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Process Safety and Environmental Protection 126 (2019) 259–268

Contents lists available at ScienceDirect

Process Safety and Environmental Protection


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

Advanced disinfecting and post-treating the biologically treated


hospital wastewater in the UVC/H2 O2 and VUV/H2 O2 processes:
Performance comparison and detoxification efficiency
Gholamreza Moussavi ∗ , Eshrat Fathi, Mahsa Moradi
Department of Environmental Health Engineering, Faculty of Medical Sciences, Tarbiat Modares University, Tehran, Iran

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

Article history: The present study compares the ultraviolet (UV)-based AOPs for the disinfection and the post-treatment
Received 23 January 2019 of the biologically-treated hospital wastewater (BHW). It was found that the vacuum UV (VUV) pho-
Received in revised form 10 April 2019 toreactor was much more efficient than the UVC photoreactor in inactivation of E. coli. A 6.4 and 3.7 log
Accepted 11 April 2019
E. coli inactivation (from an initial concentration of 1.09 × 1010 CFU/mL) was achieved in the VUV and
Available online 17 April 2019
UVC photoreactors, respectively, operated under similar conditions at the neutral pH of water. In the
case of continuous-flow operation, the complete inactivation of E. coli was achieved in the VUV photore-
Keywords:
actor in hydraulic retention time (HRT) of 3 min. However, the UVC photoreactor could not attain the
Advanced oxidation process
VUV process
same performance even at the longer HRT of 10 min. Adding H2 O2 to the VUV photoreactor improved
Hydroxyl radical the removal of total organic carbon (TOC) from the BHW. The TOC removal in the recirculated VUV pho-
TOC removal toreactor improved from 10.8%–61.7% in the reaction time of 10 min at the presence of the optimum
Disinfection H2 O2 amount of 3 mM whereas the TOC removal in the UVC/H2 O2 operated at the similar conditions
was only 13.1%. When operated under flow-through condition, 93.6% of TOC could be removed from the
BHW in the VUV/H2 O2 process at the HRT of 10 min where the complete bacterial inactivation and deter-
gent removal was also achieved. The electrical energy consumption was 52.9, 12.2, and 6.5 kW h/m3 in
the UVC/H2 O2 , VUV and VUV/H2 O2 processes, respectively, when operated at the HRT of 10 min under
identical conditions for TOC removal. The VUV/H2 O2 process could also degrade most of the residual
substances in the BHW thus efficiently detoxified the BHW to the level sufficient for discharging into
the water environment. Accordingly, the VUV/H2 O2 process is an efficient, energy-effective, and thus
emerging method for the disinfection and the post-treatment of the hospital wastewater.
© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction receiving environments, the effluent from the hospital wastewater


treatment plants need to be post-treated using advanced processes
The wastewater generated in the hospitals consists of a high efficient in the degradation of residual organic compounds. In the
concentration of bacteria and organic contaminants including other hand, the chlorination is the method of choice used for the
pharmaceuticals, which are conventionally treated in the activated disinfection of the effluents from wastewater treatment plants that
sludge process (Ooi et al., 2018). However, the activated sludge pro- is resulted in the formation of the trihalomethanes due to the inter-
cess is inefficient in bacterial inactivation as well as in removing action between chlorine and organic compounds. Therefore, the
the toxic and recalcitrant compounds such as pharmaceuticals due processes other than the chlorination need to be adopted for the
to their low biodegradability (Ooi et al., 2018; Rodríguez-Chueca disinfection of the BHW. Advanced oxidation processes (AOPs) have
et al., 2018). Therefore, a high concentration of the microbial agents been extensively investigated during recent decades for water and
and the toxic and recalcitrant organic compounds are present wastewater treatment. AOPs have been efficiently examined for the
in the biologically-treated hospital wastewater (BHW) streams degradation of different groups of recalcitrant compounds and for
(Giannakis et al., 2018). To prevent the contamination of the the microbial inactivation (Byrne et al., 2018). Several reports focus-
ing on the treatment of hospital wastewater using AOPs is available.
For instance, the efficacy of Fenton process (Munoz et al., 2016) and
the catalytic wet peroxide oxidation(CWPO)-photoassisted process
∗ Corresponding author. catalyzed by ilmenite (García-Muñoz et al., 2017) were examined
E-mail address: moussavi@modares.ac.ir (G. Moussavi).

https://doi.org/10.1016/j.psep.2019.04.016
0957-5820/© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
260 G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268

for treating the real hospital wastewater. Zheng et al. (2018) inves-
tigated the electro-peroxone AOP as a pretreatment to enhance
the performance of a sequencing batch reactor for treating sim-
ulated hospital wastewater. In addition, AOPs have been tested for
post-treating the effluent from the hospital wastewater biologi-
cal treatment plants. The UV/TiO2 /O3 process showed a potential
capacity for post-treating (disinfection and detoxification) of BHWs
(Machado et al., 2007). Giannakis et al. (2018) evaluated the UVC,
UVC/H2 O2 , and UV/Fenton processes as the post-biological treat-
ment method against enteric microorganisms in synthetic hospital
wastewater and obtained a considerable inactivation rate. The per-
formance of an electrochemical AOP was tested for post-treatment
of the effluent from a membrane bioreactor treating synthetic hos-
pital wastewater fortified with four pharmaceutical pollutants and
concluded that the combined system is a promising strategy in the
removal of pharmaceuticals from synthetic wastewater (Ouarda
et al., 2018). The reported studies indicated that the combined
biological-AOP system is a promising strategy in treating synthetic
hospital wastewater (Giannakis et al., 2018; Ouarda et al., 2018).
VUV-based AOPs are a newly developed class of advanced
oxidation technologies capable of efficiently mineralizing the dif-
ferent groups of recalcitrant compounds (Moussavi et al., 2018a).
In this processes, a high amount of hydroxyl radical (• OH) is gener-
ated from the photochemical ionization and homolysis of water
molecules irradiated with UV photons with the wavelength of
185 nm (Imoberdorf and Mohseni, 2011; Moussavi et al., 2014). It Fig. 1. Schematic of the experimental setup (1. Photoreactor, 2. Sleeve, 3. UV lamp,
has been also shown that the addition of some oxidants as H2 O2 4. Inlet/recirculation tank, 5. Peristaltic pump, 6. Outlet line, 7. Valve (open during
to the VUV photoreactor can increase the generation of • OH and recirculation operation), 8. Valve (open during continuous flow), 9. Outlet tank, 10.
thus improve the degradation efficiency (Moussavi et al., 2018a). Airflow, 11. Off-gas).

