Photocatalytic Degradation of a Herbicide Namely Glyphosate and

Hexazinone from the Surface Water which will be Used as Drinking

Water via Polyaniline/ZnWO4/WO3 and Evaluation of Acute Toxicity

Assays

RUKİYE ÖZTEKİN a , DELİA TERESA SPONZA a , *

a Department of Environmental Engineering

Dokuz Eylül University

Tınaztepe Campus, 35160 Buca/Izmir,

TURKEY

* Corresponding Author

Abstract: - Polyaniline/Zinc tungsten oxide/Tungsten trioxide nanocomposites (PANI/ZnWO4/WO3 NCs) was

prepared to remove glyphosate (GLP) and Hexazinone (HZN) herbicides from the surface water. The properties

of PANI/ZnWO4/WO3 NCs was investigated using XRD, FTIR, FESEM, HRTEM, XPS analyses. The toxicity

of NCs and treated wastewater were investigated using Microtox and Daphnia magna acute toxicity tests. The

effects of increasing values of PANI/ZnWO4/WO3 NCs concentrations (0.1, 0.4, 0.6, 1.0 and 1.5 mg/l),

PANI/ZnWO4/WO3 mass ratios (1:1:3, 1:2:3, 3:1:1 and 3:2:1), GLP concentrations (1, 2, 3 and 4 mg/l),

photodegradation times (2, 10, 15 and 20 min), and solar light powers (20, 40, 60, 80 and 100 W/m2) on the GLP

and HZN removals in the surface were examined. The results of the acute toxicity analysis performed showed

that the acute toxicity in the surface water decreased significantly after photooxidation. The maximum removal

conditions for 3 mg/l GLP (99.90%) were 1 mg/l PANI/ZnWO4/WO3 NCs with a PANI/ZnWO4/WO3 ratio of

1:2:3 after 15 min photodegradation time at 80 W/m2 sun light power while the maximum HZN removal was

obtained as 96% after 15 min photodegradation, under 300 W solar light, at pH=7.0 and at 25oC. The crystalline

monoclinic ZnWO4 and WO3 was detected from XRD analysis while PANI exhibited characteristic broad peak

at 28.91° with an amorphous nature. FTIR spectra showed that pure ZnWO4 has the Zn–O–W vibrational bands.

XPS analysis, exhibited reactive oxygen species. The charge/discharge analysis indicated that WO3 has a larger

particle size that decreases surface density increasing the interplanar spacing between atoms. The introduction of

ZnWO4 and WO3 nanoparticles into the PANI matrix enhanced the surface of the PANI/ZnWO4/WO3 NC.

Key-Words: - Glyphosate; Hexazinone; Daphnia magna acute toxicity test; Herbicie; Microtox acute toxicity

assay; Photocatalytic degradation process; Polyaniline/Zinc tungsten oxide/Tungsten trioxide nanocomposites;

Surface water.

Received: March 22, 2024. Revised: August 14, 2024. Accepted: September 18, 2024. Published: November 29, 2024.

1 Introduction

The increasing of population and industrial

discharges to the environment elevated the limits

required for drinking water supply and large-scale

food production,[1]. Under these conditions in order

to decrease the primary productivity at an

economically steady-state level, some of

agrochemicals has been extensively used to remove

the pesticides and herbicides, [2]. With the excess

utilization of some anthropogenic compounds and as

a result of excess industrialization, water pollution

was elevated, [3]. Synthetic pesticides and herbicides

are usually utilized in agricultural lands to protect the

plants. The herbicides were resistant to biological

degradation, and has high bio-accumulative capacity

consisting from their physicochemical properties

with long half-life of 10–20 years. Their bio

magnification increasing in the ecosystems and in the

humans, [4, 5]. Due to recalcitrant structure of

pesticides their persistence in soil, wastewater, and

surface water elevated excessively and cause to an

environmental problem. They can contaminate the

food chain, and can cause toxicity to human health,

[6]. Due to their high stability, these compounds

cannot be biodegraded. The recent studies showed

that exposure to the aforementioned compounds

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

cause to hormonal changes in the immune system and

as a results some neurological and cardiac disease

and some neoplasms occurred, [7, 8]. In order to

remove these organics adsorption and advanced

oxidation processes (AOPs), including Fenton,

photo-Fenton, heterogeneous photocatalysis,

ozonation systems…etc, were used, [9-11]. AOPs are

based on the generation of free radicals, e.g.,

hydroxyl (●OH) and superoxide (●O2 - ), having high

oxidizing activities in aquatic systems and pollutants

can be converted into lower molecular weight

metabolites and inorganic compounds, [12, 13].

Heterogeneous photocatalysis is an advanced process

through the photoactivation of a semiconductor via

redox reactions under sun and UV ligths, [14]. This

process is very efficient and promising for the

degradation of organic pollutants including dyes,

antibiotics, drugs and pesticides, [9, 15, 16]. Among

the nanocomposites used, metallic nano-oxides; Zinc

oxide (ZnO) and titanium dioxide (TiO2) have been

excesively employed due to their low toxicity, good

availability, chemical stability, large surface

area/porosity, and photo-corrosion, [17, 18]. Nano-

adsorbents and nanocomposites were used for

pesticide removal from wastewater for their

simplicity of operation, relatively low cost and low

energy requirements, [19], Furthermore they have

high specific surface area, chemical/thermal stability,

and affinity to organic pollutants, [20].

Glyphosate herbicide (GLP; N-

phosphomethyl[glycine] or C3H8NO5P), is

metabolized by microorganisms into

aminomethylphosphonic acid (AMPA, known as its

most active metabolite) and methylphosphonic acid

(MPA), [21-23]. After more than 40 years of global

use, GLP has been classified as “probably

carcinogenic” in humans by the International Agency

for Research on Cancer (IARC). In 2019, United

States federal health agency, the Agency for Toxic

Substances and Disease Registry, [24], part of the

Centers for Disease Control and Prevention, [25],

determined that both cancer and non-cancer hazards

derive from exposure to GLP and GLP-based

herbicides.

Hexazinone (HZN) is an example of an atypical

triazine herbicide used for control of woody plants in

reforestation areas and for selective weed control in

sugarcane, pineapple, and alfalfa. The degradation of

HZN in the rat, alfalfa, and sugarcane was reported

by Holt, [26]. The mass spectral identification of

HZN metabolites isolated from rat urine and from

sugarcane extracts was reported by Reiser et al., [26].

Established sugarcane plants grown in the

greenhouse were treated by soil drench with 14C-

HZN and harvested at plant maturity 6 months later.

The total radioactive residues in mature sugarcane

were less than 0.1 ppm, and the intact parent was not

detected, [26].

No more studies were found in the recent

literature about the removal of GLP: For the

degradation of GLP, ultimate and intermediate

metabolites such as AMPA, sarcosine, formaldehyde

and CO2 was produced during microbial

transformation. During abiotic degradation, the

amounts of GLP degraded by non-microbial forms

and biological transformation were negligible, [27].

Low GLP yields was detected in the biodegradability

studies performed by microorganisms. The

biodegradation of GLP in soils by microorganisms is

also rapid, [28]. During the photodegradation of GLP

by sunlight no GLP removals was detected in soils,

[29]. Other some chemical and physicochemical

methods are used with nanocomposites to degrade

the GLP. TiO2 photocatalyst with H2O2 under UV

ligth provided 65-70% GLP removals. TiO2 particles

doped with Mn, Ce or La under visible light provided

79-83% GLP removals. A nanocomposite namely

BiOBr/Fe3O4 consisting from TiO2 nanotubes and

photocatalytic Ce and Fe3O4 was used in GLP

photooxidation. MnO2 and BiVO4 was used as

nanocomposite for the removal of GLP, [30]. In

addition, in the removal of GLP adsorption on a

MnFe2O4-graphene hybrid compound and an

oxidative degradation process assisted with MnO2

has been used, [31]. However, in the aforementioned

studies low GLP yields (79-82%) was detected. In

recent years nnotechnology recently began to used to

photodegrade the GLP with high yields. In the studies

performed by MnO2/C nanocomposite high GLP

yields was detected (87%) due to high specific

surface and high dispersion of the aforementioned

nanocomposite, [28]. An efficient GLP removal was

further achieved using a nanosized resin (D201Cu)

modified with Cu(OH)2), [32]. However, the GLP

yields found in the study given above were not

effectively high and remained between 76% and

81%, [32]. Degradation of HZN has been

investigated by means of photocatalysis of mixed-

phase crystal nano-TiO2. Influences of adsorption,

amount of nano-TiO2, pH and irradiation time on the

photocatalytic process are studied. Results show that

hexazinone is totally degraded within 140 min of

irradiation under pH neutral conditions, [33].

More than 98% degradation of HZN was observed

under 3 J/cm2 UVC (ultraviolet C) fluence in the

presence of 0.5 mM H2O2 at pH 7.0, [34]. Moreover,

the degradation rate enhanced significantly with an

increase in the initial dosage of H2O2, UV fluence,

and contact time in the UV/H2O2 process. The rate of

degradation was lower using secondary effluent than

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

that of Milli-Q water due to the presence of dissolved

organics in wastewater. However, the reactions in

bothmatrices obeyed pseudo-first-order kinetics.

Photocatalytic kinetic information of HZN

degradation exhibited first order kinetics from the fit

in the Langmuir–Hinshelwood model with high

yields (96%), [33].

Electrochemical degradation of HZN in aqueous

solution was performed by using Bi-doped PbO2

electrodes as anodes. The main influencing

parameters on the electrocatalytic degradation of

HZN were initial HZN concentration, current

density, initial pH and Na2SO4 concentration. The

electrochemical oxidization reaction of HZN fitted

pseudo-first-order kinetics model with a yield of

95.9%, [35].

Polyaniline (PANI) is a conducting polymer and

organic semiconductor of the semi-flexible rod

polymer family, [36, 37]. PANI has low-cost and

environment-friendly conjugated semiconductor for

the fabrication and is effective under visible light

photocatalysis, [38]. It is a conducting polymer with

an extensive conjugated π-system and high

absorption coefficient under visible light during

charge carrier production. It has a simple processing

with high conductivity during production of

heterojunction nano catalysts. In recent studies many

effective data were detected during photodegradation

of organics when contacting with its interfaces and

individual pollutant components. PAI exhibited high

separation efficiency during photocatalysis for

photogenerated electron–hole pairs, [39].

Zinc tungsten oxide or zinc tungstate (ZnWO4) is

extensively used during photodegradation due to its

high UV light response, tunable band edges, optical

transparency, chemical stability, and suitable

strength, [40]. The band edge tuning of ZnWO4-

centered nanostructures can be organized through

appropriate changes such as heterostructure

construction, doped/combining with transition metal

ions, and noble metals, [41, 42]. By deposition of O2-

ions around the tungsten (W), ZnWO4 forms an

insulated trioxide-oxo-tungsten [WO6] octahedron

with an asymmetric shape showing a local atomic

structure with a wolframite-type space group of P2/c,

[43]. This is an essential inorganic ternary oxide

material with crystalle properties and exhibited

scheelite structure depending on the ionic radius,

[44]. W clusters formed a network since they are

more stable, leading to form the covalent nature of

W–O bonds. During generation of electron-hole

pairs a charge separation process was performed with

dipoles when WO6 clusters act as electron receptors.

Thus, the oxygen vacancies in the Zn/W clusters can

transfer electrons to the W cluster and permanent

dipoles were generated, [45]. The Zn and W

vacancies act as electron capture in the holes since

they are charged negatively, [46].

Tungsten trioxide (WO3) is an n-type

semiconductor photocatalyst having a wide range of

bandgap values (2.7–3.4 eV) providing a better

extension into the visible range, [47]. WO3 as alone

photocatalyst suffers from the limitation of fast

recombination of charge carriers, thereby restricting

its potential during photocatalytic applications, [48].

Several studies suggest that constructing a

heterojunction between two metal oxides with

suitable band arrangements can improve the charge

carrier separation by suppressing the fast

recombination, [49, 50]. Binary heterojunctions like

WO3/Bi2WO6, [51], WO3/ZnO, [52], and WO3/TiO2,

[53], have been constructed to achieve superior

charge separation and high photocatalytic yields.

