Thesis Forough Saffari 3 SO3

Electrochemical Degradation of Benzalkonium Chloride (BAC)
A thesis submitted to McGill University in partial fulfillment of the requirements of

the degree of Master of Science
Forough Saffari
Department of Chemical Engineering, McGill University
Montréal, Québec, Canada
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© Forough Saffari, 2024
Abstract
The common usage of benzalkonium chloride (BAC) as a disinfectant and antiseptic has led to
its accumulation in water sources, raising concerns about its environmental impact. There have
been many methods that were used previously for removal of BAC, and each had its advantages
and disadvantages, but none of them were effective enough. The focus of this thesis is to use
electrochemical degradation technique for removal of BAC. This thesis used a Boron-Doped
Diamond (BDD) anode and stainless-steel cathode to study the electrochemical degradation of
BAC. The BDD electrode is known for its exceptional electrochemical properties, such as high
chemical stability, low fouling tendency, and wide potential window, making it suitable for
advanced oxidation processes.
A laboratory-scale electrochemical cell, mostly undivided cell unless otherwise specified, with
BDD electrode serving as anode and stainless steel as cathode and a thermometer completed the
experimental setup. We tracked the concentration of BAC over time using UV-Visible
spectroscopy and did chemical oxygen demand (COD) analysis throughout a range of current
densities from 5 to 150 mA/cm 2. The effect of temperature and pH on BAC degradation was also
tested. Although BDD is known as the best, 2 other anode materials were tested. The OH
radicals scavengers indicated that BAC is most probably degraded directly on the surface of
electrodes.
The results demonstrated that the electrochemical degradation of BAC using the BDD electrode
was highly effective and in best condition which is 100 mA/cm 2, BAC degraded completely in
around 30 minutes. The degradation process’s rate and extent increased by increasing the current
density from 5 mA/cm2 to 150 mA/cm2, leading to a more pronounced reduction in COD values.
The findings contribute to our understanding of the process parameters and conditions that can
optimize the removal of BAC from water sources, thereby supporting the development of
efficient and sustainable water treatment strategies. Future research can further explore the
mechanistic aspects and scale-up possibilities of the electrochemical degradation process using
BDD and stainless-steel electrodes.
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RÉSUMÉ
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ACKNOWLEDGEMENTS
First of all, I would like to thank my co-supervisors, Dr. Viviane Yargeau, and Dr. Sasha
Omanovic for giving me this opportunity to be part of their labs for the past two years and for all
their support and guidance throughout my project.
Furthermore, I would like to express my gratitude, to my office mate, lab mate and colleague,
soon to be Dr. Kara Hughes for her endless assistance during my work at the lab. I appreciate
everything that you have done for me.
Additionally, I want to thank Marco for all his support and aid to me in the lab. His presence in
the lab was such a relief.
Also, I am sincerely grateful for IDRAK for granting me the scholarship to pursue my studies at
McGill University. Your aid has been instrumental for my success.
In addition, I would like to thank Anna, a summer internship student, for her support and help on
this project.
Finally, I want to thank my husband Vahab, my parents, my in-laws and my two sisters, Partow
and soon to be MD Rana Saffari for all they moral support. I would not be here it was not for
you.
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Table of Contents
Abstract 2
1 Introduction 9
2 Research Objectives 11
3 Background and Literature Review 12

3.1 BAC Background 12
3.1.1 Antimicrobial Tolerance and Resistance Effect of Benzalkonium Chloride (BAC) 16
3.1.2 Toxicity Effect of Benzalkonium Chloride on Living Organisms 17
3.1.3 Effects of Benzalkonium Chloride on the Natural Environment 17
3.2 Methods for Removal of BAC 18
3.2.1 Ozonation of Benzalkonium Chloride 18
3.2.2 U.V. Irradiation / Chlorine Oxidation of Benzalkonium Chloride 19
3.2.3 Oxidation of Benzalkonium Chloride by S2O82−/Fe2+ 19
3.2.4 Biological Removal of BAC 20
3.2.5 Advanced oxidation processes (AOPs) 20
3.2.6 Electrochemical Techniques for BAC Removal 21
3.3 Electrochemical Degradation Process 22
3.3.1 Advantages of electrochemical oxidation 22
3.3.2 Electrochemical Cell 23
3.3.3 Electrode Selection 24
4 Materials and Methods 26

4.1 Chemicals and Reagents 26
4.2 Electrochemical Cell Setup 26
4.3 BAC Degradation Experiment 28
4.3.1 BAC Degradation Analysis 28
4.3.2 Chemical Oxygen Demand Analysis 29
5 Results and Discussion 30

