Journal Pre-proof

Adsorption and catalytic degradation of Tartrazine in aqueous medium by a Fe-

modified zeolite

A.V. Russo, B.G. Merlo, S.E. Jacobo

PII: S2666-7908(21)00171-3
DOI: https://doi.org/10.1016/j.clet.2021.100211
Reference: CLET 100211

To appear in: Cleaner Engineering and Technology

Received Date: 18 November 2020

Revised Date: 19 June 2021
Accepted Date: 5 July 2021

Please cite this article as: Russo, A.V., Merlo, B.G., Jacobo, S.E., Adsorption and catalytic degradation
of Tartrazine in aqueous medium by a Fe-modified zeolite, Cleaner Engineering and Technology (2021),
doi: https://doi.org/10.1016/j.clet.2021.100211.

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 Adsorption and catalytic degradation of Tartrazine in aqueous
medium by a Fe-modified zeolite

Russo, A.V.a,b , Merlo, B.G.a,b, Jacobo, S.E.a,b

a.
Laboratorio Químico de Materiales Magnéticos Aplicados a la Ingeniería (LaQuiMMAI),
Facultad de Ingeniería, Universidad de Buenos Aires, Av. Paseo Colón 850, CABA,
C1063ACV. Argentina.
b.
Instituto de Química Aplicada a la Ingeniería (IQAI), Av. Paseo Colón 850, CABA,
C1063ACV. Argentina

Example

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Adsorption and catalytic degradation of Tartrazine in aqueous medium
by a Fe-modified zeolite
Analia V. Russo, Braian G. Merlo and Silvia E. Jacobo

División Química de Materiales Magnéticos de aplicación en Ingeniería.

Dpto Química. IQAI. Facultad de Ingeniería. Universidad de Buenos Aires.

E-mail: arusso@fi.uba.ar, sjacobo@fi.uba.ar

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ABSTRACT
Azo dyes, as Tartrazine (T), are one of the rawest materials in food, pharmaceutical and

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textile industries. Many dyes are difficult to degrade due to their complex structure and
xenobiotic properties. Although adsorption is considered an effective, efficient, and
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economic method for water purification, degradation of organic pollutant like synthetic
dyes by using advanced oxidation processes (AOPs), as Fenton process, has become
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increasingly significant during last decades. However, as Fenton process requires
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ferrous salt for the oxidation reaction to take place, the iron sludge formed after the
reaction, has to be removed before discharging.
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A novel composite material, which is referred to as iron- loaded natural zeolite (NZ-A-
Fe), was used for the removal of Tartrazine (T) from water through the combined
adsorption and heterogeneous catalysis. Since the adsorption step determines the rate in
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heterogeneous catalytic processes, its study becomes necessary for understanding the
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degradation mechanism.

The suitability of Langmuir and Freundlich isotherms to the equilibrium data was
investigated in the solid-liquid system. The equilibrium adsorption capacity (qe)
increases with the increase of the initial concentration of T.

The pseudo-second-order model can well describe the adsorption process of T on NZ-
A-Fe, where k2 = 0.246 ( . min) −1 is the rate constant for adsorption process.

Degradation kinetics can be described using the classical pseudo-first order.

Tartrazine degradation was high between 90 and 95% for [H O ] /[T] = 37 for [T] = 10
mg/L

The novelty of this work is the simultaneous adsorption and Fenton degradation using a
supported catalyst NZ-A-Fe that facilitates the design of filters for wastewater
treatment.

KEYWORD:
ZEOLITES, ADSORPTION, WATER REMEDIATION, FENTON LIKE,
CATALYST, TARTRAZINE
Corresponding author: arusso@fi.uba.ar

1. INTRODUCTION
Water is an essential natural resource for human being and for life forms (Boroski et al.,
2008). The produced wastewater has detrimental impacts on the environment and poses
a serious threat to the wild and human life.

