Chemical Engineering Journal Advances 19 (2024) 100627

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Chemical Engineering Journal Advances

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Exploring the role of hydrogen peroxide dosage strategies in the

photo-Fenton process: Scaling from lab-scale to pilot plant solar reactor
Bárbara N. Giménez a, b , Agustina V. Schenone a, b , Leandro O. Conte a, c, *
a
Instituto de Desarrollo Tecnológico para la Industria Química (INTEC), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) and Universidad
Nacional del Litoral (UNL), Ruta Nacional Nº 168, 3000, Santa Fe, Argentina
b
Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
c
Facultad de Ingeniería y Ciencias Hídricas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina

A R T I C L E I N F O A B S T R A C T

Keywords: This study aims to investigate the role of hydrogen peroxide (HP) continuous dosage in removing Paracetamol
Solar photo-Fenton (PCT) from different water matrices using the solar photo-Fenton process. Different parameters in the HP dosage
Pilot plant reactor strategies (initial HP pulse, dosing time, and HP concentration) were systematically analysed to assess their
Ferrioxalate
impacts on pollutant removal (XPCT), oxidant specific consumption (YtHP/PCT ), and toxicity levels (I(%)). The
Natural pH
Hydrogen peroxide dosage strategies analysis involved various water matrices (ultrapure water UW, groundwater GW, anion matrix AW, and synthetic
Pharmaceutical wastewater pharmaceutical wastewater IW0.01 or IW0.1), which were firstly treated in a laboratory reactor and subse­
quently scaled up to a solar prototype. After laboratory testing, the most effective reaction configuration
(maximum XPCT and YtHP/PCT close to the stoichiometric one) was chosen as the starting point for scaling up the
reaction system. Using the solar reactor setup, complete PCT conversion was achieved within just 60 min of
reaction time (UW matrix). However, under IW0.1 condition and employing the same HP dosing strategy, a XPCT
of 95.4 % was attained but at 180 min of reaction, highlighting the significant influence of the real matrix.
Additionally, the I(%) remained high towards the end of the reaction (close to 60 %), attributed to the presence
of hydroquinone in the system, demanding longer reaction times to completely reduce the toxicity when working
with industrial wastewater. This comprehensive approach aims to close the gap between lab results and practical
applications, offering crucial insights to address pharmaceutical wastewater pollution.

1. Introduction effluents [7], pharmaceutical industry wastewater [8], and urban

sewage treatment plants [9]. It is, therefore, unsurprising that phar­
The growing concern over Emerging Contaminants (ECs) is evident, maceuticals are identified in receiving surface water [10], groundwater
particularly with substances such as pharmaceuticals and personal care [11] and in some instances, even in drinking water [12].
products (PPCPs), pesticides, dyes, antibiotics, and antibiotic-resistant The standard technologies implemented by wastewater treatment
genes (ARGs) [1]. These pollutants have diverse sources, including in­ plants (WWTPs) are often ineffective in efficiently removing these
dustrial wastewater, domestic sewage, livestock and poultry waste­ contaminants of emerging concern [13]. Similarly, other water treat­
water, and hospital wastewater [2], having potential risks to both ment methods such as reverse osmosis [14], and carbon adsorption [15],
ecological environments and human health [3]. PPCPs have become primarily shift these pharmaceutical pollutants from one phase to
pervasive in the environment due to their extensive production and use another but do not effectively remove them [16]. Advanced Oxidation
[4]. Specifically, substantial quantities of Paracetamol (PCT) were dis­ Processes (AOPs), with a particular focus on the Fenton and
charged into water systems because of its widespread use, inadequate photo-Fenton systems, have gained significant attention. These
disposal practices by manufacturers, limited metabolic breakdown in well-established and highly efficient technologies are widely utilized for
the human body, and their biologically active structures [5]. High treating both natural waters and wastewater. They exhibit the capability
concentrations of PCT (up to 300 mg L− 1, [6]) were detected in hospital to eliminate a broad spectrum of contaminants, a task that conventional

* Corresponding author at: Instituto de Desarrollo Tecnológico para la Industria Química (INTEC), Consejo Nacional de Investigaciones Científicas y Técnicas
(CONICET) and Universidad Nacional del Litoral (UNL), Ruta Nacional Nº 168, 3000, Santa Fe, Argentina.
E-mail address: [email protected] (L.O. Conte).