Thus, the VUV/H2 O2 as an emerged promising process might be


very efficient for simultaneously disinfection and organic com- Table 1
The mean (5 samples) characteristics of the BHW effluent used in the present study.
pounds mineralization in the BHW. Nonetheless, reviewing the
available literature revealed that no report is available to date on Parameter Unit Value
the application of the VUV/H2 O2 for simultaneously disinfection Microbial density CFU/mL 3.6 × 1013
and post-treatment of the real effluent of the BHW. TSS mg/L 44
Accordingly, the present study deals with investigating the TOC mg/L 78.6
performance of the VUV/H2 O2 as a new AOP compared with COD mg/L 110
BOD5 mg/L 27.5
the UVC/H2 O2 as a classical AOP for the disinfection and the
UV absorbance (UVA) cm1− 0.458
post-treatment of the effluent from a BHW. The possibility of Specific UVA L/mg.m 0.583
continuous-flow operation of the selected AOPs was also evalu- Detergent mg/L 3.65
ated. The detoxification and degradation of the toxic compounds in pH — 7.7
Electrical conductivity mS/cm 1.85
the BWH using the VUV/H2 O2 were also examined.
Nitrate mg/L 18.2
Sulfate mg/L 163.2
Ammonia mg/L 53.1
2. Materials and methods

2.1. Experimental setup 200 nm is about 180 L/(mol.cm) while at 254 nm is approximately
19.6 L/(mol.cm) (Mierzwa et al., 2018), therefore a greater radical
The schematic of the experimental setup is shown in Fig. 1, species and thus degradation percentage would be generated by
which consisted of a tubular Pyrex photoreactor, an aeration sys- the VUV than the UVC irradiation of H2 O2 .
tem (0.8 L/min), a peristaltic pump, a sample tank, and the tubing
and valves. The photoreactor had an inner diameter of 25 mm and 2.2. Wastewater sample and experimental procedure
a height of 400 mm. A synthetic quartz sleeve (Heraeus Co.) with
a diameter of 15 mm was inserted in the reactor inside of which The synthetic microbial suspension was prepared by adding
a low-pressure mercury UV lamp was installed. The working vol- aliquots of E. coli suspension into the dechlorinated tap water.
ume of the photoreactor was 120 mL. Two types of UV lamps were The real samples were taken from the effluent of an activated
tested in the study. In the VUV experiments, a low-pressure mer- sludge process treating the wastewater of a local general hospi-
cury UV lamp (5.7 W UVC output, Heraeus Co.) emitting radiation tal. The main characteristics of the real BHW sample are given in
at both 254 nm (UVC) and 185 nm (VUV < 10%) named hereafter as Table 1. The BHW was first filtered using a 0.45 ␮m paper filter to
VUV was used. The intensity of the UV photons emitted from the remove the particles and the filtrate was used in the reaction exper-
VUV lamp was measured using a UV light detector (Boston Elec- iments. The present study was divided into two phases. Phase I
tronic Co.) at the outer surface of the sleeve to be 6.83 mW/cm2 . was designed for evaluating the inactivation of E. coli in the syn-
For UVC experiments, a 9 W low-pressure monochromatic mer- thetic microbial suspension in the UVC and VUV photoreactors.
cury lamp (Philips Co.) emitting its maximum radiation at 254 nm E. coli was selected as the conventional fecal contamination indi-
was replaced with the VUV lamp in the photoreactor. The light cator (Rodríguez-Chueca et al., 2018). Phase II was allocated for
molar absorption coefficient of H2 O2 at the wavelength around comparing the efficacy of the UVC/H2 O2 and VUV/H2 O2 processes
G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268 261