As the environment, preservation gradually becomes a matter of major social concern

and more strict legislation is being imposed on effluent discharge to deal with non-
readily biodegradable and toxic pollutants

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Industries such as textile, cosmetic, paper, leather, light-harvesting arrays, agricultural

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research, photo electrochemical cells, pharmaceutical and food produce large volumes
of wastewater polluted with high concentration of dyes and other components in
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agreement with the findings of Brillas and Martínez-Huitle (2015). The water is mainly
used for application of chemicals onto the fibers and rinsing of the final products.
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According to Ghaly et.al. (2014) it is necessary to employ about 200 L of water to
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produce 1 kg of textile.

Dyes are one of the rawest materials in food, pharmaceutical and textile industries. Azo
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dyes are complex aromatic compound characterized by one or more group (R1-N=N-
R2). Many dyes are difficult to degrade due to their complex structure and xenobiotic
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properties. Recent studies indicated that such coloured effluents have toxic effects with
carcinogenesis and may cause allergy, dermatitis, eye/skin infections, irritation, cancer
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and mutations, etc. (Morais, et al., 1999). Different methods are reported for dyes
quantification in some commercial food samples. Recently, Saleh et al. (2017) proposed
two new sensitive spectrophotometric methods for Tartrazine determination.

Adsorption is considered an effective, efficient, and economic method for water

purification. The performance of an adsorptive separation is directly dependent on the
quality and cost effectiveness of the adsorbent. The last decade has seen a continuous
improvement in the development of effective novel adsorbents in the form of activated
carbon, zeolites (Vignola et al. 2011) clay minerals, chitosan, natural inorganic minerals
and functionalized polymers. Habila et al. (2014) focused their research on economical
and effective adsorbents by the conversion of different types of wastes (palm, paper and
plastic wastes) into activated carbon via pyrolysis. According to Reck et al. (2018) a
new and low-cost adsorbent, obtained from the Moringa oleifera seed, showed to be
adequate to remove more than 95 % of a dye from aqueous solution at 15 ºC. Hussain et
al. (2015) developed an innovative process in order to remove Tartrazine from
wastewater using graphite intercalation compounds as adsorbents with electrochemical
regeneration.
Degradation of organic pollutant like synthetic dyes from aqueous solutions in industrial
wastewater has become increasingly significant during last decades by using oxidation
processes. Tartrazine can be partially removed from contaminated water by
photocatalysis, either using CuO nanostructures (Rao et al. 2017), or under solar light
(Sebti et al. 2017). Thiam et al. (2014) reported a novel method coupling
electrocoagulation with electrochemical advanced oxidation processes.

Scott et al. (2017), investigated the effect of ultraviolet light-emitting diodes (UVLEDs)
coupled with hydrogen peroxide as an advanced oxidation process (AOPs) for the
degradation of two test chemicals: Brilliant Blue (BB) and Tartrazine. These dyes
presented quite different behaviour: BB degradation resulted in faster rate constants
(83% after 300 minutes) than those observed with Tartrazine degradation (only 17%
degradation) under the same conditions. Beach et al. (2011) described a catalytic

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oxidation process for decomposing concentrated dye solutions, as a model for the
treatment of concentrated industrial effluent streams by a prepared composite (Fe-

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TAML/H2O2) which generates environmentally benign and/or biodegradable products
from Tartrazine. They informed that nearly complete dye removal could be obtained
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with performance-optimized dosing and pH control.
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Manju Kurian (2021) reported a review that demonstrates that AOPs offers a potential
for the complete solution for environmental remediation. AOP chemistry propose
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various possibilities for the degradation of organic and inorganic contaminants in

wastewaters. These processes are based on generating reactive radicals, mainly
hydroxyl radicals ( ), which oxidize the target pollutant (Georgi et al., 2016). Santos
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et al., (2011) reported that ( ) is the second most powerful oxidant next to fluorine.
The advantages of the Fenton process are a low capital cost, easy operation, and non-
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toxic by-products.
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There are few studies in the literature related to dye degradation by photo-Fenton
method, with UV radiation with enough energy to cause unstable bonds to break or
transform the dye structure, including the azo dye Yellow 5 (also known as Tartrazine).
Furthermore, they reported that several dyes were degraded showing simple decay
curves (Gupta el al., 2012) However, it should be noted that the Fe ion sludge with a
large volume after Fenton and reactions is a big drawback because the removal of the Fe
ions at the end of treatment by precipitation and dissolution is a rather costly process.
To eliminate this obvious disadvantage, some efforts have been made to develop
heterogeneous Fenton reactions.

