journal of environmental sciences 147 (2025) 688–713

Available online at www.sciencedirect.com

www.elsevier.com/locate/jes

A review on reactive oxygen species-induced

mechanism pathways of pharmaceutical waste
degradation: Acetaminophen as a drug waste
model

Saba Humayun 1,2, Maan Hayyan 3,∗, Yatimah Alias 1,2,∗

1 Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
2 Universityof Malaya Centre for Ionic Liquids, University of Malaya, Kuala Lumpur 50603, Malaysia
3 Chemical Engineering Program, Faculty of Engineering and Technology, Muscat University, Muscat P.C.130, Oman

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

Article history: Innately designed to induce physiological changes, pharmaceuticals are foreknowingly haz-
Received 4 August 2023 ardous to the ecosystem. Advanced oxidation processes (AOPs) are recognized as a set of
Revised 22 November 2023 contemporary and highly efficient methods being used as a contrivance for the removal of
Accepted 22 November 2023 pharmaceutical residues. Since reactive oxygen species (ROS) are formed in these processes
Available online 4 December 2023 to interact and contribute directly toward the oxidation of target contaminant(s), a profound
insight regarding the mechanisms of ROS leading to the degradation of pharmaceuticals
Keywords: is fundamentally significant. The conceptualization of some specific reaction mechanisms
Wastewater treatment allows the design of an effective and safe degradation process that can empirically reduce
Ionic liquid the environmental impact of the micropollutants. This review mainly deliberates the mech-
Hydroxyl radical anistic reaction pathways for ROS-mediated degradation of pharmaceuticals often leading
Superoxide to complete mineralization, with a focus on acetaminophen as a drug waste model.
Pharmaceutical contaminant © 2024 The Research Center for Eco-Environmental Sciences, Chinese Academy of
Advanced oxidation process Sciences. Published by Elsevier B.V.
Deep eutectic solvent
Hydrogen peroxide

nential growth in the last two decades. According to an es-

Introduction
The degree of upsurge in the manufacture and diversifi-
cation of pharmaceuticals outpaced one of the most early
and eminent drivers of global environmental shifts, such
as the rise in the concentration of atmospheric CO2 , loss
of biodiversity, nutrient contamination, habitat damage, etc.
(Bernhardt et al., 2017). Pharmaceuticals in the environment
as a transdisciplinary field of research have manifested expo-
timation (Council, 2018), in the United States approximately
one-third of the number of prescription items (around four
billion) turn into annual waste. The evolution and advance-
ment of the pharmaceutical industry and modern medicine
have ensued undisputed benefits in enhancing the well-being
of the masses by increasing the health span and providing
remedies to many fatal ailments.
A global threat to the ecosystem and human health is
posed by pollution caused by pharmaceutical waste. In the

∗
Corresponding authors.
E-mails: maan_hayyan@yahoo.com (M. Hayyan), yatimah70@um.edu.my (Y. Alias).

https://doi.org/10.1016/j.jes.2023.11.021
1001-0742/© 2024 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
 journal of environmental sciences 147 (2025) 688–713
1990s, the detection of estrogen in sewage discharge was
found to be a cause of alteration of sex functions of a
species of fish, which prompted curiosity in apprehending
how drug substances make their way to the environment
(Larsson, 2014). It was reported in a study that about 85 per-
cent of male smallmouth bass collected from North-eastern
U.S. had eggs growing in male testes, suggesting some sort
of hormonal disarray (Iwanowicz et al., 2016). This led to the
evaluation of the latent threats posed to the quality of water
from endocrine-disrupting compounds (EDCs) (Bhandari et al.,
2015; Blazer et al., 2007), as contemporary research specifies
that exposure to pharmaceuticals through drinking water can
also affect the human reproductive system, particularly in
males (Schreiber et al., 2011; Westerling, 2013).
A potential environmental hazard has been posed by the
pharmaceutical waste originating from an estimated 10%
of such products according to the German Environment
Agency (UBA) (Küster and Adler, 2014). Since a distinct in-
crease in the apprehension regarding the repercussions aris-
ing from pharmaceuticals polluting our environment is evi-
dent (Donnachie et al., 2016), it is also found that an enor-
mous number of pharmaceuticals have not been gauged for
their occurrence, toxicity, or fate in the environment, there-
fore making it even more challenging to generalize the harm
they might contribute to. Many researchers have put emphasis
on the dearth of knowledge concerning the effects of low-level
exposure of pharmaceutical mixtures in the environment.
Pharmaceuticals that target the endocrine system could
epitomize the excessive environmental influence and risk as
demonstrated in a recent investigation (Gunnarsson et al.,
2019). The release of hormones such as synthetic oestro-
gen ethinylestradiol (EE2) and progestin levonorgestrel (LNG),
might also have inadvertent adverse effects on humans by
way of exposure through drinking water as well as food.
Oestrogens are known to induce increased risk of breast
cancer in women (Moore et al., 2016) and prostate cancer
in men (Nelles et al., 2011). Pregnant women, fetuses and
neonates are exceptionally threatened by a continuous sub-
jection to endocrine disruptors even if the concentrations are
low. Several potential diseases associated to endocrine dis-
rupting chemicals (EDCs) include those correlated to such
systems as reproductive and endocrine (infertility, early pu-
berty, diabetes, breast or prostate cancer), immune and au-
toimmune, cardiopulmonary (heart disease or asthma), and
nervous systems (Parkinson’s disease, Alzheimer’s disease,
and ADHD) (Bergmanet al., 2013). Moreover, antimicrobial re-
sistance (AMR) is well-recognized as a phenomenon that is
posing severe risks to global health and livelihoods. Freshwa-
ter ecosystems turn out to be an ideal site for the acquire-
ment and outspread of AMR owing to the continual pollution
caused by antimicrobial and antibacterial compounds ema-
nating from anthropogenic activities.
Acetaminophen (ACT) has been selected as a drug waste
model for this study because it is one of the most acclaimed
APIs known for its ubiquitousness as a pharmaceutical con-
taminant. Published in 2022, a global study on API pollu-
tion in 258 of the world’s rivers represented the environmen-
tal influence of 471.4 million people across 137 geographic
regions (Wilkinson et al., 2022), in which samples were ac-
689
quired from 1052 locations in 104 countries appearing from all
continents, analyzing 61 different APIs. This elaborate work
reported that of the four APIs, acetaminophen/paracetamol
was the most frequently encountered, and the only over-the-
counter analgesic that has been detected across all conti-
nents (the other three being stimulant or lifestyle compounds
were caffeine, nicotine, and cotinine). Moreover, 14 APIs
were also additionally detected as contaminants in all con-
tinents except Antarctica. These compounds along with their
pharmaceutical class and chemical structure are enlisted in
Appendix A Table S1.
Oxidation processes taking place in ecological compart-
ments are one of the many natural ways to revive nutrients
and purify water by removing contaminants. Among other
treatments, the oxidation processes in engineered systems
are used as well to remove chemical pollutants and for wa-
ter purification (Connors et al., 1986; Johnson, 1988). Oxidation
reactions signify an important degradation pathway for phar-
maceuticals, and organic substances in general. Advanced ox-
idation processes (AOPs) are currently celebrated to assert an
ever-increasing implementation for green remediation of wa-
ter polluted with recalcitrant compounds, which are not easy
to remove using conventional techniques. AOPs are surmised
as viable technologies contributing to the degradation of phar-
maceutical contaminants through the in-situ formation of re-
active oxygen species (ROS) acting as strong oxidants (He et al.,
2011; Yang et al., 2013). ROS concern free radicals, e.g., hy-
droxyl radical (● OH), hydroperoxyl radical (HO2 ● ), superoxide
radical anion (O2 ●− ), sulfate radical (SO4 ●− ), as well as non-
radical species (Wang et al., 2011), for e.g., singlet oxygen (1 O2 )
and hydrogen peroxide (H2 O2 ).
The degradation of pharmaceutical waste by ROS can
involve a complex interplay of several mechanisms, such as
oxidation, reduction, radical formation, catalytic or enzymatic
degradation, and photochemical reactions (Ao et al., 2023;
Asif et al., 2023; Chen et al., 2022, 2023; Constantin et al., 2022;
Malefane et al., 2023; Flores et al., 2023; Gonzaga et al., 2023;
Honarmandrad et al., 2023; Jiang et al., 2021; Jin et al., 2023;
Mohapatra et al., 2023; Papac et al., 2023; Pérez-Lucas et al.,
2023; Piccirillo et al., 2021; Qi et al., 2022; Rapti et al., 2023;
Sarker and Ahn, 2023; Scaria and Nidheesh, 2023; Singh et al.,
2023; Usman et al., 2023; Valadez-Renteria et al., 2023;
Wang et al., 2023; Xie et al., 2023; You et al., 2023; Yu et al.,
2023; Zare et al., 2023; Zilberman et al., 2023). The specific
mechanism involved depends on the type of ROS used or
generated as well as on the chemical structure of the pharma-
ceutical being degraded. The underlying significance of these
reaction mechanisms by ROS is indicated as these critically
determine the efficiency and selectivity of the degradation
process. By explicitly understanding the comprising mech-
anisms pertaining to the degradation process, it is possible
to optimize the conditions of the reaction, particularly to
attain the preferred level of degradation while minimizing
undesirable side reactions to eventually increase the efficacy
and selectivity of the procedures.
While process efficiency and procedure selectivity are sig-
nificant considerations in designing a chemical process to de-
grade contaminants, the development and optimization of a
specific method is required. In that context as an example,
690 journal of environmental sciences 147 (2025) 688–713
some approaches and strategies that can be effectively imple-
mented to help attain these goals are specified as follows:
(a) Suitable catalysts or promoters that enhance the de-
sired degradation reactions and suppress undesired
pathways can be selected. Moreover, catalyst loading
and compatibility with the reactants and reaction con-
ditions should also be optimized.
(b) Understanding the kinetics of the reactions involved in
the degradation process is useful. This includes distin-
guishing the rate equations, identifying reaction mech-
anisms, and the influence of temperature/pressure.
(c) Selectivity for the desired reaction pathways increases
by choosing optimum reaction conditions and reagents,
such as adjusting pH, using specific solvents/media, or
altering the redox potential. Optimization of the reac-
tion conditions (pH, catalyst and reactant concentra-
tion, temperature, etc.) to favor or control the desired
reaction pathway can aid in terminating the side reac-
tions. Furthermore, selectivity can be achieved by em-
ploying reaction engineering techniques like staged re-
actions, or multi-step processes, etc.
(d) Utilizing effective separation techniques to isolate or re-
cycle the catalysts, medium or unreacted starting mate-
rials or products can also minimize waste and improve
process efficiency.
The implication of various types of ROS-mediated mecha-
nisms in the degradation of pharmaceutical waste is deemed
imperative for several reasons, which essentially revolve
around aiming the following assistive gains:
• Optimization of the degradation process: Discernment of
different types of mechanisms by which ROS can degrade
pharmaceutical waste allows optimizing the degradation
process in a way so as to achieve maximum efficiency and
selectivity. Particularly, this understanding can help tailor
the degradation process subject to the kind of ROS used
and on the specific type of waste.
• Development of new ROS-based treatment systems: Re-
viewing different types of mechanisms pertaining to ROS-
based degradation of pharmaceutical waste can also pro-
vide insight into the development of new treatments. For
example, a new ROS-based treatment could be designed
that specifically targets a particular mechanism, therefore
leading to a more efficient degradation of the waste.
• Prediction of transformation products and by-products:
The different types of mechanisms involved in ROS-
mediated degradation of pharmaceutical waste can also
impact the types and amounts of by-products that would
be more likely generated during the degradation process.
The expected transformation products, their nature and
toxicity, as well as the extent of mineralization, are con-
ceivably more predictable after comprehensively study-
ing the mechanisms. This would assist in optimizing the
degradation process so as to minimize the generation of
more by-products with higher toxicity.
• Safety considerations: The in-depth analysis of ROS-based
process mechanisms can also aid in optimizing the process
that could avoid the formation of harmful intermediates or
by-products leading to safety hazards, hence evading any
risk to the ecosystem and concerns to human health dur-
ing or after the process.
This perspective reiterates the state-of-the-art ROS-
mediated reaction mechanisms implicated in the degradation
of pharmaceutical waste which seems pivotal while designing
a degradation strategy to remove a specific target pollutant
because it largely enables the optimization of selectivity,
efficiency, by-product formation, and safety. Hence an insight
into these mechanistic routes makes it possible to scheme an
effective and safe degradation process that can precisely re-
duce the environmental impact of pollutants. While primarily
emphasizing the implication of understanding such reac-
tions, we draw the inference by outlining valuable frontiers
for imminent research and opportunities to make the most
from these underlying chemical insights for pharmaceutical
removal processes being developed in the present day.
1. ROS implicated in pharmaceutical
degradation
Once generated, the ROS reacts rapidly, most often close to
diffusion-controlled rates (Buxton et al., 1988). Some more fre-
quently concerned ROS for reaction mechanisms with phar-
maceutical waste include ● OH, O3 , O2 ●− , SO4 ●− , 1 O2, and some
organic radicals.
1.1. Hydroxyl radicals (● OH)
Hydroxyl radicals (● OH) as a frequently detected ROS engaged
in oxidative degradation reactions, are one of the strongest
oxidizers since these possess a very high electronic poten-
tial. ● OH have a very short half-life and are hence highly re-
active and very non-selective species that are able to interact
directly with dissolved solids, including most organic and in-
organic pollutants. Reactions with ● OH in water can be initi-
ated by means of certain types of substances known as acti-
vators. This ● OH activation is in fact a highly intricate process
occurring through various mechanisms.
Selected pharmaceutical contaminants in drinking water
and their second-order rate constants for oxidation via ● OH
are indicated in Table 1. It is evident from the magnitude of
these rate constants that the oxidation of many pharmaceuti-
cal pollutants with ● OH is quite rapid. Moreover, the reactivity
of ● OH is also very high with the background constituents in-
herently present in natural waters, which results in short life-
times of ● OH (in the order of microseconds). Therefore, in an
AOP system, the ● OH steady-state concentration during treat-
ment of natural waters characteristically remains very low i.e.,
10−12 –10−15 mol/L (Elovitz et al., 2008), causing the species to
not increase over time due to accumulation.
Based on mechanisms, the reactions with radicals are in
general classified into (a) addition reaction, (b) hydrogen ab-
straction, (c) electron transfer, with addition reaction as the
most preferred pathway, if possible.
 journal of environmental sciences 147 (2025) 688–713 691