https://doi.org/10.1016/j.ceja.2024.100627

Available online 4 July 2024

2666-8211/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

treatment methods often find challenging to address [17]. matrices using the Fe-Ox-PFP. Unlike many studies that typically focus
The photo-Fenton process is a photocatalytic method that generates on PPCPs degradation under controlled conditions, this research
highly reactive hydroxyl radicals (HO•) by combining chemical reagents emphasized the effectiveness of HP dosage in enhancing the iron cata­
(Fe(II)/Fe(III) salt/complex and hydrogen peroxide, HP) with UV–Vis lytic cycle. The results showed substantial improvements in both Fenton
irradiation, resulting in a synergistic effect that accelerates the pro­ and photo-Fenton reactions, indicating promising applications despite
duction of hydroxyl radicals. Nonetheless, there are significant limita­ the limitations of the experimental scale.
tions associated with this “traditional” process approach [18]. Firstly, Indeed, the assessment of purification technologies like the photo-
the regeneration of Fe(II) from Fe(III) was identified as the step that Fenton process in real-world scenarios is crucial for addressing the
limits the rate of the process. In this context, light plays a crucial role, challenges posed by persistent contaminants in complex effluents. In this
serving as an “activator” for the regeneration of Fe(II) and, conse­ context, the current research aims to address the removal of Paracetamol
quently, accelerates the overall reaction [19]. Here, the use of iron (PCT) from complex pharmaceutical wastewater effluent. The chosen
complexes proves to be advantageous, allowing operation at a neutral approach involves harnessing the solar photo-Fenton reaction, operating
pH, preventing iron precipitation, and expanding the application range at a near-neutral pH and incorporating oxalate as a complexing agent to
of the process to the visible region of the solar spectrum [20]. Giménez form ferrioxalate. A fundamental aspect of this research lies in investi­
et al. [21] have already demonstrated the feasibility of the gating different parameters in the HP dosage strategies (initial HP pulse,
Ferrioxalate-assisted Photo-Fenton Process (Fe-Ox-PFP) applied to the dosing time, and HP concentration), which play vital roles in deter­
degradation of Paracetamol (PCT). Secondly, hydroxyl radicals are mining the efficiency of the Fe-Ox-PFP in the removal of PCT present in a
highly unstable and non-selective, making them prone to unwanted simulated pharmaceutical wastewater employing a real pilot plant solar
secondary reactions, some of which involve HP consumption, reducing reactor, including considerations regarding toxicity levels. Through
the process efficiency [22]. Moreover, an oversupply of hydrogen systematic experimentation and analysis, the research aims to optimize
peroxide can undergo spontaneous decomposition into oxygen and the dosing strategy to maximize pollutant removal while minimizing
water [23]. Consequently, it is crucial to control the reaction conditions operational costs and environmental impacts.
by adjusting the oxidant dosage, which is frequently the most costly
reagent, to achieve the complete degradation of the target compound 2. Material and methods
[24]. Then, a balance between the low decontamination efficiency of the
process, caused by insufficient hydrogen peroxide dosage, and the 2.1. Experimental devices
additional expenses linked to an excess of it, need to be established. To
address this issue, researchers have explored the use of different HP In this investigation the experiments were conducted employing two
dosage strategies to enhance the performance of the photo-Fenton pro­ different photoreactors. The first one was a batch lab-scale reactor
cess [24–26]. irradiated by a solar simulator. This unit operates under perfect mixing
In recent years, solar technology has transformed the photo-Fenton conditions and at a constant temperature. Details of this experimental
process into a cost-effective and competitive method for chemical system can be referenced elsewhere [41]. Here, the local radiation flux
degradation of organic pollutants. Solar reactors offer an intriguing averaged over the reactor window (qW) was 92.80 W m− 2 (32.2 nE cm− 2
alternative for effluent treatment, eliminating expenses associated with s− 1), within the wavelength range of 300 to 500 nm (USB spectrometer,
UV lamps installation and maintenance, and reducing electrical power Ocean Optics, USB2000). This radiation level simulates the annual
consumption [27]. The literature specifically highlights the application average natural radiation condition frequently found in the city of Santa
of the solar photo-Fenton process in remediating water containing ECs, Fe (Argentina, 31◦ 39′ S, 60◦ 43′ W, 25 m above sea level). The total
including PPCPs [28], pesticides [29], dyes [30], antibiotic [31], ARGs volume of the treated solution was 3 L.
[32], effluents from municipal treatment plants [33] and hospitals [34]. The second reactor utilized in this study was a pilot-plant non-
However, cost considerations, particularly regarding the oxidizing concentrating solar photoreactor, specifically designed to capture UV/
agent, are important to address. In systems operating at natural pH and visible and near-infrared solar radiation (patent INPI P-080103697).
utilizing solar radiation, the oxidizing agent can be one of the most The entire reaction system operates within a closed recirculating circuit,
expensive reagents [35]. The pursuit of automating the photo-Fenton which is facilitated by a high flow rate centrifugal pump and a well-
process is driven by the goal of improving its performance, with a stirred storage tank. The storage tank is equipped with a pH-meter
focus on decreasing hydrogen peroxide consumption compared to and an OD sensor from HANNA Instruments. Additionally, type J ther­
manual operation. This objective is directed at lowering both the eco­ mocouples are employed to monitor temperature variations at different
nomic cost and process time, ultimately enhancing resource use positions in the system over time. To measure the UV and total broad­
efficiency. band solar radiation fluxes incident on the two-plate reactor window,
It is important to highlight that a considerable number of scientific CUV3 and CM11 Kipp and Zonen radiometers were employed. The
articles focus only on studying the degradative behaviour of PPCPs in irradiated reactor volume was 6.1 L, while the total volume of the
ideal water matrices. However, in real aqueous environments, a range of treated solution was 35 L. For further detailed information regarding
substances may coexist, posing potential obstacles to the breakdown of this solar photoreactor, please refer to [29]. Finally, both experimental
these contaminants via the photo-Fenton process. Anions (chlorides, setups (laboratory and pilot plant units) were equipped with a dia­
nitrates, bicarbonates, and sulphates) are recognized for interfering in phragm dosing pump (Acquatron® MA-CP series) for the automatic
the reaction, as they act as scavengers for the HO• produced [36]. addition of the oxidizing agent.
Cations (mainly, calcium and magnesium) can interfere with the Fe
(III)/Oxalate equilibrium/precipitation reactions, affecting the photo­ 2.2. Analytical determinations
chemical activity of the system [37]. The influence of both cations and
anions is crucial because, in many industrial pharmaceutical plants, the Paracetamol (Sigma-Aldrich, 98 % purity) served as the model
water supply for cleaning the reactors comes from underground wells. pollutant. The concentrations of PCT and its main reaction intermediate,
Furthermore, in real pharmaceutical industry effluents, many agents hydroquinone (HQ) (Fluka, 99 % purity), were analysed by HPLC-DAD
(such as detergents), are employed to clean the formulation reactors. (Waters) following the methodology outlined in Giménez et al. [21]. The
Thus, all these interferences contribute to a reduction in the pollutants mineralization achieved was monitored via TOC measurements
degradation rates and an increase in the HP consumption [38,39]. employing a Vario TOC cube analyzer (Elementar). Hydrogen peroxide
Giménez et al. [40] assessed a straightforward and punctual HP dosing (Cicarrelli, 30 %) and total iron were determined using a UV/Vis spec­
strategy within a laboratory-scale reactor across various complex water trophotometer (Lambda 35, Perkin-Elmer). For HP, a modified

