Environmental Pollution 310 (2022) 119850

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Valorisation of residual iron dust as Fenton catalyst for pulp and paper
wastewater treatment☆
João Peres Ribeiro a, Luana Sarinho a, Márcia C. Neves b, Maria Isabel Nunes a, *
a
CESAM - Centre for Environmental and Marine Studies, Department of Environment and Planning, University of Aveiro, 3810-193, Aveiro, Portugal
b
CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal

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

Keywords: In this work, the performance of residual iron dust (RID) from metallurgic industry was assessed as Fenton
Heterogeneous catalysis catalyst for the treatment of real pulp bleaching wastewater. The focus was on the removal of recalcitrant
Pulp bleaching wastewater pollutants AOX (adsorbable organic halides), by a novel, cleaner, and cost-effective circular solution based on a
AOX
waste-derived catalyst. The behaviour of RID as iron source was firstly assessed by performing leaching tests at
COD
Colour
different RID:wastewater w/v ratios and contact time. Afterwards, RID-catalysed homogeneous and heteroge­
Operating cost neous Fenton processes were conducted to maximise AOX removal from the pulp bleaching wastewater. Reus­
ability of RID was assessed by a simple collect-and-reuse methodology, without any modification.
Similar AOX removal under less consumption of chemicals was achieved with the novel heterogeneous Fenton
process. Reaction in the bulk solution was the main pathway of AOX removal, given that the low surface area and
porosity of the material did not allow for a high contribution of surface reaction to the overall performance.
Moreover, AOX removal was similar over two consecutive treatment cycles, with Fenton process being
responsible for 56.7–62.1% removal of AOX from the wastewater, and the leaching step adding 11.4–13.2%. At
the end of treatment, COD either decreased (1st cycle) or remained unchanged (2nd and 3rd cycle). The operating
cost of the optimised heterogeneous Fenton was 3–11% lower than under conventional Fenton process. This work
presented a novel, circular solution based on a low-cost waste-derived catalyst, advancing the knowledge needed
to foster industrial application of such technologies to increase industrial environmental performance and
efficiency.

1. Introduction
Pulp bleaching is a key step in pulp production, to achieve the
brightness, softness, and cleanliness required for most applications
(Sharma et al., 2020). The most concerning pollutants in pulp and paper
industry wastewater are adsorbable organic halides (AOX), which are a
family of compounds formed upon the reaction of chlorine dioxide
(bleaching agent) with lignin. Within this family of compounds, some
may present severe toxicity to fish and zooplankton (Farooqi and
Basheer, 2017; Oller et al., 2011; Savant et al., 2006), justifying the
effort that Pulp and Paper Industry (PP) applies to reduce AOX emissions
to the minimum and comply with strict regulations.
Fenton process is one of the most studied advanced oxidation pro­
cesses (AOP) for the abatement of recalcitrant compounds such as AOX.
Its basic mechanism, principles and advantages may be found elsewhere
(Ribeiro and Nunes, 2021). The main limitations of Fenton process are as
follows: (i) iron sludge formation, requiring downstream separation
from the wastewater and management (Gao et al., 2022; Ochando-Pu­
lido et al., 2017); (ii) high concentration of ions in the treated waste­
water, impacting treatment efficiency and increasing conductivity
(Domingues et al., 2019; Ramos et al., 2021); (iii) catalytic activity is
limited by the Fe2+ – Fe3+ redox cycle (Lai et al., 2021); (iv) strictly
acidic condition (pH ranging 2.5–3.5) required for maximum catalytic
activity (Guo et al., 2018; Hermosilla et al., 2015; Torrades and
García-Montaño, 2014).
To overcome these issues, recent research has focused on the
development of heterogeneous catalysts that could be easily separated
from the treated wastewater and reused, while allowing the operation at
milder pH conditions and with controlled leaching of iron (and other
ions) to the wastewater (Ganiyu et al., 2018; Pouran et al., 2014;

☆
This paper has been recommended for acceptance by Su Shiung Lam.
* Corresponding author. Departamento de Ambiente e Ordenamento, Universidade de Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal.
E-mail address: isanunes@ua.pt (M.I. Nunes).

https://doi.org/10.1016/j.envpol.2022.119850
Received 31 May 2022; Received in revised form 20 July 2022; Accepted 22 July 2022
Available online 6 August 2022
0269-7491/© 2022 Elsevier Ltd. All rights reserved.
J.P. Ribeiro et al.