Bimetallic W has always been very significance for

its chemical inertness structure with low toxicity,

exhibited corrosion-resisstant properties with large

magnetic properties, and economic feasibility, [54].

ZnWO4 possesses wolframite (WO4) structures with

six-fold coordination sites for W exhibited superior

activities under UV light, [55].

The interaction of WO3 with ZnWO4 also

provides high photocatalytic activity by changing the

electronic properties in the material. WO3 it can be

recombinated fastly providing low charge carrier

properties and leading to a lower photocatalytic

degradation efficiency compared to other metal

oxides such as TiO2 or ZnO, [56]. Conversely,

ZnWO4 presents a high ionic conductivity and long

lifetime of photogenerated carriers under sun ligth

irradiation, [56].

PANI has received increasing attention due to its

electron and hole transferring properties. It can be

easily prepared with high chemical stability, [57].

Furthermore, many studies showed that combination

of PANI with semiconductors impoved the interfacial

charge carrier's separation due to the excellent charge

carrier mobility and thus enhance the photo-

electrocatalytic activity, [58]. With g-C3N4/PANI

composite enhanced photocatalytic yields was

detected for degradation of methylene blue (MB)

dye, [59]. Wang et al., [60], synthesized ZnWO4

modified by polyaniline (PANI/ZnWO4) and found

that the photocatalytic activity of PANI/ZnWO4

composites was higher than ZnWO4. This was

attributed to the synergistic effect between PANI and

ZnWO4. ZnWO4 nanosheets were homogenously

grown on the surface of the WO3 resulting in a large

active surface area. The charge carriers separation

can be improved because of the energy band structure

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

match between WO3 and ZnWO4, This improve

significantly the photoelectrochemical activity, [60].

Barık et al., [61], investigated the degradation of

the toxic GLP herbicide (Kapp = 0.0707 min−1). In this

study, radical trapping experiment, and reactive

oxygen species (ROS) quantification (●OH and ●O2 -

) suggested a possible double electron transfer type

Z-scheme mechanism, which accounts for superior

solar light-assisted N–C bond cleavage of GLP

herbicide. Barık et al., [61], a ternary PANI–ZnWO4–

WO3 photocatalyst was synthesized via in situ

polymerization method exhibiting double Z-scheme

channelization towards photodegradation of GLP

with superior minimization of toxicity of degraded

metabolites.

Based on the assumptions and references given

above, in other to improve the removals of GLP and

HZN herbicides from the surface water via

photooxidation, in this study, PANI/ZnWO4/WO3

NCs were prepared under laboratory conditions. The

influence of different PANI/ZnWO4/WO3 NCs

concentrations (0.1, 0.4, 0.6, 1.0 and 1.5 mg/l),

PANI/ZnWO4/WO3 mass ratios (1:1:3, 1:2:3, 3:1:1

and 3:2:1), GLP and HZN concentrations (1, 2, 3 and

4 mg/l), photodegradation times (2, 10, 15 and 20

min), and solar light powers (20, 40, 60, 80 and 100

W/m2) on the photodegradation yields of GLP and

HZN was examined. The characteristics of the

synthesized NCs were assessed using XRD, FTIR,

FESEM, HRTEM and XPS analyses, respectively.

The ecotoxicities of NCs and treated wastewater

were investigated using Microtox (Aliivibrio fischeri)

and Daphnia magna acute toxicity tests.

2 Materials and Methods

2.1 Synthesis of ZnWO4 Nanoparticles (NPs)

ZnWO4 was prepared by 1-butyl-3-

methylimidazolium chloride (BMIMCl) ionic liquid

(IL)-assisted solvothermal method. In a typical

procedure, 0.005 mole of Zn(NO3)2.6H2O and the

same amount of Na2WO4 was added to a 50 ml of

deionized water and BMIMCl IL mixture solution.

The whole reaction mixture was kept under

mechanical stirring for 30 min. The pH of the

solution was balanced at 3.0 before transferring the

whole solution to the Teflon-lined stainless-steel

autoclave. The reaction was kept at 180ºC for 18 h.

After, the reaction was cooled at room temperature

naturally. The white precipitates were washed with

ethanol and deionized water followed by drying at

70ºC for 8 h before further characterization

2.2 Synthesis of WO3 NPs

WO3 was also prepared by BMIMCl IL-assisted

solvothermal method. 0.005 mole of Na2WO4 was

added to 50 ml of deionized water and BMIMCl IL

mixture solution. The resultant reaction mixture was

kept under mechanical stirring for 30 min. The pH of

the solution was adjusted to 3.0 with 0.1 M HCl

solution. The resultant mixture was transferred to the

autoclave and it was kept at 180ºC for 18 h. Then, the

reaction was cooled naturally. The final solid residue

was washed with ethanol and deionized water

followed by drying at 70ºC for 8 h before further

characterization.

2.3 Synthesis of PANI

In chemical oxidation polymerization, PANI is

synthesized by using hydrochloric acid (HCl) or

sulfuric acid (H2SO4) as a dopant and ammonium

persulfate [(NH4)2S2O8] as an oxidant in an aqueous

environment, [62, 63]. At this time, a proton can be

removed by the oxidant from the monomer of aniline

without either creating a heavy bond, or with the

absolute product.

In chemical synthesis, there are three reactants of

PANI that require aniline, oxidant, and acidic

medium. HCl and H2SO4 are common acids used in

the synthesis of PANI, whereas [(NH4)2S2O8,

hydrogen peroxide (H2O2), sodium vanadate

(NaVO3), cerium sulfate [Ce(SO4)2], potassium

dichromate (K2Cr2O7), potassium iodate (KIO3), and

potassium free cyanide {K3[Fe(CN)6]} can be used as

oxidizers. The oxidant polymerization method is the

most communal mechanism used to synthesize

PANI, while aniline reacts with an acidic substance

as a neutralizing agent and polymerizes by adding

one drop of an oxidizing agent such as [(NH4)2S2O8

at dissimilar temperatures. After realization, the

polymerization mechanism (3 h) was an aqueous

solution separated by filtration. Pure PANI can be

obtained by rinsing the above solution 5–6 times with

deionized water. Alcohol and acetone are then added

to make the filter colourless and ensure that non-

reactive materials are completely removed. The

product is slime green and is well-known as PANI

polymer aldine salt, which is unstable due to the

existence of swords. Therefore, the polymer aldine

salt converts to the PANI-EB structure, which is

naturally stable at 25oC, allowing this precipitate to

equilibrate with and ensure that non-reactive

materials, [64].

2.4 Synthesis of PANI/ZnWO4/WO3 NCs

The ternary PANI/ZnWO4/WO3 NCs was

synthesized by an ionic liquid-assisted in situ

oxidative polymerization process. In this process,

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

BMIMCI used in the polymerization of aniline using

[(NH4)2S2O8]. At the beginning, 0.8 ml of aniline

was added to the aqueous solution of BMIMCI to

determine three different PANI solutions. Then, in

every PANI mixture, 0.2 mg/l [(NH4)2S2O8] was

added at an [(NH4)2S2O8] to aniline ratio of 1/1.

Furthermore, 0.31 g of ZnWO4 and 0.21 g of WO3

were dispersed in 50 ml of 0.15 M HCl solution

during ultra sonication for 50 min. Then, the particle

mixtures were transferred into the PANI mixtures

and mixed at 21oC. The dark green products were

separated by centrifugation and washed with ethanol

to remove the residual ionic part. The three

composites (PANI/ZnWO4/WO3 NCs) obtained were

dried in a vacuum oven at 60oC.

2.5 Photocatalytic Degradation Reactor

A 2 liters cylinder quartz glass reactor was used for

the photodegradation experiments of GLP and HZN

aqueous solution at different operational conditions.

1000 ml of GLP and HZN aqueous solution was

filled into a cylindrical quartz glass reactor,

separately. Then, the photocatalyst was added into

the cylindrical quartz glass reactors. The

photocatalytic reactor was operated with constant

stirring (1.5 rpm) during the photocatalytic

degradation process. 10 ml of the reacting solution

were sampled and centrifugated (at 10000 rpm) at

different time intervals. Sunlight was used at hours

11.00, 12.30, 14.30 and 15.30 corresponding to

increasing light powers of 20, 40, 60, 80 and 100

W/m2, respectively.

2.6 GLP and HZN Photocatalytic

Degradation Experiments

The photocatalytic degradation efficiencies of PANI,

ZnWO4 NPs, WO3 NPs and PANI/ZnWO4/WO3 NCs

were investigated with a cylinder quartz glass

photocatalytic reactor under solar light irradiation.

The series of GLP and HZN photodegradation

studies were performed in aqueous solutions. The

temperature of the photocatalytic system was

maintained using a continuously circulating aqueous

solution. Typically, 20 mg/l catalysts were used for

the batch degradation study with 100 ml of 10 mg/l

GLP and HZN nder continuous magnetic stirring in

separate reactors. From 10 mg/l GLP and HZN stock

solution, dilutions were performed for GLP and HZN

concentrations of 1 mg/l, 2 mg/l, 3 mg/l and 4 mg/l in

separate reactors. The pollutant solutions were

maintained throughout the degradation process at

pH=7.0 ± 0.1 by dropwise addition of 1.2 M H2SO4

and 1.2 M NaOH solutions as necessary. Initially, the

reaction mixtures were kept in dark to check the

adsorption properties of GLP and HZN to attain

adsorption–desorption equilibrium. Next, the whole

setup was exposed to solar light for the photocatalytic

degradation study. In 20 min time gap, a 4 ml aliquot

of the pollutant solution was withdrawn and

centrifuged to separate the PANI/ZnWO4/WO3 NCs.

The initial experimental conditions are given in Table

* Table 1 can be found in the Appendix section.

The percentage degradation was calculated by the

following Eq. (1):

󰇛󰇜󰇡

󰇢 (1)

where; Co: is the pollutant concentration before

illumination, (mg/l) and Ct is the final concentration,

(mg/l) of the pollutant at time t (min).

2.7 Determination of GLP and HZN

The quantification of GLP and HZN was determined

with a gas chromatography (Agilent 8890N GC)

equipped with a mass selective detector (Agilent

MSD) Gas Chromatography-Mass Spectrometry

(GC-MS) (Agilent 8890GC/Agilent MSD). A

capillary column (HP5-MS, 30 m, 0.25 mm, 0.25 μm)

was used. The injection volume was 1 μl. The initial

oven temperature was kept at 50oC for 1 min, then

raised to 200oC at 25oC/min. Then the temperature

was elevated from 200oC to 300oC at 8oC/min for 6.5

min. High purity He(g) was used as the carrier gas at

constant flow mode (1.8 ml/min, 48 cm/s linear

velocity). The method involves the addition of 6%

borate buffer to the aqueous sample to adjust the

pH=9.3 and then mixing with 9-fluorenylmethyl

chloroformate (FMOC) in acetonitrile (C2H3N) prior

to analysis. The derivatization process was continued

for 13 h at 23°C and the process was stopped by drop-

wise addition of 7 M HCl solution where the resulting

pH was measured to be pH=1.3. Chromatographic

separation was performed with a C18 column where

the mobile phase was 4 mM acetic acid/ammonium

acetate (HAc/NH4Ac) (pH=4.5) acetonitrile. The

percentage of acetonitrile was changed from 75%

(between 0th min and 40nd min) to 100% (between

40.1st min and 46th min) and then to 5% (between

46.1st min and 53th min). For each sample the

separation process was completed in 30 min.

2.8 Photodegradation Mechanism of

PANI/ZnWO4/WO3 NCs

Under the illumination of sunlight, the electrons in

the valence band of PANI, ZnWO4, and WO3 are

excited to their respective conduction bands leaving

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

the photo-generated holes (h+) behind (Fig. 1). If the

ternary composite follows photodegradation

mechanism, the holes (h+) in the higher positive EVB

of ZnWO4 and WO3 migrate to the EVB of PANI. On

the other hand, the electrons (e-) migrate in reverse

direction to the CB of ZnWO4 and WO3. The

conduction band edge of ZnWO4 and WO3 located at

- 0.23 and 0.45 eV which is insufficient to reduce O2

into O2 - ● [E0 (O2/O2●) = - 0.33 eV vs. NHE] (Fig. 1).