Table 1 – Kinetics of the ● OH oxidation with selected pharmaceutical contaminants present in water.

Pharmaceuticals Reaction rate constant (k) Reference

(mol/(L . sec))

Carbamazepine 8.8 × 109 (Huber et al., 2003)

Diclofenac 7.5 × 109 (Huber et al., 2003)
Sulfamethoxazole 5.5 × 109 (Huber et al., 2003)
17α-Ehinylestradiol 9.8 × 109 (Huber et al., 2003)
Bezafibrate 7.4 × 109 (Huber et al., 2005)
Clofibric acid 4.7 × 109 (Huber et al., 2005)
Diazepam 7.2 × 109 (Huber et al., 2005)
Ibuprofen 7.4 × 109 (Huber et al., 2005)
Iopromide 3.3 × 109 (Huber et al., 2005)
Naproxen 9.6 × 109 (Huber et al., 2005)
Tetracycline 6.3 × 109 (Jeong et al., 2010)
Chlortetracycline 5.2 × 109 (Jeong et al., 2010)
Atorvastatin (lipitor) 1.2 × 1010 (Razavi et al., 2011)

1.1.1. Addition reactions according to Eq. (7). Therefore, a peroxyl radical being part
The ● OH readily undergoes reaction with carbon-carbon of several unimolecular reactions appears to be in a much
(Eq. (1)), carbon-nitrogen, and sulfur-oxygen double bonds (ex- more complex chemistry. These reactions include the elim-
cept SO4 2− , Eq. (2)), including reactions with the transition ination reaction of HO2 ● /O2 ●− couple via double bond for-
metal ions (Eq. (3)) via addition reaction, resulting in the for- mation, as well as carbon-carbon double bond addition or
mation of an adduct followed by its subsequent decomposi- oxygen-transfer reactions (Sonntag, 2006b).
tion. The electrophilic character of carbon atoms causes their
electron-rich positions to get preferably attacked. For instance, HRH + ● OH → HR● + H2 O (4)
C5 is more prone to the attack than C6 , when these two car-
bons are in a double bond (Sonntag, 2006), because of the more HR● + O2 → HROO● (5)
electron-rich zone localized at position C5 .
HROO● + HRH → ROOH + HR● (6)

(not at normal wastewater conditions)

HROO● → HO2 ● + R (7)

R2 S=O + ● OH → R2 S(O● )OH → RS(O)OH + R●
Tl2+ + ● OH → HOTl2+ → Tl2+ + H2 O
1.1.2. Hydrogen abstraction reactions
Since the HO–H bond has a higher dissociation energy than
that of a carbon-bound hydrogen (C–H) bond, removing a H-
atom from an organic compound (HRH) is more likely (Eq. (4)),
hence resulting in the production of carbon-centered radical
(● R) (Sonntag et al., 1997). It is suggested by many authors that
the interaction of this carbon-centered radical with molecu-
lar oxygen (Eq. (5)) initiates a chain reaction that generates
peroxyl radicals. This peroxyl radical then successively re-
acts with other target organics (Eq. (6)) ideally leading to a
final conversion into CO2 , water, and inorganic salts. On the
other hand, as hydrogen abstraction is typically utilized to
describe the oxidation of target substances, the recognition
of peroxyl radicals as weak oxidants (low reduction poten-
tial) is also noteworthy. In the case of strong electron-donor
species, these peroxyl radicals might also perform as one-
electron oxidants. Consequently, at standard AOP conditions
during water treatment, these radicals instead of undergo-
ing an auto-oxidation chain reaction prefer the elimination
of O2 ●− (Sonntag, 2006; von Sonntag and Schuchmann, 1991),
(1)
It is evident from the aforementioned reactions that the oc-
(2) currence of oxygen has a considerable influence on radical re-
action systems. In the absence or insufficiency of O2 , the radi-
(3) cal combination reaction (Eq. (8)) is prevalent and there is mi-
nor significance of the reaction represented by (Eq. (5)), specifi-
cally in comparison with other reactions. Alternatively, a large
quantity of molecular O2 increases the relative fraction of the
bimolecular recombination (von Sonntag and Schuchmann,
1991). The reaction of most carbon-centered radicals with O2
(Eq. (5)) is fast and irreversible, whereas other organic com-
pounds such as thiyl and hexandienyl radicals merely react
reversibly with molecular oxygen, while the hetero-centered
radicals like phenoxyl do not tend to react with oxygen at all
(Sonntag, 2006).
The existence of scavengers or inhibitors determines the
rate of reaction cycles. CO3 2− in several of its dissociated con-
figurations is one of the familiar scavengers; CO3 ●− formed
by reactions of CO3 2− and HCO3 − are generally recognized as
poor reactants (see Section 2.2.2).
1.1.3. Electron transfer reactions
Electron transfer reactions tend to compete with the addi-
tion reaction; despite the electron transfer reaction being
thermodynamically favorable it has been observed less of-
ten, while addition reaction pathways are generally the pre-
692 journal of environmental sciences 147 (2025) 688–713

ferred ones (Sonntag, 2006). However, the direct electron trans-

fers are favored in such reactions as those including halo-
genated phenolate ions, since ortho- and para-positions for
the favored ● OH addition are obstructed by the substituents,
in which case electron transfer could turn out to be domi-
nant (Sonntag, 2006). Furthermore, the electron transfer yield
contributing to the overall reaction is found to increase with
the involved halogen size and predominates for bromine
and iodine with 73% and 97%, respectively (Akhlaq and
Clemens, 1987). Likewise, reactions with thiol and thiolate also
preferentially undergo electron transfers.

1.1.4. Radical recombination reactions

Radical recombination reactions terminate the chain reac-
tions through the production of a combined molecule, while
larger molecules tend to decompose according to a reaction
represented in Eq. (8), as an instance.