Thomas et al., 2021). In the heterogeneous Fenton process, the •OH
production is catalysed not only in the bulk solution by leaked Fe ions,
but also on the catalyst surface, represented by “X” in Eqs. (1) and (2)
(Ribeiro and Nunes, 2021; Vorontsov, 2019). Adsorption of reactant
molecules may also occur at the active sites of the catalyst surface,
contributing to the overall removal of pollutant (Kakavandi and
Ahmadi, 2019; Pouran et al., 2014; Sruthi et al., 2018).
X − Fe2+ + H2 O2 → ​ X − Fe3+ + • O H + OH− (1)
Fe3+ + H2 O2 →X − Fe2+ + • O2 H + H+ (2)
The valorisation of waste materials in heterogeneous Fenton process
is a promising solution that has received increased attention lately.
Domingues et al. (2020) used red mud (iron-rich waste from aluminium
oxide production by the bauxite leaching process) as heterogeneous
Fenton catalyst in the treatment of a mixture of phenolic compounds
usually present in olive mill wastewater. Complete removal of the
phenolic content was reached after 60 min of treatment under pH = 3.0,
2.94 mM of H2O2 and 1 g⋅L− 1 of catalyst. Tony and Lin (2021) studied
the treatment of municipal wastewater by heterogeneous Fenton process
using acid mine drainage, which is formed through the interaction of
pyrite with water. Recovered iron oxide was coated into sand surface at
a concentration of 9.5 g Fe per kg of sand. Highest chemical oxygen
demand (COD) removal (70%) was attained after 30 min at 40 ◦ C, under
pH = 3.0, 40 mg⋅L− 1 of iron-coated sand and 11.8 mM of H2O2. Ghazzaf
et al. (2022) synthesized magnetic nanoparticles from iron rust waste by
solvothermal process and applied it as a photo-Fenton catalyst in the
degradation of Acid red 97. Degradation of 96.6% of dye was reported
within 60 min, with 80.8% TOC reduction achieved after 180 min, under
0.86 mM Fe3O4, 0.5 mM H2O2, room temperature, pH = 6, and in the
presence of 0.5 mM oxalic acid (chelating agent). The prepared catalyst
showed good stability and reusability even after five cycles.
The direct use of metallurgical industry waste as iron source in
Fenton processes could be a promising alternative, with no need for
additional technology steps, such as chemical or thermochemical pre-
treatment. Moreover, such application would also help adding value
to those wastes. Crude steel production more than doubled between
2000 and 2020; in 2020, 227.5 kg of steel products were used worldwide
per capita (Worldsteel Association, 2022). These numbers showcase the
importance of the metallurgic industry worldwide and the need to find
sustainable solutions for the huge amount of waste produced.
This work aimed at the novel application of residual iron dust (RID)
as Fenton process catalyst for the treatment of real pulp bleaching
wastewater. Contrarily to other works in this field, the waste material
was applied without any pre-treatment, i.e., as a true low-cost waste-
derived catalyst, under circular economy thinking. The focus was put on
the removal of potentially toxic compounds (AOX) from real industrial
wastewater, rather than dealing with target compounds or synthetic
wastewater, filling another major gap in the literature. The effect of the
modified Fenton process on wastewater’s COD and BOD5 was also
assessed under optimal experimental conditions, and operating costs
were quantified.
2. Materials and methods
2.1. Materials
Pulp bleaching wastewater was sampled in a Portuguese PP plant,
immediately after the first pulp bleaching stage with chlorine dioxide
(D0) since this is the wastewater stream where the majority of AOX is
found. The wastewater was characterized in terms of pH, AOX, COD,
BOD5, and iron content, according to the methods listed in section 2.4.
Residual iron dust was provided by a Portuguese metallurgical in­
dustry. This material is a waste from iron alloys handling and trans­
formation operations, such as sanding or fusion cutting, and is classified
2
Environmental Pollution 310 (2022) 119850
under the European List of Waste with code 12 01 02 – ferrous metal
dust and particles. The iron dust was sieved to a particle size below 1
mm, to remove coarse impurities, and then characterized according to
the methods and parameters listed in section 2.4.
All reagents used were analytical grade. Hydrogen peroxide solution
(H2O2 30% w/v - Panreac) was used as received. Iron sulphate (FeS­
O4.7H2O - Panreac, 99.5%), sodium sulphite (Na2SO3 – Panreac,
99.0%), and nitric acid (HNO3 - Fisher) were used, respectively, as 0.55
M, 1.70 M and 32.5% (v/v) aqueous solutions.
