treated hospital water it was found that it was between water demand and water supply.
 Uncorrected Proof
14 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater Water Science & Technology | in press | 2017

Table 3 | Guidelines for interpretations of irrigation water quality (WPCF, 2010, official gazette, number: 27527)

Degree of restriction on use

Potential irrigation problem Units None Slight to moderate Severe

Salinity (affects crop water availability)

ECw dS/m <0.7 0.7–3.0 >3.0
TDS mg/L <450 450–2,000 >2,000
Infiltration (affects infiltration rate of water into the soil. Evaluate using ECw and SAR together)
SAR ¼0–3 ECw ¼ >0.7 0.7–0.2 <0.2
¼3–6 ¼ >1.2 1.2–0.3 <0.3
¼6–12 ¼ >1.9 1.9–0.5 <0.5
¼12–20 ¼ >2.9 2.9–1.3 <1.3
¼20–40 ¼ >5.0 5.0–2.9 <2.9
Specific ion toxicity (affects sensitive crops)
Sodium (Na)
Surface irrigation SAR <3 3–9 >9
Sprinkler irrigation me/L <3 >3
Chloride (Cl)
Surface irrigation mg/L <140 140–350 >350
Sprinkler irrigation mg/L <100 >100
Boron (B) mg/L <0.7 0.7–3.0 >3.0
Miscellaneous effects (affects susceptible crops)
Nitrogen (NO3-N) mg/L <5 5–30 >30
Bicarbonate (HCO3) (overhead sprinkling only) me/L <1.5 1.5–8.5 m > 8.5
Other parameters for sodium toxicity
RSC <0 0–1 >1
SSP <60 60–80 >80
ESP 2–10 10–40 >40
pH Normal range 6.5–8.4

COST ANALYSIS NPs. Rodríguez et al. (2015) calculated a total cost of

Cost analysis was investigated for 1 liter photo–removal of
HWW using 2 g/L Nano-GO/M composite under 300 W
UV light. Electricity, UV lamp (10 UV lamps) and Nano-
GO/M composite cost were 0.014, 76.2 and 4.4 in
Euros. All the consumptions figures were calculated and
are given in Table 7. The total cost for the photodegrada-
tion of the HWW was 80.654 €. 76.2 € was spent on
10 UV lamps, while the chemical cost, electricity con-
sumption and nanocomposite cost were only 4.454 € for
the treatment of 1 liter of HWW. A study including the
cost for the photooxidation of OFL with Nano-GO/M
was not found in recent literature. Therefore, the cost
analysis in our study was compared with some other
98 € to photo degrade 76% of 1 mg/L OFL with 4 g/L
TiO2 at 360 W UV power after 120 min. In a recent
study, performed by Ahmadzadeh et al. (2017) the total
cost was calculated as 102 € to photodegrade 79% of
32.5 mg/L FQs antibiotic from HWW using electrocoagu-
lation (EC) process by aluminum electrodes under optimal
operating conditions (at pH 7.78, at reaction time 20 min,
a current density 12.5 mA/cm2 and at an electrolyte dose
of 0.07 M NaCl with an electrical energy consumption
cost of 0.613 kWh/m). Ge et al. () found a total cost
of 89 € for the photo-oxidation of 19 mg/L FQs using
290 W UV power after 78 min irradiation time using
37 mg/L Nano ZnO. These costs are slightly higher than
our study (Ge et al. ).
 Uncorrected Proof
15 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater Water Science & Technology | in press | 2017

Table 4 | Limits for chemical quality of treated wastewater for utilization as irrigation purpose (WPCF, 2010, official gazette, number: 27527)

Recovery Type Treatment Type The Quality of Recovered Watera Monitoring Period Application Distanceb

Class A

a- Agricultural irrigation: commercially unprocessed foodl

b- b-Urban Area Irrigation
At least 50 m away from the
a) Superficial and sprinkler - Secondary - pH ¼ 6-9 - pH: weekly fresh water wells.
irrigation were used and other Treatmentc - BOD5 < 20 mg/L - BOD5: weekly
foods that are directly raw - Filtrationd - Turbidity <2 NTUf - Turbidity:
edible - Disinfectione - Fecal Coliform: 0/100 mLg,h constant
b) Every kind of green field - In some cases, spesific virus, - Coliform:
irrigation (Parks, golf courses protozoa and helminth daily
etc.) analysis might be needed - Residual
- Residual Chlorine >1 mg/Li Chlorine:
constant
Class B

a- Agricultural irrigation: commerically processed foodim

b- Access restiricted irrigation sites
c- Agricultural irrigation:Non-edible plants

a) Using surface irrigation on - Secondary - pH ¼ 6-9 - pH: weekly - At least 90 m away from the
harvests like Fruit orchards and Treatmentc - BOD5 < 30 mg/L - BOD5: weekly fresh water wells.
vine yards - Disinfectione - TSS <30 mg/L - TSS: daily - Sprinkler irrigation is used,
b) Places like Grass production and - Fecal coliform <200 number/ - Coliform: at least 30 away from the
cultural agriculture where 100 mLg,j,k daily residential area.
public entrance is restricted - In some cases, spesific virus, - Residual
c) Pasture irrigation for grass-fed protozoa and helminth Chlorine:
animals analysis might be needed. constant
- Residual Chlorine >1 mg/Li