5.1 Control Experiments 30
5.2 Impact of Current Density on Rate and Extent of BAC Degradation 33
5.3 Impact of Current Density on Temperature and Voltage 37
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5.4 Impact of Different Anode Materials on BAC Degradation 39
5.5 Comparison of Divided and Undivided Cell on BAC Degradation 41
5.7 COD Analysis 42
5.8 Impact of pH on BAC Degradation 44
5.9 Impact of OH-radical Scavengers on BAC Degradation 44
6 Conclusion 46
7 Appendix 48
8 References 49
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List of Figures
FIGURE 1 SOURCES OF BAC CONTRIBUTING TO ITS RELEASE IN WATER BODIES [9] 9
FIGURE 2 STRUCTURE OF BAC [19] 12
FIGURE 3 UNDIVIDED CELL SETUP. 26
FIGURE 4 DIVIDED CELL SETUP. 27
FIGURE 5 CALIBRATION CURVE FOR BAC CONCENTRATION VS. ABSORPTION FOR SOLUTION OF
400 MG/L BAC AND 0.5 M NA2SO4 DONE BY UV-VISIBLE 29
FIGURE 6 BAC CONTROL EXPERIMENTS, ADSORPTION EXPERIMENTS ARE DONE WITHOUT ANY
CURRENT FLOW THROUGH THE SYSTEM. 30
FIGURE 7 STABILITY TESTS OVER A PERIOD OF 10 DAYS ON UNDEGRADED BAC, DILUTED BAC,
AND 2 DEGRADED BAC SAMPLES AT 100 MA/CM^2 31
FIGURE 8 TEMPERATURE PROFILE FOR BAC DEGRADATION AT CURRENT DENSITY OF 100
MA/CM2 32
FIGURE 9 THE INFLUENCE OF TEMPERATURE ON RATE OF BAC DEGRADATION AT 100 MA/CM233
FIGURE 10 IMPACT OF CURRENT DENSITY ON BAC DEGRADATION DURING 2 HOURS OF
EXPERIMENT 34
FIGURE 11 IMPACT OF CHARGE EFFICIENCY ON BAC DEGRADATION (A) RELATIVE BAC
CONCENTRATION VS. CHARGE TREND FOR 2 HOURS, (B) AND (C) ZOOMED-IN PORTIONS OF
PLOT (A) 36
FIGURE 12 IMPACT OF CURRENT DENSITY ON TEMPERATURE DURING THE DEGRADATION OF
BAC. 37
FIGURE 13 IMPACT OF CURRENT DENSITY ON CELL VOLTAGE RECORDED DURING BAC
DEGRADATION. 38
FIGURE 14 CELL RESISTANCE VS. TIME OBTAINED FROM THE SLOPES IN FIGURE 13 39
FIGURE 15 BAC DEGRADATION USING 3 DIFFERENT ANODES AT A CURRENT DENSITY OF 15
MA/CM2. 40
FIGURE 16 BAC DEGRADATION USING A DIVIDED CELL, AND AT CURRENT DENSITY OF 15
MA/CM2. 41
FIGURE 17 COMPARISON OF NUMBER OF MOLES OF BAC DEGRADED IN DIVIDED AND UNDIVIDED
CELL AT 15 MA/CM2. 42
FIGURE 18 CHEMICAL OXYGEN DEMAND ANALYSIS OF BAC EXPERIMENTAL SAMPLES AS A
FUNCTION OF TIME 43
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FIGURE 19 COMPARISON OF BAC DEGRADATION IN 0.5 M H2 SO4 AND IN NEUTRAL 0.5 M
NA2SO4 RECORDED AT 100 MA/CM2. 44
FIGURE 20 DEGRADATION OF BAC AT 100 MA/CM2 IN THE ABSENCE AND PRESENCE OF TWO
DIFFERENT OH-RADICAL SCAVENGERS. 45
FIGURE 21 COMPARISON OF DIFFERENT CALIBRATION CURVES DONE WITH 3 ELECTROLYTES
WITH THE SAME CONCENTRATION AND COMPOSITION 48
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List of Tables
TABLE 1: HALF MAXIMAL EFFECTIVE CONCENTRATION (E.C. 50) AND MEDIAN LETHAL
CONCENTRATION (L.C. 50) FOR B.A.C. WITH 95 % CONFIDENCE INTERVAL (CL) OF
DIFFERENT SPECIES 17
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1 Introduction
In recent decades, the widespread use of quaternary ammonium compounds (QACs) has
generated significant attention owing to their extensive range of uses as surfactants, disinfectants,
and preservatives in various industries ranging from pharmaceuticals to personal care products.
Among these, Benzalkonium Chloride (BAC) emerges as one of the most prevalent QACs,
finding extensive utilization in diverse consumer and industrial products [1]. Due to its potent
antimicrobial properties, BAC is widely used in a variety of disinfectants, antiseptics, and
sanitizing products for both medical and general applications. BAC has found extensive
applications in cosmetics, healthcare, and household cleaning products. BAC is abundant in
wastewater reservoirs near pharmaceutical industries [2, 3]. Improper disposal and widespread
use of BAC are significant contributors to its release into the environment, as represented in
Figure 1 [9].
Figure 1 Sources of BAC contributing to its release in water bodies [9]
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Industries that manufacture or utilize products containing BAC contribute significantly to
its presence in wastewater. Production processes, cleaning operations, and product formulation
involving BAC can lead to its release into industrial wastewater streams. Hospitals, clinics, and
other healthcare settings are notable sources of BAC contamination in wastewater. When this
wastewater from the hospitals reaches the wastewater treatment plant, these BACs are at low
concentrations and considered as micro-pollutants. The conventional wastewater treatment
sequence does not include steps to specifically remove these organic micro-pollutants [6, 7].
Hence, these organic micro-pollutants are released in the receiving streams. Irrespective of their
presence in different sources, waste water effluent is still one of the primary sources for the entry
of BAC into the environment [5].
BAC is also a common ingredient in a variety of household cleaning and personal care
products [8]. Disposal of unused or expired products containing BAC, as well as the washing of
surfaces treated with such products, can lead to its introduction into domestic wastewater. BAC
is occasionally used in agricultural settings, particularly in the preservation of certain crops and
in sanitizing equipment. BAC is also found in water samples from stormwater, wastewater
treatment plant, and grey water [10-13].
BAC is often not completely removed during conventional wastewater treatment
processes. This leads to the discharge of residual BAC into receiving water bodies. In areas not
connected to centralized wastewater treatment facilities, septic systems and on-site treatment
facilities may be used. If BAC-containing products are used in these areas, they can contribute to
the presence of BAC in the effluent. In urban areas where BAC-containing products are
commonly used, stormwater runoff can transport BAC from surfaces treated with these products
into natural water bodies. Recreational areas such as swimming pools, water parks, and spa
facilities may use BAC in water treatment processes. Improper disposal or drainage from such
facilities can introduce BAC into wastewater systems.
Given the diverse range of sources and origins of BAC in wastewater, understanding its
occurrence and behavior in treatment systems is crucial for effective management and
mitigation. Strategies for its removal are of paramount importance to ensure the environmental
sustainability of wastewater discharge [15-17]. Consequently, the presence of BAC in
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wastewater streams has become a subject of increasing concern due to its potential
environmental impact.
Additionally, its widespread presence has raised environmental concerns, particularly
regarding its fate in wastewater treatment processes. Consequently, its ubiquitous presence in
wastewater effluents has raised environmental concerns, warranting a comprehensive
investigation into its efficient and sustainable removal strategies.
Several methods have been investigated for this purpose, each with its own advantages
and limitations. Some of these techniques are ozonation, UV irradiation/cChlorine oxidation,
oxidation by S2O82- / Fe2+, biological removal of BAC, advanced oxidation processes, and
electrochemical techniques which will be discussed in detail later in literature review section.
The method used for this research is electrochemical degradation of BAC. However, the
literature reported on the electrochemical degradation of BAC is minimal, as illustrated in the
next section. This thesis aims to fill the gap by producing results on the electrochemical
degradation of BAC by investigating both oxidation and reduction.
2 Research Objectives
Benzalkonium chloride is a common organic pollutant that is part of the QACs found in
wastewaters. Due to its widespread use and adverse effects on the aquatic environment, it
indirectly affects humans, which is a source of concern. Although BAC could be degraded
employing electrochemical methods, the corresponding literature is very scarce. Further, no any
literature on BAC degradation by electrochemical reduction is available. This thesis aims to fill
the gap by presenting results on the electrochemical degradation of BAC by investigating both its
oxidation and reduction. Considering the limitations of the previously outlined water treatment
methods for the removal of BAC, there is a need to use a method that can overcome the
limitations of existing treatment approaches.
Consequently, the main objective of this project was to investigate the possibility of
employing electrochemical degradation , using a BDD anode and stainless-steel cathode, as a
method for the treatment of a BAC-containing water under various experimental conditions, and
to investigate the relative contribution of BAC oxidation and reduction in the total degradation
process.
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[3] Background and Literature Review
2.1[3.1] BAC Background
In the era of the COVID-19 pandemic, there has been a surge in the usage of cleaning
agents and disinfectants across various industries, healthcare settings, and in households. Among
these, Benzalkonium Chloride (BAC) finds predominant application as both an emulsifier and
antibacterial agent, with surfactant properties ranking second in utility. Its mechanism of action
involves inhibiting the growth of microorganisms, making it a common ingredient in antiseptic
hand wipes, antibiotic lotions, and ointments. Within organisms, BAC directly interacts with
proteins within the transmembrane or cell membrane, modifying the structure of the parent
protein by adding a hydrophobic BAC alkyl tail, ultimately altering the protein's functionality.
Given its antibacterial properties, BAC is incorporated into various cosmetics and personal-care
products to prevent product degradation. However, due to its extensive use and its potential
negative environmental impacts, there is growing concern over the increased presence of BAC in
the environment. Detectable levels of BAC have been found in wastewater influent, sewage,
sludge, pore water, and groundwater. When released into the environment, particularly in water
bodies, BAC can act as a biocidal against fungi, algae, and bacteria. It also has the capacity to
impede the spore formation process, which is crucial for fungi reproduction [15, 18].
BAC has variable chemical formula. In Ffigure 2, the BAC's structure is displayed [19]. Its
structure is made up of a positively charged quaternary nitrogen atom joined to a lengthy
hydrophobic alkyl chain and an aromatic ring, which is balanced by a chloride ion (Cl⁻).
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Figure 2 Structure of BAC [19]
BAC is typically found in the form of a colorless to pale-yellow liquid or solid,

depending on its concentration. It creates clear solutions and is very soluble in water. With
increasing temperature, the solubility rises. pH has an impact on its antibacterial action. It works
well in environments that range from slightly acidic to neutral. Because BAC decreases the
surface tension between two liquids or between a liquid and a solid, it functions as a surfactant.
Its ability to froth and emulsify makes it a useful ingredient. It is an effective antibacterial agent
that combats a wide variety of bacteria, fungi, and viruses – the integrity of m. Microorganisms'
integrity of their cell membranes is compromised in the presence of BAC. Because BAC is
positively charged, it may interact with surfaces that are negatively charged, such as the
membranes of bacteria.
The degree of BAC’s biodegradability varies based on the formulation and surrounding
circumstances. It is stable when stored normally, but a number of variables, such as pH,
temperature, and the presence of certain ions, might alter how effective it is. When BAC is
concentrated, it can be harmful to people, especially if consumed. It irritates skin and eyes as
well. The right dilution and handling are essential. BAC is frequently utilized in a wide range of
disinfectants, antiseptics, and sanitizing treatments for both medical and general purposes
because of its strong antibacterial qualities.
BAC releases into soil or water bodies can have a variety of negative consequences on the
environment. These are a few possible effects.:
1. Aquatic Ecosystems:
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It is well known that fish, crustaceans, and algae are among the aquatic creatures that are
hazardous to BAC. It can upset the equilibrium of aquatic ecosystems, interfere with their
physiological functions, and hinder reproduction. While long-term consequences may result from
chronic exposure to lesser amounts of BAC, high quantities of BAC can induce acute poisoning.
● Toxicity to Aquatic Life: Aquatic species including fish, algae, and invertebrates are
poisoned by BAC. It may disrupt their physiological functions, which might result in
less development, reproduction, and survival.
● Bioaccumulation and Biomagnification: Bacteria can bioaccumulate in living things'

tissues. This implies that it may accumulate over time in the bodies of species and
maybe reach concentrations that pose a threat to predators at the top of the food chain.
● Disruption of Microbial Communities: In aquatic settings, BAC may upset microbial

populations, which might have an impact on nutrient cycling and other ecosystem
functions.
2. Soil and Sediment Contamination:
● Persistence in Soil: BAC may linger in soil for a long time. This persistence may result
in long-term exposure to the environment and possible effects on species that live in the
soil.
● Impact on Soil Microbes: By influencing the microbial populations in the soil, BAC
may change critical soil processes such the breakdown of organic matter and the cycling
of nutrients.
3. Wastewater Treatment Plants:
● Impact on Microbial Communities: Beneficial bacteria in wastewater treatment

facilities may grow less readily when exposed to BAC, which might lessen the plants'
capacity to handle sewage.
● Release into Receiving Waters: When wastewater is treated, BAC could not be entirely
eliminated, which could result in its release into natural water bodies.
4. Resistance Development:
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● Potential for Antibiotic Resistance: Certain microbes may eventually acquire
resistance as a result of exposure to BAC. Public health may be affected by this as some
bacteria may grow less sensitive to antibiotics.
5. Ecotoxicological Effects on Non-Target Organisms:
● Effects on Non-Aquatic Organisms: Although BAC is mostly utilized in aquatic

settings, if it finds its way into terrestrial ecosystems through runoff or other channels, it
may have unexpected effects on creatures that are not aquatic.
6. Potential for Groundwater Contamination:
● Leaching and Mobility: BAC has the ability to permeate soil and pollute groundwater,
endangering ecosystems that depend on groundwater as well as perhaps human health if
drinking water is used from the groundwater.
7. Bioaccumulation:
Because of its durability and slow rate of degradation, BAC has the potential to
bioaccumulate in living things. This implies that it may gradually build up in an organism's
tissues, particularly in higher trophic levels of the food chain. Increased BAC concentrations in
organisms due to bioaccumulation may have unfavorable consequences.
8. Ecotoxicity to Non-Target Species:

BAC is meant to target and control microbes, but it can also affect non-target species in the
environment. It may have adverse impacts on beneficial microbes, insects, and other creatures
that play key roles in ecosystem functioning.
9. Disruption of Microbial Communities:

Since BAC is a broad-spectrum antibiotic, it may disturb the microbial ecosystems that
naturally exist in aquatic settings. It may have an impact on both good and bad bacteria, which
might result in unbalances in microbial populations and the way ecosystem’s function.
10. Antibiotic Resistance:
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Concern over BAC's possible involvement in the emergence and spread of antibiotic
resistance is rising. The selection and growth of resistant bacteria may be aided by the
antibacterial qualities of BAC, which may have an impact on the environment and public health.
11. Environmental Persistence:

The environmental durability of BAC, especially in water systems, is well documented. It
can withstand long-term exposure and possible buildup in the environment due to its resistance
to natural processes that break it down.
12. Disinfection Byproducts:

BAC can react to produce disinfection byproducts (DBPs) when it meets disinfectants like
chlorine during the water treatment process. Certain DBPs, like chloroform, are subject to
regulations because of possible health hazards.
To reduce the possible harm that benzalkonium chloride may do to the environment, it is
necessary to think of other options, treat wastewater appropriately, and follow all applicable laws
while using and disposing of it. Furthermore, to create effective mitigation methods and get a
deeper understanding of the ecological effects of BAC, continuous study and monitoring are
required. It i's crucial to remember that the precise impacts of BAC on the environment can
change based on a few variables, including concentration, length of exposure, ambient
circumstances, and the existence of other chemicals. To lessen possible negative effects on the
environment, regulatory bodies and environmental organizations may keep an eye on and control
the use and discharge of BAC. Furthermore, studies are being conducted to learn more about the
fate and impacts of BAC in many environmental compartments.
2.1.1[3.1.1] Antimicrobial Tolerance and Resistance Effect of Benzalkonium Chloride

(BAC)
The extensive use of antibiotics has led the pathogens to develop resistance against them.
To overcome this resistance BACs is used as biocides against the pathogens to prevent their
transmission [20]. Therefore, the bacterial volume to thrive and survive in BACs has been
investigated by tracking the outbreaks linked with the improper dilution and storage of
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disinfectant and antiseptic solutions [21]. Due to this, it is essential to mention the terms
tolerance and resistance, which have been extensively applied interchangeably, specifically
when concerned with biocides, which could lead to data misinterpretation. Resistance is widely
tacit as the “insusceptibility of a microorganism to a particular treatment under a particular set of
conditions” [22, 23]. Moreover, resistance is utilized for the decontaminant; biofilms, which
need much greater mortal concentrations than planktonic cells and form a resistance pool, are
frequently treated with disinfectants. On the other side, tolerance is applied on various occasions,
defining the strain in which antimicrobials are not increased. Still, the strain was capable of
enduring killing by reducing the growth of these antimicrobials [24]. Tolerant strains were also
termed those in which their antimicrobials enhanced compared to the controls [23]. Methicillin-
resistant Staphylococcus aureus (M.R.S.A.) strains were grown in BACs, doubling the minimal
inhibitory concentrations (M.I.C.) of BACs from 5 to 10 mg/L, after the adaptation period [25].
Similarly, M.I.C.s of BACs varied from 4 to 256 mg/L for Salmonella enterica serovar Virchow
and enhanced up to 1000 mg/L for E. coli O157 [26]. In addition, strains of the pathogen L.
monocytogenes isolated from various environments, such as animals, food products, patients, and
food-processing plants, were reported as having decreased susceptibility to BACs. Such strains
ranged from (8 %) [27], 10% [28], (40 %) [29] and up to 45% [30] of the total number of
isolates present in these environments respectively.
2.1.2[3.1.2] Toxicity Effect of Benzalkonium Chloride on Living Organisms

At environmentally relevant quantities, BAC was discovered to harm numerous aquatic
species. According to a Nature news interview with Patricia Hunt (faculty at Washington State
University), common cage-disinfection chemicals n-alkyl dimethyl benzyl ammonium chloride
and dodecyl dimethyl ammonium chloride caused a decline in mouse fertility, and BAC in the
environment may cause genetic damage to organisms [31].
2.1.3[3.1.3] Effects of Benzalkonium Chloride on the Natural Environment

Approximately 75 % of Q.A.C.s, including BACs, are discharged in the environment
along with treated wastewater. The remaining is dumped directly into the environment, resulting
in a net increase in pollution. Kreuzinger et al have studied the presence of BAC in wastewater
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effluent of a hospital in Austria and compared it to the residential wastewater effluent. According
to their research, the wastewater contained 2800 µg/L and 4.1 µg/L C12 in the hospital effluent
and the residential wastewater effluent, respectively [4]. BAC with an alkyl chain of C12 and
C14 are found in the wastewater treatment effluent in America up to 5.82 µg/L and 36.6 µg/L,
respectively [14]. Also, previous studies showed that approximately 170 µg/L of BACs are found
in sewage systems [61]. The damage caused by BAC is being studied via immobilization, lethal
concentration (L.C.), and D.N.A. damage. Table 1 shows the concentrations of BAC for different
organisms taken from previously reported works.
Table 1: Half maximal effective concentration (E.C. 50) and median lethal concentration (L.C.
50) for B.A.C. with 95 % confidence interval (Cl) of different species
Species Lethal Concentration (L.C. Effective Concentration (EC Ref.
50) a 50) a
Pseudomonas putida - 6.0 mg/L [62]
Caenorhabditis elegans 3.1 mg/L - [63]
Vibrio fischeri - 0.5 mg/L [62]
Ceriodaphina dubia 403.7 µg/L [64]
Nitrosomonas - 221 mg/kg [65]

communis
Daphina magna 38.2 µg/L - [64]
*All values are taken from references
Studies showed that BAC affected the movement and death rates of Ceriodaphina Dubai
and Daphina Magna even though the concentration was deficient, Table 1 [64]. The higher
concentrations of BAC affected larger animals like Dugesia japonica, a flatworm whose lethal
concentration was 2.27 mg/L [66]. Although Despite the harmful effects of BAC have been
proven, it is still not banned from the market, although some of the compounds having the same
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toxicity, like triclocarban and triclosan, have been banned from the market [63]. BAC is also
proven to be very toxic to zebrafish and Caenorhabditis elegans[REF]. BAC also harms the
plants. A BAC system affected the garden cress and lettuce at a concentration of 0.25 mg/L and
decreased the dry mass of both garden cress and lettuce by about 50-85 % [67].
2.2[3.2] Methods for Removal of BAC

As the toxicity and harmful effect of BAC are described in the previous sections, it is
imperative to degrade BAC present in the wastewater to reduce its adverse effects. Several
methods have been used to remove BAC and each has its advantages and disadvantages and are
presented below:
2.2.1[3.2.1] Ozonation of Benzalkonium Chloride

BAC has been continuously ozonated in two different settings: an influent sewage
treatment plant and a synthetic water matrix [39]. According to Carbajo et al.'s
investigations[Ref], BAC has been eliminated from the synthetic matrix. Twelve of the
intermediate transformation products (T.P.s) have been discovered, despite the restricted level of
mineralization in their research. The hydrophilic (benzyl and ammonium moiety) and
hydrophobic (alkyl chain) portions of the surfactant were impacted by the ozonation-initiated
breakdown pathway. BAC depletion was highly impacted by the water matrix. A total biological
community experiment utilizing activated sludge and a biotest battery including single species
(the bacteria Vibrio fischeri and Pseudomonas putida and the protozoan Tetrahymena
thermophila) were used to evaluate the aquatic toxicity of treated mixtures [40]. However, at
ozone doses lower than those necessary for complete BAC depletion, the ozonation procedure
reduced the harmful effects of treated water samples [41].
2.2.2[3.2.2] U.V. Irradiation / Chlorine Oxidation of Benzalkonium Chloride