Chekir et.al (2017) present a comparative study of the photocatalytic degradation of

tartrazine using three different systems composed of solar and UV lamp reactors
mounted separately and the combination between these two reactors as hybrid system.
The solar-reactor gives a much higher efficiency compared to the UV lamp reactor with
yields of 99% and 30% respectively. The combination between these two reactors
improves the degradation rate of the tartrazine to reach 99% after 200 min.
Heterogeneous Fenton process takes place as hydroxyl radicals are produced by
interaction of with the iron (II) species present on the porous support (X). The
main reaction mechanism of heterogeneous Fenton process is described as follow

− + → − + + (1)

− + ⇄ − + (2)

− → + − (3)

− + → − + + (4)

The hydroperoxyl radicals ( ) generated in Eq.3 are less reactive than the
species. Reactions presented in Eq.1, 3 and 4 show that the formed oxidative radicals
( and ) react with the activated dye molecules (Eq. 5) to produce intermediate

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products and then mineralization products ( + ) (Eq. 6)

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1− ⫬ − 2+ → !"#$%&#!' #'& ( $#%& ) (5)

+ !"#$%&#!' #'& ( $#%& ) →

-p + (6)
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Decolorization of the Tartrazine (T) is a result of N = N bond destruction with the
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addition of . (Fig.1)

Russo et al. (2015) reported that pollutants need to be adsorbed onto the zeolite surface
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when the catalyst is loaded in a porous material as zeolite.

The purpose of the present work is to evaluate the performance of a novel composite
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material, which is referred to as iron- loaded natural zeolite (NZ-A-Fe), for the removal
of Tartrazine (T) from water through the combined adsorption and heterogeneous
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Fenton catalysis. Since the adsorption step determines the rate in heterogeneous
catalytic processes, adsorption characterization becomes necessary for understanding
the degradation mechanism. To our knowledge, no similar studies were reported.

2. Experimental
2.1 Materials and methods

Tartrazine (Fig.1) (C16H9N4Na3O9S2) (Acid Yellow 23- CAS Number 1934-21-0) and
H2O2 (30%) were purchased from Sigma-Aldrich and from Merck, respectively.
 Fig.1. Scheme representing Tartrazine (T) structure

Powdered natural zeolite (NZ) with an average particle in the range 0.3-0.5 mm was
supplied by the DIATEC S.R.L. extracted from La Rioja, Argentina. Iron sulphate
(FeSO4·7H2O) purchased from Cicarelli p.a. was used as an iron precursor for ion
exchange.

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2.2 Preparation and characterization of catalyst

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A natural zeolite treated in NH4Cl 3M at 353 K during 8 h (sample NZ-A) was batch-
loaded with iron salts (Fe (II)) as earlier described by Russo et al. (2015)]. The sample
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was chemically reduced with sodium borohydride in order to prepare the Fenton catalyst
NZ-A-Fe (Russo et al., 2014)
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2.3 Batch adsorption isotherms and adsorption kinetic experiments

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The adsorption isotherm experiments were conducted by contacting 50 g/L of zeolite

(NZ-A-Fe) with 10 mL of T solutions of various initial concentrations (5 mg/L, 10
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mg/L, 15 mg/L and 30 mg/L).

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The vials were placed on a horizontal shaker for 24 h. After the equilibration step, the
residual concentration of the dye in the supernatant was estimated spectrophotometric
ally with a double beam spectrophotometer.

Eq.7 calculated the T uptake at equilibrium (mg/g).