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

iodometric technique was applied (measurement at 350 nm). Both the and 756 mg L− 1, respectively) was chosen. Moreover, selecting doses
samples for total Fe (pre-treated with ascorbic acid) and Fe2+ were higher than the stoichiometric value (189 mg L− 1) is based on the
analysed using the colorimetric method with 1,10-phenanthroline at demonstrated improvement in conversion levels within shorter reaction
510 nm [41]. Finally, the oxalate ion (Oxa) was quantified by an ion times [18].
chromatography-conductivity detector (Waters) with an IonPac AS22 Specifically, regarding the dosage of HP, two strategies were evalu­
anion exchange column and an IonPac AG22 guard column (Dionex). ated: 1) starting with an initial pulse of reagent, followed by a contin­
The eluent consisted of 4.5 mM Na2CO3/1.4 mM NaOH (flow rate of 1.2 uous additional dosage of HP until 75 or 150 min of reaction; 2)
mL min− 1). For the preparation of the ferrioxalate complex, a solution of beginning the test without an initial pulse of reagent, instead, starting
potassium oxalate monohydrate (Carlo Erba, 99.5 %) and a solution of with a continuous dosage of the oxidizing agent until 75 or 150 min of
iron(III) chloride were mixed in appropriate proportions. Ultrapure reaction (see Table 1 and Table 2).
water was obtained using a reverse osmosis system (Osmoion, APEMA). Finally, the treated samples consisted of: a) ultrapure water (UW), b)
A Microtox Model 500 Toxicity Analyser (Strategic Diagnostic Inc.) an artificial matrix of anions in ultrapure water (AW), c) real ground­
was utilized to assess acute toxicity of the samples throughout the water (GW) and d) synthetic industrial wastewater coming from a
oxidation process. Toxicity was computed as the percentage of light pharmaceutical plant (IW0.01 or IW0.1). In all the experiments, initial
emission inhibition by the Vibrio fischeri NRRL-B-11177 bacteria PCT, Oxa, and Fe concentrations were set at 40 mg L− 1, 47.5 mg L− 1, and
following a 15-minute incubation period. Light inhibition measurements 3 mg L− 1, respectively. The initial concentration of PCT was determined
were conducted without sample dilution. Prior to toxicity assessments, based on observed levels in actual pharmaceutical industry wastewater
sample pH was adjusted within the range of 6 to 7 and any residual [6,42]. For iron, the concentration was selected in accordance with legal
hydrogen peroxide in the aqueous sample was decomposed into water discharge limits for treated effluent into surface water bodies, set at 5 mg
and oxygen using a catalase solution (1500 mg L− 1 of >2000 U/mg L− 1 [43]. To achieve a molar ratio of Fe/Ox=1/10, the initial oxalate
bovine liver, Fluka) concentration was established at 47.5 mg L− 1, thereby preventing iron
precipitation at the operational pH. Previous studies have shown that
2.3. Experimental procedure under these conditions, approximately 90 % of the ferrioxalate species
present is the highly active Fe3+(C2O4)3− 3 , which possesses significant