2.2. Iron supply from residual iron dust – leaching assays
The potential of RID as iron source for the Fenton process was
assessed firstly. To that end, leaching assays were performed with D0
wastewater, without initial pH adjustment, in 1 L glass flasks, under
orbital shaking. Temperature was set at 60 ◦ C, which is the natural
temperature of the pulp bleaching wastewater. The variables tested in
the leaching assays were: (i) RID:wastewater ratio (1:50, 1:100 and
1:200 g:mL), and (ii) contact time (10 min, 30 min, 60 min, and 120
min). Leaching assays were conducted on the various possible combi­
nations of the two variables, and replicated four times, in a total of 48
assays. At the end of the pre-defined contact time for each assay, a
sample was taken, filtered through glass fibre filters (GFFC – pore size
1.2 μm), and analysed for pH and (total soluble) iron content.
2.3. Fenton experiments
After defining the most suitable RID:wastewater ratio and contact
time, homogeneous and heterogeneous Fenton processes were con­
ducted to treat the wastewater.
In heterogeneous Fenton experiments, RID was firstly added to the
pulp bleaching wastewater (0.5 L) at the optimal ratio and contacted for
the optimal time under orbital shaking. After the predefined time,
hydrogen peroxide was added to start Fenton reactions, which may
occur at the catalyst surface and in the bulk (with soluble Fe leached
from the RID particles). Different H2O2 concentrations (50, 100, 150 and
200 mM) were tested to establish the optimal oxidant dose that could
maximise treatment efficiency without unnecessary cost. Reactions were
run in batch mode at 60 ± 2 ◦ C for 10 min, under wastewater’s natural
pH, according to previous works (Ribeiro et al., 2020a, 2020b).
At the end of treatment, supernatant samples were taken and
immediately quenched with sodium sulphite to halt the reactions. RID
was settled and collected after each experiment, dried in an oven at
60 ◦ C and reused in subsequent treatment cycles, without further
modification. These heterogeneous Fenton experiments were always
repeated five times. Preliminary tests had shown that around 80% of the
RID particles could be recovered by the described procedure, meaning
that, after the first treatment cycle, only 20% of fresh catalyst addition
was required for each subsequent treatment cycle to ensure equal
catalyst load in all experiments. Whenever needed, pH adjustment (to
3.0 ± 0.5) between leaching step and Fenton reaction step was made
with HNO3.
For homogeneous Fenton experiments, the same procedure and
experimental conditions were adopted, with one additional intermedi­
ate step: after the leaching step, the wastewater was filtered through
glass fibre filters (GFFC – pore size 1.2 μm) to remove RID particles and
guarantee homogeneous conditions. Then, hydrogen peroxide was
added to the filtered wastewater to start Fenton reactions. The homo­
geneous Fenton experiments were repeated five times. A schematic of
the described procedures can be found in Fig. S1. Control experiments
were also performed under conventional homogeneous Fenton condi­
tions. In such experiments, iron was firstly added as an aqueous solution
of FeSO4, followed by H2O2. These experiments also lasted for 10 min
and were run in 0.5 L batch conditions at 60 ◦ C. An additional control
experiment was carried out following the same procedure but adding
only H2O2 to the wastewater, to distinguish between simple H2O2-
J.P. Ribeiro et al. Environmental Pollution 310 (2022) 119850

oxidation and actual Fenton process. All control experiments were

repeated five times.

2.4. Analytical methods and data analysis

AOX was quantified by coulometric titration, in accordance with EN

16166:2012, ISO 9562:2004 and EPA Method 1650C, using a Thermo
TOC 1200 AOX/Total Carbon Analyser. COD and BOD5 measurements
were performed using an Aqualytic® COD photometer and a WTW
Oxitop® Control equipment, respectively, following the commonly
accepted methodologies 5220D and 5210D (Greenberg et al., 1999). pH
and electrical conductivity (EC) were measured with a Denver Instru­
ment® model 25 METER (for RID, EN 12457–4:2002 was followed).
Soluble iron content was measured by atomic absorption spectroscopy,
with a PerkinElmer AAnalyst 200, RID was characterized in terms of (i)
crystallographic structures, by powder X-ray diffraction (XRD, PAN
analytical Empyrean X-ray diffractometer equipped with Cu-Kα radia­
tion source λ = 1.54178 Å at 45 kV/40 mA); (ii) surface area (SBET) by
the BET method, plus pore size and pore volume by the BJH model. The
specific surface area and pore structure characterization were deter­
mined by nitrogen adsorption at 77 K using a surface area analyser
Micromeritics Gemini V-2380; (iii) surface morphology and quantitative
analysis of elemental composition, by scanning electron microscopy
(SEM) and energy dispersive X-ray spectroscopy (EDS), using a Hitachi
S4100 operated at 25 kV coupled with a Rontec EDS system.