HROO● + HROO● → ROH + ROH + O2 (8)

1.1.5. Competition kinetics

The ● OH however, not only reacts with target contami-
nants, but also with water matrix constituents (e.g., NOM,
CO3 2− /HCO3 − , and inorganic species) and other radicals (e.g.,
HO2 ● ) collectively which act as “radical scavengers”, hence
initiating a complex flow of oxidative reactions. The impact
Scheme 1 – Pathways for various interactions of ozone with
of radical scavengers present in the water matrices is there-
organic molecules (von Gunten, 2003). (a) Formation of
fore deemed as one of the major complications encountered
ozonide (A) in dipolar cycloaddition reactions. (b)
in the application of AOPs, because there is much likelihood
Disintegration of ozonide. (c) Reaction between phenol and
of scavengers instigating an inhibition of the reaction leading
O3 .
to degradation of the target pollutant. The predominant in-
fluence of scavengers depends on all the involved moieties in
compounds existent in the type of water under investigation.
Carbonate in its various dissociation forms is the key scav-
formed during ozonation were persistent (Almomani et al.,
enger, typically prevalent in natural and wastewaters. Other
2016). This outcome also points out the need to estimate the
commonly occurring scavengers include natural organic mat-
toxicity following an ozonation process. Complete abatement
ters (NOMs) also referred to as humic substances, while amine
of investigated pharmaceuticals has been achieved using low
and phenol are among the more frequent moieties arising
doses of O3 but with incomplete mineralization rates.
from NOM (Buffle et al., 2006). Appendix A Table S2 lists the re-
During the O3 oxidation process, degradation by means of
action rate constants of some typical chemical species found
both the direct O3 molecule and indirect ● OH reactions can
in water that ● OH can react with.
occur effectively. One of these routes will predominate based
Factors that majorly influence the system of radical reac-
on several factors, for example, pH, temperature, and chemi-
tions involve the inhibiting (scavenging) or promoting species,
cal composition of the investigated water medium. O3 can ox-
which in turn depends on the composition of water or
idize organic compounds selectively and partially. In the case
wastewater (De Laat and Le, 2005). In addition to the reactions,
of direct reactions by O3 , the mechanisms of oxidation by O3
it is also required to take into consideration the fluctuations
and ozonide (O3 ●− ) are determined. It is generally known to
in pH during oxidation along with the pH-dependent disso-
undergo three categories of reactions in solution form con-
ciation equilibriums. Likewise, in the case of heterogeneous
taining organic contaminants in which O3 either behaves as
catalysis for instance, the pH value affects the surface charge
an electrophilic or nucleophilic agent or as a 1,3-dipole.
and consequently the adsorption/desorption kinetics as well.
Apart from pH, several parameters (Pignatello et al., 2006) that
might be able to frequently inhibit the removal of target con-
taminants involve carbonate/bicarbonate, dissolved oxygen, 1.2.1. Cycloaddition (Criegee mechanism)
nitrate ion (NO3 − ), NOM, hydroxyl ion (OH− ), Fe2+ , primary and Saturated compounds are capable of undergoing a 1–3 dipo-
secondary alcohols, phosphate ion (PO3 4− ) and specific chem- lar cycloaddition with O3 molecule because of its structure
icals, such as pBA, tert–butyl alcohol, etc. which is dipolar in nature. This process leads to the formation
of a species called ‘ozonide’ (Scheme 1a) (von Gunten, 2003). In
1.2. Ozone (O3 ) and ozonide radicals (O3 ●− ) water or other protic solutions, the primary ozonide disinte-
grates into an aldehyde, a ketone, or a zwitter ion (Scheme 1b),
Various reports have documented low mineralization despite which is eventually further broken down into H2 O2 and car-
the high removal rates of pharmaceuticals, as the byproducts boxyl compounds.
 journal of environmental sciences 147 (2025) 688–713 693

1.2.2. Electrophilic reactions

Electrophilic reactions essentially take place in solution forms
containing organic compounds with high electronic density
such as solutions with elevated levels of aromatic compounds
(von Gunten, 2003). Moreover, aromatic substances substi-
tuted by electron-donating groups (e.g., OH and NH2 ) possess
higher electronic density in ortho and para positions where
O3 can react more actively. For instance, hydroxyl groups in
phenol react more rapidly with O3 (Scheme 1c).