The mixture of U.V. radiation and chlorine oxidation (U.V./chlorine) had been employed
to destroy BAC [42] When it came to BAC degradation, UV/chlorine worked in concert better
than either one alone. Radical quenching tests revealed that both UV photolysis and radical
species oxidation through BAC degradation contributed to the U.V./chlorine degradation of
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BAC, accounting for 48.4% and 51.6% of the degradation, respectively. The dose and pH of
chlorine were critical factors influencing the effectiveness of the UV/chlorine treatmet [43].
Using HPLC-MS/MS, five major intermediates were found, semi-quantified, and a potential
degradation route was suggested. Hydrogen abstraction from the alkyl chain and benzyl-nitrogen
bond breakage were the two processes by which BAC was degraded by UV light and chlorine.
GC-ECD was used to identify trichloromethane (T.C.M.), dichloropropanone (D.C.P.),
dichloroacetonitrile (D.C.A.N.), trichloropropanone (TCP), and chloral hydrate (C.H.). The BAC
solution underwent nearly total detoxification after being exposed to UV/chlorine therapy for
120 minutes, which was more successful than UV irradiation or chlorination alone, according to
the luminescent bacterial test [44].
2.2.3[3.2.3] Oxidation of Benzalkonium Chloride by S2O82−/Fe2+

In their investigation, Hong et al. [45] investigated the S2O82−/Fe2+ process for treating
disinfectant-treated wastewater containing benzalkonium chloride (BAC). A microbial fuel cell
(M.F.C.) system was used as an indirect “biosensor” for the toxicity evaluation of degradation
products. The oxidation conditions under operation were optimized. pH = 5.0 and [S 2O82−]/[Fe2+]
= 1:2 were the ideal conditions for BAC degradation; after 60 minutes, BAC removal efficiency
was 91.45% and COD removal efficiency was 52.46%. Using the M.F.C. system as a biosensor,
the toxicity and biodegradability of BAC intermediates treated by S 2O82−/Fe2+ oxidation were
evaluated (so they may utilize it for monitoring the concentration of BAC degradation as they
have compared both.). The M.F.C. system's produced power was directly correlated with the
BAC concentration [45, 46]. After 100 mg L-1 BAC was treated by S2O82−/Fe2+ oxidation process,
the voltage output and maximum power density rose from 25.42 mV and 1.01 mW/m 2 to 37.80
mV and 12.13 mW/m2, which was caused by the decreased negative impact of BAC on the
microorganism in the M.F.C. According to these findings, the S 2O82−/Fe2+ oxidation improved the
intermediates' capacity to degrade [47].
2.2.4[3.2.4] Biological Removal of BAC

Korya et al. [48] successfully accomplished the complete removal of BAC from
secondary effluent using a packed bed reactor. A bench-scale continuous up-flow reactor
containing BIOMIG1-beads was run for 1.5 months on either synthetic wastewater or secondary
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effluent containing BACs at concentrations between 2 and 20 µM. The range of the empty bed
contact time (EBCT) was 0.6 to 4.7 hours. Remarkably, near-total removal of BAC was
accomplished from both synthetic and real wastewater when the EBCT was 1.2 hours or higher,
even without the need for aeration or effluent recirculation. Upon evaluating the performance of
the reactor at a specific empty bed contact time (EBCT), it was observed that a higher efficiency
in benzalkonium chloride (BAC) removal was achieved when the initial BAC concentration was
lower. This finding can be explained by the fact that fewer BAC molecules enter the reactor at
lower concentrations compared to higher concentrations. As a result, when BAC molecules are
degraded, the reactor's efficiency is increased.
2.2.5[3.2.5] Advanced oxidation processes (AOPs)

Using AOPs, BAC may be broken down by produced very reactive oxygen species, such
as hydroxyl radicals or directly on the surface of electrode. It AOP includes ozone (O3)
treatment, hydrogen peroxide (H2O2) with UV or catalysts, Fenton reaction (Fe 2+ /Fe3+ with
H2O2), and photo-Fenton reaction.
Huang et al. [36] investigated the use of UV/chlorine as an enhanced oxidation technique
to break down benzalkonium chloride. The combination of UV and chlorine exhibited enhanced
degradation of dodecylbenzyldimethylammonium chloride (DDBAC) compared to individual
treatments of UV or chlorination, indicating a synergistic effect. Overall, the combination of
UV/chlorine oxidation exhibited synergistic effects on the degradation of DDBAC. The
chlorination process alone resulted in a modest removal of approximately 7% after 12 minutes.
Similarly, UV irradiation alone led to a moderate degradation of DDBAC, with about 42% being
removed after 12 minutes. However, when DDBAC was subjected to UV/chlorine oxidation, the
removal efficiency significantly improved, reaching 65% after 12 minutes.
Ossian et al. [37] investigated the application of an AOP by combining and using ozone
(O3) and hydrogen peroxide (H2O2) on two BACs, Benzyl dimethyl dodecyl ammonium chloride
(BDDA) and benzyl dimethyl tetradecyl ammonium chloride (BDTA). The purpose of the study
was to evaluate the O3/H2O2 AOP's ability to lessen BAC-related toxicity. 90% of the original
BACs (BDDA: BDTA at a concentration of 50:25 mg L −1) were effectively broken down by the
AOP in 30 minutes using around 1.28 g h−1 of O3 and 200 mg L−1 of H2O2 at pH 11.
23
Yu et al. [38] used both ozone and ozone/UV systems to perform sophisticated oxidation
tests on benzalkonium chloride in aqueous settings. It was investigated how pH (5.0–11.0)
affected the way that O3 and O3/UV treatment broke down DDBAC. After a 20-minute reaction
period, the degradation efficiency improved from 18.6% to 98.2% with O 3 treatment, and the pH
increased from 5.0 to 11.0. On the other hand, at the same pH rise, the O 3/UV treatment only
marginally improved DDBAC degradation (from 92.9% to 99.3%).
[3.2.6] Electrochemical Techniques Removal offor BAC Removal

Electrochemical methods use an electrical current to drive oxidation reactions at an
electrode surface, leading to the degradation of BAC. The electrochemical oxidation of
benzalkonium chloride (BAC) was carried out by Huges et al [49]. This work looked on the
efficient removal of BAC by electrochemical oxidation using a boron doped diamond anode.
Various electrochemical measurements were conducted at different current densities, and it was
observed that 100 mg/L BAC underwent complete removal within a treatment duration of 20
minutes at a current density of 50 mA/cm 2. On the other hand, it took around 90 minutes to lower
the BAC concentration in the reactor to an undetectable level when the current density was set at
10 mA/cm2. However, BAC was not fully mineralized even after two hours of treatment,
according to an investigation of the chemical oxygen demand (COD) data. Given that the
background electrolyte's COD was 8 mg/L, around half of the original BAC was completely
mineralized in the two-hour degradation period.
2.3[3.3] Electrochemical Degradation Process
Electrochemical treatment of wastewater to produce harmless compounds usually referred
to as the anodic Oxidation of the pollutant, is considered a viable treatment option [50]. As a
result, it is classified as an A.O.P. [50].
Understanding the mechanics of electrochemical wastewater treatment has progressed in
recent years. Understanding many kinds of wastewater treatment systems and their workings
requires a detailed investigation. Numerous factors, such as the treatment method employed, the
materials utilized for the electrode, the composition of the electrolyte, and the operating
parameters, affect the kind, nature, and amount of reactive species generated in electrochemical
treatment processes [52]. Electrochemical oxidation is an encouraging process for wastewater
24
treatment because of its ability to efficiently remove various organic and inorganic contaminants.
The process involves applying an electrical current to the wastewater, which initiates
electrochemical reactions at the electrodes, leading to the degradation or transformation of
pollutants. This process is based on the use of two2 electrodes where both oxidation and
reduction could take place. Oxidation of pollutants could be direct where they are oxidized
directly by exchange of electrons at the anode surface or indirect by formation of hydroxyl
radicals, which then oxidize the pollutant.
2.3.1[3.3.1] Advantages of electrochemical oxidation