for the disinfection (bacterial inactivation), detergent degradation through operations, t corresponds to the hydraulic retention time
and total organic carbon (TOC) removal of the effluent of a BHW. (HRT).
In both phases of the study, the experiments were conducted
C0 − Ct
in both batch (recirculation) and continuous flow (once through) Removal efficiency (%) = × 100 (2)
C0
mode. In the recirculation operation mode, 200 mL of the aqueous
solution (phase I) or the BHW sample (phase II) was transferred The kinetics of E. coli inactivation was evaluated based on Chick’s
into the inlet/recirculation tank and was recirculated at 1 L/min model as shown in Eq. (3), assuming that the inactivation rate is first
flow rate through the photoreactor and the effluent was returned order with respect to initial cell concentration (Maddigpua et al.,
back to the recirculation tank. Then the UV lamp was switched 2018; Sreeja and Shetty, 2017).
on and the samples were collected in the sterile flasks from the N 
0
recirculation tank at the target intervals. In the continuous flow log = −kt (3)
Nt
operation, the prepared synthetic microbial suspension (phase I)
or real wastewater sample (phase II) was poured into the inlet tank where N0 and Nt are the viable E. coli colony counts (CFU/mL) at the
and the effluent was directed to the separate outlet tank and the beginning and the contact time t, respectively, and k the first order
UV lamp was switched on. Then the samples were collected in the inactivation rate constant (min−1 ).
sterile flasks from the outlet line in each HRT after passing two HRTs
from the beginning of the test. Before each test, the photoreactor 2.4. LC–MS analysis
was water-rinsed and disinfected by turning on the UV lamp lasted
for 10 min. In addition, the tanks and lab glassware were rinsed Identification of the organic constituents in the effluents of BHW
with water and then were disinfected by autoclave. The synthetic and of VUV/H2 O2 process was carried out by Waters Alliance 2695
microbial suspension was prepared by spiking E. coli suspension HPLC-Micromass Quattro micro API Mass Spectrometer using an
in the dechlorinated tap water. Fresh E. coli culture was prepared Atlantis T3-C18 column (3␮, 2.1 × 100 mm). The column tempera-
in the specific culture medium and incubated at 37 ◦ C in a shak- ture was 30 ◦ C. The mobile phase was formic acid (0.1%), acetonitrile
ing incubator (150 rpm) for 22 h. The prepared E. coli suspension and water with a flow rate of 0.25 mL/min. The mass spectroscopy
was centrifuged at 3500 rpm for 25 min and then the sediment was was conducted in two modes of ESI+, cone volt. 35 V, capillary volt:
suspended in the sterilized normal saline solution (NaCl 0.9%) and 4 kV and ESI-, cone volt. 20 V, capillary volt: 3 kV.
diluted in the dechlorinated tap water to the desired concentration.
In phase I of the study, the effect of suspension pH, salinity (NaCl) 2.5. Toxicity bioassessment
concentration and contact time under the recirculation operation
condition and the effect of hydraulic retention time (HRT) under the The acute toxicity of the BHW before and after treatment in the
continuous operation condition were evaluated on E. coli inactiva- VUV/H2 O2 process was determined by measuring the mortality of
tion in the UVC and VUV photoreactors. In phase II of the study, the Daphnia magna based on the EPA-821-R-02-012 procedure (EPA,
effect of H2 O2 and HRT was investigated on the performance of the 2002). The residual H2 O2 in the samples was removed by adding
UVC/H2 O2 and VUV/H2 O2 processes for post-treating the effluent 10 mM sodium pyruvate before toxicity measurements. The sam-
of a BHW. The bacterial inactivation, the degradation of detergents ples were evaluated by six dilutions between 6.25 and 100%, each
and the reduction of TOC were selected as the performance indices conducted in duplicates and the LC50 was estimated using the pro-
for this phase. bit analysis for the before and after samples. The toxic unit (TU) was
then calculated as TU = 100/LC50 to determine the toxicity level of
the samples (Persoone et al., 2003).
2.3. Analysis
3. Results and discussion
The bacterial inactivation was evaluated by the standard plate
counting method under sterile conditions: plating the ten-fold 3.1. Comparing UVC and VUV photoreactors in E. coli inactivation
serial dilutions of the taken samples on agar culture medium and
incubated at 37 ◦ C for 24 h. Sterile conditions were controlled with Fig. 2 compares the inactivation of E. coli in the UVC and VUV
plating blank samples during the microbial plate count proce- photoreactors at the pHs of 6, 7 and 8. Based on Fig. 2, no consid-
dure. Plating was conducted in duplicate and the mean values of erable difference is observed for E. coli inactivation between the
viable bacteria (E. coli in phase I and total heterotrophs in phase II) selected pHs neither in the UVC photoreactor nor in the VUV one,
were reported as colony forming unit (CFU) per mL of the sample suggesting that the performance of these photoreactors will not be
(CFU/mL). affected by the pH of normal waters. Yoon et al. (2017) also found
The performance of the UVC and VUV photoreactors in bacterial that after increasing pH from 7 to 8, the rates of E. coli inactivation
inactivation was evaluated based on the log removal value (LRV). did not vary for UVC and UVC/H2 O2 processes. The average LRV of
The LRV was determined from Eq. (1) taking the logarithm of the E. coli calculated from Eq. (1) in the neutral pH was 3.7 and 6.4 in
ratio of bacteria concentration in the influent and effluent of the the UVC and VUV photoreactors, respectively.
reactor. An LRV of 1 equals to 90% removal of bacteria. It is seen that E. coli inactivation in the VUV photoreactor was
around three orders of magnitude greater than that in the UVC
 Influent bacteria concentration  photoreactor. E. coli was inactivated in the UVC reactor by the
LRV = log10 (1) germicidal effect of UVC photons, which produced photochemical
Effluent bacteria concentration modifications of DNA pyrimidine bases and damaged the proteins
resulted in the cell death (Gayán et al., 2013; Giannakis et al., 2018).
The concentration of detergents was determined as per method It has been indicated that VUV photons are not directly efficient for
5540 C. in standard method (APHA, 2017). The TOC concentration water and wastewater disinfection (Wang et al., 2010). In another
was measured using a Shimadzu TOC analyzer. The removal per- word, achieving a high degree of E. coli inactivation in the VUV pho-
centages of detergents and TOC were calculated from Eq. (2) in toreactor can be related to the formation of the powerful oxidative
which C0 and Ct stand for the concentrations of detergent or TOC at ȮH through the reactions given in Eqs. (4) and (5), which is more
the beginning and time t of the contact, respectively. In the flow- efficient for the inactivation of microorganisms.
262 G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268

Fig. 2. Comparing the inactivation of E. coli using the recirculated-flow (a) UVC and (b) VUV photoreactors at the pHs of 6, 7 and 8 as a function of contact time.