*+, (-./ -0) . 2 (7)

1

where C0 and Ce (mg/L) are the liquid-phase concentrations of T at the initial and at the
equilibrium phase, respectively. V is the volume of the solution (L) and m is the mass of
dry adsorbent used (g).
For adsorption kinetic batch experiences, a Tartrazine solution of 10 mg/L was selected
in contact with 0.5 g of NZ-A-Fe zeolite. All adsorption experiments were performed in
triplicate, at 20°C and pH=3.
Langmuir and Freundlich models were tested to describe the adsorption equilibrium
data.
2.4 Heterogeneous Fenton experiments
Samples (from stock solution [T] = 10 mg/L), in contact with the catalyst (NZ-A-Ze),
added with 5 µl of hydrogen peroxide (30% w/w), were mixed on a horizontal shaker
during all the experiences. Aliquots of 1ml were extracted at fixed time.
The concentrations of mentioned samples were determined through (Co-Ct)/Co where Co
and Ct are the initial and the freely dissolved T concentration, respectively.

2.5 Analytical Method

XRD patterns were measured in a Philips PW1800/10 diffractometer with an applied
voltage of 40 kV and a 30 mA current, using a Cu-Kα radiation source. Scanning
electron microscope (SEM-Edax) images were obtained with a FE-SEM Sigma Zeiss,
with a working voltage of 5 kV. Tartrazine decomposition was evaluated by measuring

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the absorbance (427 nm) with spectrophotometer UV-VISIBLE type Shimatzu UV-
2401PC.

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UV–vis/diffuse reflectance spectra (DRS) of the zeolites composites were recorded
using UV–vis spectrophotometer with an additional integrating sphere Diffuse
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Reflectance Accessory and BaSO4 as standard. The software used in this analysis is
Peak Fit by SYSTAT Software Inc.
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3. Results and Discussion

3.1 Characterization of zeolite (NZ) and catalyst (NZ-A-Fe) samples
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Fig. 2 shows the diffractogram corresponding to natural zeolite (NZ) and the zeolite
preliminary treated with ammonium chloride and batch-loaded with iron and later
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reduced with sodium borohydride (NZ-A-Fe). The diffractogram of NZ can be fitted

with the pattern corresponding to clinoptilolite (Ref. code 01-083-1260), which
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crystallizes in the monoclinic system, space group C2/m. Iron loaded zeolite almost
remain NZ crystalline structure.
 250

200
intensity (a.u)

150 NZ-A-Fe

100

50

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NZ

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0

10 20 30 40
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2 theta
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Fig. 2. Diffractograms corresponding to NZ (natural zeolite) and NZ-A-Fe.
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Fig. 3 shows SEM images and Edax results from both samples: NZ and NZ-A-Fe.
Clinoptilolite is mainly composed of O, Si and Al, in addition to small amounts of Na,
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K, Mg and Ca. It also contains a small amount of iron. The element Si is partially
replaced by Al, so a negative charge is introduced in the zeolite structure. The ratio of
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Si/Al in the clinoptilolite which has the formula [(Na, K, Ca)6Al6Si30O72. 24H2O], is
4.6. Iron percentage considerably increases in the iron loaded zeolite (NZ-A-Fe) (Fig.3).
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Fig. 3. SEM image and EDAX composition of natural (NZ) and iron reduced (NZ-A-
Fe) clinoptilolite
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SEM images show that clinoptilolite (NZ) is composed of crystals with a well-defined
shape as plates and sheaves of plates. Both samples (NZ and NZ-A-Fe) present similar
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morphology. This is according to Fig.2, which indicates that iron loading procedure
does not modify NZ structure. NZ-A-Fe image show small nanoparticles, probably
related to iron species.
Iron in zeolite structure can be considered in three different species (Fe ions, Fe clusters
or Fe oxides). Spectra are presented in Fig.4.

1,2

4
1,0
Absorbance (a.u.)
Absorbance (a.u.)

0,8 3

0,6 2

0,4
1

0,2
0
0,0
200 300 400 500 600 700 800
200 300 400 500 600 700
wavelength (nm)
wavelength (nm)
 a) NZ b) NZ-A-Fe
Fig.4. UV–vis/DRS spectrum of Fe-zeolites and deconvoluted sub-bands for a) NZ and
b) NZ-A-Fe, respectively.