Compared to alternative other removal techniques, electrochemical oxidation of BAC has
a number of benefits, especially when it comes to wastewater treatment. Targeting certain
substances, such as BAC, electrochemical oxidation has the potential to be extremely selective.
Its effectiveness in removal is aided by its selectivity. It's possible that many traditional
wastewater treatment techniques—like chemical coagulation, biological treatment, and activated
sludge—are not as precise. Their reduced removal effectiveness stems from their reliance on
physical or chemical procedures that might not particularly target BAC. Not only can
electrochemical technologies tackle BAC, but they can also handle a wide range of pollutants
and be tailored to different wastewater matrices. Their adaptability renders them worthwhile in a
variety of industrial environments. Certain treatment techniques might not be as flexible in
handling different kinds of wastewater or would need major modifications in order to be
effective with a particular contamination. The operational parameters of electrochemical
systems, such as pH, potential, and current density, may be precisely controlled. Efficiency can
be increased by optimizing this control to remove BAC specifically. The inability to fully modify
the operational parameters of some conventional procedures might be a disadvantage when
handling particular pollutants. Unlike biological treatments, electrochemical oxidation can
reduce the production of secondary waste products. The process typically converts contaminants
into simpler, less harmful forms, reducing the need for further treatment. Some conventional
treatment methods may produce sludge or other waste byproducts that require additional
handling and disposal measures. While electrochemical methods do require electricity to operate,
advancements in electrode materials and system designs have led to improved energy efficiency.
25
The traditional treatment methods may also consume significant amounts of energy, especially
processes involving aeration, pumping, or chemical reactions. Overall, electrochemical oxidation
stands out as a promising method for the removal of BAC from wastewater due to its excellent
selectivity, high efficiency, versatility in treating various contaminants, adaptability, and
potential for minimizing environmental impact. It works especially well to remove some heavy
metals, emerging contaminants, and persistent organic pollutants from wastewater.
2.3.2[3.3.2] Electrochemical Cell

There have been a few experiments that have combined the electrochemical oxidation
and electro-reduction processes. According to Feng et al [53], the combined approach was more
effective than the oxidative process alone. Most research uses combined oxidation and reduction
experiments in an undivided electrochemical cell. In some instances, it is advantageous to use a
divided cell by introducing a separating membrane when considering both separately oxidation
and reduction [56]. It prevents interference between the electrolytes (analyte and catholyte),
resulting in oxidation and reduction value-added products created in two electrode
compartments and their easier separation [57]
2.3.3[3.3.3] Electrode Selection

Works on using boron-doped-diamond (BDD) [57, 58] and metal oxides like that PbO2
and SnO2 [54, 55], Ti-doped, and Sb-doped Sn0.8W0.2-Ox [59] anodes for electrochemical
purification of wastewater by indirect anodic oxidation have been published. The primary
challenges associated with the different oxide-based anode materials previously discussed are
their long-term stability and the sluggish kinetics of the degradation reaction, which varies
depending on the pollutant. Better anode materials are thus needed for wastewater treatment.
Anodes used in electrochemical wastewater treatment must also possess a high over-potential for
the oxygen evolution reaction (O.E.R.), which is another crucial feature. This unintended
parallel response raises power usage and decreases wastewater treatment process efficiency [60].
Consequently, BDD has been proven to be the ideal anode material for the
electrochemical oxidative treatment of aqueous organic wastes. Due to its additional exceptional
qualities, which include high stability, a broad electrochemical potential window for water
discharge reactions in aqueous and non-aqueous electrolytes, and quick electron transfer rates
26
for soluble redox systems, it has been employed effectively. Therefore, BDD will be used as the
anode in the current project. It should be noted that BDD anodes are expensive and, thus, rarely
used in practice. However, since the current project will focus on the fundamentals of BAC
degradation, and the use of BDD is, thus, justified.
When utilized in wastewater treatment procedures involving electrochemical oxidation,
boron-doped diamond (BDD) electrodes provide a few benefits. The following are the main
benefits of BDD electrodes:
1. Chemical Stability: BDD electrodes have exceptional chemical stability, even under
challenging circumstances. They can be used to treat wastewater that contains aggressive or
corrosive compounds since they are resistant to corrosion and deterioration. Longer
electrode lives and fewer electrode replacements are made possible by this stability.
2. Wide Potential Window: Because of its broad potential window, BDD electrodes may
function at high anodic potentials without experiencing undesirable reactions like
passivation or oxygen evolution. This characteristic makes it possible to effectively oxidize
a variety of pollutants, including inorganic and refractory organic molecules.
[3.] High Oxygen Evolution Potential: Because of its high potential for oxygen evolution,
BDD electrodes can produce reactive oxygen species (ROS) during the electrochemical
oxidation process, including hydroxyl radicals (•OH). These ROS are essential for the
breakdown and effective removal of organic pollutants.
3.[4.] Low Fouling and Maintenance: Because BDD electrodes have minimal fouling
tendencies, impurities or reaction byproducts are less likely to collect on their surface. This
feature makes cleaning and maintenance less frequent, which over time results in more
stable and consistent performance.
4.[5.] Electrochemical Efficiency: Because of their great electrochemical efficiency, BDD
electrodes can transform a sizable amount of electrical energy into beneficial chemical
processes. Because of its efficiency, BDD electrodes are more cost-effective for wastewater
treatment applications than other electrode materials in terms of both energy usage and
operating expenses.
5.[6.] Versatile Application Range: Numerous wastewater sources, including contaminated
groundwater, municipal wastewater, and industrial effluents, can be treated with BDD
27
electrodes. They are excellent in getting rid of a lot of pollutants, such as organic
compounds, phenols, pesticides, medicines, and some heavy metals.
28
3[4] Materials and Methods
3.1[4.1] Chemicals and Reagents
Benzalkonium chloride (BAC, ≥ 95%) was purchased from Sigma-Aldrich (Lot No.
BCCD7515). The stock solution of BAC with concentration of 10,000 mg/L was prepared by
diluting BAC in MilliQ water, and the working solution of 400 mg/L of BAC was produced by
diluting the stock solution in MilliQ water. Sodium sulfate (Na 2SO4, ≥ 99%, Anhydrous, Fisher
Scientific) was used to prepare a 0.5 M Na 2SO4 electrolyte by dissolving the salt in MilliQ water.
Sodium thiosulfate (Na2S2O3, ≥ 98%, Sigma-Aldrich) was prepared in concentration of 250 μg/L
using MilliQ water to quench OH radicals. Sulfuric acid (H2SO4, ≥ 95%, Fisher Scientific) was
used in selected experiments in concentration of 0.5M. Isopropanol (C 3H8O, ≥ 99.9%, Fisher
Scientific) and tert-butanol ((CH3)3COH, ≥ 99%, Sigma-Aldrich) were used as OH- radicals’
scavengers in selected experiments in a 3:1 molar ratio with BAC.
3.2[4.2] Electrochemical Cell Setup

Two electrochemical setups were used throughout this research. One was an undivided cell
that is presented in Figure 3, and the other wais a divided cell that is presented in Figure 4.
Electrochemical degradation experiments were mostly performed in an undivided
electrochemical cell, unless specified otherwise.
Figure 3 undivided cell setup.
29
Figure 4 divided cell setup.
In the undivided cell, a commercial BDD was used as the anode. The size of the electrode
was 5cm×5cm 25 cm2 but 22.5 cm2 was exposed to the electrolyte, while a larger stainless steel
316 L electrode was used as a cathode (??? cm2). The cell contained 160 mL of the electrolyte
containing 400 mg/L BAC in and 0.5M Na2SO4 dissolved in milliQ water. In addition, during
some experiments, two reference electrodes (RE) were introduced and the potential of each of
the electrodes vs. RE was measured, as well as the total cell potential. For selected experiments,
two2 different commercial dimensionally-stable anodes (DSAs) were employed instead of BDD.
One of them was pure a coating of RuO2 on a Ti substrate, and the other was the a coating of
88mol.% of RuO2 and 12mol.% of IrO2 on a Ti substrate, both coatings having that had a
thickness of 10 μm.
Selected experiments were performed in a divided cell and the purpose of theatse was to
monitor BAC oxidation and reduction reactions separately and investigate if BAC could not only
be oxidized, which is claimed in literature, but also reduced on the stainless-steel cathode. In this
setup, BDD was used as anode with 22.5 cm2 exposed to electrolyte and 316 L stainless-steel
30
was used as cathode (??? cm2). Each cell contained 160 mL of the same electrolyte composition
of 400 mg/L BAC and in 0.5M Na2SO4 dissolved in milliQ water, resulting in total volume of
320 mL.
In all the experiments, a thermometer has wabeen used to measure the temperature
throughout the process and the total cell voltage was also recorded. Also, a stir bar (magnetic
bar) has beenwas used and the solution was continuously stirred at 300 rpm.
3.3[4.3] BAC Degradation Experiment