In the VUV photoreactor, OH is generated from the photo- Since ȮH has much stronger oxidative and thus germicidal
chemical reactions between VUV radiations and water molecules potential than the UVC photons, E. coli inactivation was much more
(Bagheri and Mohseni, 2015; Moussavi et al., 2018b). efficient in the VUV photoreactor than in the UVC one.
 =185 nm In order to confirm the contribution of ȮH in the inactivation
H2 O + VUV → ȮH + Ḣ (4) of E. coli, the performance of the UVC and VUV photoreactors was
 =185 nm compared at the absence and presence of tert-Butyl alcohol (TBA) as
H2 O + VUV → ȮH + H+ + e− (5)
aq a strong ȮH scavenger (k = 3.8 × 108 – 7.6 × 108 M−1 s−1 ). As Fig. 3
Indeed, in the VUV process, in addition to the direct action of shows, the inactivation of E. coli in the VUV photoreactor decreased
UVC photons, the generated ȮH could inactivate bacteria through considerably at the presence of TBA and was very close to that in the
the microbial membrane oxidation and the capsid proteins denat- UVC photoreactor. For instance, the LRV achieved in the VUV pho-
uration (Giannakis et al., 2018). Therefore, the performance of the toreactor at the contact time of 10 s was 6.4 and 4.1 in the absence
VUV was much better than the UVC process operated under the and presence of TBA, respectively. Considering TBA as a selective
same experimental conditions. ȮH scavenger (Moussavi et al., 2018c), the decrease in the per-
Since the reactor was aerated during the reaction, a considerable formance of the VUV photoreactor at the presence of tert-butanol
amount of oxygen was dissolved in water. The direct photolysis of clearly confirm that ȮH played the main role in the inactivation of
O2 by VUV photons could result in the production of ozone (Eqs. (6) E. coli.
and (7)). Ozone was further converted to extra ȮH by irradiation In addition, the LRV did not considerably affect in the UVC pho-
with part of UVC photons (Eq. (8)) (Bagheri and Mohseni, 2015; toreactor at the absence and presence of TBA (Fig. 3), suggesting
Moussavi et al., 2018a,b). that the UVC photons were the main disinfection agent in this reac-
tor. Indeed, since maximum absorption wavelength of TBA does not
O2 + VUV →  = 185 nm2O• (6) coincided with the UVC wavelength, it did not absorbthe UVC pho-
• tons and thus could not adversely affect the performance of UVC
O2 + O → O3 (7)
photoreactor in the inactivation of E. coli.
 =254 nm
O3 + H2 O + UVC → 2ȮH + O2 (8)
G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268 263

Table 2
E. coli plate count in the VUV and UVC photoreactors at different NaCl concentrations.

VUV photoreactor

Time (s) NaCl = 0 g/L NaCl = 0.5 g/L NaCl = 1 g/L NaCl = 2 g/L NaCl = 3 g/L NaCl = 4 g/L NaCl = 5 g/L

0 1.09E+10 1.09E+10 1.09E+10 1.09E+10 1.09E+10 1.09E+10 1.09E+10


5 1.5E+04 2.0E+04 2.4E+04 2.9E+04 3.3E+04 4.6E+04 5.5E+04
10 4.0E+03 9.0E+03 1.2E+04 1.8E+04 2.6E+04 3.2E+04 4.1E+04
15 0.0E+00 3.0E+03 8.0E+03 1.1E+04 1.8E+04 2.4E+04 3.2E+04
20 1.0E+03 5.0E+03 8.0E+03 1.4E+04 1.9E+04 2.6E+04
30 0.0E+00 2.0E+03 5.0E+03 9.0E+03 1.3E+04 1.9E+04
40 0.0E+00 3.0E+03 5.0E+03 8.0E+03 1.3E+04
50 0.0E+00 3.0E+03 4.0E+03 6.0E+03
60 0.0E+00 2.0E+03 3.0E+03
120 0.0E+00 0.0E+00

UVC photoreactor

Time (s) NaCl = 0 g/L NaCl = 0.5 g/L NaCl = 1 g/L NaCl = 2 g/L NaCl = 3 g/L NaCl = 4 g/L NaCl = 5 g/L

0 1.09E+10 1.09E+10 1.09E+10 1.09E+10 1.09E+10 1.09E+10 1.09E+10


10 2.4E+06 2.2E+06 2.0E+06 1.9E+06 1.7E+06 1.6E+06 1.4E+06
20 3.4E+05 3.0E+05 2.8E+05 2.1E+05 1.8E+05 1.4E+05 1.0E+05
30 5.0E+04 1.5E+05 2.0E+04 1.5E+04 1.0E+04 0.0E+00 0.0E+00
40 3.0E+04 1.0E+04 1.0E+04 0.0E+00 0.0E+00
50 0.0E+00 0.0E+00 0.0E+00

Fig. 3. Effect of radical scavenger on E. coli inactivation in the recirculated-flow UVC