Regarding data processing, results from the wastewater treatment
experiments were firstly analysed by Shapiro-Wilk and Levene tests, to
check the normality of data and the homogeneity of variances, respec­
tively. Once such assumptions were verified, ANOVA and Bonferroni test
were conducted to search for statistically significant differences between
the results obtained with different treatment methods. A 95% confi­
dence level was adopted.
3. Results and discussion
3.1. Characterization of wastewater and residual iron dust
The main characteristics of the pulp bleaching wastewater and RID
can be found in Table S1.
High content of AOX (47.0 ± 3.78 mg⋅L− 1) in D0 bleaching waste­
water highlights the advantages of applying an AOP to this stream,
before mixing it with the other streams. High levels of COD, EC and
colour are also common in untreated pulp mill wastewater (Ashrafi
et al., 2015; Brink et al., 2017; Kamali and Khodaparast, 2015; Toczy­
łowska-Mamińska, 2017). The biodegradability indicator of this waste­
water was low (BOD5/COD = 0.064), so an AOP was suitable for its
treatment.
RID had a very small pore volume, in the range of mesopores, ac­
cording to the IUPAC Guidelines (Thommes et al., 2015). Surface area
was also small, but in line with the ones reported by Martins et al. (2013)
for iron shavings (1.14 m2⋅g− 1), Minella et al. (2014) for commercial
magnetite (1.70 m2⋅g− 1), or Domingues et al. (2020) for red mud (0.60
m2⋅g− 1).
The adsorption/desorption isotherms of RID (Fig. S1) can be classi­
fied as type IV(a) according to IUPAC, meaning a mesoporous structure
(Thommes et al., 2015). A hysteresis loop was observed in the multilayer
range of the isotherms, which is generally associated with capillary
condensation. The hysteresis loop can be described as type H3, which is
normally associated to non-rigid aggregates of plate-like particles and to
a pore network containing narrow slit-shaped pores which are not
completely filled with pore condensate (Guo et al., 2014; Thommes
et al., 2015; Zhu et al., 2022a, 2022b).
The SEM analysis of RID showed scattered clusters of different sizes
laying over a compact solid surface (Figs. S3a and S3b). As observed
from EDS analysis, RID particles were mainly composed of Fe, Ca, and O,
with trace amounts of Si, Ti, Cu and Mn (Fig. S3c). The XRD patterns
Fig. 1. RID X-ray diffractogram.
(Fig. 1) show a high background noise as a consequence of the great
amount of iron (Hussain et al., 2021). RID particles contain mainly
wϋstite (FeO) and magnetite (Fe3O4), described by codes 04-008-2748
and 01-084-9337 in the ICDD PDF4+ database, respectively. In partic­
ular, magnetite presents a set of unique characteristics that has drew
increasing attention to its catalytic potential, namely: (i) it is the most
abundant iron oxide with Fe2+ in its structure; (ii) the presence of
octahedral sites at the surface of the crystal, (iii) the easiness of sepa­
ration of magnetite from the reaction system due to magnetic property,
(iv) higher dissolution rate of magnetite compared to other iron oxides
and accordingly, higher electron mobility in its spinel structure (Pouran
et al., 2014). The absence of peaks related to crystalline compounds
containing Ca, Mn, or Cu, which were identified by EDS, indicates that
these elements are most likely present in RID in amorphous phases.
3.2. Iron supply from the RID
Fig. 2 shows the soluble iron content ([Fe]) and pH of the wastewater
measured after the leaching assays. Regarding contact time, iron
leaching was not statistically different for times above 30 min, meaning
that this time would be enough for maximum iron mobilisation from the
RID particles to the wastewater. Minimisation of contact time between
RID and the wastewater is advantageous when dealing with high
wastewater flows, to minimise reactor volume.