Once the cell was assembled, 160 mL of the electrolyte containing 400 mg/L BAC and 0.5
M Na2SO4 was placed in each cell and the treatment was started immediately by applying a
specific current density using B&K Precision 1760A power supply. 1 mL of samples were
collected from the cell at various time intervals for a period of 2 hours and diluted with 1 mL of
0.5 M Na2SO4. Then, 2 microliters of sodium thiosulfate were added to quench OH- radicals that
might be present in solution and prevent BAC from further degradation. AfterSubsequently, all
the samples were analyzed using UV-Visible spectroscopy (Thermo Scientific Evolution 220
UV-Visible Spectrometer) to determine the concentration of BACfor the adsorption results. A
calibration curve for each experimental run of experiment was produced in order to get the final
concentration of BAC. At the time of sampling, the total cell potential (difference between the
potential of BDD and 316 L S.S.) was recorded, as well as the temperature of the electrolyte.
3.3.1[4.3.1] BAC Degradation Analysis

The concentration of BAC was monitored using UV-Visible spectroscopy. The light
absorption spectrum of the BAC solution was measured in the range of 200 nm - 400 nm
wavelength, in a quartz cuvette with an optical path of 1 cm length to get their absorbance. The
blank (reference solution) used for this method was 0.5 M Na 2SO4 solution. The calibration
curve was done using the electrolyte (400 mg/L BAC and in 0.5 M Na2SO4) and then dilutinged
it further with the addition of 0.5 M Na 2SO4 comprising a concentration range from 5 mg/L to
400 mg/L and the absorption data was collected. The data was plotted as absorption versus BAC
concentration values (Figure 5). This data was used to calculate the value of error (R 2) and get
the equation of the linear line to use for calculation of BAC concentration. An example of the
resulting linear graph of BAC concentration vs. absorption is shown in Figure 5.
31
0.5
0.45
f(x) = 0.00111592927597921 x + 0.00174679736422054
R² = 0.999677018622926
0.4
0.35
0.3
Absorbance
0.25
0.2
0.15
0.1
0.05
0
0 50 100 150 200 250 300 350 400 450
Concentration, mg/L
Figure 5 Calibration Curve for BAC concentration vs. absorption for solution of 400 mg/L BAC and 0.5 M Na2SO4 done by UV-
Visible spectroscopy.
All the measurements were repeated three3 times to obtain acceptable reliable results.
Another important factor for all experiments was the limit of detection. Our LOD for UV-Visible
was 5 mg/L; consequently, so on all the graphs presented further in the thesis, all the
concentrations that are shown as zero, are actually those not actually zero but since they are
below the LOD, we changed them all to zero. Also, the concentrations that are below LOD are
not reliable.
3.3.2[4.3.2] Chemical Oxygen Demand Analysis
The chemical oxygen demand (COD) is a measure of the organic content in a water sample,
and it provides an indication of the overall organic pollutant concentration. The chemical oxygen
demand (COD) was evaluated by following the standard method provided by CHEMetrics using
32
a Hach DRB 200 COD Reactor and Hach DREL/2400 Spectrophotometer with LR COD vials
from CHEMetrics.
33
4[5] Results and Discussion
BAC degradation using a BDD anode and stainless-steel cathode was investigated under
various experimental conditions such as current density, temperature, and pH of the electrolyte.
Two different cell setups, divided and undivided, were tested. In addition to BDD, two additional
metal-oxide-based anode materials were tested, and the mechanism of BAC removal (direct vs.
hydroxyl-radicals mediated) was determined using OH radicals scavengers.
4.1[5.1] Control Experiments

BAC can be adsorbed on the surface of electrochemical cell or electrodes. In order to
investigate how much of BAC was removed by adsorption on the walls of electrochemical cell,
the control experiments at concentration of 400 mg/L of BAC was performed. The setup and
chemicals used are the same as in regular BAC electrochemical degradation experiments, but no
current flew through the system. The results are presented in Figure 6.
Control Experiment, 400 mg/L BAC

1.02
0.98
0.96
C/C0
0.94
0.92
0.9
0 20 40 60 80 100 120 140
Time, min
Figure 6 BAC control experiments, Adsorption Experiments are done without any current flow through the system. 3 runs of this
experiment have been done. Error bars are standard deviation. The y-axis of this graph is zoomed in.
34
It can be seen that there is a very minor removal of BAC from the liquid phase by
adsorption, i.e. 0.5%. As it will be shown later, this is indeed a negligible amount of BAC
removed, compared to the amount of BAC removed by electrochemistry.
Since samples for analysis during the BAC degradation test were collected at different
time intervals, and then analyzed, it was necessary to determine the stability of BAC in the
original and electrochemistry-treated solutions, and the results are shown in Figure 7.
400 mg/L BAC t=0 min, 200 mg/L BAC t=60 min
450
400
350
300
Concentration, mg/L
250
200
150
100
50
0
0 2 4 6 8 10 12
Time, Day
Figure 7 Stability tTests over a period of 10 days on undegraded BAC, diluted BAC, and a degraded BAC sample at current
density of 100 mA/cm^2
As it can be seen in the figure, regardless of the initial concentration of BAC, before and
during degradation, BAC appears to be stable over time, even in the possible presence of other
degradation products.
The two above-presented control experiments demonstrate that no significant removal of
BAC is done through its adsorption on the electrochemical cell walls, and that BAC is a stable
35
molecule and its presence in the sample can be determined even after 10 days (possibly even
after longer time, but this was not investigated).
Next, a control experiment was done to investigate the influence of temperature on the
electrochemical BAC removal. Namely, one BAC experiment was done by degrading it
without controlling the electrolyte temperature, while the other one was done by keeping
the electrolyte temperature constant, at 60oC. However, in the first experiment, the
temperature significantly increased with time, as shown in Figure 8.
60.0
50.0
Temperature, Degrees Celsius
40.0
30.0
20.0
10.0
0.0
0 20 40 60 80 100 120 140
Time, min
Figure 8 Temperature profile for BAC degradation at current density of 100 mA/cm2
36
Nevertheless, the BAC degradation results in Figure 9 show that the two trends
overlap (at this point, the trend of the two curves will not be commended - this will be
done shortly), indicating that the way the two experiments were performed (without and
with temperature control) does not influence the outcome. Consequently, all further
experiments were performed without temperature control (also, as it will be shown later, at
lower current densities, the rise in temperature with time is smaller).
No Temperature Control Temperature Control

1.2
0.8
0.6
C/C0
0.4
0.2
0
0 20 40 60 80 100 120 140
Time, min
Figure 9 The influence of temperature on rate of BAC degradation at 100 mA/cm2, 3 runs of these experiments have been done.
Error bars are standard deviation.
4.2[5.2] Impact of Current Density on Rate and Extent of BAC Degradation

As it is commonly known, the rate and extend of electrochemical removal of organic
compounds found in wastewaters depends on the current density. To investigate the influence of
current density on the BAC removal rate and extent, a range of experiments were done between
5 to 150 mA/cm2, and the results are shown in Figure 10.
37
5 mA/cm^2 10 mA/cm^2 15 mA/cm^2
20 mA/cm^2 30 mA/cm^2 50 mA/cm^2
75 mA/cm^2 100 mA/cm^2 150 mA/cm^2
1
0.9
0.8
0.7
0.6
0.5
C/C0
0.4
0.3
0.2
0.1
0
0 20 40 60 80 100 120 140
Time, min
Figure 10 Impact of current density on BAC degradation during 2 hours of experiment, 3 runs of experiment for each current
density have been done and each graph shows the average of 3 runs. Error bars are standard deviation.
In general, with the increase in current density, the rate of degradation increases. Initially,
the BAC concentration drops sharply, followed by a “plateau”, noticeable at all current densities,
and then the BAC concentration gradually continues to decrease. At 5 and 10 mA/cm 2, the
percentage of non-degraded BAC after 2 hours of degradation was ca. 31 and 13%, respectively,
while at higher current densities it dropped below the level of detection (shown as “zero” in the
graph). Also, the higher current densities i.e., 100 and 150 mA/cm 2 showed the higher
degradation kinetics. However, the optimum current density was determined to be 100 mA/cm 2,
since increasing current density beyond value did not have any significant impact.
As seen in the previous figure, with increase in current density, the BAC degradation
extent increases, however, the drawback of that could be that the current efficiency of the
process decreases because part of the charge could be used to increase the rate of parallel
processes like oxygen evolution at the anode and hydrogen reduction at the cathode. In order to
38
investigate the current efficiency for BAC degradation, we normalized the results presented in
Figure 10 and presented them in terms of relative BAC concentration vs. charge in Figure 11. It
should be noted that if the current efficiency does not change, all the curves should overlap.
5 10 15 20 30
50 75 100 150
1
0.9 a
0.8
0.7
0.6
0.5
C/C0
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000 1200
Charge, C
39
5 10 15 20 30
1 50 75 100 150
0.9
b
0.8
0.7
0.6
0.5
C/C0
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60 70 80 90 100
Charge, C
5 10 15 20 30 50 75 100 150
1
0.9
0.8
c
0.7
0.6
0.5
C/C0
0.4
0.3
0.2
0.1
0
0 20 40 60 80 100 120 140 160 180 200
Charge, C
40
300
d
250
charge needed for complete removal, C
200
150
100
50
0
5 10 15 20 30 50 75 100 150
Current Density, mA/cm^2
Figure 11 (a) Impact of charge current density on its efficiency on for BAC degradation presented as the extent of BAC
degradation on the charge passed through the cell (a) relative BAC concentration vs. Charge trend for 2 hours, . (b) and (c) are
zoomed-in portions of plot (a), ). (d) represents the charge needed to reach zero BAC concentration.
As summarized in Figure 11(d), with an increase in current density, the charge needed to
degrade BAC to zero (i.e. below the LOD) increases. This indicates that the current efficiency
decreases with the increase in current density, which is due to the increase in rate of oxygen
evolution reaction (OER) at the BDD electrode, and, as it will be shown later, due to the increase
in hydrogen evolution reaction (HER) rate at the 316L SS cathode, both competing with the
BAC degradation reaction. After reaching 50 mA/cm2, the current efficiency remains relatively
constant, indicating that the fractions of current used for the BAC degradation and OER and
HER remained constant. Thus, from the practical (energy input) point of view, 50 mA/cm 2 would
be the optimum current density for BAC degradation, but as presented in Figure 10, from the
kinetic point of view it is 100 mA/cm2.
41
Based on the results, up to 50 mA/cm2, the higher the current density, the lower the
efficiency, so it means that more current goes to oxygen evolution reaction. As a result, it takes
more of total charge to degrade BAC.
[5.3] Impact of Current Density on Temperature and Voltage