1.2.3. Nucleophilic reactions

Nucleophilic reactions generally occur in the presence of or-
ganic compounds having unavailability of electrons, in par-
ticular with compounds having electron-withdrawing groups,
e.g., carboxyl and nitro groups. However, the rate of reaction
for such groups is significantly slower.
Therefore, to summarize, the reaction mechanisms in-
volving direct oxidation of organic pollutants are relatively
selective, during which the compounds containing double
(or triple) bonds, activated aromatic rings or amines are
oxidized by O3 . Furthermore, with ionized and dissociated
molecules O3 reacts more rapidly than with the neutral or
non-dissociated type of organics (von Gunten, 2003).
1.3. Superoxide anion radical (O2 ●− )
O2 ●− can initiate the mineralization of organic pollutants
by hydrogen abstraction as a primary step often resulting in
the generation of some carbon-based radicals (Baum, 1984;
Sawyer and Valentine, 1981). Peroxy intermediates are gener-
ated after the combination of oxygen with these carbon-based
radicals. A consecutive breakdown of peroxy-intermediates
results in the production of degradation compounds
(Frimer et al., 1986). Degradation of various pollutants
like dyes and bisphenol A involves O2 ●− as a major contribut-
ing species as reported in numerous studies (Fu et al., 2015;
Wang et al., 2017b). Moreover, O2 ●− is even capable of breaking
the carbon-chlorine bonds (Li et al., 2011), thereby forming
dechlorinated products.
Since hydrogen abstraction is recognized as a predomi-
nant route for O2 ●− reaction in the case of (poly)phenols such
as hydroquinone (Nakarada and Petković, 2018), concurrently,
during the electron transfer by HO2 ● may also result in the
same product as with H-abstraction by O2 ●− (Nolte and Peij-
nenburg, 2018), presented in Eq. (9).
(9)
The reaction of O2 ●− with an extensive range of pollu-
tants or organic compounds takes place by means of hydro-
gen transfer, reduction, and one-electron oxidation. The in-
vestigations involving O2 ●− and organic species are intrin-
sically complicated because of the competing oxidative and
reductive routes, which may become even more challenging
Scheme 2 – Schematic representation of probable
movements for transfer of protons (green) and electrons
(blue/red) between superoxide ion (O2 ●− /HO2 ● ) and the
organic compound (XH/X− ). The constant red and blue
arrows relate to the oxidation and reduction, respectively.
The black arrows indicate transfer of hydrogen, viz.
combined transfer of electrons and protons. The
significance of hydrogen transfer is linked with the relative
BDE (bond dissociation energy) of X–H. Adapted with
permission from Nolte and Peijnenburg (2018). Copyright
2018 Elsevier.
by speciation of the organic substance as a function of pH
(Nolte and Peijnenburg, 2018). The O2 ●− reacts with the hy-
drogen donors (such as, (poly)phenols) through the hydrogen
abstraction process (top left pointer in Scheme 2). Although it
is noted yet again that the HO2 ● may also perform as an H-
donor species (bottom-right dashed pointer in Scheme 2), ow-
ing to the frail bonding between oxygen and hydrogen (O–H;
49 kcal/mol) (Fuller, 2008). This event is estimated to take place
essentially at a pH that is considered acidic. At this pH (< 4.9)
it might also exhibit a competition with the one-electron oxi-
dation.
1.4. Sulfate radicals (SO4 ●− )
SO4 ●− -based oxidative degradation of pharmaceuticals has
been receiving more and more consideration in wastewater
treatment technology as SO4 ●− has a high redox potential
(Eberson, 1982). The reduction potential (standard) of SO4 ●−
(E0 = 2.5 to 3.1 V) is much comparable to that of ● OH (E0 = 1.9
to 2.7 V), which allows SO4 ●− to perform as a potent oxidant
for contaminant degradation (Zhang et al., 2015). Despite the
similar oxidation potential for both SO4 ●− and ● OH (Oh et al.,
2016), the SO4 ●− -driven oxidations are much more selective
(Lee et al., 2020). In order to bring this higher selectivity of
SO4 ●− into perspective, the rate of reaction between humic
acids and SO4 ●− can be related to humic acids and ● OH, which
is approximately 103 L mg/C and 104 L mg/C, respectively
(Lutze et al., 2015b). While SO4 ●− and ● OH have analogous re-
dox potentials, it is of note to specify that the reaction rate of
organic compounds with SO4 ●− is usually lower, around 106 to
694 journal of environmental sciences 147 (2025) 688–713
107 mol/(L. sec) relative to that with ● OH (Buxton et al., 1988;
Lee et al., 2020; Lutze et al., 2015b; Sonntag et al., 1997), with
reaction rates between 108 and 109 mol/(L. sec).
Nevertheless, SO4 ●− is suggestively more stable than ● OH,
and largely undergoes reaction with organic substances via
electron transfer mechanism (Neta et al., 1977). It has also
been established that compared to ● OH, the decay of SO4 ●−
by the non-target compounds present in water (e.g., NOM) is
quite lower. This infers that AOPs based on SO4 ●− as the re-
active species may possibly be more effective than ● OH-based
processes, particularly in the treatment of real water matri-
ces (Ghauch and Tuqan, 2012; Lutze et al., 2015a). Therefore,
for such applications, remediation through in-situ oxidation
using activated PS (persulfate) could be favored over ● OH or
peroxide-based treatment processes (Waldemer et al., 2007;
Yan et al., 2013), because the more stable persulfate anion
might be transferred beyond, to the sub-surface prior to be
able to get activated for oxidation of the target pollutants.
SO4 ●− may undergo a reaction with organic pollutants
through electron transfer, hydrogen abstraction, and ad-
dition to the double bond (Neta et al., 1977). Owing to
the electrophilic nature of SO4 ●− , electron-donating groups
demonstrate rates of reaction with SO4 ●− which are way
more rapid when compared to electron-withdrawing groups
(Tsitonaki et al., 2010). Persulfate (PS) directly undergoes reac-
tion with some organic compounds, generating SO4 ●− which
can propagate secondary reactions (Eq. (10)) or might form or-
ganic radicals (Eq. (11)) (Huang et al., 2002; Tanner and Os-
man, 1987), thus progressively decomposing the target con-
taminant (He et al., 2014; Wang and Liang, 2014). The overall
rates of pollutant degradation are reliant on an interrelated
sequence of the SO4 ●− chain involved in propagation and ter-
mination reactions. However, unlike H2 O2 , PS also efficiently
oxidizes some organics directly, without the contribution of
reactive radical species (Ahn et al., 2019; Duan et al., 2018a,
2018b; Yang et al., 2018b; Zhou et al., 2015; Zhu et al., 2019).
S2 O8 2− + R → SO4 2− + SO4 ●− + R∗ (10)
S2 O8 2− + R → 2SO4 ●− + R● (11)
Furthermore, SO4 ●− is reported to be highly sensitive to-
ward substituent groups of the aromatic molecules (Luo et al.,
2017), however, the nature of substituent groups determines
the route of the reaction. For example, following the initial
step of oxidation via SO4 ●− , the aromatic radical cations gen-
erated could rearrange themselves in a way so as to undergo
oxidation of the side chain while substituent moieties may
act as electron donors (Caregnato et al., 2008). Contrary to this
when the substituents act as electron acceptors, dehalogena-
tion of the halo-aromatic radical cations is a preferred path-
way (Madhavan et al., 1978).
1.5. Singlet oxygen (1 O2 )
1O is known to be an extremely selective oxidant capa-
2
ble of oxidizing unsaturated organic substances either via
electron abstraction or an electrophilic attack (Kearns, 1971;
Thomas and Foote, 1978). For example, reactions of 1 O2 with
alkenes have been reported to form various degradation prod-
ucts depending on the structure of alkenes (Frimer, 1979;
Kearns, 1971). 1 O2 tends to function as an electron acceptor
to form O2 ●− with phenolic molecules comprising electron-
donating groups. Concurrently, such compounds may also
generate corresponding phenolic radicals eventually yielding
ring-opening and also quinone-like products, as a result of re-
arrangement or further combination with oxygen (Scully and
Hoigné, 1987). In general, 1 O2 exhibited higher reactivity to-
wards compounds comprising electron-rich sites, e.g., unsat-
urated sulfide and amino groups (Kim et al., 2012; Min and
Boff, 2002; Schweitzer and Schmidt, 2003; Xiao et al., 2021;
Zhou et al., 2015).
The rates of reaction of 1 O2 with many organic compounds
are lower (about 104 to 107 mol/(L. sec) (Lee et al., 2020) as com-
pared to ● OH and SO4 ●− , on account of the low redox potential,
i.e., 0.65 V (Rayaroth et al., 2023), indicating that 1 O2 is a weak
oxidant relative to other radical species. More specifically, a
probe compound for 1 O2 such as furfuryl alcohol has a range
of reaction rate reaching approximately 108 mol/(L. sec), which
is too high to detect the rapid removal of an organic contami-
nant by 1 O2 implicated in real wastewater application.
Although several reports have studied 1 O2 as a major ROS
for degradation of organic compounds (Cheng et al., 2017;
Luo et al., 2019; Zhu et al., 2020), on account of its lower re-
dox potential, mineralization of these pollutants via 1 O2 does
not seem to be a much prudent approach. Hence such infer-
ences are more of a dubious nature and need to be reaffirmed
via further experimentation as additional evidence. Moreover,
while exhibiting a rate constant of ∼105 mol/(L. sec), water can
also act as a 1 O2 scavenger (Cheng et al., 2017). In most cases
where the medium is water, its concentration is naturally
much higher as compared to the organic compounds. A major
contribution by 1 O2 is supposedly provided for the degrada-
tion of waste chemicals present in water compartments; from
the viewpoint of competitive kinetics, the reaction rate of 1 O2
with organics should be at least higher than 108 mol/(L. sec) in
that instance. The second-order rate constants for reactions of
different contaminants with 1 O2 are summarized in Appendix
A Table S3.
Recent findings (Hu et al., 2021) reported a 1 O2 -dominated
activation of PMS for catalytic degradation of tetracycline
through a non-radical oxidation production pathway. A com-
prehensive mechanism for the generation of 1 O2 in the
process has been described which was supported through
quenching experiments, as well as EPR studies. The produc-
tion of other reactive species, such as ● OH, SO4 . ●− and O2 ●− ac-
companied the activation process of PMS by biochar but were
observed to be reduced in the subsequent reactions. The H2 O2
generated during activation of PMS reacted with ● OH to pro-
duce HO2 ● , which further decomposed to yield O2 ●− (Eqs. (12)-
(14)) (Reshetnyak et al., 2003; Yan et al., 2017). The recombina-
tion of O2 ●− , along with the reaction of ● OH with O2 ●− succes-
sively resulted in the formation of 1 O2 as depicted in Eqs. (15)-
(18) (Duan et al., 2020, 2018a; Qi et al., 2020).
HSO5 − + H2 O → HSO4 − + H2 O2 (12)
H2 O2 + ● OH → HO2 ● + H2 O (13)
HO2 ● → O2 ●− + H+ (14)
● OH + O2 ●− → 1 O2 + OH− (15)
 journal of environmental sciences 147 (2025) 688–713
2O2 ●. − + 2OH+ → 1 O2 + H2 O2 (16)
2O2 ●− + 2H2 O → H2 O2 + 1 O2 + 2OH− (17)
HO2 ● + O2 ●− → 1 O2 + HO2 − (18)
Another prominent production pathway for 1 O2 during
Fenton-like reactions is specifically during PS activation by
metal ions. Although their contribution differs in each system,
the 1 O2 is either generated by direct reaction of oxidants with
the heterogeneous catalyst or by the interconversion of differ-
ent ROS, particularly the O2 ●− . This has been abundantly re-
ported in processes involving metal ion-based heterogeneous
catalysts, such as zerovalent iron-based materials and tran-
sition metal-doped catalysts (Hayat et al., 2021; Huang et al.,
2022; Tan et al., 2021a). For example, in the instance of Mn-
doped g-C3 N4 , Mn(III) as the primary form of Mn functions
to activate PMS to produce O2 ●− and Mn(II). The reaction of
Mn(II) with PMS can result in the regeneration of Mn(III). Both
reactions are followed by the creation of a medium copious
with O2 ●− , which predominantly serves as the precursor of
1 O (Eqs. (19)-(25)) (Fan et al., 2019).
2 sumption while decreasing the concentration during degra-
Mn(III) + HSO5 − + H2 O → Mn(II) + 3H+ + O2 ●− + SO4 2− (19)
Mn(II) + 2HSO5 − → O2 ●− + Mn(III) + 2HSO4 − (20)
2O2 ●− + 2H2 O → 1 O2 + H2 O2 + 2OH− (21)
S2 O8 2− + 2OH− → 2SO4 2− + HO2 − + H+ (22)
S2 O8 2− + HO2 − → SO4 ●− + 2SO4 2− + O2 ●− + H+ (23)
S2 O8 2− + 4OH− → 2SO4 2− + 1 O2 + 2H2 O (24)
HSO5 − + SO5 − → HSO4 − + SO4 2− + 1 O2 (25)
Therefore, this non-radical pathway involving 1 O2 for the
degradation of contaminants by AOPs is largely relevant
(Rayaroth et al., 2023). The highly selective 1 O2 is produced in
the medium through various pathways, the most significant
of which involves activated persulfates, modified photocata-
lysts, and photosensitizers.
It is also observed through literature (Gao et al., 2018;
Xiao et al., 2021) that in many systems based on the activa-
tion of persulfate (PMS or PDS), 1 O2 is emphasized as the dom-
inant ROS contributing toward degradation rather than the
SO4 ●− . In effect, the predominant ROS in a persulfate-based
system might not be the same for all contaminants or under
all conditions. Both the SO4 ●− and 1 O2 can contribute to pol-
lutant degradation, and the relative significance of each ROS
can vary. The prevalence of SO4 ●− vs. 1 O2 as the primary re-
active species in a system based on the activation of PS de-
pends on various factors, including reaction conditions, reac-
tant concentrations, and the nature of the contaminants being
degraded (Shao et al., 2023; Xia et al., 2020). The contribution of
SO4 ●− or 1 O2 toward pollutant degradation in a given system
seems to be reliant upon some considerations, for example:
Reaction mechanisms: The formation of SO4 ●− occurs when
persulfate ions (S2 O8 2− ) are activated via different methods,
such as heat, UV radiation, or the presence of catalysts (e.g.,
695
Fe2+ ). A wide range of organic contaminants can be oxidized
using SO4 ●− due to its high reactivity. 1 O2 , on the other hand,
is typically formed through the reaction of molecular oxygen
(O2 ) with a photosensitizer, such as organic matter or certain
transition metals, upon exposure to light (Dong et al., 2023;
Gao et al., 2020; Jin et al., 2023b; Xie et al., 2022; Yang et al.,
2019).
Reaction conditions: The conditions under which PS activa-
tion takes place can influence the relative contribution or sig-
nificance of SO4 ●− and 1 O2 (Ghanbari and Moradi, 2017). For
example, several catalysts or pH conditions may favor the
abundant generation of one ROS over the other.
Complex reaction pathways: In some cases, multiple ROS can
be produced concurrently and their relative role in degrada-
tion may shift during the process as reaction intermediates
are being formed and consumed (Wang et al., 2021).
Contaminant reactivity: The choice between SO4 ●− and 1 O2
as the dominant ROS might also depend on the specific con-
taminants present in the medium. Some contaminants are
more susceptible to oxidation by SO4 ●− , while others may be
more reactive in the presence of 1 O2 , resulting in their con-
dation of target pollutant.
Detection methods: Identifying and quantifying the particu-
lar ROS involved in a given system can be challenging, and
various analytical techniques might be utilized for monitor-
ing and detection purposes. Also, some techniques are better
suited to detect one ROS over the other which can potentially
lead to variations in the dominant ROS that are reported.
1.6. Hydroperoxyl radicals (HO2 ● )
HO2 ● are also formed in AOPs (in addition to the production
of aforementioned reactive radicals). Although, owing to the
lower oxidizing potential of this ROS, there barely exists any
data regarding the degradation of pharmaceuticals by HO2 ● (or
even organic pollutants in general (Wang and Wang, 2020c).
Nonetheless, in the course of indirect (● OH-based) reac-
tions of the ozonation process, HO2 ● are formed during the
terminal phase which may play a role in initiating the radical
reactions all over again. Consequently, a chain reaction is pre-
served by the supposed promoters, which can be specified as
substances (including organic molecules) that transform ● OH
to O2 ●− .
Some properties of the reactive oxygen species (ROS) piv-
otally involved in AOPs have been abridged in Table 2, since the
degradation efficiency of AOPs tends to vary with the proper-
ties of the ROS contributive in a process.
2. The case of acetaminophen (ACT)
degradation
Also renowned as paracetamol, acetaminophen (ACT) is
known for its pervasive detection as pharmaceutical waste
residues in drinking water (Gusseme et al., 2011), wastewater
(Chen et al., 2021), surface water (Yang et al., 2020), groundwa-
ter (Vulliet and Cren-Olivé, 2011) and landfill leachate (Yu et al.,
2020). For the most part, this antipyretic and analgesic drug
696 journal of environmental sciences 147 (2025) 688–713
Table 2 – Properties of ROS.
ROS Reduction Half-life in water
potential
●
OH 2.8 V 10−9 sec (Morris et al., 2022)
SO4 ●− 2.5 – 3.1 V 10−6 sec
(Uthirakrishnan et al., 2020)
O2 ●− 0.95 V 10−6 sec (Morris et al., 2022)
1
O2 0.65 V 10−6 sec (Morris et al., 2022)
enters the water matrices by excretion of humans and an-
imals, a major part of which is known to reach the water
bodies following incomplete elimination by the sewage treat-
ment plants (Langford and Thomas, 2009; Phillips et al., 2010;
Wu et al., 2012). Pharmaceutical contamination brings po-
tential risks to human health and ecological niches essen-
tially because of bioaccumulation, strong persistence, and
poor biodegradability (Akhtar et al., 2016; Papageorgiou et al.,
2016). The impending adverse impacts of ACT in small con-
centrations include inhibited cell proliferation, as well as re-
productive damage (Van et al., 2020).
The concentrations of ACT detected in effluents of Euro-
pean STP rose to 6 μg/L (Ternes, 1998), about 10 μg/L in natural
water bodies in the USA (Kolpin et al., 2002), and a concen-
tration of more than 65 μg/L was determined in Tyne River in
the UK (Roberts and Thomas, 2006). The maximum concen-
trations of ACT in China (Jiulong), Portugal (Arade), Spain (Bil-
bao), and USA (New York Bay) have been reported as 13 ng/L,
88 ng/L, 440 ng/L, and 162 ng/L, respectively (Letsinger et al.,
2019). Owing to the simplicity of chemical structure and am-
ple investigation on the degradation of ACT via various ROS, it
was chosen to thoroughly explore the in-depth mechanisms
of ACT oxidation with various oxygen-based radicals.
The structure of the parent compound, acetaminophen
(ACT), has two vulnerable locations; (a) the acetamido group
(–NH–CO–CH3 ) and (b) an aromatic ring. The reactive oxida-
tive species (● OH, O2 ●− , SO4 ●− , 1 O2 ) and the free electrons can
readily attack such susceptible sites in a molecule. Therefore,
the various ACT degradation mechanisms can recurrently and
most likely follow the ROS attacking the acetamido moiety or
the aromatic ring.
The ideal consequence of any ROS-mediated degradation
for pharmaceuticals is considered to be the total mineraliza-
tion of target contaminants, as represented in Eq. (26):
ROS + API → CO2 + H2 O (26)
2.1. The ● OH attack on ACT
2.1.1. Hydroxylation of the ACT aromatic ring mediated by
●
OH
The nature or type of the contributing ROS has a strong role
in determining the degradation pathway during an oxidative
Mechanism/pathway Ref.
H-abstraction, one-electron oxidation, (Buxton et al., 1988)
and aromatic substitution reaction
(non-selective reactions)
One-electron oxidation (Neta et al., 1988)
Disproportionation, one-electron transfer, (Hayyan et al., 2016)
deprotonation, and nucleophilic
substitution
Oxidation of the electron-rich sites (Min and Boff, 2002)
treatment process. As an instance, the ACT molecules default
to ● OH attack since ● OH are generated in profusion which is
responsible for the degradation of ACT, as highlighted by a re-
cent report on its ultrasonic treatment (Gao et al., 2022). The
tendency of ● OH as a non-selective oxidant to undergo reac-
tion with organic compounds is depicted through three key
mechanisms, viz., electron transfer, hydrogen abstraction, and
addition of hydroxyl group (hydroxylation) to unsaturated car-
bons.
Initiation of the different degradation routes shown in
Scheme 3a occurs by parallel attacks of the oxidant radical
either on the C(2)-position or C(4)-position of ACT. In these
transformations, the first pathway corresponds to the ACT
aromatic ring hydroxylation giving rise to the emergence of
its hydroxylated product (TP1) (El Najjar et al., 2014). This was
subsequently followed by cleavage of the aromatic ring of TP1
resulting in the generation of the ring-opening compound;
TP2 (Moctezuma et al., 2012).
An initiating ● OH attack on the para-position of
phenol-formed hydroquinone during a second pathway,
with consequent oxidation of hydroquinone yielding TP3
(Moctezuma et al., 2012). Whereas, as a third pathway,
the acetyl-amino group underwent ● OH attack preceding
the appearance of TP4, which was further oxidized to TP5
(Wang et al., 2019).
2.1.2. Attack of ● OH on aromatic and acetamido group of ACT
A study recently reported on catalytic degradation of ACT
through potassium peroxydisulfate (PDS) activation via N-
doped CNT (carbon nanotube) modified surfaces elucidates
a mechanism pathway that might pursue the attack by ● OH
on ACT aromatic ring, as well as on the acetamido group
(Govindan et al., 2022). This attack could result in the produc-
tion of N-(3,4-dihydroxylphenol)-acetamide (m/z = 167) and
hydroquinone (m/z = 110) (Li et al., 2020). Additionally, the
hydroquinone underwent oxidation through ● OH and subse-
quently formed 1,4-benzoquinone (m/z = 108) and acetamide
(m/z = 60).
Contrariwise, the incursion by ● OH can also propagate di-
hydroxylation, hence generating a dehydroxylated ACT prod-
uct (m/z = 167), which possibly could undergo additional
conversion to malonic acid (m/z = 104)) and 1-amino-1,3,4,-
trihydroxybutan-2-one (m/z = 135) as illustrated in Scheme 3b.
 journal of environmental sciences 147 (2025) 688–713 697