According to the literature, absorption bands below 300 nm (I1) are caused by O Fe
Ligand to Me Charge Transfer transitions of isolated Fe (III) ions and oxygen-bridged
binuclear Fe (III) species in tetrahedral and octahedral coordination, respectively.
Octahedral Fe (III) ions in small oligonuclear iron-oxo clusters give bands between 300
and 400 nm (I2). Russo et al. (2014) considered these isolated Fe3+ species as the most
active catalytic species for the heterogeneous Fenton reaction. Main signals in the range
> 400 nm can be ascribed to large iron oxide particles.

Sample I1 I2 I3
NZ 81.1 13.8 5.1

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NZ-A-Fe 65.5 34.5 0

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Table 1. Percentage of the area of sub‐bands (I1 at λ < 300 nm, I2 at 300 < λ < 400 nm,
I3 at λ > 400 nm) of UV‐visible diffuse reflectance spectra (Fig. 4)
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In NZ, the dominant fraction consists of iron species of low nuclearity (isolated or
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binuclear), which according to literature can be subdivided into Fe (III) in tetrahedral
(band at λ ≈ 220 nm, 81.1%) and octahedral coordination (band at λ ≈ 285 nm, 13.8%).
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Only 5.1% can be attributed to large Fe (III) species of low nuclearity (I3). Zeolite
treatment, during Fe loading and borohydride reduction, modifies Fe distribution as NZ-
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A-Fe placed loaded iron in tetrahedral and octahedral sites (I1 + I2). (Table 1). These
results partially explain why NZ has practically no catalytic activity in Fenton
processes.
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3.2 Batch adsorption kinetic experiments

Prior to coupling the adsorption with the catalytic oxidation, a series of preliminary
experiments were performed to determine the optimal conditions for T adsorption.
Fig.5 shows the course of adsorbed T fraction on NZ-A-Fe. The adsorption process
practically reaches equilibrium after 60 minutes.
The pseudo-first-order (a) and pseudo-second-order (b) kinetics models were applied to
analyze the kinetic data.

a) The pseudo-First-Order Kinetic Model given by Langergreen and Svenska defined

as:

ln(q 5 -q 6 ) = ln(qe)- k1.t (8)

where qe and qt are the mg the pollutant adsorbed at equilibrium and at any time (min),
respectively. This model was discarded as neither the plot of ln (q 5 -q 6 ) vs time followed
a linear behavior (not shown) nor the calculated parameters agreed with the
experimental values.
 0,16
qads(mg T/g NZ-A-Fe)

0,12

0,08

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0,00
0 20 40 60
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t (min)
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Fig.5 Tartrazine adsorption kinetics ([T]o =10 mg/L, [NZ-A-Fe] =50 g/L, pH= 3,

T= 20°C)
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The pseudo-Second-order Kinetic Model is expressed as:

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6 < 6
7 :=7 :+7 : (9)
89 => 8>? 8?
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where the equilibrium adsorption capacity (qe) and the second order constant k2
(g/mg.min) can be determined experimentally from the slope and intercept of plot t/qt
versus t (Fig.6). k2 and qe determined from the model are presented in Table.2a) along
with corresponding correlation coefficient. Tartrazine uptake mainly takes place after 60
min, in agree to the experimental k2 value (Table 2a)). NZ-A-Fe adsorption capacity qe
represents 85% of [T]o =10 mg/L (qe =0,203 mgT/gNZ-A-Fe). Ouassif et al. (2020)
reported higher values for T adsorption, by a layered double hydroxide (LDH) for dye
concentrations ranging from 20 to 240 mg/L
Kinetic data were further analyzed using the Intraparticle diffusion model (Weber and
Morris, 1963). It is an empirically found functional relationship where the adsorption
fraction (qt) varies proportionally to a function of t1/2
E
q 6 = k AB ∗ t > + CB (10)