On the other hand, when a minimum of 30 min of contact was
allowed, lower ratios (1:100 and 1:200 g:mL) resulted in higher leaching
of iron to the wastewater than the higher ratio (p < 0.05), probably due
to enhanced solid-liquid contact for a smaller number of RID particles,
and to the lower pH, favouring the solubilisation of iron, particularly
Fe2+ (Duarte et al., 2013; Kakavandi and Ahmadi, 2019). Similar (p >
0.05) iron supply was observed under ratios 1:100 and 1:200 g:mL,
regardless of contact time. Therefore, the lowest ratio tested in this work
could be used, minimising the quantity of material needed for similar
iron supply. Additionally, high quantity of particles could hinder process
performance, due to agglomeration of fine particles into a cluster that
may settle and reduce the exposure of active sites, as well as scavenge
•
OH by excess iron ions (Erhardt et al., 2021; Hussain et al., 2021;
Kakavandi and Ahmadi, 2019).

3
J.P. Ribeiro et al.
Fig. 2. (a) Iron concentration and (b) pH of the wastewater after RID leaching step, at the different RID:wastewater [g:mL] ratios tested.
Globally, the iron concentration varied in accordance with the elu­
ate’s pH – lower pH allowed for higher [Fe]. pH increased in all tested
conditions, ranging between 3.61 (for 10 min of contact at 1:200 g:mL
ratio) and 7.91 (for 60 min of contact at 1:50 g:mL ratio). The highest pH
increase was observed for 1:50 g:mL ratio, leading to the minimum iron
mobilisation registered, and the lowest for 1:200 g:mL ratio, showing
once again that this was the most favourable experimental condition
tested. At the latter ratio, change in pH was not statistically different (p
> 0.05) for contact times above 30 min.
Based on these results, an RID:wastewater ratio of 1:200 g:mL and a
contact time of 30 min were established as the most favourable exper­
imental conditions among the ones tested.
3.3. Fenton experiments
The removal of AOX under increasing oxidant concentration,
[H2O2], was measured to establish the optimal oxidant dose, as
described in section 2.3 (Fig. 3).
Increasing the H2O2 concentration from 50 mM to 100–150 mM
increased AOX removal in both homogeneous and heterogeneous Fen­
ton processes. Oxidant concentration of 200 mM was detrimental in the
Fig. 3. AOX removal under different H2O2 concentrations, for both types of
Fenton processes. RID:wastewater ratio = 1:200 g:mL, with 30 min of solid -
liquid contact before H2O2 addition.
4
Environmental Pollution 310 (2022) 119850
homogeneous Fenton process, probably due to self-scavenging of the
oxidant (Brink et al., 2017; Guo et al., 2018; He and Zhou, 2017; Ramos
et al., 2019; Wang et al., 2016). This effect was not observed in the
heterogeneous Fenton process, which is not unprecedented. Rodríguez
et al. (2016) tested homogeneous and heterogeneous (Fe2O3/SBA-15
nanocomposite) Fenton for the treatment of pharmaceutical waste­
water, and the latter showed its best performance under four times the
[H2O2] to yield equal COD removal. Such observations may be
explained by the slower kinetics, limited by mass transfer of H2O2 to the
active sites on the catalyst surface, and to the lower reaction between
H2O2 and Fe3+, in all iron-based catalysts (Bokare and Choi, 2014;
Garcia-Segura et al., 2016). Additionally, decomposition of H2O2 via a
non-radical pathway to H2O and O2 may also occur at the catalyst sur­
face, lowering the •OH yield (Ahile et al., 2020).
In the present work, such limitations to heterogeneous Fenton
chemistry were most likely masked by the effectiveness of the reactions
in the bulk solution, potentiated by the previous leaching step, not
adopted in the cited works. Therefore, AOX removal remained similar
within [H2O2] ranging 100–200 mM.
Taking economic efficiency into account, 100 mM and 150 mM were
defined as the optimal H2O2 doses for heterogeneous and homogenous
Fenton processes, respectively. The heterogeneous Fenton process
allowed for similar results under less consumption of chemicals, so the
reusability of the catalyst therefore studied under heterogeneous Fenton
conditions, considering a recovery of RID between cycles of 80% (data
not shown). The herein presented RID-catalysed heterogeneous Fenton
process is always a combination of proper heterogeneous chemistry and
homogeneous Fenton reactions with iron ions mobilized from the RID
particles. Interface chemistry is always the most desirable heteroge­
neous Fenton mode of action, comprising the formation of both hydroxyl
radicals and oxoferryl reactive intermediates on the surface of the solid
catalyst (Vorontsov, 2019). However, iron leaching from the particles
occurs mainly due to the corrosion of the particles surface layer in
presence of H2O2, causing in-situ production of Fe2+, which is dissolved
into solution at low pH (Dos Santos et al., 2021; Segura et al., 2013;
Sevimli et al., 2014).