(a) Degradation route followed by ACT under the attack of OH.

(b) Attack of OH on aromatic and acetamido group of ACT. (c) Electrophilic adduct reaction of ACT with ROS.

Scheme 3 – ● OH-mediated reactions with ACT (a) Degradation route followed by ACT under the attack of ● OH. Adapted with
permission from Gao et al. (2022). (b) Attack of ● OH on aromatic and acetamido group of ACT. Adapted with permission from
Govindan et al. (2022). (c) Electrophilic adduct reaction of ACT with ROS. Adapted with permission from Govindan et al.
(2022). Copyright 2022 Elsevier.

2.1.3. Electrophilic adduct reaction
An electrophilic adduct reaction has also been reported to
have occurred either between ACT and ● OH or through
electron transfer utilizing other ROS, i.e., SO4 ●− , O2 ●− , 1 O2
(Govindan et al., 2022). This mechanistic pathway (Scheme 3c)
resulted in the generation of dehydroxylated byproducts, such
as N-(3,4,5-trihydroxylphenyl)acetamide (m/z = 167), along
with the elimination of CH3 CO- group hence forming 4-
aminophenol (m/z = 109) via SO4 ●− having greater oxida-
tion potential. These dehydroxylated and deacetylated prod-
ucts were further oxidized to produce simpler molecules like
2-hydroxypropanoic acid (m/z = 90) along with acetamide
(m/z = 59).
2.1.4. Oligomerization of ACT mediated by ● OH
Another investigation (Tong et al., 2021) reports the reac-
tion of ACT with saturated ferric (Fe3+ ) clay particles under
UV–visible irradiation which was observed to be 1.7 times
698 journal of environmental sciences 147 (2025) 688–713
Scheme 4 – ACT photo-transformation through ● OH attack. Adapted with permission from Tong et al. (2021). Copyright 2021
Elsevier.
greater than the ACT removal in the dark. This could be as-
cribed to ROS formation in the presence of light. The study
involved the elucidation of six products via mass spectra
of which three (TP4, TP5, and TP6) were specifically gen-
erated under light conditions, most likely after undergo-
ing ● OH-based reactions, as represented in Scheme 4. N-(5–
hydroxyl-1,6-dioxohex-3-en-2-yl)acetamide (C8 H11 NO4 ) and
dimer of ACT or 2,4-hexadienal (C14 H13 NO3 ) were referred
as TP4 (m/z = 186.031) and TP5 (m/z = 246.242) respec-
tively, while 9-nitrodibenzofuran-2,3,6,7-tetraone (C12 H3 NO7 ),
the compound yielded via cross-linking of the phenol-based
radicals was referred as TP6 (m/z = 274.274) according to the
MS analysis (Zhang et al., 2018). Induced by an initial at-
tack by ● OH on the benzene ring, followed by subsequent de-
protonation and formation of the double bond between car-
bon and oxygen, eventually leading to the breakage of the
carbon-carbon bond resulting in the production of TP4. More-
over, the attack of ● OH on ACT could also lead to the gen-
eration of hydroquinone and p-hydroxyaniline (Liang et al.,
2016; Zhang et al., 2008). Further hydroxylation of these in-
termediates was likely to take place, along with the dona-
tion of an electron to form cationic radicals with consequent
oligomerization. Successively, the adjacent hydroxyl groups of
the dimer underwent an intermolecular cyclization reaction.
Moreover, the formation of TP6 was prompted by oxidation
in the para-position of the amido in, followed by the abstrac-
tion of an electron by ● OH from the hydroxyl group of ACT to
produce phenoxyl radicals (Deng et al., 2010). This was subse-
quently followed by the transformation process similar to the
ACT degradation pathway via single electron transfer (SET) as
illustrated in Scheme 5a. TP1 was yielded as a result of ● OH
attack or hydrolysis leading to the elimination of acetamide
from the dimer (Li et al., 2017). Furthermore, oxidation by ● OH
in the para-position of P1 formed TP3 (Zhang et al., 2008).
Also, TP1 might as well be produced by the cross-coupling
between ACT and hydroquinone, while further oxidation of
TP1 could subsequently lead to TP5 formation. The photo-
transformation of ACT included two reaction pathways, in-
cluding both single electron transfer and the attacking ● OH
pathway (as proposed in Scheme 4).
 journal of environmental sciences 147 (2025) 688–713 699

Scheme 5 – Electron transfer processes for ACT (a) Single electron transfer pathway for ACT transformation. Adapted with
permission from Tong et al. (2021) Copyright 2021 Elsevier.. (b) Electron-transfer process in ACT. Adapted with permission
from Govindan et al. (2022). Copyright 2022 Elsevier.