For the tests conducted in the pilot plant solar reactor, each experi­ molar absorption coefficients in the UV/Vis spectrum [41].
mental assay began with the introduction of PCT and ferrioxalate solu­ In the case of UW, AW, and GW, a PCT standard drug was added to
tions into the storage tank of the system. At the beginning of these obtain 40 mg L− 1 in the total reaction volume (3 L). The AW matrix was
experiments, a solar-opaque plate protected the reactor window to prepared so that the final concentrations of each anion in the reaction
prevent solar radiation entry. In all cases, the medium pH was adjusted volume were: 80, 50, and 100 mg L− 1, for Cl− , SO2− 4 , and HCO3 ,
−

to 5 using either a concentrated sodium hydroxide solution (3 mol L− 1, respectively. For this, NaCl, Na2SO4, and NaHCO3 obtained from
Cicarelli) or sulphuric acid (3 mol L− 1, Cicarelli), depending on the Cicarelli were used. The main characteristics of the GW sample and its
initial pH of the solution under treatment. The oxidizing agent was composition can be found elsewhere [40].
added according to the evaluated dosing strategy, and upon addition, For the synthetic industrial effluent, the source of PCT was a com­
the first sample was taken, and the reactor cover was removed to initiate mercial pill (LIF, Cert. ANMAT Nº 54.235), containing pre-gelatinized
the photochemical reaction. The solar experiments began at 10.0 LST starch, stearic acid, and povidone K30 as excipients. The effluent prep­
and the reaction progress was monitored over 180 min, taking samples aration involved the following steps. First, five commercial pills (each
at predefined times for various analyses and parameter assessments. An containing 500 mg of paracetamol) were weighed and pulverized. The
analogous procedure was performed when operating the laboratory- mass equivalent to one pill was dissolved in 500 mL of ultrapure water,
scale reactor, although a constant temperature of 25 ◦ C was main­ resulting in a solution of 1 g PCT L− 1. Subsequently, 120 mL of the
tained throughout the reaction time, in order to avoid inefficient use of concentrated commercial PCT solution was added to achieve a final
hydrogen peroxide at higher temperatures. More details of the experi­ concentration of 40 mg L− 1 of PCT in the total reaction volume (with
mental procedure can be found in [29]. TOC = 30.54 mgC L− 1 for the diluted drug solution). Finally, CIP300® (a
To determine the oxidant concentrations for dosing, the stoichio­ neutral pH detergent commonly used in the pharmaceutical industry)
metric quantity necessary to achieve complete mineralization was was added at a concentration of 0.01 % (IW0.01) or 0.1 % (IW0.1) in the
calculated assuming HP as the sole oxidant in the medium and PCT system (TOC = 54.74 mgC L− 1 for a solution of CIP 0.1 %), contributing
concentration at 40 mg L− 1. The calculated value was 189 mg L− 1. Then, to a total carbon amount of 85.28 mgC L− 1 in the simulated effluent
a range between a quarter and four times the stoichiometric dose (47.25 when using the 0.1 % CIP solution.

Table 1
180
Experimental conditions and PCT conversion (XPCT (%)) after 180 min of reaction for lab-scale reactor.
Run ID HP Dosing time (min) Radb Matrixa Flow X180
PCT (%)
(mg L¡1) (mgHP min¡1)

N1* 378_IP_150_OFF_UW 378 150 OFF UW 8.41 3.5

N2 47.25_NP_75_ON_UW 47.25 75 ON UW 2.13 96.0
N3 94.5_NP _75_ON_UW 94.5 75 ON UW 4.81 94.3
N4* 189_IP_150_ON_UW 189 150 ON UW 3.61 93.3
N5 189_NP _150_ON_UW 189 150 ON UW 4.81 93.9
N6* 378_IP_150_ON_UW 378 150 ON UW 8.41 90.7
N7 378_NP _75_ON_UW 378 75 ON UW 14.88 85.9
N8* 378_IP_75_ON_UW 378 75 ON UW 16.63 87.8
N9 756_NP _75_ON_UW 756 75 ON UW 34.03 79.0
N10 378_NP _75_ON_GW 378 75 ON GW 16.63 99.5
N11 189_NP _75_ON_AW 189 75 ON AW 8.51 97.7
N12 378_NP _75_ON_IW 378 75 ON IW0.1 16.63 18.9
a
UW: ultrapure water; GW: ground water; AW: artificial anion matrix; IW0.1: simulated industrial wastewater with 0.1 % CIP300.
b
Rad = Radiation. ON: qW = 92.80 W m− 2; OFF: without radiation.
*
Runs with an asterisk are those that were carried out with an Initial Pulse (IP) of HP = 47.25 mg L− 1.