Again, the photo-generated holes on the valence band

of ZnWO4 and WO3 cannot lead to formation of OH●

from the OH- ions/H2O molecules [E0 (OH-/OH●) =

1.99 eV vs. NHE, E0 (H2O/OH●) = 2.72 eV vs. NHE]

(Fig. 1). This clearly banishes the formation O2 - ●

from O2 and the formation OH● from the OH-

ions/H2O molecules. But the radical trapping test and

ROS quantification have already confirmed O2 - ● and

OH● as the major active species behind the

photocatalytic degradation (Fig. 1). For this reason,

the possibility of photodegradation mechanism has

ruled out. These results were also supported by GC-

MS analysis.

* Fig. 1 can be found in the Appendix section.

2.9 Characterization of Photocatalyst

2.9.1 X-Ray Diffraction (XRD) Analysis

Powder XRD patterns were recorded on a Shimadzu

XRD-7000, Japan diffractometer using Cu Kα

radiation (λ=1.5418 Å, 40 kV, 40 mA) at a scanning

speed of 1o min-1 at a 10-80o 2θ range. Raman

spectrum was collected with a Horiba Jobin Yvon-

Labram HR UV-Visible NIR (200-1600 nm) Raman

microscope spectrometer, using a laser with a λ=512

nm. The spectrum was collected from 10 scans at a

resolution of 2 cm-1.

2.9.2 Fourier Transform Infrared Spectroscopy

(FTIR) Analysis

The FTIR spectra of samples was recorded using a

FT-NIR spectroscope (RAYLEIGH, WQF-510).

Experimental samples were scanned using infrared

light and their chemical properties were observed in

FTIR spectra.

2.9.3 Field Emission Scanning Electron

Microscopy (FESEM) Analysis

The morphological features and structure of the

synthesized catalyst were investigated by FESEM

(FESEM, Hitachi S-4700), to investigate the

composition of the elements present in the

synthesized catalyst.

2.9.4 High Resolution Transmission Electron

Microscopy (HRTEM) Analysis

The structure of the samples was analyzed by

HRTEM data. HRTEM analysis was recorded in a

Technai G2 20 X-TWIN TEM (FEI, USA) under 200

kV accelerating voltage. Samples were prepared by

applying one drop of the suspended material in

ethanol onto a carbon-coated copper HRTEM grid

and allowing them to dry at 25oC.

2.9.5 X-Ray Photoelectron Spectroscopy (XPS)

Analysis

The valence state of the samples was investigated and

was analyzed using XPS (ESCALAB 250Xi,

England). In XPS analysis it was used an Al Kα

source and surface chemical composition and

reduction state analyses was done by the core levels

recorded using a pass energy of 30 eV

(resolution≈0.10 eV). The peak fitting of the

individual core-levels was done using XPS-peak 41

software, achieving better fitting and component

identification. All binding energies were calibrated to

the C 1s peak originating from C–H or C–C groups

at 284.6 eV.

2.9.6 N2-Adsorption-Desorption Curves

Micromeritics ASAP 2020 M porosimeter was used

to measure the N2-adsorption-desorption curves of

the material. The supercapacitive behavior of the

synthesized samples was investigated using

Princeton Applied Research Center.

2.9.7 Band gap from the UV−vis absorbance

Detailed bandgap calculations were performed along

with the proposal of an accelerated double electron

transfer Z-scheme type channelization mechanism in

the ternary heterojunction system.

The UV-DRS and photoluminescence (PL)

spectra of the synthesized materials were recorded

using Jasco V-650 spectrophotometer and Jasco FP-

8200 Fluorescence spectrometer respectively.

2.9.8 AC Impedance Spectra and Electrochemical

Impedance Spectroscopy (EIS) Analyses

The analysis of impedance data for reduction of

ferricyanide [Fe(CN)6]3− in a potassium chloride

(KCl) supporting electrolyte is used to demonstrate

the error structure for impedance measurements, the

use of measurement and the sensitivity of impedance

to the evolution of nanocomposite properties.

2.9.9 Cyclic Voltammogram Records

Cyclic voltammetry is an electrochemical technique

used to measure the current response of a redox active

solution to a linearly cycled potential sweep using a

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Henken potentiostat. It is a useful method if you need

to quickly find information about the

thermodynamics of redox processes and the energy

levels of the nanocomposite.

2.9.10 Galvanostatic Charge/Discharge Curves

All electrochemical characterization was done using

the Metrohm 128 N AUTOLAB Potentiostat from

the Netherlands in 1 M KOH electrolyte.

2.10 Acute Toxicity Assays

Acute toxicity tests were applied to the raw surface

water containing GLP and HZN, and to

photodegraded surface water at maximum GLP and

HZN removals was taken after treatment.

2.10.1 Microtox Acute Toxicity Test

Ecotoxicity to the bioluminescent organism

Aliivibrio fischeri (also called Vibrio fischeri) was

assayed using the Microtox measuring system

according to DIN 38412L34, L341, (EPS 1/ RM/24

1992). Microtox testing was performed according to

the standard procedure recommended by the

manufacture, [65]. A specific strain of the marine

bacterium, V. fischeri-Microtox LCK 491 Kit, [65],

was used for the Microtox acute toxicity assay. Dr.

LANGE LUMIX-mini type luminometer was used

for the Microtox toxicity assay, [66].

2.10.2 Daphnia magna Acute Toxicity Test

To test ecotoxicity, 24-h born Daphnia magna were

used as described in Standard Methods, [67], sections

8711A, 8711B, 8711C, 8711D and 8711E,

respectively, [68]. After preparing the test solution,

experiments were carried out using 5 or 10 Daphnia

magna introduced into the test vessels. These vessels

had 100 ml of effective volume at 7.0–8.0 pH,

providing a minimum dissolved oxygen (DO)

concentration of 6 mg/l at an ambient temperature of

20–25°C. Young Daphnia magna was used in the test

( ≤ 24 h old); 24–48 h exposure is generally accepted

as standard for a Daphnia magna acute toxicity test.

The results were expressed as mortality percentage of

the Daphnia magna. Immobile animals were reported

as dead Daphnia magna.

All experiments were carried out three times and

the results are given as the means of triplicate

samplings. The data relevant to the individual

pollutant parameters are given as the mean with

standard deviation (SD) values.

2.11 Statistical Analysis

Regression analysis between variables was

performed using the EXCELL in Microsoft

WindowsTM (HP, USA), [69]. The linear correlation

was assessed with r2. The r2 value is the correlation

coefficient and reflects statistical significance

between dependent and independent variables.

Analysis of variance (ANOVA) (SAS ANOVA

procedure) test was used to assess the data obtained

in reactors using the EXCELL in Microsoft

WindowsTM (HP, USA), [69].

3 Results and Discussions

3.1 XRD Analysis Results

The results of XRD analysis for PANI, WO3 NPs,

ZnWO4 NPs, PANI-WO3 NCs, PANI-ZnWO4 NCs

and PANI/ZnWO4/WO3 NCs after photocatalytic

degradation process during GLP removal was

illustrated in Fig. 2. The characterization peaks were

observed at a 2θ value of 27.88°, corresponding to the

(002) for PANI (Fig. 2a). The characterization peaks

were obtained at 2θ values of 22.17o, 39.97o, 53.25o

and 55.11o, respectively, corresponding to the (001),

(131), (100) and (112), respectively, for WO3 NPs

(Fig. 2b). The characterization peaks were found at

2θ values of 35.10o, 41.34o and 51.04o, respectively,

corresponding to (110), (220) and (132),

respectively, for ZnWO4 NPs (Fig. 2c). The

characterization peaks were observed at 2θ values of

25.61o, 40.36o, 55.47o and 58.79o, respectively,

corresponding to (111), (033), (022) and (202),

respectively, for PANI-WO3 NCs (Fig. 2d). The

characterization peaks were obtained at 2θ values of

28.75o, 30.11o, 40.42o and 51.65o, respectively,

corresponding to the (124), (312), (021) and (121),

respectively, for PANI-ZnWO4 NCs (Fig. 2e). The

characterization peaks were measured at 2θ values of

29.11o, 32.40o, 40.02o, 55.09o and 59.78o,

respectively, corresponding to the (010), (225),

(130), (103) and (211), respectively, for

PANI/ZnWO4/WO3 NCs (Fig. 2f).

* Fig. 2 can be found in the Appendix section.

All the reflection peaks from the crystal planes are

exhibited highly crystalline nature. The monoclinic

crystal structure exhibited an agreement with the

reported values in JCPDS file no.: 88-0251, with

space group of ZnWO4, [65]. From Fig. 2 it is seen

that the monoclinic structural peak of ZnWO4

indicates the crystalline nature in the whole

composite. The bi-metal oxide ZnWO4 also exhibited

also a crystalline monoclinic-structure in the PANI

matrix during chemical polymerization reaction.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

3.2 FTIR Analysis Results

The FTIR spectrum of PANI, ZnWO4 NPs and WO3

NPs were determined after photocatalytic

degradation process during GLP removal (Fig. 3).

The main peaks of FTIR spectrum for PANI was

observed at a wavenumber of 850 cm-1 (Fig. 3a). The

main peaks of FTIR spectrum for ZnWO4 NPs was

obtained at 458 cm-1, 570 cm-1 and 785 cm-1

wavenumbers, respectively (Fig. 3b) while the main

peaks of FTIR spectrum for WO3 NPs was

determined at wavenumber of 740 cm-1 (Fig. 3c).

* Fig. 3 can be found in the Appendix section.

Prominent peaks and their assignment are found

at 3434 cm-1 originated from NH bond-stretching

while the maximum abundaces at 520 and 639 cm-1

are defined as Benzenoid and Quinoid ring bond

stretching. The maximal disturbances at 725 cm-1 is

N=H and + C-C bond-stretching. In the region of 631

cm-1, 750 cm-1 and 1700 cm-1 the characteristic

stretching maximums were defined as pure PANI and

PANI/ZnWO4 composites. Comparison of stretching

frequencies of PANI and composites confirms that,

frequencies of bond-stretching of the composites are

sligtly elevated in the nano structure. This indicates a

weak bond interaction between ZnWO4 and PANI

moeities. The peaks at 621 cm−1 and 629 cm−1 are

stretching frequencies of metal and oxygen bond in

pure ZnWO4 composite. This strongly indicates the

formation of PANI/ZnWO4. The intensity of metal

oxygen stretching peaks of FTIR spectra grows with

increase in weight percent of ZnWO4 in PANI.

3.3 FESEM Analysis Results

The morphological features of PANI, ZnWO4 NPs,

WO3 NPs and PANI/ZnWO4/WO3 NCs were

characterized through FESEM images (Fig. 4). The

FESEM images of PANI, ZnWO4 NPs, WO3 NPs and

PANI/ZnWO4/WO3 NCs were illustrated in Fig. 4a,

4b, 4c and 4d, respectively, after photocatalytic

degradation of GLP and HZN.

* Fig. 4 can be found in the Appendix section.

Although, a spherical morphology was detected

the nanocomposite particles exhibited cubic shapes.

The average sizes of the NPs were 25 nm and 27 nm,

respectively. Moreover, all metal oxide particles

were well dispersed in the PANI matrix. In addition,

the general morphology of all hybrid materials was

found to be spherical.

3.4 HRTEM Analysis Results

The HRTEM images of PANI/ZnWO4/WO3 ternary

NCs was performed to detect the

micromorphological structure level after

photocatalytic degradation process of GLP and HZN

(HRTEM image scale: 220 nm) (Fig. 5).

* Fig. 5 can be found in the Appendix section.