and VUV photoreactors at pH = 7.
Fig. 4. Effect of NaCl concentration on the rate of E. coli inactivation in the
recirculated-flow UVC and VUV photoreactors.
The effect of water salinity based on NaCl concentration was
evaluated on the performance of the UVC and VUV photoreactors
anion on ȮH. In fact, chloride ions could react with ȮH (Eq. (10)) and
under neutral pH and the results are given in Table 2. To better
scavenge it (k = 2 × 107 M−1 s−1 ) (Nakatani et al., 2007) and thereby
illustrate the effect of salinity, the E. coli inactivation rate constant,
further limited the ȮH available for the inactivation of E. coli.
k, was determined based on Table 2 for the different NaCl concen-
trations and the results are shown in Fig. 4. As seen in Fig. 4, the Cl− + ȮH → ClOH•− (10)
presence of NaCl markedly decreased the performance of the VUV
photoreactor for the inactivation of E. coli and caused the reduc- In contrast, the inactivation rate constant increased in the UVC
tion of E. coli inactivation rate constant. It is known that chloride photoreactor with the increase in NaCl concentration (Fig. 4). It can
anion strongly absorb 185 nm photons to generate chloride radical be attributed to the generation of Cl• and Cl2 •− reactive species
(Cl• ) thus, the greater fraction of 185 nm photons emitted from the from the photochemical reactions between UVC photons and chlo-
VUV lamp are absorbed by chloride anions than by water molecules ride anions (Huang et al., 2018; Yang et al., 2014). These radicals are
(Furatian and Mohseni, 2018). more powerful than UVC photons resulted in improving the inac-
tivation rate of E. coli. The full-scale water disinfection systems are
Cl− →  = 185 nmCl• + e−
aq (9) conventionally operated in a continuous-flow mode. Therefore, the
effect of HRT was evaluated on the performance of the UVC and VUV
Therefore, the production of ȮH (Eqs. (4) and (5)) in the VUV photoreactors in the inactivated of E. coli. Fig. 5 shows the effluent
photoreactor would be limited at the presence of chloride anions E. coli concentration as a function of HRT in the UVC and VUV pho-
resulted in the decrease in E. coli inactivation rate. Although Cl• is toreactors under neutral pH. It is seen in Fig. 5 that the complete
generated from the photochemical reaction between 185 nm pho- inactivation of E. coli was achieved in the VUV photoreactor at an
tons and chloride anions, Cl• has much lower oxidation potential HRT as short as 3 min (liquid flow rate = 40 mL/min) whereas in the
than ȮH (Moussavi and Rezaei, 2017), causing an overall reduction UVC photoreactor the same performance could not be reached even
in the inactivation performance. The reduction in E. coli inactiva- in an HRT of 10 min (liquid flow rate = 12 mL/min). The inactivation
tion rate can be also attributed to the scavenging effect of chloride rate constant was 0.221 and 0.874 min−1 in the UVC and VUV pho-
264 G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268

Fig. 6. Effect of H2 O2 on the performance of the recirculated-flow UVC and VUV


Fig. 5. Effect of HRT on the performance of E. coli in the continuous-flow UVC and photoreactors in TOC removal from the BHW.
VUV photoreactors under neutral pH.

to 61.7%, whereas a further increase in H2 O2 to 4 and then 5 mM


toreactors, respectively. Much greater rate of E. coli inactivation resulted in the reduction of TOC removal to 51.4 and then 47.3%,
in the VUV photoreactor (4 times) is related to the generation of respectively. The increase in the performance of the UVC photore-
reactive ȮH , which was discussed above. Attaining the complete actor at the presence of H2 O2 can be related to the formation of
inactivation of a high population of E. coli in a relatively short con- highly oxidative species of ȮH upon the photolysis of H2 O2 by the
tact time of 3 min in the VUV photoreactor suggests that this system UV254 photons (Aguilar et al., 2018) as shown in Eq. (11).
can be efficiently applied for water and wastewater disinfection.
Several studies have been published on E. coli inactivation H2 O2 + UV254 → 2ȮH (11)
using different AOPs and following results were reported: 6 log
In the VUV photoreactor, in addition to Eqs. (4), (5), (11), ȮH was
inactivation in 180 min (0.119 min−1 ) in the solar light/carbon
also generated from the irradiation of H2 O2 by the UV185 photons
nanoparticles process (Maddigpua et al., 2018), 100% inactivation
(Eq. (12)) as well as from the interaction between H2 O2 and e− aq
in 60 min (0.711 min−1 ) in an electrochemically assisted photo-
(Eq. (13)) (Moussavi et al., 2018a). Since the molar absorption coef-
catalysis process with Ag-Ti/TiO2 as catalyst (dos Santos et al.,
ficient of H2 O2 at 185 nm is much higher than at 254 nm (Mierzwa
2017), 100% of 4 × 109 CFU/mL inactivation in 60 min (0.043 min−1 )
eta l., 2018), therefore a greater amount of ȮH could be produced in
in a photocatalytic process with Ag@TiO2 nanoparticles as cata-
the VUV photoreactor than in the UVC one in the presence of H2 O2 ,
lysts under solar light irradiation (Sreeja and Vidya, 2017), 100%
resulting in the achievement of a better TOC removal.
of 105 –106 inactivation in 90 min (0.18 min−1 ) in a HSO− 5 /UV − A
LED photocatalytic process (Rodríguez-Chueca et al., 2017), 100% H2 O2 (aq) + UV185 → 2ȮH (12)
of 105 E. coli inactivation in 60 min (0.18 min−1 ) in a pilot-scale −
H2 O2 (aq) + e−
aq → ȮH + OH (13)
ilmenite/persulfate/solar light reactor (Xia et al., 2018), 6 log inac-
tivation in 45 min (107 CFU/mL) in the UV/H2 O2 process (Miranda The reduction of TOC removal in the VUV photoreactor in
et al., 2016), 100% of 105 -106 inactivation in 5 min (0.92 min−1 ) the elevated H2 O2 levels can be related to the recombination of
in the H2 O2 /solar light (50 W/m2 ) process (Nahim-Granados et al., increased ȮH to form H2 O2 (Eq. (14)) (Imoberdorf and Mohseni,
2018), 4-log inactivation (107 CFU/mL) in the microbial electrolytic- 2011; Moussavi et al., 2018a). Therefore, the amount of 3 mM was
Fenton process (Zhou et al., 2018). selected as the optimum level of H2 O2 in the next experiments.
HO• + HO• → H2 O2 (14)
3.2. Comparing UVC and VUV processes for treating the BHW
effluent Kern et al. (2013) investigated the treatment of a hospital
laundry wastewater with photocatalytic ozonation process and
In order to confirm the real-case applicability potential of the reported 59.1% removal of COD and complete inactivation of total
VUV photoreactor, the disinfection and post-treating the BHW sam- coliforms and E. coli in the UV/O3 /Fe2+ process at a reaction time of
ple was investigated in the VUV photoreactor in comparison with 180 min. Around 46% of COD removal was obtained within 60 min
the UVC system. when treating hospital wastewater in the O3 /UV/H2 O2 process
(Arslan et al., 2014). Real hospital wastewater with initial TOC con-
3.2.1. Effect of H2 O2 on TOC removal from BHW effluent using the centration of 110 mg/L and total coliform of 4.16 × 106 was treated
recirculated-flow UVC and VUV systems in a Fenton process working at or above 70 ◦ C and around 50% of
Fig. 6 depicts the effect of H2 O2 on the performance of the UVC TOC reduction and complete bacterial inactivation were achieved
and VUV photoreactors in TOC removal from the BHW effluent within 4 h (Munoz et al., 2016). The combined VUV + UVC pho-
under recirculated-flow operation condition. It is seen in Fig. 6 that toreactor could reduce the chemical oxygen demand (COD) from a
the TOC removal was around 1% and 10.8% in the UVC and VUV hospital laundry wastewater by around 25% (Schwaickhardt et al.,
photoreactors at the reaction time of 10 min in the absence of H2 O2 , 2017). A 74% TOC removal and complete bacterial inactivation in
indicating that the single UVC or VUV irradiation are not efficient real hospital wastewater having the initial TOC concentration of
processes for the sufficient reduction of the carbon content of the 110 mg/L and bacterial concentration of 3.8 × 106 was obtained
BHW. To improve the TOC removal percentages, the photoreactors when treated for 5 h in the CWPO-photoassisted process (García-
were operated at the presence of different concentrations of H2 O2 . Muñoz et al., 2017). Around 50% of TOC (from 103.9 mg/L) reduction
Based on Fig. 6, the TOC removal increased from 9.2 to 14.7% in the was achieved in an electro-peroxone process pretreating simulated
UVC photoreactor when the amount of H2 O2 added was increased hospital wastewater within 60 min under the optimal O3 concen-
from 1 to 5 mM. In the VUV photoreactor, the increase in H2 O2 from tration of 5 g/h, current of 400 mA and solution pH of 9 (Zheng et al.,
1 to 3 mM caused the improvement of the TOC removal from 18.3 2018).
G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268 265