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

Table 2
Experimental conditions in the pilot plant solar reactor.
Run HP (mg L¡1) Tt0( ◦ C) Tt180 ( ◦ C) Accumulated energya (KJ L¡1) Flow (mgHP min¡1) Matrixb XPCT c (%)

S1 47.25 23.8 38.9 5.23E+04 21.88 UW 98.90 (60 min)

S2 378 25.8 35.9 2.50E+04 175 UW 98.70 (60 min)
S3 756 26.2 41.9 4.97E+04 350 UW 98.90 (45 min)
S4 378 28.0 39.9 3.35E+04 175 IW0.01 97.90 (60 min)
S5 378 29.0 44.2 4.02E+04 175 IW0.1 95.40 (180 min)
a
Calculated at 180 min reaction time.
b
UW: ultrapure water; IW0.01: simulated industrial wastewater with 0.01 % CIP300; IW0.1: simulated industrial wastewater with 0.1 % CIP300.
c
Between parenthesis: time (min) at which the conversion value was reached.

3. Results and discussion min (Dosing Time), and non-irradiated reaction conditions (Rad).
The influence of radiation on the system is significant. Under dark
Two different photoreactors were utilized in this study: a batch lab- conditions, using UW matrix (Run N1), PCT conversion only reached 3.5
scale and a pilot plant solar reactor. These reactors were employed to % after 180 min of reaction. In contrast, a minimum conversion of 79.0
assess the scalability and efficiency of hydrogen peroxide dosage in PCT % was obtained under irradiated conditions (Fig. 1d, Run N9), where an
photo-Fenton degradation. excess of oxidizing agent was present in the system. Moreover, when
radiation was applied, even at the lowest final concentrations of
oxidizing agent (Fig 1c, HP = 47.5 mg L− 1, Run N2, and HP = 94.5 mg
3.1. Lab-scale reactor
L− 1, Run N3), high PCT conversions were still achieved (greater than 94
%).
Table 1 lists the set of experiments carried out in the lab-scale reactor
In second place, it can be observed that the influence of the initial
in different matrices. The identification code (ID) used to describe each
pulse of HP was not significant in the achieved contaminant conversion
experimental condition includes: the theoretical target/final oxidizing
levels (Fig. 1c, Run N4 vs. Run N5, and Fig. 1d, Run N7 vs. Run N8).
agent concentration reached (“HP”: 47.25, 94.5, 189, 378 or 756 mg
There were also no substantial differences between contaminant con­
L− 1), the addition of an initial punctual dosage of oxidant (“Initial
version for a dosing time of 75 min (Run N7) vs. 150 min (Run N6).
Pulse”: IP, initial pulse; or NP, no initial pulse), the period during which
However, the main operational differences were found in the observed
the oxidizing agent was added (“Dosing Time”: 75, or 150 min); the
oxidizing agent consumption (YtHP/PCT ). At this point, the specific con­
radiation condition (“Rad”: ON, or OFF), and the water matrix treated
(“Matrix”: UW, GW, AW and IW0.1). Thus, as an example, Run N1, sumption of HP was defined as the difference between the mass of HP
ID:378_IP_150_OFF involves a final oxidant concentration of 378 mg L− 1 added to the reaction medium (HPtdosed ) and the mass of HP quantified
(HP), an initial pulse of oxidizing agent (IP), oxidant dosing time of 150 experimentally in the system (HPtmeasured ), as a function of the mass of

Fig. 1. Specific consumption of hydrogen peroxide for a) low HP concentrations (Runs N2 - N5) and b) medium and high HP concentrations (Runs N6 - N9); c)
relative PCT concentrations for low HP conditions (Runs N2 - N5); d) relative PCT concentrations for medium and high HP concentrations (Runs N6 - N9).