High-resolution HRTEM images indicated the

monocrystalline structure of the NCs. The HRTEM

images demonstrate the polycrystalline structure of

the investigated NCs, with average diameter of

21.9±10 nm. The lattice distance of the NCs was

0.9±0.03 nm corresponding to the (002) crystal

planes. HRTEM images exhibited that a compact

interface is formed between WO3 nanorods and

ZnWO4 nanosheets. The lattice fringes was measured

as 0.489 nm and 0.359 nm corresponding to the

crystal planes (101) and (012) of the ZnWO4 phase,

respectively (data not shown). The lattice space of

0.379 nm is corresponded to the (003) planes of

monoclinic WO3. This indicates that WO3 and Zn2+

were transformed into ZnWO4 during in situ reaction.

Such surface/interface are beneficial for the

formation of oxygen vacancy, and also helpful for

improving the electronic transmission. WO3 nanorod

indicates that the WO3 have a single-crystalline

structure with a diameter of 0.386 nm and can be

attributed to the (002) plane defining the monoclinic

WO3. The pattern of the WO3 confirmed the single-

crystalline structure of WO3.The data shows that

(002) and (020) facets with an angle of 90o indicates

the crystal structure of WO3. This component is

growing along the (100) direction (data not shown).

3.5 XPS Analysis Results

The XPS analysis of PANI, ZnWO4 NPs, WO3 NPs

and PANI/ZnWO4/WO3 NCs were perforned during

photo catalytic oxidation of GLP and HZN (Fig. 6).

Absorption peaks were observed at binding energy of

396.14 eV for PANI (red line) (Fig. 6a), at 399.63 eV

for ZnWO4 NPs (green line) (Fig. 6b), at 402.91 eV

for WO3 NPs (blue line) (Fig. 6c) and at 398.36 eV

for PANI/ZnWO4/WO3 NCs (black line) (Fig. 6d),

respectively, after photocatalytic degradation of

GLP.

* Fig. 6 can be found in the Appendix section.

The survey spectra of PANI, ZnWO4 NPs, WO3

NPs and PANI/ZnWO4/WO3 NCs exhibiting four

peaks at 411, 399, 398.9, and 399 eV shows the

existence of W, Zn, O, and C elements. Pristine

ZnWO4 surface absorbed only to carbon species Fig.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

6b exhibits the binding energy peaks of ZnWO4 at

1021.4 and 1044.5 eV, which are indicating the Zn

2p3/2 and the Zn 2p1/2 respectively. This confirm the

presence of Zn2+ ions in the ZnWO4.

3.6 N2 Adsorption–Desorption Isotherms

Fig. 7 presents the N2 adsorption–desorption

isotherms of the ZnWO4, WO3–PANI, PANI–

ZnWO4 samples to analyze their respective surface

area, pore size, and pore volume. The surface areas

of the ZnWO4, WO3, WO3–PANI and

PANI/ZnWO4/WO3 NCs samples were found to be

194, 214, 264, and 248, m2/g, respectively. Notably,

the introduction of ZnWO4 and WO3 NPs into the

PANI matrix enhanced the surface area of the binary

nanocomposites, which was further increased for the

ternary nanocomposite. The nanostructures can act as

spacers increasing the pore size distribution and pore

volume of the ternary nanocomposite as determined

from Barrett–Joyner–Halenda (BJH) analysis.

* Fig. 7 can be found in the Appendix section.

The pore size and pore volume of the

PANI/ZnWO4/WO3 NCs was found to be 5.6 nm and

0.43 cm3/g, respectively, which were much higher

than those of the single nanostructures and binary

nanocomposites. Typicaly, the samples exhibit an

H3-hysteresis loop suggesting a type-IV isotherm

plot. The surface analysis demonstrated about a 28%

surface area increase due to the incorporation of the

ZnWO4 and WO3. Besides, the “cation–π” and

electrostatic interactions established by these

compounds considerably affect the pore structure of

the ternary nanocomposite. This can provide more

adsorption sites and can act as a better charge carrier

for light harvesting.

3.7 Band Gap from the UV−vis Absorbance

The band gap can also be estimated from the onset of

UV−vis absorbance. Fig 8a shows the UV−vis

absorbance divided by film thickness for WO3, 8%

Zn/WO3, and ZnWO4 samples of approximately the

same thickness (0.20, 0.22, and 0.27 μm,

respectively). Using the absorbance data, Tauc plots

were created for each of the three samples (Fig. 8b).

* Fig. 8 can be found in the Appendix section.

A Tauc plot can be used to estimate the band gap

of a semiconductor because, near the absorption

edge, a direct band gap is governed by Eq. 2:

󰇛󰇜 

󰇜   (2)

where; h is the Planck constant, ν is the photon’s

frequency, Eg is the band gap energy, and B is a

constant. The γ factor depends on the nature of the

electron transition and is equal to 1/2 or 2 for the

direct and indirect transition band gaps, respectively.

The band gap energy of PANI/ZnWO4/WO3 NC was

calculated as 3.22 eV.

3.8 Cyclic Voltammogram Records

Cyclic voltammogram (CV) records of WO3, PANI

and WO3/PANI was detected in 0.7 M LiClO4-PC

electrolyte at the scanning rate of 100 mV/s. The inset

represents CV of PANI sample. Fig. 9 compares the

cyclic voltammetric changes of the films recorded in

0.7 M LiClO4-PC electrolyte in a potential window

of -0.8 to 0.6 V, -0.5 to +0.6 V and -1.1 to +0.8 V for

WO3, PANI and WO3/PANI films. PANI displayed

oxidation peak at approximately +0.6 V in orwarding

scan, though the oxidation of aniline was not clearly

seen in the forward scan, the reverse scan shows a

small shoulder at +0.3 and -0.1 V, which was due to

the reduction of PANI formed on the electrode. The

WO3 thin film showed a small oxidation and

reduction peak at -0.6 and -0.3V vs SCE.

* Fig. 9 can be found in the Appendix section.

However, WO3/PANI film illustrated a large

difference among the CV of PANI and WO3. The

enhancement of the peak current density of about

0.16 A/cm2 could be observed in WO3/PANI

composite film with respect to pure PANI and WO3

films and is comparable to the earlier reports. This

could be due to the anoporous structure of

WO3/PANI which provided more reactive centers on

the film to contact with the electrolyte and so assist

the charge transfer process with improved charge

density. This also indicated the catalytic behavior of

PANI in WO3. The capacitance from CV curve of all

the film calculated using following relation in Eq. 3:

 

 (3)

where, Imax is the maximum current (in Ampere) and

ds is the potential scan rate in V/s. Mass of WO3,

PANI and WO3/PANI films were measured using a

high precision weight balance and is evaluated as

0.0117, 0.0117 and 0.0138 g respectively.

3.9 AC Impedance Spectra (EIS)

AC impedance spectra (EIS) of PANI, WO3, and

WO3/PANI were measured to substantiate our

approach of injecting PANI over WO3 nanotablets

using a hydrothermal method that contributed

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

superior strength in electricity, ion diffusion process,

and structural cyclability]. Fig. 10 displayed the

impedance spectra of a WO3, PANI, and WO3/PANI

measured at +0.38V, +0.07V, and -0.4V respectively.

* Fig. 10 can be found in the Appendix section.

Strikingly, the diffusion layer resistance of

WO3/PANI was lower than their sole performance.

An impedance spectrum in the Nyquist plot possesses

a straight line inclined by 45º at a higher frequency

and a semicircle at a lower frequency. However, the

compressed semicircle indicated irregular electrode

surface that compensates double layer capacitance by

a constant phase element. Particularly, the Nyquist

plot of WO3/PANI exemplified small straight line at

higher frequencies as a result of the diffusion process

and a broad semicircle in the smaller frequency

attributed to fast electron transfer and its prolonged

existence in the film.

3.10 Galvanostatic Charge/Discharge Curves

The galvanostatic charge-discharge is a trustworthy

technique to measure the electrochemical behavior of

the material under controlled conditions using three

electrode systems with 0.5 M LiClO4-PC electrolyte.

Fig. 11(a) exhibited charge/discharge curves of

PANI, WO3, and WO3/PANI for initial cycles at

constant current density of 0.05, 0.5 and 0.05

mA/cm2 respectively, while Fig. 11(b) represents

charge-discharge cycles for initial 10 cycles of

WO3/PANI films.

* Fig. 11 can be found in the Appendix section.

The potential responses of the composite film

during charge-discharge were more symmetrical than

the sole performance of WO3 and the working

potential could be extended to 0.8 V. The discharge

curve represented the characteristic profile of a

pseudocapacitance showing the potential dependent

nature of faradic reaction. When we correlated

charge/discharge with the morphological study, it

indicated that WO3 has a larger particle size that

decreases surface density increasing the interplanar

spacing between atoms. Thus, during the charging

process, it utilizes less coulombic force that

accumulates large charges in a short time.

Subsequently, the capacity of WO3 increases with

less charge-discharge time n PANI, the charge-

discharge time increases because it is highly

conductive consisting of many electrons that

enhances displacement of the electron cloud.

Accordingly, it utilizes more coulombic force with

the increase in charge-discharge time. However,

when PANI coated over WO3, it enhances the surface

area of WO3 with the reduction in the distance.

Ultimately the resistance decreases intrinsically with

the improved charge transport process. Owing to this,

WO3/PANI uses more coulombic force with more

time for charging and discharging process. Therefore,

the charge storing capacity of the system enhances.

The capacitance from charge/discharge curves

evaluated using following relation in Eq. 4:

  

 (4)

where; I and td are the in applied current density and

time discharge, ΔV is the potential range, m is the

mass of deposited film mentioned above.

3.11 The Effect of Increasing

PANI/ZnWO4/WO3 NCs Concentrations on

GLP and HZN Removals

Maximum 99% GLP removal was observed at 1.0

mg/l PANI/ZnWO4/WO3 NCs, after 180 min

photodegradation, under 300 W solar light at pH=7.0

and at a temperature of 25 oC (Table 2). The cost of a

nanocomposite in practical application depends to a

large extent on its specific dosage to achieve the

wastewater treatment standards. In this work, the

correlation of the NCs dosage and the removal

efficiency of GLP was explored. It can be clearly

observed that the removal efficiency of GLP

increases from about 68% to almost 99% as the

PANI/ZnWO4/WO3 NCs dosage increases from 0.1

to 1.5 mg/l. However, there is no evident growth

anymore when the dosage exceeds 1.5 mg/l. The

reason for this might be that more available binding

sites are provided to capture GLP molecules in

solution with the increased content of the

nanocomposite. To reduce the expense of GLP

disposal, an optimal PANI/ZnWO4/WO3 NCs dosage

of 1 mg/l is suggested for the efficient elimination of

GLP.

* Table 2 can be found in the Appendix section.

The maximum HZN removal was 96% at 1.0 mg/l

PANI/ZnWO4/WO3 NCs, after 180 min

photodegradation, under 300 W solar lights at

pH=7.0 and at a temperature of 25oC (data not

shown). A significant linear correlation between

nanocomposite concentration and herbicide yields

was observed up to a nanocomposite concentration of

15 mg/l (r2 = 0.91, p = 0.07, F = 0.76). ANOVA test

indicated that there were significant differences

between nanocomposite concentration and herbicide

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

removals for PANI/ZnWO4/WO3 NCs concentration

> 1.00 (p = 1.87, F =9.14, d.f. = 2).

3.12 The Effect of Different

PANI/ZnWO4/WO3 Mass Ratios on GLP and

HZN Removals

Maximum 99% GLP removal was measured at 1:2:3

mass ratio of PANI to ZnWO and to /WO3 NCs after

180 min photodegradation, under 300 W solar light,

at pH=7.0 and and at 25oC temperature (Table 3). It

could be seen from this table that the increase in

ZnWO4 and WO3 percentages in the whole NCs

resulted in an increase from 68 to 99.7% in the

photooxidation yields of GLPs(V). This may be due

to the greater availability of the exchangeable sites or

surface area at higher concentrations of the ZnWO4

and WO3 percentages.

* Table 3 can be found in the Appendix section.