The initial rate of intraparticle diffusion can be obtained by linearization of the curve
qt= f (t1/2) where kpi is the kinetic parameter of stage i) and gives an idea about the
thickness of the boundary layer. The graph plotted in Fig.6 (inset) is non-linear over the
whole-time range, implying that more than one process affected the adsorption.

qt (m gT/gNZ-A-Fe)
0 ,16

800
0 ,12

0 ,08
t (min)/qt (mgT). g-1

600 0 ,04

2 4 6 8 10 12

t1/2 (min)1/2

400

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200

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0 20 40 60 80 100 120 140

t(min)
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Fig.6 Linear plot of t/qe vs t for kinetic adsorption results of tartrazine on NZ-A-Fe
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(Eq.9) on NZ-A-Fe zeolite at 20°C; (inlet) Intraparticle diffusion model for adsorption
fraction qt of Tartrazine (T).
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The first region up to 30 min can be attributed to an external surface adsorption (film
diffusion) (Kpt1). Until 120 min the equilibrium was not achieved. Fig.6 (inlet) shows
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that film diffusion and intraparticle diffusion (Kpt2 ) were simultaneously occurring
during the adsorption process because zeolite structure shows a rigid surface (Fig.3),
low surface area values (9.7 m2/g) and its average pore radius and pore volume are
higher than the dye molecular size (Fig.1). These characteristics facilitates T molecules
diffusion within the zeolite (NZ-A-Fe) (Russo et al.,2018).

H IJKLKM5 < mg T
k G ∗ 7NBP:Q q 58 R Z R
g NZ − A − Fe
(a)
NH O

Adsorption kinetics
0.246 0.203 0.9653
parameters

First stage (4 – 30 min) Second stage (6-137 min)

(b) k A6< C< R2 k A6 C R
NH O NHO NH O NHO
7H IJKLKM5 ∗ 7HIJKLKM5: 7H IJKLKM5 ∗ 7HIJKLKM5:
 < <
: :
NBPE/> NBPE/>

Intraparticle 2.33 10-2 3.55 10-2 0.9602 7.37 10-4 3.92 10-2 0.8616
diffusion
Table 2. Adsorption kinetics parameters (a); Intraparticle diffusion model constants (b)
and correlation coefficients for tartrazine adsorption on NZ-A-Fe zeolite at 20°C

Table 2b) show theoretical parameters calculated from Fig.6 (inset). Kpt1 >> Kpt2 as it
was reported for different pollutants on zeolites (Tan et al., 2009). The low value of kpt2
for T is in accordance with the slow diffusion process into the NZ-A-Fe (Seifi et al.,
2011).

Adsorption isotherm of T solutions at pH= 3 is presented in Fig. 7.T adsorption reaches

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a maximum loading near 0.33 mg Tartrazine/g NZ-A-Fe and can be well fitted with

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either the Langmuir or the Freundlich model. Such isotherms are often encountered
when the adsorbate has a strong intermolecular attraction to the surface of the adsorbent
-p
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0,35
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0,30
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mg Tads/g NZ-A-Fe)

0,25
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0,20
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0,15

0,10

0,05
1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0

Ceq (mg/L)

Fig.7 Tartrazine equilibrium concentrations after T adsorption onto NZ-A-Fe at pH= 3

The equilibrium adsorption capacity (qe) increases with the increase of the initial
concentration of T.

Langmuir isotherm is based on the assumption that maximum adsorption occurs when a
saturated monolayer of adsorbate molecules is present on the adsorbent surface, the
energy of adsorption is constant, and there is no migration or interaction between the
adsorbate molecules in the surface plane. The Langmuir equation is:

qads = KL qm Ceq /(1 + KL Ceq), (11)

where Ceq (mg/L) and qads (mq/g) are the equilibrium T concentration (mg/L) in the
aqueous phase and in the solid phase, respectively. The Langmuir parameter qm (mq/g)
represents the maximum adsorption capacity and KL (L/mg) is the site energy factor.