Fig. 4 shows the removal of AOX by heterogeneous Fenton process
and simple H2O2-oxidation, plus the iron leached, for three consecutive
treatment cycles.
Global (i.e., leaching step plus Fenton process) AOX removal was
similar (p < 0.05) between the first and second cycles, showing that RID
can be reused without any modification. In these two cycles, the
leaching step was responsible for 11.4 and 13.2% average AOX re­
movals, respectively. The following step, i.e., the Fenton process,
J.P. Ribeiro et al.
Fig. 4. Heterogeneous Fenton process performance: (a) AOX removal, and (b) iron concentration in the wastewater (leached from the RID).
removed 62.1 and 56.7%, respectively. These results suggest that the
adsorption of contaminants on the surface of the solid catalyst was not
the primary mechanism for their removal. Removal below 15% by the
RID may be explained not only by low affinity of the AOX molecules to
this material, but also by the low surface area and porosity that RID
particles showed, since it is known that adsorption and Fenton reactions
rate at the interface increase with the increase in those properties (Ahile
et al., 2020; Blanco et al., 2014; Vorontsov, 2019). Analogous obser­
vation was reported by Domingues et al. (2019), when dealing with
phenol degradation by heterogeneous Fenton process catalysed by red
mud (below 10% removal by the solid). Hussain et al. (2021) used steel
scale waste as heterogeneous Fenton catalyst for the treatment of
leachate, achieving TOC abatement of 75% (after 150 min of treatment
under pH = 3, T = 70 ◦ C, 411 mM of H2O2 and 1 g⋅L− 1 of catalyst), of
which only 5–15% were attributed to adsorption by the steel scale
waste. For the first two treatment cycles, global AOX removal was in the
same range of the one reported by Erhardt et al. (2021), who achieved
around 80% AOX removal from pulp bleaching wastewater using 2 g⋅L− 1
of nZVI, 80 mM of H2O2, at room T and pH around 2.7.
At the 3rd cycle, overall AOX removal sharply decreased to 36.7%,
despite the AOX removed during the leaching step in this cycle (8.4%)
did not differ significantly from the previous two cycles (p > 0.05). On
the other hand, the decay in Fenton process’ performance was also not
due to lack of available iron in solution, since Fig. 4b shows that the iron
leached from the RID was similar between 2nd and 3rd cycles (p < 0.05).
In fact, a significant decrease (p < 0.05) in the leaching of iron was
observed from the 1st cycle to the following ones. Considering this, the
lack of impact in AOX removal between the 1st and 2nd cycle proves that
the amount of iron leached to the solution was enough to allow for
homogeneous Fenton reactions to take place in the bulk wastewater.
Moreover, only in the 1st cycle the iron leached from the RID after the
overall Fenton treatment was significantly different (p < 0.05) from the
amount leached after the leaching step. These results also suggest that
the 20% fresh catalyst mass added between cycles, to make up for lost
RID, had little influence in the process outcome. The reduction in AOX
removal from the 2nd to the 3rd cycle may have been due to deactivation
of the catalyst surface due to the occupation of the active sites by the
organic intermediates from the wastewater, hindering the reaction be­
tween H2O2 and catalyst (Sruthi et al., 2018; Tony and Lin, 2021).
Another factor that may have possibly contributed to final AOX content
was the desorption of organics from the RID surface to the wastewater
and transport of organic compounds and fibres with the recovered RID
particles between cycles. This increase in organics would compete with
AOX for •OH, decreasing the efficacy of the treatment process. This
subject has been discussed in the recent literature in this field, with
several authors pointing out some limitations of heterogeneous catalysts
which contribute to reduced efficiency over reusability cycles, such as
limitation in mass transfer of H2O2 to the active sites on the catalyst
5
Environmental Pollution 310 (2022) 119850
surface, lower reaction between H2O2 and Fe3+, and potential formation
of catalyst agglomerates, reducing free surface availability (Bokare and
Choi, 2014; Garcia-Segura et al., 2016; Wang et al., 2016). Dos Santos
et al. (2021) used steel nails as Fenton catalyst in the treatment of sur­
face waters, reporting decreased efficacy after the 1st cycle, due to the
formation of a passive oxide layer during the ZVI/H2O2 process,
reducing the concentration of reactive Fe sites on the ZVI nail. This is a
major challenge in using magnetite-rich materials, due to the atmo­
spheric oxidation of Fe2+ to Fe3+, forming an oxide layer passivating the
magnetic surface of the catalyst (Ahile et al., 2020).