2.2. The electron-transfer process
2.2.1. ACT dimerization via single electron transfer (SET)
The degradation of ACT through single electron transfer in-
volves the formation of three dimers of ACT, referred to as
TP1, TP2, and TP3 in Scheme 5a, with molecular formulae
C14 H13 NO4 , C16 H16 N2 O4 and C14 H11 NO4 respectively. Compa-
rable compounds have been documented on phenol oligomers
forming via the electron transfer process (Gu et al., 2008,
2011; Polubesova et al., 2010; Qin et al., 2015). The ACT un-
derwent a transformation into cationic radicals after the loss
of one electron from the hydroxyl functional group. Carbon-
centered radicals were produced as an outcome of the elec-
tron (unpaired) in phenoxyl radical being delocalized via res-
onance in the adjacent conjugated benzene ring positions
(Lu and Huang, 2009). These carbon-centered radicals would
react among one another to produce carbon-carbon or carbon-
oxygen bonds at several positions as cross-connecting dimers
observed as TP2, which successively yielded TP1 and TP3 after
hydrolysis and oxidation (Li et al., 2017; Zhang et al., 2017b).
This electron transfer process has been stated in reports as
the predominant pathway in the absence of light (Tong et al.,
2021).
2.2.2. Electron transfer from the acetamide group of ACT
Another degradation pathway has been reported very recently
(Govindan et al., 2022) as depicted in Scheme 5b. It represents
an electron-transfer process occurring in the acetamide group
which could produce an N-radical cation (m/z = 151). This N-
radical cation intermediate species could likely be stabilized
through the neighboring phenyl ring and the carbonyl group.
Consequently, the intermediate reacted with the oxidative
species to yield a peroxide-based product (m/z = 141), namely
4-(hydroperoxyamino)phenol, and the dehydration product
(m/z = 123) called 4-nitrosophenol. Such transformation prod-
ucts have been identified and experiential in prior studies
(Li et al., 2017). Owing to this electron-transfer process taking
place in ACT, the formation of phenoxyl radical (m/z = 150)
was observed as well, which could be oxidized further to pro-
duce a transformation product of ACT, i.e., N-(3–hydroxy–4-
oxocyclohexa-1,5–dien–1-yl)acetamide with m/z of 168. Hence
it was evidenced that the electron transfer in the acetamido
700 journal of environmental sciences 147 (2025) 688–713

radical addition elimination reaction (Anipsitakis et al., 2006;

Table 3 – The reduction potentials (E0 ) of ● OH and organic
Li et al., 2020b).
radicals. Adapted with permission from (Li et al., 2021).
Copyright 2021 Elsevier. By means of SET reaction of CH3 COO● and ACT, it is possi-
ble to directly generate the cationic radical of ACT (ACT●+ ), to
Radical species Reaction equation E0 (V)
which HO− might further add to produce the adduct of HO (IM-
2). These HO-adducts could subsequently undertake H-atom
● ●
OH OH + e− → − OH 1.90a shift, oxygen addition, and eventually the exit of HO2 , hence
●
OH + e− + H+ → H2 O 2.73a
yielding the hydroxylated product (TP1) of ACT. Such ACT-
CH3 COO● CH3 COO● + e− → CH3 COO− 2.12
CH3 COO● + e− + H+ → CH3 COOH 2.25
based hydroxylated products have been identified in recent re-
CH3 O● CH3 O● + e− → CH3 O− 0.65 ports on AOPs with peracetic acid as oxidants (Ghanbari et al.,
CH3 O● + e− + H+ → CH3 OH 2.08 2021).
● ●
CH3 CH3 + e− → CH3 − − 0.68 A reaction between CH3 COO-adduct and molecular oxy-
●
CH3 + e− + H+ → CH4 1.94 gen in a parallel route toward the HO-adduct was predicted,
CH3 COOO● CH3 COOO● + e− → CH3 COOO− 1.22
which finally resulted in the formation of an acetoxylated
CH3 COOO● + e− + H+ → CH3 COOOH 1.64
product (TP2) of ACT. The anticipated formation pathway of
CH3 OO● CH3 OO● + e− → CH3 OO− 0.55
CH3 OO● + e− + H+ → CH3 OOH 1.26 TP2 seemed to be more promising, while the acetoxylated
CH3 C● O CH3 C● O + e− → CH3 CO− − 0.77 products of aromatics have not been particularly detected dur-
CH3 C● O + e− + H+ → CH3 COH 1.39 ing AOPs based on PAA (Ghanbari et al., 2021; Kim et al., 2019;
a
Wang et al., 2020c). Benzoate esters were previously reported
The E0 values for the reference compound (Wardman, 1989).
to catalytically hydrolyze via base to form benzoates (Xu et al.,
2021, 2019). As observed in Scheme 6, TP2 was likely to un-
group of ACT is also capable of inducing degradation of the dergo base-catalyzed hydrolysis.
drug compound. The initiated attack of HO− on TP2 formed IM-4 followed
by the withdrawal of CH3 COOH from IM-4. All the pathways
proposed for CH3 COO● -mediated hydroxylation of ACT were
2.3. Hydroxylation mechanisms of act mediated by observed to be thermodynamically possible. A viable hydroly-
CH3 COO● sis may lead to no accumulation of acetyl compounds.
In this observed scenario, the ACT reaction rate constants
Further investigations (Li et al., 2021) disclosed that among with organic radicals and ● OH were found to be linearly
the studied organic radicals, CH3 COO● is the most potent related to the reduction potential values of these radicals
as an oxidizing species. According to some other studies on (Li et al., 2021). Enlisted in Table S4 are the second-order re-
UV/peracetic acid (PAA) processes (Zhang and Huang, 2020), action rate constants (kACT ) calculated for ACT with the or-
CH3 COOO● was the most abundantly generated organic rad- ganic radicals and ● OH at 298 K in the aqueous solution. The
ical but it possesses a lower reduction potential. With ref- order of kACT was reported as CH3 COO● > ● OH > CH3 O● >
erence to ● OH, the E0 (one-electron reduction potentials) of CH3 COOO● >> ● CH3 > CH3 C● O > CH3 OO● . Therefore, it can be
several organic radicals produced in the PAA-based system deduced that among these radicals, CH3 COO● demonstrates
were investigated and enlisted in Table 3 for comparisons. the maximum reactivity for ACT, followed by ● OH, CH3 O● and
At pH 7, the E0 values calculated for ● OH were 2.73 V, and CH3 COOO● .
2.12 V and 2.08 V for CH3 COOO● and CH3 O● respectively, while The degradation of ACT via ● OH was initiated via numer-
the E0 values for all other organic radicals turned out to be ous reaction paths, with 58.78% of branching ratios (, %) for
< 2 V. RAF (radical adduct formation), 17.55% for HAA (H-atom ab-
The ACT degradation reactions initiated by the organic straction), and 23.67% for SET (single electron transfer). It can
radicals have been assumed to comprise the radical adduct be further interpreted from the values reported in Table 3, that
formation (RAF) channels on both the benzene ring and ac- the reaction rate constant of CH3 COO● with ACT (5.44 × 1010 )
etamide group, H-atom abstraction (HAA) channels from the is even higher than that with ● OH. ACT degradation initi-
benzene ring, the -OH group, and the acetamide group, and ated by CH3 COO● appeared to be dominated by multiple re-
single electron transfer (SET) channels. Moreover, in order to action channels, involving RAF channels on the benzene ring
abstract an H-atom from ACT, as well as for addition to oc- as well as the acetamide group, HAA channels of the OH group
cur in the ACT unsaturated bonds, such sites of organic rad- and the acetamide group, and the SET channel. The prevalent
icals are speculated which possess maximum unpaired elec- pathways for CH3 COOO● and CH3 O● with ACT were HAA reac-
tron spin density. tions alone, whereas the analyzed reaction rate constants for
The proposed CH3 COO● -mediated hydroxylation route of ACT with ● CH3 , CH3 C● O, and CH3 OO● could be overlooked for
ACT is illustrated in Scheme 6. The successive investigated re- being too low.
actions of RAF and SET channels revealed that CH3 COO● pos-
sibly will react with ACT and hence lead to yield an adduct of 2.4. Degradation mechanism of ACT mediated by 1 O2
acetoxyl (CH3 COO-adduct, IM-1) via the RAF channel. It was
further found that CH3 COO-adduct underwent a unimolecu- More recent works (Lin et al., 2021) revealed that peroxymono-
lar reaction hence eliminating CH3 COO− . This phenomenon sulfate (PMS) was exploited as an oxidant for the efficient
of the addition of CH3 COO● to a molecule proceeding to the degradation of ACT in hydrolyzed urine (HU). It was found that
elimination of CH3 COO− is recognized as SRAE, i.e., sequential 1 O and ● OH both occurred in the HU/PMS system, however,
2
 journal of environmental sciences 147 (2025) 688–713 701

Scheme 6 – Proposed CH3 COO● -mediated hydroxylation mechanisms of ACT. Adapted with permission from Li et al. (2021).
Copyright 2021 Elsevier.

Scheme 7 – Proposed photocatalytic 1 O2 -mediated degradation process of ACT. Adapted with permission from Lin et al.
(2021). Copyright 2021 Elsevier.

