PHOTO-CATALYTIC DEGRADATION OF THE PHARMACEUTICAL

AZO DYE TARTRAZINE IN AQUEOUS SOLUTION USING

ULTRAVIOLET—ANO TITANIUM DIOXIDE SYSTEM WITH THE
COMPARATIVE EFFECT OF HYDROGEN PEROXIDE AND
BENZOIC ACID.

IHEANACHO MERCY C.
CHAPTER 1: INTRODUCTION
1.1 Background of the Study
1.2 Statement of the Problem
1.3 Justification of the Study
1.4 Aim of the Study
1.5 Objectives of the Study

CHAPTER 2: LITERATURE REVIEW

CHAPTER 3: MATERIALS AND METHODS

 CHAPTER ONE
INTRODUCTION

1.1 Background to the Study

Water pollution caused by organic chemicals from pharmaceutical, food, mineral, and other

processing industries is a growing problem (Shannon, Bohn, Elimelech, Georgiadis, Marinas,

& Mayes, 2008) mainly caused by the presence of synthetic dyes in effluents. Almost every

industry uses dyestuffs to dye their products. Over 700,000 tons and approximately 10,000

different types of dyes and pigments are produced worldwide annually. Statistics show that

approximately 10–15% of dyes used in the industry will end up in wastewater during and

after the manufacturing process (Iqbal & Ashiq, 2007; Bilba, Suteu, Malutan, 2008). These

effluents are often discharged without treatment, leading to hazardous effects on water and

habitat quality (Odika et al., 2020). The presence of these dyes in effluents compromises

water properties, such as color, pH, sunlight penetration, and chemical oxygen demand, and

important ecological impacts, as most of these dyes are carcinogenic and genotoxic −

associated with oxidative stress (Sun, Sun, Wang, & Qiao, 2007; Hameed, 2009). The

produced wastewater from pharmaceutical, food, textile, paper, and agricultural industries has

detrimental impacts on the environment and poses a serious threat to the wild and human life

(it affects the physiology of aquatic life as well as humans, which impinge upon water

resources for supply).

The pharmaceutical industry uses various inorganic and organic dyes. Azo compounds

represent about two-thirds of all synthetic dyes. Their usage in the pharmaceutical industry

has many purposes, which include commercial, psychological, and practical purposes. One of

the most important is the colouring of pharmaceutical agents which improves their easy

identification. It also helps to give pharmaceutical products unique and attractive packaging

for easy acceptance among consumers. Different colors of drugs also can help patients to

distinguish different strengths of the same drug which can reduce the risk of an overdose or

underdose (Šuleková, Smrčová, Hudák, Heželová, & Fedorová, 2017). Azo dyes often used

in the manufacturing of pharmaceuticals are E102 Tartrazine, E110 Sunset Yellow FCF,

Ponceau 4R (Cochineal Red A), Azorubine (Carmoisine), Amaranth, E133 Brilliant Blue and

E129 Allura Red; with tartrazine being the most widely used. Many azo dyes show

carcinogenic and mutagenic activities, and they can provoke allergic reactions.

Although tartrazine is used as a food coloring, long-term consumption of foods containing

excessive amounts of it may cause allergies and diarrhea, may also cause hyperactivity, and

even affect children’s intellectual development; when the intake exceeds the liver load, it will

increase the burden of self-regulation and cause some damage to the kidneys and liver (Dotto,

Moura, Cadaval, & Pinto, 2013, Mittal, Mittal, & Kurup, 2006; Basu, & Kumar, 2017). In the

last decades, many works have reported tartrazine hazards, identifying its potentially

deleterious effects, such as mutagenic, carcinogenic, and phototoxicity (Soares, Araújo,

Ramos, Pinto, Khayat, De Oliveira, Bahia, Montenegro, Burbano, & Khayat, 2015; Khayyat,

Essawy, Sorour, & Soffar, 2017; Tripathy, Patnaik, & Nabi, 1989; Merville, Decuyper,

Lopez, Piette, & Van De Vorst, 1984). Recent studies also indicated that such colored

effluents have toxic effects with carcinogenesis and may cause allergy, dermatitis, eye/skin

infections, irritation, cancer, etc. (Morais, Freitas, Goncalves, Vasconcelos, & Gonzalez

Beca, 1999).
Based on the aforementioned issues with respect to water and environmental pollution and

risks to aquatic and human lives, there is a need to adopt efficient treatment methods that will

remove these recalcitrant, toxic pollutants in wastewater. Tartrazine is an azoic dye, and most

of these azo dyes possess complex and stable molecular structures, making them resistant to

conventional biological and chemical degradation processes (Gautam, Banerjee, Lofrano,

Sanroman, Chattopadhyaya, & Pandey, 2015). Some conventional treatment methods include

adsorption on different adsorbents, membrane filtration, electrodialysis, floatation,

coagulation, electrochemical deposition, chemical deposition, etc. Each of these methods has

its limitations, which constitute challenges in their utilization. For some of them, efficiency

over a range of pollutants is not achieved, while others generate by-products, which also

themselves, have to be subjected to further secondary treatments before being let off into the

environment. Methods and processes utilized in the treatment of wastewater include

technologies that enable the reduction and eradication of toxic substances in effluent water, to

conform to environmental standards.