The Maximum HZN removal yield was 95% at

1:2:3 mass ratio of PANI/ZnWO4/WO3 NCs after 180

min photodegradation, under 300 W solar lights, at

pH=7.0 and and at 25oC temperature (data not

shown). A significant linear correlation between

mass ratio of PANI to ZnWO and to WO3 in the

nanocomposite and herbicide yields was observed up

to a mass ratio of 3:1:1 and 3:2:1 (r2 = 0.91, p = 0.07,

F = 0.76). ANOVA test indicated that there were

significant differences between mass ratio of PANI

to ZnWO4 and to /WO3 and herbicide yields at ratios

> 1:2:3 (p = 1.87, F =9.14, d.f. = 2).

3.13 The Effect of Different GLP and HZN

Concentrations on GLP and HZN Removals

Maximum 99% GLP removal was found at 3 mg/l

GLP, after 180 min photodegradation, under 300 W

solar lights at pH=7.0 and at 25 oC (Table 4). An

increase in the GLP concentration from 1 mg/l up to

4 mg/l increased the photodegradation yields of GLP.

This may be due to the almost all GLP

photocatalyzed by PANI/ZnWO4/WO3 NCs and the

establishment of equilibrium between the NCs and

GLP and none of a GLP photocatalyst was not

remained in the solution. At 3 mg/l GLP more NCs

surface or more adsorption spots were available for

the solute to be photocatalyzed. A further increase in

photocatalyst dosage (4 mg/l) did not cause a

significant improvement in GLP adsorption. This

may be due to the adsorption of almost all GLP to the

photocatalyst and the establishment of equilibrium

between the GLP adsorbed to the NCs and those

remaining unabsorbed and unphotocatalyzed in the

solution. The loading amount of catalyst is a

significant factor in the photocatalytic degradation

process, because the efficiency could be strongly

affected by the number of active sites and photo-

adsorption ability of the catalyst used. However, it

was observed that above a certain optimum catalyst

mass, the reaction rate decreases and becomes

independent of the catalyst concentration.

* Table 4 can be found in the Appendix section.

The maximum HZN removals was 96% at 3 mg/l

GLP, after 180 min photodegradation, under 300 W

solar light at pH=7.0 and at 25oC (data not shown). A

significant linear correlation between GLP and HZN

concentrations and herbicide yields was observed up

to a nanocomposite concentration of 4 mg/l (r2 = 0.91,

p = 0.07, F = 0.76). ANOVA test indicated that there

were significant differences between nanocomposite

concentration and herbicide removals for

PANI/ZnWO4/WO3 NC concentration > 4.00 mg/l (p

= 1.87, F =9.14, d.f. = 2).

3.14 The Effect of Increasing

Photodegradation Time on GLP and HZN

Removals

Maximum 99% GLP removal was obtained after 15

min photodegradation, under 300 W solar lights, at

pH=7.0 and at 25oC (Table 5). As the photooxidation

times were increased from 2 min up to 15 min the

GLP yields increased from 68% up to 99% under sun

light. Further increase of time did not affect the GLP

removals. Data obtained from this study showed that

the GLP yields at longer retention time was low. In

an elevated ratio of contact at long contact times; no

hydroxyl radicals production was achieved for GLR

reduction. As a result, low conversion rates were

observed at shorter residence times. The optimum

illumination time for maximum removal of GLP was

obtained as 15 min.

* Table 5 can be found in the Appendix section.

The maximum HZN removal was obtained as

97% after 15 min photodegradation, under 300 W

solar light, at pH=7.0 and at 25oC (data not shown).

A significant linear correlation between

photodegradation time and herbicide yields was

observed up to a time of 20 min (r2 = 0.91, p = 0.07,

F = 0.76). ANOVA test indicated that there were

significant differences between photodegradation

time and herbicide removals for time > 15 min (p =

1.87, F =9.14, d.f. = 2).

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

3.15 The Effect of Increasing Solar Light

Power on GLP and HZN Removals

Maximum 99% GLP removal was measured at 80

W/m2 solar light power after 180 min

photodegradation, under 300 W solar lights at

pH=7.0 and at 25oC (Table 6). Photocatalytic

reaction rate depends largely on the radiation

absorption of the photocatalyst, where the increase in

light intensity enhances the degradation rate and the

yield in photocatalytic degradation. At low light

intensities (20–60 W/m2), the rate would increase

linearly with increasing light intensity, whereas at

intermediate light intensities, above 14 W/m2, the rate

would depend on the square root of the light intensity.

This is likely, because at low light intensity, reactions

involving electron–hole formation are predominant,

and electron–hole recombination is negligible.

However, at increased light intensity, electron–hole

pair separation competes with recombination,

thereby causing lower effect on the reaction rate like

a solar light power of 100 W/m2. The enhancement

of the photodegradation of GLP increased as the light

intensity increased up to 100 W/m2.

* Table 6 can be found in the Appendix section.

Maximum 96% HZN removal was measured at 80

W/m2 solar light power after 180 min

photodegradation, under 300 W solar lights at

pH=7.0 and at 25oC (data not shown). A significant

linear correlation between sunligth power and

herbicide yields was observed up to a sunligth power

of 350 W/m2 (r2 = 0.91, p = 0.07, F = 0.76). ANOVA

test indicated that there were significant differences

between sunligth power and herbicide removals for

sun ligth power > 300 W/m2 (p = 1.87, F =9.14, d.f.

= 2).

3.16 Acute Toxicity Assays

3.16.1 Effect of Increasing GLP and HZN

Concentrations on the Microtox Acute Toxicity at

Increasing Photocatalytic Degradation Time and

Temperature

It was found a high toxicity in raw surface water

based on Microtox bacteria (Aliivibrio fischeri also

called Vibrio fischeri). In Microtox with Aliivibrio

fischeri acute toxicity test, the initial EC90 =825 mg/l

was found at pH=7.0, at 25oC (Table 7: SET 1). The

EC90 values decreased to EC57=414 mg/l to EC22=236

mg/l and to EC12=165 mg/l at GLP=3 mg/l, after 60,

120 and 180 min photocatalytic degradation time, at

30oC (Table 7: SET 3). The Microtox acute toxicity

removal efficiencies were 40.86%, 79.75% and

90.86% after 60, 120 and 180 min photocatalytic

degradation time, respectively, at GLP=3 mg/l, and a

temperature of 30oC (Table 7: SET 3).

* Table 7 can be found in the Appendix section.

The EC90 values decreased to EC51=550 mg/l,

EC17=214 mg/l and EC7=5 mg/l after 60, 120 and 180

min photocatalytic degradation time, respectively, at

GLP=3 mg/l at 60oC (Table 7: SET 3). The toxicity

removal efficiencies were 46.41%, 85.30% and

96.41% after 60, 120 and 180 min photocatalytic

degradation time, respectively, at GLP=3 mg/l, and a

temperature of 60oC (Table 7: SET 3). 96.41%

maximum Microtox acute toxicity removal was

found in GLP=3 mg/l after 180 min photocatalytic

degradation time, at 60oC (Table 7: SET 3).

The EC90 values decreased to EC62=422 mg/l, to

EC21=241 mg/l and to EC17=168 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, at GLP=1 mg/l at 30oC (Table 7: SET

3). The EC90 values decreased to EC62=421 mg/l, to

EC27=239 mg/l and to EC11=167 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, at GLP=2 mg/l at 30oC. The EC90 values

decreased to EC67=408 mg/l, to EC32=230 mg/l and to

EC22=162 mg/l after 60, 120 and 180 min

photocatalytic degradation time, respectively, at

GLP=4 mg/l at 30oC. The Microtox acute toxicity

removals were 85.30%, 85.28% and 79.75% in 1

mg/l, 2 mg/l and 4 mg/l GLP, respectively, after 180

min photocatalytic degradation time, at 30oC. It was

obtained an inhibition effect of GLP=4 mg/l to Vibrio

fischeri after 180 min photocatalytic degradation

time, at 30oC (Table 7: SET 3).

The EC90 values decreased to EC57=419 mg/l, to

EC22=266 mg/l and to EC12=150 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, at GLP=1 mg/l at 60oC (Table 7: SET

3). The EC90 values decreased to EC57=414 mg/l, to

EC22=232 mg/l and to EC12=161 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, in GLP=2 mg/l, at 60oC. The EC90

values decreased to EC62=403 mg/l, to EC27=218

mg/l and to EC17=148 mg/l after 60, 120 and 180 min

photocatalytic degradation time, respectively, in

GLP=4 mg/l at 60oC. The Microtox acute toxicity

removals were 90.86%, 90.83% and 85.30% in 1

mg/l, 2 mg/l and 4 mg/l GLP, respectively, after 180

min photocatalytic degradation time, at 60oC. It was

observed an inhibition effect of GLP=4 mg/l to

Vibrio fischeri after 180 min photocatalytic

degradation time, at 60oC (Table 7: SET 3). The

Microtox acute toxicity removals were 88.80%,

86.83% and 80.38% in 1 mg/l, 2 mg/l and 4 mg/l

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

HZN, respectively, after 180 min photocatalytic

degradation time, at 60oC (data not shown).

3.16.2 Effect of Increasing GLP and HZN

Concentrations on the Daphnia magna Acute

Toxicity at Increasing Photocatalytic Degradation

Time and Temperature in the Raw Surface Water

A high toxicity was found for raw surface water

before photooxidation in the acute toxicity tests

performed by Daphnia magna. The initial EC50=850

mg/l was observed at 25oC (Table 8: SET 1). After

60, 120 and 180 min photocatalytic degradation time,

the EC50 values decreased to EC31=350 mg/l, to

EC17=240 mg/l and to EC12=90 mg/l in GLP=3 mg/l,

at 30oC (Table 8: SET 3). The Daphnia magna acute

toxicity removals were 42.96%, 72.87% and 82.65%

after 60, 120 and 180 min photocatalytic degradation

time, respectively, in GLP=3 mg/l, at 30oC (Table 8:

SET 3).

* Table 8 can be found in the Appendix section.

The EC50 values decreased to EC27 =150 mg/l, to

EC12=60 mg/l and to EC7=6 mg/l after 60, 120 and

180 min photocatalytic degradation time,

respectively, in GLP=3 mg/l, at 60oC (Table 8: SET

3). The toxicity removal efficiencies were 52.94%,

82.62% and 92.36% after 60, 120 and 180 min

photocatalytic degradation time, respectively, in

GLP=3 mg/l, at 60oC (Table 8: SET 3). 92.38%

maximum Daphnia magna acute toxicity removal

was obtained in GLP=3 mg/l after 180 min

photocatalytic degradation time, at 60oC,

respectively (Table 8: SET 3).

The EC50 values decreased to EC37=450 mg/l, to

EC22=145 mg/l and to EC17=260 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, in GLP=1 mg/l at 30oC (Table 8: SET

3). The EC50 values decreased to EC37=450 mg/l, to

EC22=175 mg/l and to EC17=100 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, in GLP=2 mg/l and at 30oC. The EC50

values decreased to EC42=300 mg/l, to EC27=170

mg/l and to EC22=52 mg/l after 60, 120 and 180 min

photocatalytic degradation time, respectively, in

GLP=4 mg/l, at 30oC. The Daphnia magna acute

toxicity removals were 72.22%, 72.56% and 63.21%

in 1 mg/l, 2 mg/l and 4 mg/l GLP, respectively, after

180 min photocatalytic degradation time, at 30oC. It

was observed an inhibition effect of GLP=4 mg/l to

Daphnia magna after 180 min photocatalytic

degradation time, at 30oC (Table 8: SET 3).