Fig. 8. The electrical energy per TOC removal order (EE/O) in the VUV,
UVC/H2 O2 , and VUV/H2 O2 processes (HRT = 10 min, H2 O2 concentration (when
needed) = 3 mM).

BHW effluent in an HRT of 10 min while a high concentration of


viable bacteria was present in the effluent of the other examined
processes operated under the same conditions. It should be noted
the control experiments conducted with only H2 O2 (UV lamp was
off) for the BHW sample indicated that the direct bacterial inac-
tivation by H2 O2 was negligible under the selected condition due
mainly to the short reaction time.
It is found in Fig. 7a–c that performance of the investigated
processes was lower for the degradation of organic compounds
(TOC and detergent removals) than for the disinfection, suggest-
ing that the process should be designed based on HRT required
for the achievement of the desired TOC removal. Similarly, Wols
et al. (2015) reported that the desired degradation efficiency in the
UV/H2 O2 process is lower than the desired disinfection levels.

3.2.3. Energy efficiency


The selected processes were also compared based on the elec-
trical energy per order (EE/O), which is defined as the electrical
energy (kWh) required to decrease the concentration of TOC by
one order of magnitude in a unit volume (Estefan, 2018). As the
selected processes were operated in flow-through mode, the EE/O
value (kWh/m3 /order) was calculated from Eq. (15) (Estefan, 2018).
 
P
EE/O = (15)
Q × log(C i /Cf )
Fig. 7. Comparing the performance of the continues-flow UVC, VUV, UVC/H2 O2 and
VUV/H2 O2 processes in (a) TOC removal, (b) detergent removal and (c) bacterial
inactivation of the BHW in an HRT of 10 min and H2 O2 concentration (when needed) where P (kW) and Q (m3 /h) stand for total input electrical power
of 3 mM. (9 W for UVC and 5.7 W for VUV lamps) and volumetric flow rate,
respectively. Ci and Cf are inlet and outlet concentrations of the
3.2.2. Effect of HRT on the performance of continuous-flow target parameter.
UVC/H2 O2 and VUV/H2 O2 processes Fig. 8 depicts the values of EE/O for the VUV, UVC/H2 O2 , and
In order to evaluate the field applicability of the VUV/H2 O2 VUV/H2 O2 processes calculated based on TOC removal (Fig. 7). The
process as the most efficient process, it was operated in continuous- EE/O was not calculated for UVC photoreactor as it attained insignif-
flow mode corresponding to the steady-state behavior and the icant TOC removal (<1%). The values of EE/O were calculated to be
effect of HRT was evaluated on TOC removal from the effluent of 52.9, 12.2, and 6.5 kW h/m3 in the UVC/H2 O2 , VUV and VUV/H2 O2
BHW in the VUV/H2 O2 process compared to the UVC, VUV and processes, respectively, when operated under identical experimen-
UVC/H2 O2 processes. It is observed in Fig. 7a that the TOC con- tal conditions at an HRT of 10 min and the same H2 O2 concentration
centration in the BHW effluent decreased from 78.9 mg/L (before (in the UVC/H2 O2 and VUV/H2 O2 processes) for TOC removal. It
post-treatment) to 78.5, 45.8, 17.8 and 4.9 mg/L (corresponding is seen that the VUV/H2 O2 had the lowest EE/O value among the
to <1, 45.8, 77.3 and 93.6%) after post-treating in the UVC, VUV, tested processes for TOC removal, which is related to the high
UVC/H2 O2 and VUV/H2 O2 processes, respectively, in an HRT of rate of TOC removal in this process (Moussavi et al., 2018a). TOC
10 min. The VUV/H2 O2 process could also completely degrade elimination between 5% and 32% was achieved in post-treating the
the detergents in the BHW effluent within a short HRT of 4 min biologically pre-treated hospital wastewater using the UVC/H2 O2
(Fig.7b). Based on the results shown in Fig. 7c, the performance process when 4 kW h/m3 of electrical energy were used (Köhler
order of the investigated processes for the disinfection of the BHW et al., 2012). Figs. 7 and 8 clearly indicate that the VUV/H2 O2 pro-
is as VUV/H2 O2 > VUV > UVC/H2 O2 > UVC processes. Indeed, the cess is a very technically and energetically efficient technique for
VUV/H2 O2 could completely inactivate the viable bacteria in the disinfecting and post-treating the BHW.
266 G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268