However, the degradation of organic pollutants like synthetic dyes from aqueous solutions in

industrial wastewater has become increasingly significant during the last decades by using

oxidation processes. Hence, photo-catalytic oxidation has attracted researchers’ attention

because of its many advantages which include high processing efficiency, simple process

equipment, easy control of operating conditions, no secondary pollution, and easy availability

of catalytic materials in recent years (Wang, Tadé & Shao, 2015; Chen, Ma & Zhao, 2010).

Based on the foregoing therefore, this research employs photo-catalytic oxidation for the

degradation of tartrazine in solution, with the semiconductor titanium dioxide (Ti O2 ¿ surface

as photo-catalyst under UV light, with the use of an electron acceptor (e.g. hydrogen

peroxide) and an electron donor (e.g. benzoic acid) to comparatively monitor the degradation

process. The photo-catalytic degradation using the titanium dioxide (Ti O2)-UV system is a
promising approach for water pollution remediation. Ti O2-based photocatalysis has been

shown to effectively degrade tartrazine, with the degradation efficiency influenced by various

factors. This research is concerned with the optimization of the process parameters that are

needed to enhance the efficiency and applicability of this technology. This degradation

method has the advantages aforementioned.

1.2 Statement of the Problem

The increased population growth of Nigeria has been accompanied by intensive urbanization,

an increase in industrial activities, as well as an increase in wastewater generation, with

consequent challenges for waste management. However, there is a deficit in technology and

sufficient manpower with the necessary technical and managerial training/skills to properly

handle waste in a safe and sound manner in the country. The usual methods of waste disposal

are landfills, dumpsites, land spreads, and incineration. Many factories in Nigeria are located

on river banks and use the rivers as open sewers for their effluents. The major industries

responsible for water pollution in Nigeria include pharmaceuticals, petroleum, mining (gold,

tin, and coal), wood and pulp, textiles, plastics, iron and steel, brewing, distillery

fermentation, paint, and food. Wastewater from the textile, pharmaceutical, paper, cosmetic,

and food industries is characterized by high chemical and biological oxygen demands (COD

and BOD, respectively), suspended solids, and intense colors as a result of the extensive use

of synthetic dyes. These dyes are highly visible even at low concentrations (<1 mg/L). Many

of the dyes are difficult to degrade because of their complex structures and xenobiotic

properties. For the pharmaceutical industries, for example, improper disposal of

pharmaceutical dye wastewater contributes to the contamination of freshwater aquatic

habitats (4), which has been recently confirmed by survey campaigns worldwide. The

pharmaceutical industry can release a range of organic chemicals, including active

pharmaceutical ingredients (APIs), into water bodies through wastewater discharges. For

example, a study conducted in Nigeria highlighted the presence of pharmaceutical residues in

water bodies such as rivers and streams, with potential impacts on aquatic ecosystems

(Onwudiwe et al., 2017). Such documented evidence raised a novel and intricate

toxicological and environmental issue. In the long term, the present level of environmental

degradation usually creates health problems from water-borne diseases for most of the

population and serious harm to aquatic life. According to FEPA (1991), each effluent should

be detoxified with the installation of population abatement equipment based on the best

practical technology (BPT) approach.

Unfortunately, the aforementioned scenario has not been addressed with a suitable

wastewater treatment plan for domestic and industrial effluents. Most cities in Nigeria lack

efficient waste management systems and industrial waste discharge is not properly

monitored. Industries are not held to account for the haphazard or improper discharge of their

effluents. In the Niger Delta region, there is oil spillage into water bodies with no

corresponding repercussions to the responsible parties. Furthermore, the 1988 Koko toxic

waste dumping saga has reiterated the exigent need to ostensibly address environmentally

related issues in the country. An instance of the risks associated with inefficient waste

management is the Bhopal disaster. On December 3, 1984, more than 40 tons of methyl

isocyanate gas leaked from a pesticide plant in Bhopal, India, which killed about 3,800

people and caused significant morbidity and premature deaths of people.

Thus, appropriate treatment of dye wastewater to remove color and dye compounds is

important. Biological treatment has been used to reduce the COD of effluents, but many

pollutants from wastewater can be removed only by chemical and physical methods such as

adsorption, coagulation, flocculation, oxidation, and filtration.1-3 Currently, the most widely

used physical method is adsorption by activated carbon, but this process creates a huge
amount of sludge, which becomes a pollutant on its own, creating disposal problems.