It was shown in Figures 8 and 9 that the kinetics of BAC degradation is not temperature-
dependent, under the experimental conditions investigated. However, the variation of
temperature during the BAC degradation process is important since it influences the electrolyte
conductivity, and thus, ultimately, power consumption. The dependence of temperature and cell
voltage on the current density employed during the BAC degradation process (Figure 10) is
presented in Figures 12 and 13.
t=0 t=2 t=5 t=10 t=20 t=30 t=40 t=60 t=90 t=120
70
60
50
40
Temperature
30
20
10
0
0 20 40 60 80 100 120 140 160
Current, mA/cm2
Figure 12 Impact of current density on temperature during the degradation of BAC.
42
From Figure 12 it can be observed that with the increase in current density the
temperature increases by a larger extent and at a higher rate. This is due to the Joule heating
effect. Joule heating occurs when electrical current passes through a resistive material, such as
the electrolyte solution or electrodes in the cell. The resistive material dissipates electrical energy
in the form of heat, leading to a temperature rise. When a higher current density is applied in the
electrochemical cell, more electrical energy is being converted to heat. This increased heat
generation can cause the temperature to rise. We can conclude that at low current density,
temperature increase is negligible, however as the current density increases, temperature also
increases because of the resistance of electrolyte.
Apart from temperature measurements, we also measured total cell voltage during the
experiments and the results are shown in Figure 13.
t=0 t=2 t=5 t=10 t=20 t=30 t=40 t=60 t=90 t=120
16
14
12
10
Voltage, V
0
0 20 40 60 80 100 120 140 160
Current, mA/cm2
Figure 13 Impact of current density on cell voltage recorded during BAC degradation.
43
It can be seen see that as the current density increases, the cell voltage increases too,
following the Ohm law. The slope of each of the curves that is shown in Figure 13 is the
resistance, which is in this case the sum of internal (electrolyte, redox kinetics) and external
(wires) resistances, the latter being relatively negligible the corresponding resistance values are
presented in Figure 14.
0.07
0.06
0.05
Resistance, Ohm cm2
0.04
0.03
0.02
0.01
0
0 20 40 60 80 100 120 140
Time, min
Figure 14 Cell Resistance vs. Time obtained from the slopes in Figure 13
With time the slope decreases, indicating that the resistance decreases, which is due to the
increase in mobility of ions with temperature (Figure 11). However, at higher current densities
and longer times, the trend deviates from linearity, which is due to the large increase in
temperature of the electrolyte. This increases the mobility of ions at higher temperatures, thus,
resistance decreases.
44
4.3[5.4] Impact of Different Anode Materials on BAC Degradation
All the previous results shown used BDD as the anode electrode material, which is known
as the best (state-of-the-art) anode material; however, it is also the most expensive one. In order
to investigate if other more cost-effective electrode materials, which are commonly used in
electrochemical industry, could be used for the BAC degradation, we employed additional two
different anode materials, one being pure RuO 2 and the other being the mixture of Ru and Ir
oxides coatings on Ti plate. The corresponding results are presented in Figure 15.
RuO2 on Ti Plate Anode IrRuOx on Ti Plate Anode BDD
0.9
0.8
0.7
0.6
0.5
C/C0
0.4
0.3
0.2
0.1
0
0 20 40 60 80 100 120 140
Time, min
Figure 15 BAC degradation using 3 different anodes at a current density of 50 mA/cm2. 3 runs of each experiment have been
done. Error bars are standard deviation.
As it could be seen from the figure, both oxide electrodes degrade BAC, but the process is
very slow compared to BDD. After two hours of degradation, RuO 2 and IrRuOx degraded around
11% and 15% of BAC respectively, but BDD degraded BAC completely in around 100 minutes.
The reason for this is because most of the current passing through the cell when the two metal-
45
oxide electrodes are used, is used to produce oxygen, mainly because both Ir and RuO 2
electrodes are well-known oxygen evolution catalysts, while BDD has a very large overpotential
for oxygen evolution, enabling (current) efficient BAC degradation.
4.4[5.5] Comparison of Divided and Undivided Cell on BAC Degradation

In all the previous experiments, we used the undivided cell since it is reported in the
literature that BAC is mostly oxidized. However, to investigate if BAC could be degraded by
reduction, we did the measurements in a divided cell in which we can monitor the oxidation of
BAC on BDD and its reduction on stainless steel separately/independently. These experiments
were performed at 15 mA/cm2, and the results are shown in Figure 16.
Oxidation Reduction
1.2
0.8
0.6
C/C0
0.4
0.2
0
0 20 40 60 80 100 120 140
Time, min
Figure 16 BAC degradation using a divided cell at current density of 15 mA/cm2. 3 runs of this experiment have been done.
Error bars are standard deviation.
46
As the graph shows, indeed part of BAC could also be removed by reduction; however,
BAC oxidation is much more efficient and kinetically faster. After 120 minutes, 98% of BAC
was oxidized, but during the same time only 23% of BAC is reduced. Therefore, the result in
Figure 16 clearly shows that BAC is degraded predominantly by oxidation, but its reduction
should not be dismissed as mechanism of its degradation, under the experimental conditions
employed.
In order to see if in the divided cell the amount (number of moles) of BAC degraded by
reduction and oxidation sums up to give the total number of moles degraded in the undivided
cell, we compare the two trends in Figure 17.
Divided Cell Undivided Cell
1.2
0.8
Nt/N0
0.6
0.4
0.2
0
0 20 40 60 80 100 120 140
Time, min
Figure 17 Comparison of number of moles of BAC degraded in divided and undivided cell at 15 mA/cm2. 3 runs of each
experiment have been done. Error bars are standard deviation.
47
As it can be seen, the amount of BAC degraded in the undivided cell is significantly larger
compared to that one degraded in the divided cell. We currently do not know the origin of this
behavior and is something to be investigated later.
5.7 COD Analysis

The previous experiments show that in the undivided cell, electrochemical treatment of
BAC can reduce its concentration to below the detection limit. However, it is most likely that
during this process, under the experimental conditions employed. transformation products are
formed. In order to see how much of BAC was completely mineralized, chemical oxygen
demand (COD) experiments were performed, and the results are presented in Figure 18.
15 mA/cm^2 100 mA/cm^2

250
200
150
COD, mg/L
100
50
0
0 20 40 60 80 100 120 140 160 180 200
Time, min
Figure 18 Chemical Oxygen Demand Analysis of BAC experimental samples as a function of time. 3 runs of each experiment
have been done. Error bars are upper/lower deviation from the average.
As seen in Figure 18, for both current densities, there is a general trend of decreasing COD
values over time. However, the higher current density (100 mA/cm²) leads to a faster COD
48
decrease and to a larger extent of its decrease compared to the lower current density (15
mA/cm²). Looking in the COD decrease trend at 100 mA/cm 2 after two hours of degradation, it
might be hypothesized that if the experiment continued past three hours, the COD would have
decreased to close to zero; however, this will be investigated in the future to confirm the
hypothesis. In conclusion, the results in Figure 18 indicate that the electrochemical process is
effective in reducing the organic content of the solution. However, these results show that
although BAC is completely degraded, it is not completely mineralized.
5.8 Impact of pH on BAC Degradation