The EC50 values decreased to EC32=130 mg/l, to

EC17=425 mg/l and to EC12=340 mg/l after 60, 120

and 180 min photocatalytic degradation time,

respectively, in GLP=1 mg/l, at 60oC (Table 8: SET

3). The EC50 values decreased to EC32=425 mg/l, to

EC17=140 mg/l and to EC7=90 mg/l after 60, 120 and

180 min photocatalytic degradation time,

respectively, in GLP=2 mg/l, at 60oC. The EC50

values decreased to EC37=250 mg/l, to EC22=110

mg/l and to EC17=10 mg/l after 60, 120 and 180 min

photocatalytic degradation time, respectively, in

GLP=4 mg/l, at 60oC. The Daphnia magna acute

toxicity removals were 83.06%, 92.65% and 73.11%

in 1 mg/l, 2 mg/l and 4 mg/l GLP, respectively, after

180 min photocatalytic degradation time, at 60oC. It

was observed an inhibition effect of GLP=4 mg/l to

Daphnia magna after 180 min photocatalytic

degradation time, at 60oC (Table 8: SET 3).

Increasing the GLP concentrations from 1 mg/l to

3 mg/l did not have a positive effect on the decrease

of EC50 values as shown in Table 8 at SET 3. GLP

concentrations > 3 mg/l decreased the acute toxicity

removals by hindering the photocatalytic degradation

process. Similarly, a significant contribution of

increasing GLP concentration to acute toxicity

removal at 60oC after 180 min photocatalytic

degradation time was not observed. Low toxicity

removals found at high GLP concentrations could be

attributed to their detrimental effect on the Daphnia

magna (Table 8: SET 3). The Daphnia magna acute

toxicity removals were 78.09%, 88.60% and 70.14%

in 1 mg/l, 2 mg/l and 4 mg/l HZN, respectively (data

not shown).

3.17 Aplication of PANI/ZnWO4/WO3 NCs to

the Surface Water which is Going to be Used

as Drinking Water

Water treatment and purification in environmental

protection are the worldwide issues to relieve the

water shortage. At present, various treatment

technologies for drinking water or wastewater have

been developed. Firstly, the purification processes for

drinking water are introduced including the

efficiency and mechanism of filtration and

sedimentation, flocculation and disinfection. In order

to remove the GLP and HZN herbicides with

maximum yields of 99% and 96%, respectively, 3 mg

PANI/ZnWO4/WO3 NCs should be added to 1 liter of

surface water to the sedimentation tank of the

drinking water treatment process. The retention time

should be 180 min, at 300 W solar light at pH=7.0

and at 25 oC.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

4 Conclusion

PANI/ZnWO4/WO3 NCs was produced under

laboratory conditions to remove GLP and HZN

herbicides from the surface water via photooxidation.

In order to detect the maximum GLP and HZN

photodegradation yields for optimum operational

conditions (the effects of increasing

PANI/ZnWO4/WO3 NCs concentrations,

PANI/ZnWO4/WO3 mass ratios, GLP and HZN

concentrations, photocatalytic degradation times and

solar light powers on GLP and HZN removals) was

investigated. The maximum removal conditions for

GLP (99.90%) and HZN (96.00%) were 3 mg/l

PANI/ZnWO4/WO3 NCs with a mass ratio of 1:2:3

of PANI to ZnWO4 and to WO3, after 15 min

photocatalytic degradation time at 80 W/m2 power, at

25oC.

The toxicity of raw and photodegraded surface

water was examined using Microtox (with Aliivibrio

fischeri) and Daphnia magna acute toxicity tests. The

acute toxicity decreased significantly in

photodegraded surface water. The acute toxicity

analysis showed that the surface water was toxic and

the toxicity decreased after photocatalytic treatment.

PANI/ZnWO4/WO3 NCs exhibited slightly toxicity

after a concentration of 5 mg/l and 6 mg/l for

Microthox and Daphnia magna acute toxicity,

respectively.

The crystalline structure of monoclinic ZnWO4

and WO3 was detected from XRD analysis while

PANI exhibited a broad characteristic maximum

peak at 28.91° with an amorphous structure. FTIR

spectra showed that pure ZnWO4 has the Zn–O–W

vibrational bands. For WO3 nanostructures, the

vibrational band at 740 cm−1 represent the presence

of W–O–W stretching while PANI was observed at

850 cm−1 describing the C/-C vibrational mode of the

quinoid and benzenoid rings. Therefore, in the XPS

the radical trapping and ROS quantification (OH●

and O2˙−●) analysis explained the double electron

transfer type of Z-scheme mechanism ending with

the cleavage of N–C bonds in the GLP and HZN

herbicides. The survey spectra of PANI, ZnWO4

NPs, WO3 NPs and PANI/ZnWO4/WO3 NCs, which

displays four peaks at 410 eV, 397 eV, 398.9 eV, and

399 eV, shows the existence of W, Zn, O, and C

elements. Pristine ZnWO4 shows the adsorption of

carbon species by ZnWO4 surface.

A novel, efficient, and non-toxic

PANI/ZnWO4/WO3 NCs, synthesized following an

IL-assisted in situ oxidative polymerization method.

The prepared nanocomposite was utilized towards

improved photocatalytic wastewater treatment and

acute toxicity removal. Comprehensive analysis of

the structural and morphological properties of the

nanocomposite revealed high structural integrity and

close contact between the individual components.

Very high photocatalytic degradation efficiencies

were obtained with the effect of sunlight irradiation

in the use of PANI/ZnWO4/WO3 NCs to remove the

GLP and HZN herbicides from surface water.

PANI/ZNWO4/WO3 NCs are non-toxic, costly-

effective, easy to apply and can be successfully

applied in the removal of different toxic and

refractory pollutants from surface waters.

Abbreviations

Al: Aluminum

(NH4)2S2O8: Ammonium persulfate

AMPA: Aminomethylphosphonic acid

AOPs: Advanced oxidation processes

ATSDR: Agency for Toxic Substances and Disease

Registry

BiOBr: Bismuth oxobromide

BiVO4: Bismuth vanadate

Bi2WO6: Bismuth tungstate

C: Carbon

Co: the pollutant concentration before illumination

CDC: the Centers for Disease Control and

Prevention

Ce: Cerium

CO2: Carbon dioxide

Ct : the final concentration of the pollutant at time t.

C2H3N: Acetonitrile

Cu: Copper

Cu(OH)2: Copper hydroxide

CV: Cyclic voltammogram

DIN: “Deutsches Institut für Normung”, meaning

"German institute for standardization"

DO: Dissolved oxygen

D201Cu: Nanosized copper hydroxide modified

resin

EC: Effective concentration in toxicity measurement

EC50: 50% Effective concentration in toxicity

measurement

Fe3O4: Iron (II, III) oxide or Magnetite

FESEM: Field emission scanning electron

microscopy

FMOC: 9-fluorenylmethyl chloroformate

FTIR: Fourier transform infrared spectroscopy

GC-MS: Gas Chromatography Mass Spectrometry

GLP: Glyphosate

g-C3N4: Graphitic carbon nitride

He: Helium

H2O: Water

H2O2: Hydrogen peroxide

H2SO4: Sulfuric acid

HAc: Acetic acid

HCl: Hydrogen chloride

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

HRTEM: High resolution transmission electron

microscopy

IARC: International Agency for Research on Cancer

IR: Infrared

La: Lanthanum

MB: Methylene blue

Mn: Manganese

MnFe2O4: Manganese iron oxide

MnO2: Manganese dioxide

MPA: Methylphosphonic acid

MSD: Mass selective detector

NaOH: Sodium hydroxide

NBT: Nitro blue tetrazolium dichloride

NCs: Nanocomposites

NH4Ac: Ammonium ethanoate

NPs: Nanoparticles

O: Oxygen

O2- : Oxygen ion

O2- ●: Superoxide radicals

OH●: hydroxyl radicals

PANI: Polyaniline

PO4-P: Orthophosphate

ROS: Reactive oxygen species

SD: Standard deviation

TiO2: Titanium dioxide

US: United States

UV: Ultraviolet

W: Tungsten

WO3: Tungsten trioxide

WO4: Wolframite

WO6: Trioxido-oxo-tungsten

XPS: X-Ray photoelectron spectroscopy

XRD: X-Ray diffraction

Zn: Zinc

Zn2+: Zinc ions

ZnO: Zinc oxide

ZnWO4: Zinc tungsten oxide or Zinc tungstate

Acknowledgement:

Experimental analyzes in this study were performed

at the Laboratories of the Canada Research Center,

Ottawa, Canada. The authors would like to thank this

body for providing financial support.

References:

[1] P.R. Rout, T.C. Zhang, P. Bhunia, P.Y.

Surampalli, Treatment Technologies for

Emerging Contaminants in Wastewater

Treatment Plants: A Review, Science of the

Total Environment, Vol.753, 2021, 141990.

[2] B. Song, P. Xu, M. Chen, W. Tang, G. Zeng, J.

Gong, P. Zhang, S. Ye, Using Nanomaterials to

Facilitate the Phytoremediation of

Contaminated Soil, Critical Reviews in

Environmental Science and Technology, Vol.49,

No.9, 2019, pp. 791–824.

[3] H. Xiang, Y. Zhang, D. Atkinson, R. Sekar,

Effects of Anthropogenic Subsidy and

Glyphosate on Macroinvertebrates in Streams,

Environmental Science and Pollution Research,

Vol.27, No.17, 2020, pp. 21939–21952.

[4] C.R. García-García, T. Parrón, M. Requena, R.

Alarcón, A.M. Tsatsakis, A.F. Hernández,

Occupational Pesticide Exposure and Adverse

Health Effects at the Clinical, Hematological

and Biochemical Level, Life Sciences, Vol.145,

2016, pp. 274–283.

[5] I.A. Saleh, N. Zouari, M.A. Al-Ghouti, Removal

of Pesticides from Water and Wastewater:

Chemical, Physical and Biological Treatment

Approaches, Environmental Technology &

Innovation, Vol.19, 2020, 101026.

[6] A. Sharma, V. Kumar, B. Shahzad, M. Tanveer,

G.P.S. Sidhu, N. Handa, S.K. Kohli, P. Yadav,

A.S. Bali, R.D. Parihar, O.I. Dar, K. Singh, S.

Jasrotia, P. Bakshi, M. Ramakrishnan, S.

Kumar, R. Bhardwaj, A.K. Thukral, Worldwide

Pesticide Usage and its Impacts on Ecosystem,

SN Applied Sciences, Vol.11, No.1, 2019, pp.

1446-1462.

[7] S. Mostafalou, M. Abdollahi, Pesticides and

Human Chronic Diseases: Evidences,

Mechanisms, and Perspectives, Toxicology and

Applied Pharmacology, Vol.268, No.2, 2013,

pp. 157–177.

[8] J.E. Casida, K.A. Durkin, Pesticide Chemical

Research in Toxicology: Lessons from Nature,

Chemical Research in Toxicology, Vol.30,

2017, pp. 94–104.

[9] M. Abdennouri, M. Baâlala, A. Galadi, M. El

Makhfouk, M. Bensitel, K. Nohair, M. Sadiq, A.

Boussaoud, N. Barka, Photocatalytic

Degradation of Pesticides by Titanium Dioxide

and Titanium Pillared Purified Clays, Arabian

Journal of Chemistry, Vol.9, 2016, pp. S313–

S318.

[10] G. Liu, L. Li, X. Huang, S. Zheng, X. Xu, Z. Liu,

Y. Zhang, J.D. Wang, D. Xu, Adsorption and

Removal of Organophosphorus Pesticides from

Environmental Water and Soil Samples by

Using Magnetic Multi-Walled Carbon

Nanotubes@ Organic Framework ZIF-8,

Journal of Materials Science, Vol.53, No.15,

2018, pp. 10772–10783.

[11] R. Pandiselvam, R. Kaavya, Y. Jayanath, K.

Veenuttranon, P. Lueprasitsakul, V. Divya, A.

Kothakota, S.V. Ramesh, Ozone as a Novel

Emerging Technology for the Dissipation of

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Pesticide Residues in Foods—A Review, Trends

in Food Science & Technology, Vol.97, 2020,

pp. 38–54.

[12] N. Barka, S. Qourzal, A. Assabbane, A. Nounah,

Y. Ait-Ichou, Photocatalytic Degradation of an

Azo Reactive Dye, Reactive Yellow 84, in

Water Using an Industrial Titanium Dioxide

Coated Media, Arabian Journal of Chemistry,

Vol.3, No.4, 2010, pp. 279–283.