Table 3
Identified organic constituents in the BHW effluent (UVC/VUV influent).

RTa ESI mode Experimental m/z Exact m/z Exact mass Best possible compound Best possible molecular formula Adduct ion

7.29 Negative 553 553.04 554.05 Cefsulodin sodium salt C22 H19 N4 NaO8 S2 [M−H]−
8.58 Negative 192 191.99 193.00 2,6-difluorobenzenesulfonamide C6 H5 F2 NO2 S [M−H]−
8.58 Negative 199 198.97 217.98 5-Sulfosalicylic acid C7 H6 O6 S [M−H-H2 O]−
8.58 Negative 383 383.10 402.12 Saphenamycin C23 H18 N2 O5 [M−H-H2 O]−
8.58 Negative 491 491.18 492.18 Cilnidipine C27 H28 N2 O7 [M−H]−
8.58 Negative 535 535.07 490.07 Cefamandole Nafate C19 H18 N6 O6 S2 [M+Formate]−
8.58 Negative 567 567.11 568.12 2”-O-p-Hydroxybenzoylorientin category C28 H24 O13 [M−H]−
9.095 Negative 267 266.94 285.96 Fenticlor C12 H8 Cl2 O2 S [M−H-H2 O]−
9.095 Negative 352 352.16 371.18 Lysidine C15 H25 N5 O6 [M−H-H2 O]−
9.095 Negative 388 388.01 389.02 Cyclothiazide C14 H16 ClN3 O4 S2 [M−H]−
9.095 Negative 467 467.09 468.10 Tartrazine acid C24 H20 O10 [M−H]−
9.095 Negative 617 617.04 572.04 Isorhamnetin 3-glucuronide-7-sulfate C22 H20 O16 S [M+Formate]−
9.357 Negative 438 437.96 438.97 Polythiazide C11 H13 ClF3 N3 O4 S3 [M−H]−
9.357 Negative 473 473.10 492.12 Isopyrenin C23 H24 O12 [M−H-H2 O]−
9.357 Negative 475 474.91 429.91 4,4’-azodibenzenearsonic acid C12 H12 As2 N2 O6 [M+Formate]−
9.357 Negative 485 485.14 486.15 Mycothiol C17 H30 N2 O12 S [M−H]−
9.357 Negative 500 500.11 519.13 Estramustine phosphate C23 H32 Cl2 NO6 P [M−H-H2 O]−
9.357 Negative 552 551.98 506.98 Phosphoadenosine phosphosulfate C10 H15 N5 O13 P2 S [M+Formate]−
10.487 Negative 209 208.98 228.00 3,5-dinitrosalicylic acid C7 H4 N2 O7 [M−H-H2 O]−
11.031 Negative 275 275.09 230.09 Bis-(4-hydroxybenzyl)ether C14 H14 O3 [M+Formate]−
11.707 Negative 207 206.86 161.86 Bromodichloromethane CHBrCl2 [M+Formate]−
25.773 Negative 103 103.00 104.01 Hydroxypyruvic acid C3 H4 O4 [M−H]−
25.773 Negative 530 503.19 504.20 Chlorhexidine C22 H30 Cl2 N10 [M−H]−
1.512 Positive 101 101.04 200.08 Monobenzone C13 H12 O2 [M+2H]2+
1.512 Positive 129 129.01 128.00 4-chlorophenol C6 H5 ClO [M+H]+
1.512 Positive 165 164.88 163.87 Tetrachloroethene C2 Cl4 [M+H]+
1.512 Positive 286 286.14 285.13 Morphine C17 H19 NO3 [M+H]+
1.512 Positive 300 300.15 299.15 Heterocodeine C18 H21 NO3 [M+H]+
1.512 Positive 315 315.15 332.15 Spectinomycin C14 H24 N2 O7 [M+H-H2 O]+
1.512 Positive 331 331.16 289.12 Ophthalmic acid C11 H19 N3 O6 [M+H+CH3 CN]+
1.512 Positive 336 335.95 352.96 Luliconazole C14 H9 Cl2 N3 S2 [M+H-H2 O]+
1.512 Positive 365 365.03 364.02 Chloramphenicol 3-acetate C13 H14 Cl2 N2 O6 [M+H]+
1.512 Positive 794 794.15 752.12 Loropetalin D C35 H28 O19 [M+H+CH3 CN]+
2.954 Positive 287 286.91 303.91 Dichlorphenamide C6 H6 Cl2 N2 O4 S2 [M+H-H2 O]+
2.954 Positive 392 392.12 350.09 Penicillin V C16 H18 N2 O5 S [M+H+CH3 CN]+
5.142 Positive 111 111.05 128.06 Naphthalene C10 H8 [M+H-H2 O]+
5.142 Positive 123 122.93 243.86 Tetrachloro-1,4 benzoquinone C6 Cl4 O2 [M+2H]2+
5.142 Positive 167 167.07 166.06 3,4-Dimethoxybenzaldehyde C9 H10 O3 [M+H]+
5.142 Positive 208 208.01 165.98 Hexafluoroacetone C3 F6 O [M+H+CH3 CN]+
5.142 Positive 392 392.14 350.11 Neorautenane C21 H18 O5 [M+H+CH3 CN]+
6.775 Positive 122 122.02 139.02 2-nitrophenol C6 H5 NO3 [M+H-H2 O]+
6.775 Positive 207 207.05 224.05 Phenazine-1-carboxylic acid C13 H8 N2 O2 [M+H-H2 O]+
6.775 Positive 236 236.04 253.05 Sulfamethoxazole C10 H11 N3 O3 S [M+H-H2 O]+
6.775 Positive 291 291.07 308.08 Alprazolam C17 H13 ClN4 [M+H-H2 O]+
6.775 Positive 372 372.10 371.10 Nedocromil C19 H17 NO7 [M+H]+
6.775 Positive 389 389.12 347.09 Cephalexin C16 H17 N3 O4 S [M+H+CH3 CN]+
6.775 Positive 462 462.05 461.04 Necrosulfonamide C18 H15 N5 O6 S2 [M+H]+
6.775 Positive 537 537.04 554.04 Ceftriaxone C18 H18 N8 O7 S3 [M+H-H2 O]+
8.278 Positive 426 426.05 425.04 Thiamine diphosphate C12 H19 N4 O7 P2 S [M+H]+
16.09 Positive 105 105.02 104.02 Urea-1-carboxylic acid C2 H4 N2 O3 [M+H]+
16.09 Positive 376 376.10 375.10 Azidocillin C16 H17 N5 O4 S [M+H]+
16.09 Positive 420 420.05 437.05 Cycloprothrin C24 H17 Cl2 NO3 [M+H-H2 O]+
16.09 Positive 463 463.19 421.16 Topotecan C23 H23 N3 O5 [M+H+CH3 CN]+
16.09 Positive 719 719.16 718.15 Salvianolic acid L C36 H30 O16 [M+H]+
26.829 Positive 757 757.08 757.08 P(1),P(3)-bis(5’-adenosyl) triphosphate C20 H27 N10 O16 P3 [M+H]+
a
Retention time (min).