It must also be noted that for every cycle, the AOX removal was al­
ways much higher than the one registered in the assays carried out only
with H2O2 (19.9 ± 1.1%). Two control experiments were performed
under conventional Fenton conditions, with iron being supplied as
FeSO4.7H2O: (i) 2.31 mM Fe were supplied, to compare with the 1st
cycle of heterogeneous Fenton; (ii) 1.35 mM Fe were supplied, to
compare with the 2nd and 3rd cycles of heterogeneous Fenton process.
AOX removal of the two control experiments were, respectively, 65.6 ±
1.0% and 55.3 ± 4.0%, which did not differ statistically from the
correspondent heterogeneous Fenton processes. These results show­
cased the effectiveness of the RID as substitute of conventional iron salts
as source of Fenton catalyst. In a comparable work, Martins et al. (2012)
used iron shavings as Fenton catalyst in urban landfill leachate treat­
ment, concluding that the main pathway of pollutant abatement was
homogeneous Fenton reactions between H2O2 and iron leached from the
metallic particles to the bulk solution, in agreement with the results of
the present work.
Effect of this treatment on wastewater COD was also measured
(Fig. 5). Heterogeneous Fenton process successfully removed 34.6 ±
1.4% COD from the pulp bleaching wastewater, exclusively due to the
oxidation step, which is not unprecedented. For instance, Sruthi et al.
(2018) applied heterogeneous Fenton process to treat landfill leachate,
and could not observe any COD reduction due to adsorption of pollutant
over the catalyst (iron-loaded zeolite) surface.
When reusing the RID, no significant reduction in COD was observed
(p > 0.05), probably due not only to the inactivation of the solid catalyst,
but especially due to the enrichment in organic matter that the simple
collect-and-reuse method brought to the wastewater. The RID particles
carried additional organic load, in the form of particles and fibres
attached to them, which was easily observable during the experiments.
This material most likely contributed to increase COD, masking any COD
removal achieved, particularly in the last cycle. Indeed, COD increased
significantly (p < 0.05) after the leaching step of the 3rd treatment cycle,
proving the need for some regeneration at that point. Nonetheless, by
the end of treatment, COD either decreased (1st cycle) or remained un­
changed (2nd and 3rd cycle), which was a positive feature of the het­
erogeneous Fenton process studied.
BOD5 was measured after the first and last treatment cycle. A
J.P. Ribeiro et al.
Fig. 5. COD of the raw pulp bleaching wastewater and the heterogeneous
Fenton-treated wastewater.
significant decrease from 169 mg O2⋅L− 1 in the raw wastewater to 42 mg
O2⋅L− 1 in the treated wastewater was observed in the 1st cycle. On the
contrary, after the 3rd treatment cycle, BOD5 increased 71% after
treatment (288.5 mg O2⋅L− 1). These values mean that biodegradability
of the wastewater, expressed as BOD5/COD ratio, decreased in the 1st
cycle from 0.064 in the raw wastewater to 0.024 in the treated waste­
water, and increased substantially to 0.100 after the 3rd cycle. This is
relevant to assess the combination of Fenton process with conventional
biological processes, and the impact that the oxidation step may have on
microorganisms’ activity. Ma et al. (2018) also observed increase in
BOD5/COD ratio in landfill leachate after heterogeneous Fenton treat­
ment. The reason for this is that the fraction of oxidant which could not
be activated by the catalyst would have been spent in direct primary
degradation of organic matter, yielding larger fraction of more biode­
gradable by-products, without reaching further stages of degradation
that could lead to complete mineralisation to CO2, water, and inorganic
compounds.
3.4. Estimation of operating costs
Operating costs were determined based on average market prices of
H2O2 (30% w/v), FeSO4.7H2O (used as a 0.90 mM aqueous solution),
and electricity, plus a management cost of 30 €⋅ton− 1 for the RID.
Operating cost was computed for each treatment cycle, and then nor­
malised to allow comparison: the overall cost of each treatment was
expressed as a relative (dimensionless) cost, obtained by dividing the
absolute cost of treatment by the absolute cost of conventional Fenton
process’ reference costs, in terms of €⋅m− 3 and €⋅gAOX −removed
1
(Table 1).
The cost of conventional Fenton process carried out under 100 mM
H2O2 and 2.31 mM Fe2+ was assumed to be the reference cost (equal to
1) for the 1st cycle, while the cost of conventional Fenton process carried
out under 100 mM H2O2 and 1.35 mM Fe2+ was assumed to be the
Table 1
Relative cost (dimensionless) of the different treatments.