The Freundlich isotherm is introduced as an empirical model:

</b
*]^_ = `a + (12)

Where qad represents the amount adsorbed per amount of adsorbent at the equilibrium

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(mg/g), Ce represents the equilibrium concentration (mg/L), and 1/n is the heterogeneity
factor that represents the bond distribution.

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Fig.8 shows the linear form of both isotherms where experimental parameters model
can be calculated. These parameters are presented in Table 3.
-p
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Langmuir
12
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10
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8
1/qads

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2 CTeq/qads = CTeq/Smaz +1/(Smax KL )

0,2 0,4 0,6 0,8 1,0

1/Ceq (L/mg)
 -0,2

Freundlich
-0,4
log (qads/mZN-A-Fe)

-0,6

-0,8

-1,0

of
log(qads/mNZ-A-Fe)=log(KF)+1/n log(Ceq)

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-1,2
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7

-p
log Ceq (mg/L)
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Fig.8 Linear plot of Langmuir and Freundlich model for T adsorption on NZ-A-Ze. The
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linear expression of each isotherm is inserted in the graph.

The calculated parameters for Langmuir and Freundlich model with R2 values are
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presented in Table 3.
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The essential characteristics of the Langmuir isotherm can be expressed in terms of a

dimensionless constant separation factor c that is given by
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c = 1 / (1 + `c #) (13)

where # (mg/L) is the highest initial concentration of adsorbate and c values between
0 and 1 imply favorable adsorption. c = 0.373 in the present investigation which
indicates a favorable adsorption of Tartrazine dye onto NZ-A-Fe nanoparticles surface.

Langmuir Freundlich
d c E/
E E
R2
* R Z `g R Z hi jgj
KF ( )
Sample n
e−f− i

NZ-A-Fe 1.30 0.0560 - - 0.99540

- - 0.0589 0.769 0.99805
Table 3. Langmuir and Freundlich model results for T adsorption on NZ-A-Fe (pH= 3
and 20°C)

The n value indicates the degree of nonlinearity between solution concentration and
adsorption. n =1, indicates linear adsorption; n < 1, indicates a chemical process, while
n > 1, indicates a physical process. Table 3 shows that the n values in Freundlich
equation 0.769 which shows a cooperative adsorption.
Experimental data can be almost fitted with both isotherm models in accordance to good
correlation R2 values (Table 3).

3.3 Heterogeneous Fenton experiments

3.3.1 Influence of the dose of H2O2 in the Fenton experiments

In Fenton reaction H2O2 plays an important role as a source of generation. As side
reactions (Eq.14-16) consume hydrogen peroxide, stoichiometric ratio results generally
quite different.
+ → + (14)
+ → + + (15)

of
+ → + (16)

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In order to explore our system behavior, different hydrogen peroxide concentrations
ranging from 0.5 to 60 mM were employed (corresponding to 0.5 to 72 the
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stoichiometric dose) for a fixed initial T concentration (10 mg/L).
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Eq.17 shows that 46.5 mols of H O /mol T are necessary for complete T mineralization
(oxidation up to CO , eq.6)):
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st
C<k Hl Nm Na Ol S + 46. 5 H O uv 16CO + 50H O + NaNO + 3HNO + 2NaHSOm
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(17)

Different ratio ([H O ] /[T]) explored in these experiences are presented in Table 4.
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R1 R2 R3 R4 R5 R6 R7 R8 R9
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[ H O ] 7.7 15 37 73 150 223 367 733 1100

/[T]
[ H O ] 0.5 0.9 2.0 4.1 8.1 12.5 19.8 40 60
(mM)
Table 4. Samples denomination for several [H2O2] /[T] ratio

Kinetic % T degradation data can be fitted with the pseudo-first-order model:

ln C – ln C0 = -k1t (18)

where C is the concentration of the dye at any time (t), Co is the initial concentration
after sorption process and k1 is the pseudo-first-order rate constant
 100

80
% Degradation T

60

40

20

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0
0 5 10 15 20 25 30 35 40 45 50 55 60
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[H2O2] mM
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Fig.9 Tartrazine (T) solution (10 mg/L) degradation by heterogeneous Fenton for
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different [H2O2]/[T] ratio, at pH= 3 and 20°C.