All the previous results presented were done in neutral pH. In order to see if kinetics of
BAC degradation changes in acidic medium, we did the measurements in the 0.5 M H 2SO4, and
the results are presented in Figure 19, together with the trend in the neutral solution.
Neutral Acidic
1.2
0.8
0.6
C/C0
0.4
0.2
0
0 20 40 60 80 100 120 140
Time, min
Figure 19 Comparison of BAC degradation in the absence and presence of 0.5 M H2 SO4 at 100 mA/cm2. 3 runs of each
experiment have been done. Error bars are standard deviation.
49
The plot demonstrates that the kinetics of BAC degradation appears to be approximately
similar in both neutral and acidic mediums, so the pH does not appear to have any effect on the
kinetics of BAC degradation, under the experimental conditions employed.
5.9 Impact of OH-radical Scavengers on BAC Degradation

BDD is a well-known anode for generation of hydroxyl radicals which are very strong
oxidants for degradation of many pollutants. In order to investigate if BAC is degraded by OH-
radicals or directly on the electrode surface, we did the BAC degradation measurements in the
absence and presence of two different hydroxyl radical scavengers, isopropanol, and tert-butanol
in the molar ratio of 3:1 with BAC and the results are presented in Figure 20.
Without Scavenger isopropanol Tert Butanol
1.2
0.8
0.6
C/C0
0.4
0.2
0
0 20 40 60 80 100 120 140
Time, min
Figure 20 Degradation of BAC at 100 mA/cm2 in the absence and presence of two different OH-radical scavengers. 3 runs of
each experiment have been done. Error bars are standard deviation.
50
Based on the results in Figure 20, since the three graphs overlap, we can say that BAC is
most probably directly degraded on the surface of the electrodes, rather than by OH-radicals.
6 Conclusion
In this research project, we investigated the electrochemical degradation of benzalkonium
chloride (BAC) using a Boron-Doped Diamond (BDD) anode and stainless-steel cathode. The
results obtained provide valuable insights into the feasibility and effectiveness of this process for
the removal of BAC from aqueous solutions.
The degradation efficiency of BAC was found to be highly dependent on the current density.
The highest removal percentage of BAC was achieved at an applied potential of 100 and 150
mA/cm2, indicating that the electrochemical degradation process is highly sensitive to this
parameter. Moreover, as the current density increases the temperature also increases. As current
density increases, the resistance in the cell increases, resulting in more heat being generated.
Same behavior is observed for voltage.
The RuO2 anode showed less degradation of BAC (11.26 %) than IrRuOx (15.33%) after
120 minutes, while BDD shows complete removal of BAC in around 100 minutes at 15 mA/cm 2.
In an undivided cell, degradation occurred faster than a divided cell.
In general, the data indicated that higher current density, specifically increasing it from 15
mA/cm2 to 100 mA/cm2, amplifies the electrochemical degradation of BAC. This, in turn, leads
to a more significant reduction in COD values, hence mineralization of BAC. Additionally, in
0.5 M H2SO4 and at 100 mA/cm2, the degradation was achieved very fast, in 30 minutes.
However, the degradation kinetics was somehow similar in neutral and acidic mediums.
BAC degradation was achieved in 40 minutes at constant temperature of 60 oC and 100
mA/cm2. However, the results of variable and constant temperatures overlap, so we decided to
proceed with all the experiments without temperature control. Thus, these conditions were most
suitable for efficient BAC degradation.
51
The findings of this study have significant implications for practical applications,
particularly in the field of wastewater treatment and disinfection. The electrochemical
degradation of BAC using a BDD anode and stainless-steel cathode offers a sustainable and
efficient approach for the removal of this commonly used disinfectant and surfactant. It is crucial
to remember, nonetheless, that more study is required in order to maximize the process
parameters and investigate viable scale-up tactics for practical uses.
In summary, this work shows the potential of the BDD electrode as a useful instrument for
the extraction of benzalkonium chloride from aqueous solutions and makes significant
contributions to the field of electrochemical degradation of organic contaminants. The
knowledge gathered from this study opens the door for more research to improve the procedure
and make it applicable to a wider variety of pollutants.
52
7 Appendix
It is possible to access the accuracy and precision of the measurements by employing
numerous calibrating curve working solutions. Figure 20 shows 3 different calibration curves
done with 3 electrolytes with the same concentration and composition that are 400 mg/L BAC
and 0.5 M Na2SO4.
0.25
f(x) = 0.00115036797173977 x − 0.00149013835737416

R² = 0.999539288660466
0.2 f(x) = 0.00104372485526445 x + 0.00295849278775391
R² = 0.997265911210609
f(x) = 0.000968050240408203 x + 0.00235707977627319
R² = 0.999481206146531
0.15
Absorbance
0.1
0.05
0
0 50 100 150 200 250
Concentration, mg/L
Figure 21 Comparison of different calibration curves done with 3 electrolytes with the same concentration and composition.
All three electrolytes show a positive linear correlation between concentration and
absorbance. Using different working solutions for calibration curves helps assess the accuracy,
53
precision, instrument performance, and method validity. It allows for sample-specific calibration,
enhancing the reliability and comparability of the results obtained in subsequent experiments.
The comparison of the calibration curves reveals differences in sensitivity and baseline response
among the three electrolytes. Electrolyte 3 exhibits the highest sensitivity with a larger slope,
while electrolyte 2 and electrolyte 1 have lower sensitivities, so I decided to do a calibration
curve for each run of experiment (for each electrolyte used for each specific experiment), so that
the corresponding results are accurate and reliable.
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Thesis Forough Saffari 3 SO3

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Electrochemical Degradation of Benzalkonium Chloride (BAC)

A thesis submitted to McGill University in partial fulfillment of the requirements of

Montréal, Québec, Canada

their support and guidance throughout my project.

everything that you have done for me.

the lab was such a relief.

McGill University. Your aid has been instrumental for my success.

3 Background and Literature Review 12

4 Materials and Methods 26

5 Results and Discussion 30

Figure 1 Sources of BAC contributing to its release in water bodies [9]

BAC is typically found in the form of a colorless to pale-yellow liquid or solid,

● Bioaccumulation and Biomagnification: Bacteria can bioaccumulate in living things'

● Disruption of Microbial Communities: In aquatic settings, BAC may upset microbial

● Impact on Microbial Communities: Beneficial bacteria in wastewater treatment

● Effects on Non-Aquatic Organisms: Although BAC is mostly utilized in aquatic

8. Ecotoxicity to Non-Target Species:

9. Disruption of Microbial Communities:

10. Antibiotic Resistance:

11. Environmental Persistence:

12. Disinfection Byproducts:

2.1.1[3.1.1] Antimicrobial Tolerance and Resistance Effect of Benzalkonium Chloride

2.1.2[3.1.2] Toxicity Effect of Benzalkonium Chloride on Living Organisms

2.1.3[3.1.3] Effects of Benzalkonium Chloride on the Natural Environment

Pseudomonas putida - 6.0 mg/L [62]

Caenorhabditis elegans 3.1 mg/L - [63]

Vibrio fischeri - 0.5 mg/L [62]

Ceriodaphina dubia 403.7 µg/L [64]

Nitrosomonas - 221 mg/kg [65]

Daphina magna 38.2 µg/L - [64]

*All values are taken from references

2.2[3.2] Methods for Removal of BAC

2.2.1[3.2.1] Ozonation of Benzalkonium Chloride

2.2.2[3.2.2] U.V. Irradiation / Chlorine Oxidation of Benzalkonium Chloride

2.2.3[3.2.3] Oxidation of Benzalkonium Chloride by S2O82−/Fe2+

2.2.4[3.2.4] Biological Removal of BAC

2.2.5[3.2.5] Advanced oxidation processes (AOPs)

[3.2.6] Electrochemical Techniques Removal offor BAC Removal

2.3.1[3.3.1] Advantages of electrochemical oxidation

2.3.2[3.3.2] Electrochemical Cell

2.3.3[3.3.3] Electrode Selection

3.2[4.2] Electrochemical Cell Setup

Figure 3 undivided cell setup.

3.3[4.3] BAC Degradation Experiment

3.3.1[4.3.1] BAC Degradation Analysis

3.3.2[4.3.2] Chemical Oxygen Demand Analysis

4.1[5.1] Control Experiments

Control Experiment, 400 mg/L BAC

No Temperature Control Temperature Control

4.2[5.2] Impact of Current Density on Rate and Extent of BAC Degradation

Current Density, mA/cm^2

[5.3] Impact of Current Density on Temperature and Voltage

Figure 12 Impact of current density on temperature during the degradation of BAC.

RuO2 on Ti Plate Anode IrRuOx on Ti Plate Anode BDD

4.4[5.5] Comparison of Divided and Undivided Cell on BAC Degradation

Divided Cell Undivided Cell

5.7 COD Analysis

15 mA/cm^2 100 mA/cm^2

5.8 Impact of pH on BAC Degradation

5.9 Impact of OH-radical Scavengers on BAC Degradation

Without Scavenger isopropanol Tert Butanol

f(x) = 0.00115036797173977 x − 0.00149013835737416

vol. 37, no. 7, pp. 1443-1467, 2003.