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

PCT converted (Eq. (1), [41]). achieved (Fig. 2c), the oxidizing agent consumptions were lower than
∑t ( t ) the stoichiometric amount (Fig. 2a), indicating the formation of reaction
0 HPdosed − HPtmeasured
intermediates [44]. Conversely, when evaluating synthetic industrial
YtHP/PCT = (1)
PCT 0 − PCT t wastewater, PCT was poorly degraded (Fig. 2c, 18.9 % at 180 min) and
The specific consumptions of oxidizing agent and PCT evolution are the specific consumption was much greater than 4.72 mg HP mg PCT− 1,
depicted in Fig. 1. For low doses of hydrogen peroxide (Fig. 1a, Runs N2 demonstrating a high unproductive consumption of the oxidant
to N5), regardless of the reagent dosing rate used (75 or 150 min), the (Fig. 2b). Both effects can be associated with the contribution of organic
consumption of oxidizing agent remained below the stoichiometric matter to the reaction medium due to the components of CIP300® and
value required for the mineralization of PCT (4.72 mgHP mgPCT− 1, Eq. the excipients in the pills of PCT. Furthermore, even though the
(2)). Considering that a consumption value close to the stoichiometric composition of the detergent is not informed, it is known that anionic
one is associated with the complete removal of reaction intermediates, surfactants can form complexes with Fe ions, interfering with the cata­
the studied dosing conditions were not sufficient to degrade the gener­ lytic cycle and the performance of the process [45].
ated by-products [44]. For all the tests conducted in the laboratory reactor, the temporal
evolutions of the catalyst (Fe+3/Fe+2) and the complexing agent (oxa­
C8 H9 NO2 + 21H2 O2 →8CO2 + 25H2 O + H+ + NO−3 (2)
late ion) were analysed. The maximum recorded oxalate conversion at
180
In the case of medium and high HP doses (Fig. 1b, Runs N6 to N9), 180 min was XOXA = 19.69%, under the conditions of test N9 (using the
variable levels of oxidizing agent consumption were observed. Using maximum concentration of the oxidising agent, HP= 756 mg L− 1).
maximum HP concentrations and HP dosage rates (Run N9), the specific However, no catalyst (Fe) precipitation was observed in any of the
unproductive consumption reached its maximum value (8.05 mgHP laboratory tests.
mgPCT− 1 for 15 min of reaction). This excess of HP, besides interfering Regarding TOC analysis, the highest conversions achieved were
in the PCT degradation process, leads to excessive and nonspecific observed in Run N6 (378_IP_150_ON_UW), reaching a maximum of
consumption of the oxidizing agent itself. This phenomenon arises from 180
XTOC = 20.15%. Conversely, the lowest values were recorded in the case
the reaction of HP with HO• radicals (Eq. (3)) or the self-decomposition of simulated industrial wastewater in Run N12 (0.1 % CIP300), with
of HP (Eq. (4)) [40]. However, for medium HP concentrations and 180
XTOC = 1.3%. Furthermore, for the conditions of tests N10 (GW) and N11
dosage rates (Runs N6 and N7), this unproductive consumption 180
(AW), the XTOC were less than 14%.
decreased. In the conditions of Run N7, this value was close to the
stoichiometric one (4.72 mgHP mgPCT− 1).
H2 O2 + HO⋅ → HO⋅−2 + H2 O (3) 3.2. Pilot plant solar reactor

2H2 O2 → 2H2 O + O2 (4) Table 2 presents the operating conditions of the runs performed in
the solar reactor. The temperature increment, the total accumulated
Based on these results, the conditions of Run N7 (continuous addition of energy (between 300 and 550 nm), and PCT conversions were moni­
HP until 75 min of reaction without initial punctual dosage) will be tored for 180 min of reaction. For all the tests carried out, the dosing
considered as the starting point for experiments with more complex time of the oxidizing agent was set at 75 min and no initial HP pulse was
matrices (Runs N10 to N12). PCT temporal evolution and calculated HP employed. These conditions were defined considering the preliminary
consumptions can be analysed in Fig. 2. In the case of AW and GW results obtained in the laboratory reactor.
matrices, although high conversion levels of the pharmaceutical were Firstly, it’s important to note that for each of the tests outlined in

Fig. 2. a) and b) Specific consumption of hydrogen peroxide and c) relative PCT concentrations for complex matrices in the lab-scale reactor. GW: groundwater (Run
N10, HP = 378 mg L− 1); AW: artificial anion matrix (Run N11, HP = 189 mg L− 1); IW0.1: simulated industrial wastewater with 0.1 % CIP300 (Run N13, HP = 378
mg L− 1).