1O was the predominant ROS contributing toward the ACT
2
degradation.
While reacting with ACT, 1 O2 was able to fragment the
amide bone between the C and N in the benzene ring, be-
sides possibly resulting in the appearance of three major
transformation products, namely 4-nitrophenol (TP1), 1,2,4-
benzentriol (TP2), and benzaldehyde (TP3) (Le et al., 2017) as
shown in Scheme 7. In addition, ACT and its byproducts un-
derwent decomposition into oxalic acid (TP4) and maleic acid
(TP5) since breakage of the benzene ring occurred (Mu et al.,
2020).
2.5. Degradation mechanism of ACT mediated by O2 ●−
Wang and Bian (2020) prepared and utilized a photocatalytic
system comprising small, highly dispersed Pd nanoparticles
in Pd-BiVO4 for the degradation of ACT to afford simpler
molecules leading to complete mineralization. Under visible
light irradiation, Pd-BiVO4 displayed remarkable activity for
ACT achieving 100% removal in one hour. During the degra-
dation process, ACT mineralization percentage stretched to
about 40% as depicted by values of TOC removal. This sys-
tem for ACT degradation involves O2 ●− (superoxide radicals)
as well as photo-induced holes as vital contributors in the re-
moval process.
A photocatalytic pathway for ACT degradation mediated by
O2 ●− was suggested as depicted in Scheme 8. Assisted by Pd-
BiVO4 photocatalyst under the irradiation of visible light, the
study implicated two reaction routes. In the initial course, the
decomposition of the amide group of ACT takes place as an-
ticipated by the outcomes of DFT (density functional theory)
calculation data of ACT optimization (Wang and Bian, 2020). In
addition, the monophenyl aminophenol derivative (TP2) was
found to be produced subsequent to the elimination of the
COCH3 group from ACT. Eventually, the benzene ring of TP2
underwent the attack by reactive species resulting in its open-
ing, resulting in the production of the maleic acid intermedi-
ate (TP1). In the presence of the employed photocatalyst, such
acids with minimal molecular weights were further mineral-
ized to CO2 and H2 O.
The radical activation results in a second process which
comprises ACT dimerization via an amide-methyl func-
tional group to produce the dimer (TP6). The link composed
of amide and carbonyl species of the dimer TP6 under-
went cleavage via light-induced ROS to form TP5 (N,N-bis(4-
hydroxyphenyl)oxalamide) after loss of the ethene group.
702 journal of environmental sciences 147 (2025) 688–713

Scheme 8 – Proposed photocatalytic O2 ●− -mediated degradation process of ACT. Adapted with permission from Wang and
Bian (2020). Copyright 2020 Elsevier.

This was followed by the transformation of TP5 to TP4 and
TP3 when the carbonyl group was cleaved. TP4 and TP3 were
then converted to ACT and TP2 (4-(hydroxyamino)phenol),
respectively, after undergoing the addition of the hydroxyl
group. By way of further oxidation via the addition of HO-
groups in the presence of O2 ●− , ring cleavages of ACT and TP2
can take place to yield maleic acid (TP1), which can in turn
afford small molecules leading to complete mineralization.
Another study recently explored O2 ●− as an oxidant
for degradation of ACT in a binary system consisting
of bis(trifluoromethylsulfonyl)imide-based hydrophobic ionic
liquids (ILs) and acetonitrile (AcN) as an aprotic solvent. The
 journal of environmental sciences 147 (2025) 688–713
Scheme 9 – Suggested pathway for SO4 ●− -dominated degradation process of ACT. Adapted with permission from
Rodríguez-Narvaez et al. (2020). Copyright 2020 Elsevier.
subsequent in situ degradation of ACT occurred via O2 ●−
which was chemically generated by the dissolution of potas-
sium superoxide (KO2 ) (Humayun et al., 2021). O2 ●− was
demonstrated as the major ROS in the reaction system con-
tributing to 98% removal of the drug under optimum condi-
tions. This opens the door to explore further the potential
use of ILs as multi-task agents, namely as media to gener-
ate radical species and as extractive agents for pharmaceu-
tical wastes. It can also be extended to investigate the use of
IL analogues, and deep eutectic solvents, being more biocom-
patible, less cost of synthesis, and more sustainable, as they
can prepared from natural metabolites.
2.6. Degradation mechanism of ACT mediated by SO4 ●−
Degradation based on SO4 ●− has been lately acclaimed as one
of the most effective ROS used in recent AOPs, primarily owing
to its high oxidizing power (E0 = (SO4 ●− /SO4 2− ) = 2.5 to 3.1 V)
as compared to that of ● OH (E0 = (● OH/H2 O) = 1.9 to 2.7 V)
(Wang et al., 2017a; Zhang et al., 2019).
The investigation of the Co3 O4 /PMS system for ACT re-
moval (Rodríguez-Narvaez et al., 2020) reports a negligible
concentration of ● OH in the heterogeneous process, which
was hence predominated by the SO4 ●− -based degradation re-
actions. By means of the identified by-products and kinetic
data, a mechanistic degradation pathway for ACT was put for-
ward. The outcomes suggested that simpler structures, such
as malic acid along with succinic acid were generated suc-
ceeding the Co3 O4 /PMS process, which could be mineralized
suitably by conventional water treatment processes (Le et al.,
2017; Pérez-Estrada et al., 2005). Another study (Le et al., 2017)
also agreed with these results which studied ACT degrada-
tion via the electro-Fenton process. It has been found that
● OH-based conversions using an electro-Fenton process re-
quired 60 mins of reaction time to form several carboxylic
acids (for example, oxalic, maleic, and formic acids). However,
for the degradation dominated by SO4 ●− as in the case of the
Co3 O4 /PMS system, merely 5 min of reaction was sufficient
to yield the carboxylic acids, such as succinic and malic acid,
703
therefore underlining the higher oxidizing power of SO4 ●− in
comparison with ● OH.
N-(3,4- dihydroxyphenyl) acetamide (TP1), 4-aminophenol
(TP2), benzene-1,4-diol (TP3) and 3,4-dihydroxybenzene-1-
sulfonic acid (TP4) were the primary reaction byproducts af-
ter the treatment via Co3 O4 /PMS process. Scheme 9 explicitly
indicates the pathway for ACT oxidation presenting the by-
products generated by the contribution of SO4 ●− . This route
for ACT degradation via ● OH and SO4 ●− has also been stated in
other reports (Zhang et al., 2017b). The study speculated that
either the ● OH oxidizes ACT at carbon-3 of its benzene ring
to form N-(3,4- dihydroxyphenyl) acetamide (TP1) or a substi-
tution reaction would be carried out at carbon-1 of ACT ben-
zene ring giving rise to the formic and amino group, thus pro-
ducing benzene-1,4-diol (TP3). Both of these transformation
products (TP1 and TP3) have been identified in the work of
Rodriguez-Narvaez et al. (2020) as well, suggesting that some
degradation pathways may implicate ● OH. However, as illus-
trated in Scheme 9, the ACT oxidation by SO4 ●− was initi-
ated by replacing the amide group followed by generating the
acetic acid derivatives leading to produce TP2, which was fol-
lowed by the likely substitution of the amine group by ● OH or
SO4 ●− to generate TP3 or TP4, respectively. TP5 was formed by
further oxidation of TP4 by ● OH, whereas not any linear or-
ganic arrangement comprising connected sulfate groups was
detected. After several oxidation steps, either TP3 or TP5 even-
tually yielded carboxylic acids TP6 and TP7.
Although the study byZhang et al. (2017a) never identified
the by-products produced due to SO4 ●− intervention, they pro-
posed that SO4 ●− -mediation would be releasing formic acid
from the amino group pursued by rupturing of the benzene
ring hence generating carboxylic acids as well as amines.
As the aforementioned mechanisms elucidate the differ-
ence in pathways acquired, intermediates, and transforma-
tion product formation which could arise depending on the
ROS employed in the process, Table 4 summarizes the var-
ious systems and processes reported to generate these ROS
along with their relative efficiencies and outcomes through
each mechanism which was adopted by each ROS after its in-
teraction with a specific chemical structure such as ACT.

Table 4 – Proposed oxidation routes of ACT for various recent AOPs and the transformation products (TPs) produced.
AOP systems/ Conditions
US irradiation (555 kHz/
60 W) /ACT 20 μmol/L
UV/PAA (peracetic
acid-based) process
Pd-BiVO4 /visible light
system
Co-FeOCl/H2 O2 system, ACT
10 μmol/L, Co-FeOCl 0.2 g/L,
H2 O2 0.5 mmol/L, pH 7
Fe3+ saturated
montmorillonite clay
(Fe-SMF) (a) in dark and (b)
under simulated sunlight,
Clay 5 g/L, ACT 50 μmol/L,
pH 3
ROS Mechanism of degradation
●
OH (i) hydroxylation of the aromatic
ring
(ii) attack of the ● OH on the para
position to the phenolic functional
group
(iii) attack of ● OH on the
acetyl-amino group
CH3 COO● , ● OH and CH3 COO● -mediated hydroxylation
CH3 COOO● of aromatics with radical adduct
formation (RAF) reaction as the
dominant channel (addition as the
dominant pathway)
O2 ●− (i) ACT amide group
decomposition → removal of ACT
COCH3 group → benzene ring
opening leading to carboxylic acid
formation
(ii) ACT dimerization → cleavage
of the carbonyl and amide groups
dimer → oxidative addition of
hydroxyl groups → ring cleavage
of ACT → maleic acid formation
leading to small molecules
O2 ●− – 87.5%
●
OH (a) in dark: Electron transfer
process → hydrolysis and
oxidation
(b) under simulated sunlight:
attack of ● OH on the benzene
ring → deprotonation → hydroxy-
lation
→ oligomerization → electron
abstraction → transformation as
in dark conditions
704
Removal efficiency TP formation Ref.
50.6% – 86.9% in (i) ACT → m/z 168 → m/z 200 (Gao et al., 2022)
10 min (ii) ACT → hydroquinone → m/z
127
(iii) ACT → m/z 110 → m/z 140
journal of environmental sciences 147 (2025) 688–713
– Hydroxylated products (Li et al., 2021)
(HO-adduct) of ACT and
acetoxylated products
(CH3 COO-ACT) of ACT
100% in 1 hr (40% TOC (i) ACT → monophenyl (Wang and
removal) aminophenol derivative → Bian, 2020)
maleic acid → CO2 and H2 O
(ii) ACT → dimer of
ACT → N,N-bis(4-
hydroxyphenyl)oxalamide → 1,3-
bis(4-
hydroxyphenyl)urea → 4,4-́(hydrazine-
1,2-diyl)diphenol → 4-
(hydroxyamino)phenol/ACT→
maleic acid → CO2 and H2 O
– (Tan et al., 2021)
47.6% ± 1.1% in dark / (a) ACT → cationic (Tong et al., 2021)
78.9% ± 0.5% in light radicals → carbon-centered
after 10 hr radicals → cross-coupling dimers
of ACT → dimer of ACT and
hydroquinone and dimer of ACT
and benzoquinone
(b) N-(5–hydroxy–1,6-dioxohex-3-
en-2-yl)
acetamide → 9-nitrodibenzo-
furan-2,3,6,7-
tetraone → hydroquinone and
p-hydroxyaniline → phenoxyl
radicals → dimerization as in (a)
(continued on next page)
Table 4 (continued)

AOP systems/ Conditions ROS Mechanism of degradation Removal efficiency TP formation Ref.