Moreover, effluents that contain azo-reactive dyes are very difficult to treat in environmental

systems, because of their sulfonic acid groups, which make the dyes very water-soluble and

polar (Zwiener, 2000; Chagas, 2001). Heterogeneous photocatalytic oxidation, one of the

Advanced Oxidation Processes (AOPs), has proved to be a promising technology for the

remediation of organic pollutants at ambient conditions, see the equation below: Organic

molecule + O2 → CO2 + H 2O + Mineral acids

1.3 Justification of the Study

Enormous extant literature for example Paya, Halliwell, Hoult (1992); and Okamoto,

Kobayashi, Yoshida; (2005) are inundated with the degradation of tartrazine using oxidation

methods. Despite the fact that this study area has received vast scholarly attention in recent

years, this research employs photo-catalytic oxidation for the degradation of a pharmaceutical

azo dye, tartrazine in solution, with the semiconductor titanium dioxide (TiO2) surface as pa

hoto-catalyst under UV light. It will further attempt to comparatively monitor the degradation

process with the use of an electron acceptor (e.g. hydrogen peroxide) and an electron donor

(e.g. benzoic acid), which may enhance its relevance in industrial applications. The photo-

catalytic degradation using the TiO2-UV system is a promising approach for water pollution

remediation. TiO2-based photo-catalysis has been shown to effectively degrade tartrazine,

with the degradation efficiency influenced by various factors. This research is concerned with

the optimization of the process parameters that are needed to enhance the efficiency and

applicability of this technology.

1.4 Aim of the Study

The aim of this study is to photo-catalytically degrade the pharmaceutical azo dye, tartrazine

in an aqueous solution using titanium dioxide under UV light and the comparative effect of

an electron acceptor ( H 2 O2) and an electron donor (benzoic acid) on the entire process.
1.5 Objectives of the Study
The specific objectives of this study are:

i To design a suitable UV-Nano TiO2 system.

ii Investigate the photo-catalytic degradation potential of the synthetic dye, tartrazine in

an aqueous solution by the UV-Nano TiO2 system

iii To measure the influence of some parameters (catalyst concentration/dose, substrate

concentration, pH of the reaction medium) on the photo-catalytic degradation process.

iv Investigate the comparative effect of an electron acceptor and an electron donor on the

whole process.

v Estimate the kinetics of the photo-degradation process by the UV- TiO2system.

 CHAPTER THREE

MATERIALS AND METHODS

3.1 Materials and Reagents

All reagents are of analytical grade unless otherwise stated. They include;

 5-hydroxy-1-p-sulfophenyl-4-(p-sulfophenylazo)-pyrazol-3-carboxylic acid (CAS

1934-21-0) purchased from

 Sodium Hydroxide (NAOH)

 Hydrochloric acid (HCl)

 Benzoic acid (C 6 H 5COOH)

 Hydrogen peroxide ( H 2 O2 ¿

 Titanium dioxide, TiO2 (80% anatase, 20% rutile, 20nm, CAS No. 13463-67-7),

supplied by SkySpring Nanomaterials, Inc. Houston, TX, USA.

Equipments to be used include;

 Photoreaction box, measuring 67 × 33 × 30 cm

 25 W UV bulb

 Magnetic stirrer

 Centrifuge
  UV/Vis Spectrophotometer

 Digital pH meter

 Weighing balance

Methodology to be adopted:

1. Preparation of Tartrazine solution

2. Preparation of Benzoic acid solution

3. Preparation of Hydrogen peroxide solution

4. Photocatalytic degradation experiment/process:

i. Set up a photocatalytic reactor system, which includes a UV light source, a reactor

vessel, and a magnetic stirrer (Gupta et al., 2011; Zhou et al., 2019).

ii. Introduce the prepared tartrazine solution into the reactor vessel

iii. Add the desired amount of TiO2 photocatalyst to the tartrazine solution

iv. Add the hydrogen peroxide/benzoic acid solution to the reactor vessel

v. Stir the solution to ensure uniform mixing and contact between the photocatalyst,

tartrazine, and hydrogen peroxide/benzoic acid (Zhou et al., 2019).

vi. Irradiate the solution with UV light for a predetermined duration (Gupta et al.,

2011; Zhou et al., 2019).

vii. Collect aliquot samples at regular intervals to monitor the degradation of

tartrazine.

5. Analysis of Degradation Efficiency:

i. Measure the concentration of tartrazine in the collected aliquot samples using

UV/Vis spectrophotometer (Gupta et al., 2011).

ii. Calculate the degradation efficiency of tartrazine.

6. Optimization and Parameter Study:

i. Conduct comparative experiments to investigate the effects of different

parameters (catalyst concentration/dose, substrate concentration, pH values,

hydrogen peroxide and benzoic acid concentrations). (Gupta et al., 2011, Zhou et

al., 2019).

ii. Analyze the results to determine the optimal conditons for achieving the highest

degradation efficiency.

7. Mechanism Study

i. Conduct additional experiments and analysis to gain insights into the mechanism

of the photocatalytic degradation process (Gupta et al., 2011).

ii. Investigate the roles of hydrogen peroxide and benzoic acid in enhancing the

degradation efficiency of tartrazine by TiO2 (Gupta et al., 2011; Zhou et al.,

2019).
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