Treatment condition Relative cost based on Relative cost based on
€⋅m− 3 1
€⋅g−AOX rem
Heterogeneous Fenton 1st 0.899 0.891
Cycle
Heterogeneous Fenton 2nd 0.970 0.903
Cycle
Heterogeneous Fenton 3rd 0.970 1.462
Cycle
Homogeneous Fenton 0.927 0.918
6
Environmental Pollution 310 (2022) 119850
reference cost for the 2nd and 3rd cycle. The cost of conventional Fenton
process carried out under 150 mM H2O2 and 2.31 mM Fe2+ was assumed
to be the reference cost for the homogeneous Fenton process.
Heterogeneous Fenton was less expensive than the conventional
Fenton process, particularly considering the 1st cycle, where higher iron
supply was observed. The first two cycles, in which AOX removal was
higher, were even cheaper than conventional Fenton process when the
1
€⋅gAOX −removed indicator is considered, since slightly higher performance
was achieved with RID as catalyst. In the 3rd cycle, despite the cost per
m3 being lower, the cost per gAOx removed was higher than the one of
conventional Fenton, since the removal decreased sharply, as discussed
in section 3.3. These results showcase the advantage of using RID as
heterogeneous Fenton catalyst, yielding similar AOX removal with
3–11% savings in operating cost over two consecutive cycles. Beyond
that, fresh RID particles must be used, or some regeneration technique
must be sought.
4. Conclusions
Residual iron dust was successfully used as Fenton catalyst for the
removal of AOX from pulp bleaching wastewater. The lowest solid:liquid
ratio tested (1:200 g:mL) and 30 min of contact were enough to supply
all the catalyst iron needed for the reaction to occur in the bulk solution,
which was the main pathway of AOX removal, given that the low surface
area and porosity of the material did not allow for a high contribution of
surface reaction to the overall performance.
Global AOX removal was similar between the first and second
treatment cycles, with Fenton process being responsible for 56.7–62.1%
removal of AOX from the wastewater, and the RID leaching step adding
11.4–13.2% AOX removal. Therefore, it was possible to reuse the RID as
iron source without any modification. At the 3rd cycle, overall AOX
removal significantly decreased to 36.7%. At the end of treatment, COD
either decreased (1st cycle) or remained unchanged (2nd and 3rd cycle),
while biodegradability of the wastewater decreased in the 1st cycle from
0.064 in the raw wastewater to 0.024 in the treated wastewater and
increased significantly to 0.100 after the 3rd cycle.
The cost of treating 1 m3 of wastewater by the heterogeneous Fenton
process was lower than under conventional Fenton process. This saving
was even more pronounced when the comparison was made in terms of
1
€⋅gAOX −removed , since slightly higher performance was achieved with RID
as Fenton catalyst.
The solution presented in this work, aligned with circular economy
principles, would contribute to reduce pollution, and increase industrial
environmental performance and efficiency, while complying with eco-
label criteria. This work also shed some light on the potential of using
wastes as true low-cost catalysts, without the need for high technology
pre-treatment steps or synthesis. Further research should focus on
increasing the reusability of this type of material and on its immobili­
sation to facilitate recovery and recycling after use. The identification of
the main chemical compounds formed after treatment can help estab­
lishing the chemical routes of treatment and guide future research in this
field.
Credit author statement
João Peres Ribeiro – Conceptualization; Methodology; Investigation;
Formal analysis; Writing – original draft, Luana Sarinho – Investigation;
Writing – Review & Editing, Márcia C. Neves – Investigation; Formal
analysis; Writing – Review & Editing, Maria Isabel Nunes – Methodol­
ogy; Resources; Writing – Review & Editing; Supervision; Project
administration.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
J.P. Ribeiro et al.
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
Thanks are due to FCT/MCTES for the financial support to CESAM
(UIDP/50017/2020 + UIDB/50017/2020 + LA/P/0094/2020),
through national funds. This work was developed within the scope of the
project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 &
UIDP/50011/2020, financed by national funds through the Portuguese
Foundation for Science and Technology/MCTES. J. P. Ribeiro ac­
knowledges FCT – Fundação para a Ciência e a Tecnologia, I.P. for his
PhD Grant (SFRH/BD/141133/2018). Márcia C. Neves acknowledges
FCT, I. P. for the research contract CEECIND/00383/2017 under the
CEEC Individual 2017.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.envpol.2022.119850.
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