Table 5 | Limits for maximum allowable heavy metal and toxic element concentrations in irrigation (WPCF, 2010, official gazette, number: 27527) and their removals

Maximum permissible concentrations

The maximum total Limit values for When irrigating less than Effluent
quantities that can be continuous irrigation 24 years on clayey soil Influent Removal concentrations of
given to the unit area, on all types of ground with pH value between concentrations efficiencies of HWW after 2nd
Elements kg/ha mg/L 6.0-8.5, mg/L of raw HWW treated HWW (%) treatment

Chromium (Cr) 90 0.1 1.0 0.06 99 0.0006

Cobalt (Co) 45 0.05 5.0 0.09 99 0.0009
Copper (Cu) 190 0.2 5.0 0.25 99 0.0025
Iron (Fe) 4,600 5.0 20.0 0.18 99 0.0018
Lead (Pb) 4,600 5.0 10.0 1.11 99 0.0111
Lithium (Li) – 2.5 2.5 0.02 99 0.0002
Nickel (Ni) 920 0.2 2.0 0.08 99 0.0008
Zinc (Zn) 1,840 2.0 10.0 0.45 99 0.0045
 Uncorrected Proof
16 D. T. Sponza & P. Alicanoglu | Reuse and recovery of a raw hospital wastewater Water Science & Technology | in press | 2017

Table 6 | Quality criteria according to the class of continuous water resources (SWQMR- Surface Water Quality Management Regulation, 2012, official gazette, number: 28483)

1. Class 2. Class 3. Class 4. Class Our results after 1st treatment Our results after 2nd treatment

COD (mg/L) 25 50 70 >70 75.6 7.56

BOD5 (mg/L) 4 8 20 >20 28.6 2.228
TKN (mg/L) 0.5 1.5 5 >5 0.695 0.02085
pH 6.5–8.5 6.5–8.5 6.0–9.0 6.0–9.0 7.8 7.8

Table 7 | Cost analysis for photocatalytic treatment of HWW under UV light

Cost Analysis Treatment of HWW under UV light

UV 1 UV lamp: 7.62 €
10 UV lamp: 10*7.62 ¼ 76.2 €
Electricity consumption 60 min UV irradiation: 0.014 €
Chemicals Magnetite (Fe3O4) (1 kg): 12.99 €
Graphene (1,000 g): 151.95 €
Cost analysis for treatment of 1 liter HWW: For 2 g Nano-GO/M:
2 g Nano-GO/M was used for treatment of 1 liter HWW under UV light. 100 mg magnetite: 1.4 €
100 mg magnetite, 20 g graphene was used for prepare 2 g Nano-GO/M. 20 g: 3.04 €
Total cost for treatment of 1 liter HWW: 76.2 þ 0.014 þ 1.4 þ 3.04 ¼ 80.654 €

The cost of chemicals is calculated according to market prices. Electricity costs are calculated according to the consumer price industrial units.

CONCLUSION levels. The best results were obtained at the original pH of

The adsorption and the photocatalytic degradation of HWW
were investigated in the presence of Nano-GO/M NPs. Low
adsorption yields were obtained for pollutant removals
(39%, 42%, 30%, 45%, 21% and 60% for COD, BOD5
TSS, TKN, TP and OFL, respectively) in the HWWs with
5 g/L Nano-GO/M after 90 min contact time at a pH of
7.8; compared to the photodegradation process. The maxi-
mum pollutant photodegradation yields (COD, BOD5 TSS,
TKN, TP and OFL were found as 88%, 89%, 82%, 95%,
79%, and 97%, respectively) which were obtained with
2 g/L Nano-GO/M concentration after 60 min irradiation
time under 300 W UV power. At this optimum Nano-GO/M
dose, the diameter of the nano-particle increased, leading
to an increase in the production of reactive species such
as OH. A high dosage of the catalyst (5 and 10 g/L) led
to an increase in the suspension turbidity which can mask
the penetration of photons. Increasing the UV powers
from 100 W to 300 W also increased the removal efficien-
cies of all pollutants in the HWWs. With the increase of
the UV power to the optimum, the catalyst absorbs more
photons, producing more electron-hole pairs in the catalyst
surface, and this increases the concentration of hydroxyl
radicals. Photodegradation of the HWW depended on pH
HWW (pH: 7.8). The photo-degradation yields decreased
under acidic and basic conditions while is high at neutral
pH. The total cost of the photodegradation process was
80.654 €. The Nano-GO/M composite was able be syn-
thesized easily and reused two times. Furthermore, after
the 2nd treatment of the HWW, the water quality obtained
was 1st class according to the Turkish Water Pollution Con-
trol Regulations criteria (SWQMR, 2012, official gazette,
number: 28483). This treated water could be used for the
irrigation of green places, cooling water or process water
in different industries.
ACKNOWLEDGEMENTS
The authors would like to express appreciation for the sup-
port of the sponsors Dokuz Eylul University Scientific
Research Project (KB.FEN.020) and TUBITAK 2210-C
National grant for Master Thesis relevant to priority subjects.
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