CuMgFe2 O4 /PS system,
temperature 30 °C, ACT
20 mg/L, catalyst loading
0.1 g/L and PS 1.5 mmol/L
Electron transfer Non-radical pathway (direct e−
(from ACT to PS) transfer route) → oxidation of
aminophenol → cleavage of the
aromatic ring
90% in 40 min (59% ACT → dimeric product of ACT (Ali et al., 2021)
TOC removal in 60 (N,N-(5,6-dihydroxy-[1,1-
min) biphenyl]−2,3-diyl)diacetamide)
and aminophenol.
Aminophenol → hydroquinone or
to other open-chain compounds,
including N-acetylacetamide,
acetylcarbamic acid and

journal of environmental sciences 147 (2025) 688–713

UVA/BiOCl process, ACT
50 μmol/L, catalyst 0.3 g/L,
pH 5.4
Modified CNT/PDS
(peroxydisulfate) system,
ACT 10 mg/L, catalyst
100 mg/L, PDS 1 mmol/L
Ag/ZnO@NiFe2 O4
nanorod/UVA/PMS process,
ACT 12 mg/L, catalyst
loading 0.1 g/ L, PMS
0.2 mmol/L
acetamide, etc. and many
open-chain compounds (acetone,
acetamide, formic and acetic acids,
etc.)
HO2 ● /O2 ●− – > 80% TOC removal – (Wang et al., 2020a)
after 180 min
SO4 ●− , ● OH, O2 ●− , (i) ● OH attacks the aromatic ring 95% TOC removal after (i) ACT →N-3,4-dihydroxylphenol)- (Govindan et al.,
1
O2 and acetamido group 60 min acetamide and 2022)
(ii) electrophilic adduct reaction hydroquinone → 1–4-
among AAP and ● OH benzoquinone and acetamide
(iii) e− -transfer process to the ACT → dehydroxylated ACT
acetamide group (N-(4-hydroxyphenyl)acetamide)
→1-amino-1,3,4-trihydroxybutan-
2-one and malonic acid
(ii) ACT → dehydroxylated
by-products → acetamide and
2-hydroxypropanoic acid
(iii) ACT → N-radical
cation → peroxide product or
dehydration product/
ACT → phenoxyl radical → N-(3–
hydroxy–4-oxocyclohexa-1,5–dien–
1-yl)acetamide
●
OH and SO4 ●− Hydroxylation → oxidation of 100% in 15 min (at pH ACT → m/z 168 → (Kohantorabi et al.,
aromatic structure and amide 7.0) 1,4-dihydroxybenzene (m/z 110) 2021)
bonds and glycolic acid (m/z 76) /
m/z 110 and m/z
149 → 1,4-benzoquinone (m/z
108) → 3- hydroxypropanoic acid
(m/z 90) → formic acid (m/z
46) → CO2 and H2 O / nitrate (NO3 − )
(m/z 62)

(continued on next page)

705

Table 4 (continued)
AOP systems/ Conditions
PAA/UVC-LED/ Fe(II)
system, ACT 20 mg/L, PAA
4 mmol/L, Fe(II) 0.5 mmol/L,
pH 5
HU/PMS (hydrolyzed
urine/peroxymonosulfate)
system, ACT 5 μmol/L, PMS
3 mmol/L, T = 10–50 °C, pH
9 ACT → dimer of ACT (m/z = 299)
Co3 O4 /PMS process,
3 mmol/L PMS, 0.2 g/L
Co3 O4
Fabricated Mn-g-C3 N4
composited (MnCN) for PMS
activation (PMS/MnCN
system), ACT 20 mg/L,
0.8 g/L PMS, 0.2 g/L catalyst
0.5-MnCN, initial pH 6.5
706
ROS Mechanism of degradation Removal efficiency TP formation Ref.
●
OH and RO● –NH– bond disruption, > 95% in 30 min ACT → acetamide, 4-aminophenol (Ghanbari et al.,
hydroxylation, -OH addition, and N-(3,4- dihydroxyphenyl) 2021)
aromatic ring opening /ACT acetamide → 4-aminobenzene-
polymerization with 1,2-diol → 4-aminophenol and
journal of environmental sciences 147 (2025) 688–713
intermediates/organic radicals hydroquinone
4-aminophenol→ hydroquinone
and 4-nitrophenol→
hydroquinone
4-nitrophenol and
hydroquinone → carboxylic acids
(acetic acid - m/z 60) /
ACT → unknown polymerized
product (m/z = 203)
1
O2 Chlorine substitution and electron 96.1% (at 25 °C) in 60 ACT → 4-nitrophenol, (Lin et al., 2021)
transfer → benzene ring breakage min 1,2,4-benzentriol and
benzaldehyde → oxalic acid,
maleic acid
●
OH and SO4 ●− Substitution in the amide group 99% in 30 min ACT → 4- (Rodríguez-
aminophenol → benzene-1,4-diol Narvaez et al.,
or 4-hydroxybenzene-1-sulfonic 2020)
acid,
benzene-1,4-diol → malic acid and
succinic acid,
4-hydroxybenzene-1-sulfonic
acid → 3,4-hydroxybenzene-1-
sulfonic acid → malic acid and
succinic acid
1
O2 and O2 ●− 100% in 15 min ACT → hydroquinone (Fan et al., 2019)
–
 journal of environmental sciences 147 (2025) 688–713
Numerous types of treatment systems and AOPs can be
used for the degradation and mineralization of ACT as is ev-
ident from the recent literature (Table 4). The preference of
the most appropriate method depends on factors, such as ef-
ficiency, cost-effectiveness, and the recyclability of the mate-
rials used in the process to avoid any risks of pollution caused
by the remediation process.
The most recommended systems, nevertheless as an opin-
ion, for the degradation of ACT can be the AOPs producing ex-
clusively either O2 ●− or SO4 ●− as the preferred ROS, the rea-
son being that these are found to counterpoise the reactiv-
ity/selectivity phenomenon which is primarily at the heart of
any contaminant degradation process. It is discernible from
the data in Table 2 indicating the relative properties of ROS,
that O2 ●− and SO4 ●− have a medial value of reduction poten-
tial in contrast to the values for other frequently used ROS
which is either considerably high or too low. This makes ● OH
highly reactive while 1 O2 is too selective in nature. Alteration
in the redox potential is indeed a key factor governing the bal-
ance such that the ROS is neither too reactive to attack ev-
ery background substance in the medium nor too selective to
cease to react before the complete mineralization of the target
contaminant. Although the choice of the most suitable system
or AOP for ACT degradation would be based on the specific
requirements of the application, including the concentration
of the API, the presence of other contaminants, available re-
sources, and the desired level of removal. Furthermore, pilot
studies and a thorough assessment of the local conditions are
often necessary to determine the best treatment approach.
3. Conclusion and perspective
An understanding of the degradation mechanisms is im-
portant to the design or optimization of a new ROS-based
transformation. This Review has presented myriad examples
of ROS-mediated reactions with acetaminophen (ACT) that
reflect the most probable pathway for each ROS discussed
therein. This analytical compilation could help chemists at
all experience levels to predict the degradation products of
ACT with nearly any type of reactive species that will be com-
monly encountered in numerous sorts of advanced oxidative
treatment processes. As the field of radical chemistry and its
applications in environmental remediation continues to ex-
pand, it is anticipated that this review will serve as a means
for providing familiarity with the mechanistic insights into
drug degradation processes necessary for the optimization of
the reaction process, selectivity and efficiency, prediction of
by-product formation, as well as the safety considerations.
Some feasible system design strategies to help steer the op-
timization of reaction performance and improvement of pro-
cess safety are summarized as follows:
(i) Implementing process intensification techniques, such
as continuous processing, microreactors, or multiphase
systems, to improve reaction efficiency and reduce by-
product formation.
(ii) Designing or selecting sustainable and eco-friendly cat-
alysts that can enhance the desired reaction pathways
while minimizing unwanted side reactions in parallel.
707
(iii) Conducting thorough kinetic studies to comprehend
the rate and mechanism of reactions, enabling better
control and optimization.
(iv) Applying real-time monitoring and analytical systems
to maintain optimal conditions and adjust parameters
as needed.
(v) Ensuring that the quality of raw materials and purity
of reagents is not compromised as it might lead to by-
product formation. Similarly, precise control over tem-
perature and/or pressure needs to be maintained to fa-
vor intended reactions.
(vi) Screening for reaction medium (consisting of solvents
or solvent mixtures) that are most selective for the de-
sired reactions.
(vii) Employing efficient separation and purification tech-
niques to isolate or recycle the products or catalysts.
(viii) Designing processes with inherent safety features, such
as utilizing safer (less reactive) chemicals, reducing the
use of hazardous materials, and putting passive safety
mechanisms into practice.
(ix) Considering the scalability and potential changes in re-
action kinetics while transitioning from lab-scale to pi-
lot and industrial-scale processes.
(x) Emphasizing the use of environmentally friendly or
benign reagents to make the processes sustainable.
More recyclability would help curtail the waste and by-
products.
(xi) Utilizing computational modeling, optimization algo-
rithms, and simulation tools to explore various design
scenarios and identify optimal conditions.
(xii) Conducting a comprehensive risk assessment to iden-
tify potential hazards and safety concerns early in the
design process. Performing a life cycle assessment (LCA)
to estimate the environmental impact of the process,
since such assessments would ensure compliance with
regulations and diminish harm to the ecosystem.
Although seemingly counterintuitive, studies on reactions
of pharmaceutical compounds with various ROS have exhib-
ited simplistic degradation values for in-lab environments
which recently has brought to light a greatly enhanced mech-
anistic perception. The predominant objective of this study is
to portray the distinctive and inherent reaction mechanisms
at a molecular scale that eventually factor in pharmaceuti-
cal removal via ROS. Since this study relates to the develop-
ment of new transformations in pharmaceutical removal, it
might help to break down the barriers in the way of scheming
an apparently unpredictable form of advanced treatment pro-
cesses. More investigations into enhancing the selectivity in
the degradation of pharmaceuticals by making use of varied
ROS will retrench the costs in addition to widening the scope
of their applications.
Declaration of Competing Interest
The authors declare that they have no known competing fi-
nancial interests or personal relationships that could have ap-
peared to influence the work reported in this paper.
708 journal of environmental sciences 147 (2025) 688–713
Acknowledgments
The authors would like to express thanks to the Ministry of
Higher Education, Research and Innovation − Oman for their
support of this research through TRC block funding grant No.
BFP/RGP/EBR/22/378.
Appendix A Supplementary data
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jes.2023.11.021.
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