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Fig.9 shows an increase % T degradation with the oxidant dose up to [H2O2] = 2 mM.
This dose is near 80% of the stoichiometric one (Eq.17). For well above the
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stoichiometric dose ([H2O2] > 20 mM), % T discoloration diminishes as the oxidant is

consumed in scavenging reactions
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Simultaneous adsorption- Fenton catalytic processes comprise several steps, such as

physical or chemical adsorption, chemical reactions occurring between the species
formed at the catalyst surface followed by degradation and reaction products formation
and adsorption/desorption of these products (Lim et al.,2019).

Fig.10 shows the Kinetics profiles of % [T] decay through simultaneous adsorption-
Fenton process for three different R= [H2O2] / [T] ratio. It shows that hydrogen peroxide
dose, not only affects % T degradation but also modifies the removal kinetic profiles
For low hydrogen peroxide concentrations (up to R3) lower initial kinetic rate values
are observed. For higher oxidant concentration (from R5 to R9 (not shown), a visible
increase in % T degradation process is observed in the first 10 minutes which increase
ko values (Table 5).
 % Degradation T 100

80
ko k1
R5
60

40 R4 R3

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0

0 50 100-p 150 200 250

t (min)
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Fig.10 Effect of hydrogen peroxide concentration (mM) in color removal in T solution

(10 mg/L) at pH= 3 and 20°C for three different ratio R= [H2O2] / [T]
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R= [H2O2] / [T] R3 R4 R5
-1
k1 (min ) 0.0081 0.0047 0.0032
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-1
k0 (min ) 0.41 1.39 2.78
Table 5. Kinetic rate (k1) and initial kinetic rate (k0) for R3, R4 and R5

In the first 30 min., the initial kinetic rate (Table 5), involves an adsorption step (k2 =
g NZ−A−Fe 1
0.246 ∗7 : , Table 2) and degradation process which rate is related to
mg T min
[H2O2]o After 30 min, it could be assumed that simultaneous adsorption-Fenton
catalysis process took place. The system reached a pseudo-equilibrium stage exhibiting
a monotonic profile until the end of the experiment (240 min). R3 rate constant (low
[H2O2]o) is greater compared to that of R4 and R5. These results are in accordance with
scavering reactions which take place for high [H2O2]o (Eq.14-16).
These assays show that the optimum [H2O2] concentration for T degradation is 2 mM.
Under these experimental conditions, 95% of the T can be degraded onto NZ-A-Fe
(molecules are simultaneously adsorbed and degraded onto NZ-A-Fe, therefore enabling
the continuous adsorption and degradation of new dye molecules). As a result, the
longevity of NZ-A-Fe as a surface can be extended, making this a sustainable process.
4. Conclusions

A novel Fe-composite (NZ-A-Fe) was prepared by loading iron onto a natural zeolite.
Iron is placed in tetrahedral and octahedral sites. These isolated Fe3+ species are
considered as the most active catalytic species for the heterogeneous Fenton reaction.
Catalyst morphological characteristics facilitates T molecules diffusion within the
zeolite (NZ-A-Fe)
The maximum adsorption capacity in [T]=10 mg/L is 85%. Adsorption process
occurred by film and intraparticle diffusion, however, intraparticle diffusion was the
rate-limiting step.
The optimum [H2O2] concentration for T degradation is 2 mM. Under these
experimental conditions, 95% of the T can be degraded.

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The simultaneous adsorption and Fenton degradation suggests that NZ-A-Fe is an
attractive material for maintainable remediation of organic pollution in the environment

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prolonging the catalyst lifetime
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The evaluation of Tartrazine mineralization degree through total organic carbon (TOC)
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removal is in process.
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Acknowledgments
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The authors thank Gustavo Panizza from DIATEC S.R.L. for zeolite supply and to P.
Bercoff for SEM and Edax images. This project was partially funded by UBACyT
(2014-2017).
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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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