3.2.4. Identification of organic constituents an additional treatment step was needed after the conventional
In order to conduct a wide-scope screening of the BHW sam- biological treatment process to efficiently degrade such toxic con-
ple before and after treating in the VUV/H2 O2 process, LC–MS stituents. Based on Table 4, the number of detectable constituents
analysis was carried out and the findings from the mass spec- dramatically decreased after treating the BHW in the VUV/H2 O2
tra (Figs. S1–S4) are summarized in Tables 3 and 4, respectively. process. Regarding the simultaneous multilateral mechanisms
As in Table 3, a notable number of constituents was identified occurring in the vacuum UV region (advanced oxidation, advanced
in the BHW; the majority of which included pharmaceuticals, reduction, direct photolysis, etc.), various categories of compounds
microbial metabolites, solvents, etc. and their transformation with different molecular structures and tendencies undergo degra-
products. These constituents were in forms of either unchanged dation towards mineralization (Moradi and Moussavi, 2019) as it
parent compounds or free/conjugated metabolites. In compliance was well-exhibited as TOC decrement for the studied sample. It
with previous studies (Brown et al., 2018; Ibáñez et al., 2017; shows that the VUV/H2 O2 process is a very efficient technique for
Martínez-Alcalá et al., 2017; 1-3), this screening also endorsed degradation of toxic synthetic compounds present in the wastew-
that conventional WWTP is not successful for efficient degrada- ater and thus an advanced post-treating process justifying the
tion of a variety of constituents and micropollutants with varying achievement of a high degree of TOC reduction in the experi-
concentrations such as pharmaceuticals, solvents, etc. Therefore, ment.
G. Moussavi et al. / Process Safety and Environmental Protection 126 (2019) 259–268 267

Table 4
Identified organic constituents in the UVC/VUV effluent.

RTa ESI mode Experimental m/z Exact m/z Exact mass Best possible compound Best possible molecular formula Adduct ion

7.21 Negative 213 213.03 214.03 Clofibric acid C10 H11 ClO3 [M−H]−
11.39 Negative 388 388.01 389.02 Cyclothiazide C14 H16 ClN3 O4 S2 [M−H]−
14.83 Negative 239 239.01 240.02 d-cystine C6 H12 N2 O4 S2 [M−H]−
19.49 Negative 354 354.02 355.02 Succinylsulfathiazole C13 H13 N3 O5 S2 [M−H]−
20.006 Negative 398 398.09 399.10 Nocardicin E C19 H17 N3 O7 [M−H]−
1.249 Positive 151 151.06 150.05 2-Deoxyribonucleic acid C5 H10 O5 [M+H]+
1.249 Positive 192 192.02 209.03 2-(oxaloamino)benzoic acid C9 H7 NO5 [M+H-H2 O]+
1.38 Positive 288 287.91 245.88 Tetrachlorocatechol C6 H2 Cl4 O2 [M+H+CH3 CN]+
11.48 Positive 344 344.07 302.04 Quercetin C15 H10 O7 [M+H+CH3 CN]+
17.047 Positive 386 386.07 385.07 Hydroxylansoprazole C16 H14 F3 N3 O3 S [M+H]+
a
Retention time (min).

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