[13] M.H. Dehghani, Y. Karamitabar, F. Changani,

Z. Heidarinejad, High Performance Degradation

of Phenol from Aqueous Media Using

Ozonation Process and Zinc Oxide

Nanoparticles as a Semiconductor Photo

Catalyst in the Presence of Ultraviolet

Radiation, Desalination and Water Treatment,

Vol.166, 2019, pp. 105–114.

[14] A.O. Ibhadon, P. Fitzpatrick, Heterogeneous

Photocatalysis: Recent Advances and

Applications, Catalysts, Vol.3, No.1, 2013, pp.

189–218.

[15] W.L. Silva, M.A. Lansarin, P.R. Livotto, J.H.Z.

Santos, Photocatalytic Degradation of Drugs by

Supported Titania-Based Catalysts Produced

from Petrochemical Plant Residue, Powder

Technology, Vol.279, 2015, pp. 166–172.

[16] R.S. Dariani, A. Esmaeili, A. Mortezaali, S.

Dehghanpour, Photocatalytic Reaction and

Degradation of Methylene Blue on TiO2 Nano-

Sized Particles, Optik-International Journal for

Light and Electron Optics, Vol.127, 2016, pp.

7143–7154.

[17] P.V. Kamat, TiO2 Nanostructures: Recent

Physical Chemistry Advances, The Journal of

Physical Chemistry C: Nanomaterials and

Interfaces, Vol.116, No.22, 2012, pp. 11849–

11851.

[18] S. Hernández, D. Hidalgo, A. Sacco, A.

Chiodoni, A. Lamberti, V. Cauda, E. Tresso, G.

Saracco, Comparison of Photocatalytic and

Transport Properties of TiO2 and ZnO

Nanostructures for Solar-Driven Water

Splitting, Physical Chemistry Chemical Physics,

Vol.17, 2015, pp. 7775–7786.

[19] M. Yoldi, E. Fuentes-Ordoñez, S. Korili, A. Gil,

Zeolite Synthesis from Industrial Wastes,

Microporous and Mesoporous Materials,

Vol.287, 2019, pp. 183–191.

[20] S. Mintova, M. Jaber, V. Valtchev, Nanosized

Microporous Crystals: Emerging Applications,

Chemical Society Reviews, Vol.44, 2015, pp.

7207–7233.

[21] G. Williams, R. Kroes, I. Munro, Safety

Evaluation and Risk Assessment of the

Herbicide Roundup and its Active Ingredient,

Glyphosate, For Humans, Regulatory

Toxicology and Pharmacology, Vol.31, No.2 Pt

1, 2000, pp. 117–165.

[22] C. Benbrook, Trends in Glyphosate Herbicide

Use in the United States and Globally,

Environmental Sciences Europe, Vol.28, No.1,

2016, Article number:3.

[23] Y. Huang, Z. Li, K. Yao, C. Chen, C. Deng, Y.

Fang, R. Li, H. Tian, Supressing Toxic

Intermediates During Photocatalytic

Degradation of Glyphosate by Controlling

Adsorption Modes, Applied Catalysis B:

Environment and Energy, Vol.299, 2021,

120671.

[24] ATSDR, Toxicological Profile for Silica,

Atlanta, GA, U.S. Department of Health and

Human Services, Public Health Service, United

States, 2019.

[25] CDC, Fourth National Report on Human

Exposure to Environmental Chemicals, Atlanta

(GA), United States, 2019.

[26] B.J. Simoneaux, T.J. Gould, Chapter 7 - Plant

Uptake and Metabolism of Triazine Herbicides,

The Triazine Herbicides: 50 years

Revolutionizing Agriculture, 2008, pp. 73-99.

[27] A.F. Méndez –Villaquiran, Aislamiento e

Identificación de Bacterias Capaces de

Degradar Glifosato, Universidad ICESI,

Facultad de Ciencias Naturales, Departamento

Ciencias Química - Programa Química

Farmacéutica, Santiago de Cali – Colombia,

2015.

[28] M. Wang, G. Zhang, G. Qiu, D. Cai, Z. Wu,

Degradation of Herbicide (Glyphosate) Using

Sunlight-Sensitive MnO2/C Catalyst

Immediately Fabricated by High Energy

Electron Beam, Journal of Chemical

Engineering, Vol.306, 2016, pp. 693-703.

[29] U. Ahrens, E. Seemüller, Detection of

Mycoplasmalike Organisms in Declining Oaks

by Polymerase Chain Reaction, European

Journal of Forest Pathology, Vol.24, No.1,

1994, pp. 55-63.

[30] X. Cao, C. Xu, X. Liang, J. Ma, M. Yue, Y.

Ding, Rationaly Designed/Assembled Hybrid

BiVO4-Based Photoanode for Enhanced

Photoelectrochemical Performance, Applied

Catalysis B: Environment and Energy, Vol.260,

2020, 118136.

[31] Y. Yang, Q. Deng, W: Yan, C. Jing, Y. Zhang,

Comparative Study of Glyphosate Removal on

Goethite and Magnetite: Adsorption and Photo-

Degradation, Chemical Engineering Journal,

Vol.352, 2018, pp. 581-589.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

[32] C. Zhou, D. Jia, M. Liu, X. Liu, C. Li, Removal

of Glyphosate from Aqueous Solution Using

Nanosized Copper Hydroxide Modified Resin:

Equilibrium Isotherms and Kinetics, Journal of

Chemical & Engineering Data, Vol.62, No.10,

2017, pp. 3585–3592.

[33] M. Mei, Z. Du, R. Xu, Y. Chen, H. Zhang, S.

Qu, Photocatalytic Degradation of Hexazinone

and Its Determination in Water via UPLC–

MS/MS, Journal of Hazardous Materials,

Vol.221–222, 2012, pp. 100-108.

[34] T. Jasemizad, L.P. Padhy, Photodegradation and

Adsorption of Hexazinone (HZN) in Aqueous

Solutions: Removal Efficiencies, Kinetics, and

Mechanisms, Environmental Science and

Pollution Research, Vol.29, 2022, pp. 48330–

48339.

[35] Y. Yao, M. Li, Y. Yang, L. Cui, L. Guo,

Electrochemical Degradation of Insecticide

Hexazinone with Bi-doped PbO2 Electrode:

Influencing Factors, Intermediates and

Degradation Mechanism, Chemosphere,

Vol.216, 2019, pp. 812-822.

[36] Y. Okamoto, W. Brenner, Organic

Semiconductors, New York: Reinhold

Publishing Corporation, United States, 1964.

[37] A. Heeger, Nobel Lecture: Semiconducting and

Metallic Polymers: The Fourth Generation of

Polymeric Materials, Reviews of Modern

Physics, Vol.73, No.3, 2001, pp. 681–700.

[38] S. Chen, D. Huang, G. Zeng, W. Xue, L. Lei, P.

Xu, R. Deng, J. Li, M. Cheng, In-situ Synthesis

of Facet-Dependent BiVO4/Ag3PO4/PANI

Photocatalyst with Enhanced Visible-Light-

Induced Photocatalytic Degradation

Performance: Synergism of Interfacial Coupling

and Hole-Transfer, Chemical Engineering

Journal, Vol.382, 2020, 122840.

[39] J. Jiang, H. Li, L. Zhang, New Insight into

Daylight Photocatalysis of AgBr@Ag:

Synergistic Effect Between Semiconductor

Photocatalysis and Plasmonic Photocatalysis,

European Journal of Chemistry, Vol.18, No.20,

2012, pp. 6360–6369.

[40] C.V. Reddy, R. Koutavarapu, I.N. Reddy, J.

Shim, Effect of a Novel One-Dimensional Zinc

Tungsten Oxide Nanorods Anchored Two-

Dimensional Graphitic Carbon Nitride

Nanosheets for Improved Solar-Light-Driven

Photocatalytic Removal of Toxic Pollutants and

Photoelectrochemical Water Splitting, Journal

of Materials Science: Materials in Electronics,

Vol.32, 2021, pp. 33–46.

[41] J. Ke, M.A. Younis, Y. Kong, H. Zhou, J. Liu,

L. Lei, Y. Hou, Nanostructured Ternary Metal

Tungstate-Based Photocatalysts for

Environmental Purification and Solar Water

Splitting: A Review, Nano-Micro Letters,

Vol.10, 2018, Article number:69.

[42] D.P. Ojha, H.J. Kim, Investigation of

Photocatalytic Activity of ZnO Promoted

Hydrothermally Synthesized ZnWO4 Nanorods

in UV–Visible Light Irradiation, Chemical

Engineering Science, Vol.212, 2020, 115338.

[43] G. He, H. Fan, L. Ma, K. Wang, D. Ding, C. Liu,

Z. Wang, Synthesis, Characterization and

Optical Properties of Nanostructured ZnWO4,

Materials Science in Semiconductor Processing,

Vol.41, 2016, pp. 404–410.

[44] G. Chen, F. Wang, J. Yu, H. Zhang, X. Zhang,

Improved Red Emission by Codoping Li+3 in

ZnWO4:Eu+3 Phosphors, Journal of Molecular

Structure, Vol.1128, 2017, pp. 1–4.

[45] A.F. Gouveia, M. Assis, L.S. Cavalcante, L.

Gracia, E. Longo, J. Andres, Reading at

Exposed Surfaces: Theoretical Insights into

Photocatalytic Activity of ZnWO4, Frontier

Research Today, Vol.1, 2018, 1005.

[46] B. Zhai, L. Yang, Y. Huang, Intrinsic Defect

Engineering in Eu+3 Doped ZnWO4 for

Annealing Temperature Tunable

Photoluminescence, Nanomaterials, Vol.9,

No.1, 2019, 99.

[47] S. Wei, Y. Ma, Y. Chen, L. Liu, Y. Liu, Z. Shao,

Fabrication of WO3/Cu2O Composite Films and

Their Photocatalytic Activity, Journal of

Hazardous Materials, Vol.194, 2011, pp. 243–

249.

[48] F. Wang, C. Di Valentin, G. Pacchioni, Rational

Band Gap Engineering of WO3 Photocatalyst for

Visible Light Water Splitting, ChemCatChem,

Vol.4, No.4, 2012, pp. 476–478.

[49] G. Swain, S. Sultana, J. Moma, K. Parida,

Fabrication of Hierarchical Two-Dimensional

MoS2 Nanoflowers Decorated upon Cubic

CaIn2S4 Microflowers: Facile Approach to

Construct Novel Metal-Free p–n Heterojunction

Semiconductors with Superior Charge

Separation Efficiency, Inorganic Chemistry,

Vol.57, No.16, 2018, pp. 10059–10071.

[50] C. Zhou, S. Wang, Z. Zhao, Z. Shi, S. Yan, Z.

Zou, A Facet-Dependent Schottky-Junction

Electron Shuttle in a BiVO4{010}–Au–Cu2O Z-

Scheme Photocatalyst for Efficient Charge

Separation, Advanced Functional Materials,

Vol.28, No.31, 2018, 1801214.

[51] M.S. Gui, W.D. Zhang, Y.Q. Chang, Y.X. Yu,

One-step Hydrothermal Preparation Strategy for

Nanostructured WO3/Bi2WO6 Heterojunction

with High Visible Light Photocatalytic Activity,

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Chemical Engineering Science, Vol.197, 2012,

pp. 283–288.

[52] J. Sun, L. Sun, N. Han, J. Pan, W. Liu, S. Bai,

Y. Feng, R. Luo, D. Li, A. Chen, Ordered

Mesoporous WO3/ZnO Nanocomposites with

Isotype Heterojunctions for Sensitive Detection

of NO2, Sensors and Actuators B: Chemical,

Vol.285, 2019, pp. 68–75.

[53] J.H. Pan, W.I. Lee, Preparation of Highly

Ordered Cubic Mesoporous WO3/TiO2 Films

and Their Photocatalytic Properties, Chemistry

of Materials, Vol.18, No.3, 2006, pp. 847–853.

[54] A.S. Rajpurohit, N.S. Punde, C.R. Rawool, A.K.