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

Table 2 (Runs S1 to S5), variable values of accumulated energy and simulated industrial wastewater (Run S5). This contrasts with the con­
temperature increase were recorded due to the environmental condi­ version value of 18.9 % achieved in the lab-scale reactor (Run N12,
tions encountered during each experimental test. Therefore, the accu­ Table 1).
mulated radiation (Q300 − 550nm, t, KJ L− 1) in each experiment with solar For all tests conducted in the solar reactor, the maximum recorded
radiation was calculated according to Eq. (5), [46]: oxalate conversion was XOXA 180
= 74.53%, under the conditions of test S3
Ar (using the maximum concentration of the oxidising agent, HP= 756 mg
Q300− 550nm, t = Q300− 550nm, t− 1 + Δtt RAD300− 550nm,t (5) L− 1). Unlike the laboratory tests, in this case, a maximum final precip­
Vt
itation of the catalyst close to 75 % was observed.
where Q300 − 550nm, t is the total accumulated radiation (KJ L− 1), Δt Dissolved oxygen (DO) profiles were monitored throughout the re­
represents the time interval (s), RAD300− 550nm,t is the average total ra­ action as an easily quantifiable variable associated with the evolution of
diation (W m− 2), Ar is the irradiated area (0.24 m2), and Vt is the total the photo-Fenton process and its efficiency [48]. Fig. 4a illustrates the
volume of treated wastewater (35 L). The accumulated radiation was evolution of DO as a function of accumulated energy for Runs S1 (HP
calculated between 300 and 550 nm, considering the photochemical deficit) and S3 (HP excess). Under the conditions of run S1, a constant
characteristics of the employed ferrioxalate complex [47], which en­ decay in the DO concentration was observed (up to 40 % of the satu­
ables the utilization of both, UV and visible radiation. Therefore, this ration value of 7.10 mg L− 1) during the progress of the reaction. This
accumulated radiation represents the energy required for the photo­ observation suggests a Dorfman-type mechanism in the system, where
chemical activation of the process. dissolved oxygen actively participates in the oxidative process [23].
Fig. 3 shows the evolutions associated with PCT degradation, as a However, using an excess of oxidizing agent (Run S3), two distinct
function of accumulated energy. behaviours were observed in the evolution of the DO. Initially, for low
The results presented in Table 2 and Fig. 3 illustrate the efficacy of reaction times, the amount of the oxidizing agent (Fig. 4b) was insuffi­
the examined process. First, complete conversion of PCT was attained cient. Considering the high initial reaction rate of the system, a DO
within just 60 min of reaction (Runs S1 to S3) for UW conditions. consumption of up to 75 % of the saturation value was reached. In a
However, when employing low doses of oxidizing agent (Run S1), a subsequent stage, hydrogen peroxide accumulated in the system and
notable decrease in the rate of contaminant degradation was evident. In began to be in excess (up to 250 mg L− 1). At this point, it initiated
fact, up to 200 % more accumulated energy was needed (5.23 × 104 KJ parallel reactions, such as self-decomposition and reaction with free
L− 1 vs. 2.50 × 104 KJ L− 1) to achieve complete conversion of the radicals, resulting in the production of O2 and subsequent increase in the
contaminant compared to an intermediate oxidant concentration of 378 DO profile up to 130 % of the saturation value (Eq. (3) and Eq. (4)) [26].
mg L− 1 (Run S2). Finally, dosing an excess of HP (Run S3) did not lead to Analysing the achieved TOC conversion is crucial for assessing the
any benefit in the degree of PCT degradation. overall effectiveness of the degradation process. In the case of pure
It is noteworthy to emphasize the effectiveness of the investigated water samples (Runs S1-S3), the relative TOC concentration (Fig. 5)
process even under conditions that simulate an industrial effluent values obtained at 180 min ranged between 32.7 % and 38.7 % (cor­
(IW0.01 and IW0.1). Remarkably high contaminant conversions (up to responding to conversions between 61.3 % and 67.3 %). However, an
98 %) were achieved within just 60 min of reaction for low detergent analysis of the system mineralization as a function of accumulated en­
concentrations (Run S4, IW0.01). However, when a higher detergent ergy reveals that the presence of detergent and the drug excipients (Run
percentage was introduced under the same HP level (Run S5, IW0.1), a S4 and S5) negatively affected the rate and final conversion of TOC
conversion of 95.4 % was attained but at 180 min, indicating the sig­ (Fig. 5), only reaching 10 % mineralization for the conditions of Run S5
nificant influence of the real matrix (and consequent consumption of (IW0.1). Indeed, the performance of the photo-Fenton process in the
hydroxyl radicals). It’s important to note that despite using the same solar pilot plant device surpassed that observed in the laboratory-scale
hydrogen peroxide (HP) concentration (378 mg L− 1) and dosing strat­ test. The laboratory reactor achieved maximum TOC conversions close
egy, the combined effect of UV/visible and thermal sunlight was able to to 20 % (Run N6), whereas the solar system exhibited enhanced effi­
almost completely degrade PCT after 180 min of reaction in the ciency (up to 67.3 % conversion of TOC, Run S2).

Fig. 3. Relative PCT concentration as a function of accumulated energy (Runs S1-S5) in the solar reactor experiments.

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

Fig. 4. Evolution of a) DO in percentage of saturation and b) HP concentration vs. accumulated energy.

Fig. 5. Relative TOC concentration as a function of accumulated energy (Runs S2, S4 and S5) in the solar reactor experiments.

Finally, the toxicity in the system was evaluated considering the quantity (blank test). Here, the presence of HQ at the end of the reaction,
commonly proposed pathway for PCT photo-Fenton decomposition. despite the great accumulated energy, caused that I(%) remained high
This mechanism involves the direct attack of hydroxyl radicals on the (close to 60 %).
PCT molecule, leading to the generation of acetamide and hydroquinone The HPLC chromatograms are shown in Fig. 7 for Runs S2 and S5,
(HQ), which is subsequently oxidized to p-benzoquinone. These aro­ registered at 243 nm (wavelength used to quantify PCT). The disap­
matic compounds undergo progressive transformation into non- pearance of PCT can be seen (tr= 7.29 min) and some peaks can be
aromatic molecules [21]. Fig. 6 depicts the changes in the percentage distinguished as reaction intermediates, of which only HQ was identified
of inhibition of bioluminescence of V. fischeri bacteria after 15 min of (tr= 5.23 min). Here, the difference between working with ideal and real
incubation (I(%)), alongside the concentration of the formed HQ (the matrices is also noted. In the case of pure water, PCT and HQ were
main reaction intermediate detected and quantified) as a function of the completely degraded at near 60 min of reaction, while in the simulated
accumulated energy. This emphasizes that the observed toxicity mainly effluent there were still low quantities of both analytes at 180 min.
originates from HQ generated during PCT degradation. Taking into account the low EC50 value of HQ (0.04 mg L− 1) for
In each case, the evolution of toxicity in the system was closely V. fischeri [49] and the presence of no identified peaks (between 1.5 and
linked to the appearance and disappearance of HQ, reaching the 3.3 min), it might be necessary to implement longer reaction times so as
maximum I(%) when the concentration of HQ in the reaction medium to completely reduce the toxicity when working with industrial
was the highest. wastewater.
It’s noteworthy that for the conditions depicted in Fig. 6a, a signif­
icant reduction in the toxicity of the system is observed after only 60 min 4. Conclusions
of reaction (accumulated energy exceeding 1.10×104 KJ L− 1). Secondly,
it can be seen that IW0.01 matrix did not represent a great addition of This study highlights the crucial role of hydrogen peroxide dosing
the initial toxicity to the system (Fig. 6b). However, a slight slowdown of strategies in optimizing the ferrioxalate-assisted solar photo-Fenton
the reaction was observed, since HQ disappeared at a higher accumu­ process to remove Paracetamol. Through systematic analysis of
lated energy than in the Run S1, which implied that the toxicity in the various dosing methods, this research provides significant insights into
reaction medium also lasted longer. On the other hand, when the their impact on pollutant removal efficiency, oxidant consumption, and
detergent was used at a concentration of 0.1 %, there was an extra toxicity levels across diverse water matrices.
addition on the initial toxicity of 23.71 % caused by only CIP300 at that The lab-scale reactor experiments highlighted the role of radiation

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

Fig. 6. Percentage of luminescence inhibition at 15 min (⬤) and HQ concentration (■) vs accumulated energy. a) Run S2 (UW); b) Run S4 (IW0.01) and c) Run S5
(IW0.1). HP= 378 mg L− 1.

Fig. 7. HPLC chromatograms at 243 nm for solar experiments. a) Run S2 in ultrapure water; b) Run S5 in simulated industrial wastewater with 0.1 % CIP300. HP =
378 mg L− 1.

and the initial point dose of HP on the contaminant conversion effi­ 180 min of reaction in the case of simulated industrial effluent treated in
ciency. In particular, irradiation conditions significantly improved the the solar reactor. However, the persistence of high toxicity levels (IW0.1
process compared to dark conditions, with high conversion rates. matrix) underscores the need for continued research on mitigation
However, excessive doses of HP led to unproductive consumption, strategies for harmful by-products, such as hydroquinone, to ensure the
which hindered the degradation of contaminants and generated un­ environmental sustainability of wastewater treatment processes.
wanted reaction by-products. Overall, this comprehensive approach bridges the gap between lab­
The transition from lab-scale experiments to a pilot plant solar pro­ oratory findings and practical applications, providing valuable insights
totype demonstrated the scalability and effectiveness of the photo- for the development of effective solutions to address pharmaceutical
degradation process. Nonetheless, challenges emerged when confront­ wastewater pollution. The robustness of the solar photo-Fenton process,
ing real industrial effluents, demanding extended reaction times to even under conditions simulating industrial effluents, reaffirms its po­
attain comparable conversion rates. The combined effect of UV/visible tential as a sustainable and scalable technology for wastewater treat­
and thermal sunlight was able to almost completely degrade PCT after ment in pharmaceutical industries.

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B.N. Giménez et al. Chemical Engineering Journal Advances 19 (2024) 100627

Funding aquatic environment, their characteristics, and adopted legislations, J. Water

Process Eng. 52 (2023) 103490, https://doi.org/10.1016/J.JWPE.2023.103490.
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The authors are grateful to Universidad Nacional del Litoral (UNL, paracetamol (acetaminophen) from synthetic waters and real wastewaters by
CAI+D 2020 50620190100040LI), Consejo Nacional de Investigaciones direct, hybrid catalytic, and sequential ozonation processes, Chemosphere 313
Científicas y Técnicas (CONICET, PIBAA 28720210100303CO, PIBAA (2023) 137411, https://doi.org/10.1016/j.chemosphere.2022.137411.
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