Srivastava, Fabrication of High Energy Density

Symmetric Supercapacitor Based on Cobalt-

Nickel Bimetallic Tungstate Nanoparticles

Decorated Phosphorus-Sulphur Co-Doped

Graphene Nanosheets, Chemical Engineering

Science, Vol.371, 2019, pp. 679–692.

[55] C. Zhang, H. Zhang, K. Zhang, X. Li, Q. Leng,

C. Hu, Photocatalytic Activity of ZnWO4: Band

Structure, Morphology and Surface

Modification, ACS Applied Materials &

Interfaces, Vol.6, No.16, 2014, pp. 14423–

14432.

[56] J. Li, C. Guo, L. Li, Y. Gu, K.B. Hee, J. Huang,

In Situ Fabrication of 1D WO3 Nanorod/2D

ZnWO4 Nanosheet Heterojunction for Enhanced

Photoelectrochemical Performance, Catalysis

Letters, Vol.152, No.1-3, 2022, pp. 1611–1620.

[57] A. Hsini, M. Benafqir, Y. Naciri, M. Laabd, A.

Bouziani, M. Ez-zahery, R. Lakhmiri, N. El

Alem, A. Albourine, Synthesis of an Arginine-

Functionalized Polyaniline@FeOOH

Composite with High Removal Performance of

Hexavalent Chromium Ions from Water:

Adsorption Behavior, Regeneration and Process

Capability Studies, Colloids and Surfaces A:

Physicochemical and Engineering Aspects,

Vol.617, 2021, 126274.

[58] P.P. Liu, X. Liu, X.H. Huo, Y. Tang, J. Xu, H.

Ju, TiO2–BiVO4 Heterostructure to Enhance

Photoelectrochemical Efficiency for Sensitive

Aptasensing, ACS Applied Materials &

Interfaces, Vol.9, No.32, 2017, pp. 27185-

27192.

[59] L. Ge, C. Han, J. Liu, In Situ Synthesis and

Enhanced Visible Light Photocatalytic

Activities of Novel PANI–g-C3N4 Composite

Photocatalysts, Journal of Materials Chemistry,

Vol.22, 2012, pp. 11843-11850.

[60] F. Wang, X: Liu, X., S. Hou, Z. Yang, K. Zhao,

M. Zhang, Characterization and Performance

Study of GR/ZnWO4 and MoS2/ZnWO4

Nanocomposite Photocatalysts, Journal of

Materials Science: Materials in Electronics,

Vol.34, 2023, Article Number 291.

[61] B. Barik, M. Mishra, P. Dash, Ionic Liquid-

assisted Synthesis of a Novel

PANI/ZnWO4/WO3 Ternary Nanocomposite: A

Facile Double Electron Transfer Photocatalyst

for Efficient Degradation of an Herbicide,

Environmental Science: Nano, Vol.8, No.9,

2021, pp. 2676-2692.

[62] G. Ciri´c-Marjanovi´c, Recent Advances in

Polyaniline Research: Polymerization

Mechanisms, Structural Aspects, Properties and

Applications, Synthetic Metals, Vol.177, 2013,

pp. 1–47.

[63] S. Tan, J. Zhai, B. Xue, M. Wan, Q Meng, Y. Li,

L. Jiang, D. Zhu, Property Influence of

Polyanilines on Photovoltaic Behaviors of Dye-

Sensitized Solar Cells, Langmuir, Vol.20, 2004,

2934–2937.

[64] N. Kumari Jangid, S. Jadoun, N. Kaur, A

Review on High-throughput Synthesis,

Deposition of Thin Films and Properties of

Polyaniline, European Polymer Journal,

Vol.125, 2020, 109485.

[65] B. Lange, LUMISmini, Operating Manual,

Düsseldorf, Germany: Dr Bruno LANGE, 1994.

[66] B. Lange, Vibrio fischeri -Microtox LCK 491

Kit, Germany: Dr LANGE, 2010.

[67] W.C. Lipps, E.B. Braun-Howland, T.E. Baxter,

Standard Methods for the Examination of Water

and Wastewater, (24th. Edition). W.C. Lipps,

E.B., Braun-Howland, T.E. Baxter, (editors),

American Public Health Association (APHA),

American Water Works Association (AWWA),

Water Environment Federation (WEF), Elevate

Your Standards. American Public Health

Association 800 I Street, NW Washington DC:

20001-3770, United States, December 1, 2022;

ISBN:9780875532998.

[68] B. Lange, LUMIXmini Type Luminometer,

Dusseldorf: Dr LANGE Company, 1996.

[69] F. Siddique, S. Gonzalez-Cortes, A. Mirzaei, T.

Xiao, M.A. Rafiq, X. Zhang, Solution

Combustion Synthesis: The Relevant Metrics

for Producing Advanced and Nanostructured

Photocatalysts, Nanoscale, Vol.14, No.33,

2022, pp. 11806-11868.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Contribution of Individual Authors to the

Creation of a Scientific Article (Ghostwriting

Policy)

Prof. Dr. Delia Teresa Sponza and Post-Dr. Rukiye

Öztekin took an active role in every stage of the

preparation of this article.

The authors equally contributed in the present

research, at all stages from the formulation of the

problem to the final findings and solution.

Sources of Funding for Research Presented in a

Scientific Article or Scientific Article Itself

This research study was undertaken in the

Environmental Microbiology Laboratories at Dokuz

Eylül University Engineering Faculty Environmental

Engineering Department, İzmir, Turkey. The authors

would like to thank this body for providing financial

support.

Conflict of Interest

The authors have no conflicts of interest to declare

that are relevant to the content of this article.

Creative Commons Attribution License 4.0

(Attribution 4.0 International, CC BY 4.0)

This article is published under the terms of the

Creative Commons Attribution License 4.0

https://creativecommons.org/licenses/by/4.0/deed.en

_US

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

APPENDIX

Table 1. The initial experimental conditions for this study.

PANI/ZnWO4/WO3 NCs

Concentrations (mg/l)

PANI/ZnWO4/WO3

Mass Ratios

GLP

Concentrations

(mg/l)

Photodegradation

Time (min)

Solar Light

Powers

(W/m2)

0.1

1:1:3

0.4

1:2:3

0.6

3:1:1

1.0

3:2:1

1.5

100

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 1. Photodegradation Mechanism of PANI/ZnWO4/WO3 NCs

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 2. The XRD patterns of (a) PANI, (b) WO3 NPs, (c) ZnWO4 NPs, (d) PANI-WO3 NCs, (e) PANI-ZnWO4

NCs and (f) PANI/ZnWO4/WO3 NCs, respectively, in surface water after photocatalytic degradation process for

GLP removal.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 3. FTIR spectrum of (a) PANI, (b) ZnWO4 NPs and (c) WO3 NPs, respectively, in surface water after

photocatalytic degradation process for GLP removal.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

(a)

(b)

(c)

(d)

Fig. 4. FESEM images of (a) PANI, (b) ZnWO4 NPs, (c) WO3 NPs and (d) PANI//ZnWO4/WO3 NCs,

respectively, in surface water after photocatalytic degradation process for GLP removal (FESEM images scale:

200 nm).

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 5. HRTEM images of PANI/ZnWO4/WO3 NCs in micromorphological structure level in surface water after

photocatalytic degradation process for GLP removal (HRTEM image scale: 200 nm).

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 6. The XPS spectra of (a) PANI (red) (b) ZnWO4 NPs (green), (c) WO3 (blue) and (d) PANI/ZnWO4/WO3

NCs (black), respectively, in surface water after photocatalytic degradation process for GLP removal.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig 7. N2 adsorption desorption isoterm of PANI, ZnWO4, WO3 and PANI/ZnWO4/WO3 NCs

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig 8a. UV−vis absorbance for WO3, 8% Zn/WO3, and ZnWO4

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig 8b. Tauc plots for WO3, ZnWO4 and 8% WO3

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig 9. Cyclic voltammogram data of WO3, PANI, ZnWO4 and PANI/ZnWO4/WO3 NCs in 0.7 M LiClO4-PC

electrolyte.

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 10. Nyquist plots of WO3, PANI, and PANI/ZnWO4/ WO3 NCs in 0.7 M LiClO4-PC electrolyte

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 11a. Galvanostatic charge/discharge curve of PANI/WO3 and PANI/ZnWO4/WO3 NCs

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Fig. 11b. Galvanostatic charge/discharge curve of PANI/WO3 NCs

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Table 2. The effect of increasing PANI/ZnWO4/WO3 NCs concentrations for GLP removal

PANI/ZnWO4/WO3 NCs Concentrations (mg/l)

GLP Removal Efficiency (%)

0.1

0.4

0.6

1.0

1.5

Table 3. The effect of different PANI/ZnWO4/WO3 mass ratios for GLP removal

PANI/ZnWO4/WO3 Mass Ratios

GLP Removal Efficiency (%)

1:1:3

1:2:3

3:1:1

3:2:1

Table 4. The effect of different GLP concentrations for GLP removal

GLP Concentrations (mg/l)

GLP Removal Efficiency (%)

Table 5. The effect of increasing photodegradation time for GLP removal

Photodegradation Time (min)

GLP Removal Efficiency (%)

Table 6. The effect of increasing solar light power for GLP removal

Solar Light Power (W/m2)

GLP Removal Efficiency (%)

100

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

Volume 3, 2024

Table 7. Effect of increasing GLP concentrations on Microtox acute toxicity in surface water after

photocatalytic degradation process, at 30oC and at 60oC.

Parameters

Microtox Acute Toxicity Values, * EC (mg/l)

25oC

0. min

60. min

120. min

180. min

*EC90

*EC

Control

825

EC70=510

EC60=650

EC49=638

30oC

60oC

min

60.

min

120.

min

180.

min

60.

min

120.

min

180.

min

*EC90

*EC

*EC90

*EC

Control

825

EC70=

580

EC50=

580

EC39=

548

825

EC55=

550

EC40=

590

EC29=

688

GLP=1 mg/l

825

EC62=

422

EC27=

242

EC17=

168

825

EC57=

419

EC22=

266

EC12=

150

GLP=2 mg/l

825

EC62=

421

EC27=

239

EC17=

167

825

EC57=

414

EC22=

232

EC12=

161

GLP=3 mg/l

825

EC57

=414

EC22=

236

EC12=

16.5

825

EC52=

550

EC17=

214

EC7=

GLP=4 mg/l

825

EC67=

408

EC32=

230

EC22=

162

825

EC62=

403

EC27=

218

EC17=

148

* EC values were calculated based on CODdis (mg/l). Control: raw ww.

Table 8. Effect of increasing GLP concentrations on Daphnia magna acute toxicity in surface water after

photocatalytic degradation process, at 30oC and at 60oC.

Parameters

Daphnia magna Acute Toxicity Values, * EC (mg/l)

25oC

0. min

60. min

120. min

180. min

*EC50

*EC

Control

850

EC45=625

EC40=370

EC29=153

30oC

60oC

min

60.

min

120.

min

180.

min

60. min

120.

min

180.

min

*EC50

*EC

*EC50

*EC

Control

850

EC39=

468

EC34=

228

EC23=

111

850

EC34=

373

EC29=

210

EC18=

GLP=1 mg/l

850

EC32=

450

EC22=

145

EC17=

260

850

EC32=

130

EC17=

425

EC12=

340

GLP=2 mg/l

850

EC37=

450

EC22=

175

EC17=

100

850

EC32=

425

EC17=

140

EC7=

GLP=3 mg/l

850

EC32=

350

EC17=

240

EC12=

850

EC27=

150

EC12=

EC7=

GLP=4 mg/l

850

EC42=

300

EC27=

170

EC22=

850

EC37=

250

EC22=

110

EC17=

* EC values were calculated based on CODdis (mg/l). Control: Raw ww

International Journal of Chemical Engineering and Materials

DOI: 10.37394/232031.2024.3.9

Ruki

ye Özteki

n, Deli

a Teresa Sponza

E-ISSN: 2945-0519

100

Volume 3, 2024