Environmental Pollution 259 (2020) 113796

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

Treatment of biodigested coffee processing wastewater using Fenton’s

oxidation and coagulation/flocculation*
Valciney Gomes de Barros a, b, Carmen S.D. Rodrigues c, *, Wilmar Alirio Botello-Sua
rez a, b,
Rose Maria Duda a, d, Roberto Alves de Oliveira a, Eliana S. da Silva e, Joaquim L. Faria e,
Rui A.R. Boaventura e, Luis M. Madeira c
a
rio de Saneamento Ambiental, Departamento de Engenharia Rural, Faculdade de Ci^
Laborato encias Agra
rias e Veterina

rias, Universidade Estadual Paulista,
UNESP, Ca^mpus de Jaboticabal, Av. Prof. Paulo Donato Castallene, Km 5, 14884-900, Jaboticabal, SP, Brazil
b
Programa de Po
s-Graduaça~o em Microbiologia Agropecua
ria, Faculdade de Ci^
rias e Veterina
encias Agra
rias, Universidade Estadual Paulista (UNESP),
Campus de Jaboticabal, Jaboticabal, SP, Brazil
c
LEPABE - Laboratory for Process Engineering, Environment, Biotechnology and Energy, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias,
4200-465, Porto, Portugal
d
Faculdade de Tecnologia de Jaboticabal, “Nilo St

efani”, Av. Eduardo Zambianchi, 31, 14883-130, Vila Industrial, Jaboticabal, Sa~o Paulo, Brazil
e
Laboratory of Separation and Reaction Engineering e Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

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

Article history: Biodigested coffee processing wastewater (CPW) presents a high organic load and does not meet the
Received 4 July 2019 limits imposed by legislation (namely in Brazil) for discharge into water bodies. Anaerobic digestion
Received in revised form generally cannot provide a satisfactory organic matter reduction in CPW as a significant fraction of
22 October 2019
recalcitrant compounds still persists in the treated effluent. So, this study aims to find alternative ways to
Accepted 10 December 2019
remove refractory organic compounds from this wastewater in order to improve the biodegradability and
Available online 13 December 2019
reduce the toxicity, which will allow its recirculation back into the anaerobic digester. Three treatment
approaches (Fenton’s oxidation - Approach 1, Coagulation/flocculation (C/F) - Approach 2, and the
Keywords:
Coffee processing wastewater
combination of C/F with Fenton’s process - Approach 3) were selected to be applied to the biodigested
Fenton oxidation CPW in order to achieve that objective.
Coagulation-flocculation The application of the Fenton process under the optimal operating conditions (initial pH ¼ 5.0;
Biodegradability T ¼ 55  C, [Fe3þ] ¼ 1.8 g L1 and [H2O2] ¼ 9.0 g L1) increased the biodegradability (the BOD5:COD ratio
Toxicity raised from 0.34 ± 0.02 in biodigested CPW to 0.44 ± 0.01 after treatment) and eliminated the toxicity
(0.0% of Vibrio fischeri inhibition) along with moderate removals of organic matter (51.3%, 55.7% and
39.7% for total organic carbon e TOC, chemical oxygen demand e COD and biochemical oxygen demand
- BOD5, respectively). The implementation of a coagulation/flocculation process upstream from Fenton’s
oxidation, under the best operating conditions (pH 10e11 and [Fe3þ] ¼ 250 mg L1), also allowed to
slightly increase the biodegradability (from 0.34 to 0.47) and reduce the toxicity, whereas providing a
higher removal of organic matter (TOC ¼ 76.2%, COD ¼ 76.5 and BOD5 ¼ 66.3% for both processes
together). Approach 1 and Approach 3 showed to be the best ones, implying similar operating costs
(~74 R$ m3/~17 V m3) and constitute an attractive option for managing biodigested CPW.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction residues of the coffee industry, which is generated in large amounts

Coffee processing wastewater (CPW) represents one of the main
*
This paper has been recommended for acceptance by Charles Wong.
* Corresponding author.
E-mail address: csdr@fe.up.pt (C.S.D. Rodrigues).
during post-harvest procedures, mainly by the application of the
wet processing technology (Alves et al., 2017). The uncontrolled
disposal of this effluent is of great concern in coffee-producing
countries, since it shows high concentration of suspended or-
ganics like sugars, pectins, proteins and polyphenols, and generates
adverse effects on the receiving water bodies (Dadi et al., 2018).
This scenario led to the development of economically attractive and

https://doi.org/10.1016/j.envpol.2019.113796
0269-7491/© 2019 Elsevier Ltd. All rights reserved.
2 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796
easily adaptable treatment processes aiming at an efficient reduc-
tion of the polluting potential of CPW.
Anaerobic digestion (AD) is the most widely used technology for
treating CPW. This treatment process provides several benefits
including generation of methane (renewable energy) along with
low sludge production (Beyene et al., 2014). However, even with the
application of high-rate anaerobic reactors such as upflow anaer-
obic sludge blanket (UASB) reactors, anaerobic digestion generally
cannot provide a satisfactory organic matter reduction as a signif-
icant fraction of recalcitrant compounds still persists in the treated
effluent (Bruno and Oliveira, 2013; Campos et al., 2013; Villa-
Montoya et al., 2017), namely lignin, tannins and humic acid that
are resistant to biological degradation (Zayas et al., 2007).
The presence of recalcitrant compounds in the biodigested
effluent is very undesirable when part of the treated CPW is
intended to be recirculated back into the anaerobic reactor (Sua
rez
et al., 2018). Actually, this strategy is adopted to benefit from the
alkalinity of biodigested CPW, then reducing the consumption of
chemicals to raise the pH of CPW fed to the anaerobic digester and/
or to maintain an appropriate organic loading rate in the system,
especially for wastewaters with high concentration of organic
matter (Barros et al., 2017; Sua
rez et al., 2018). In order to improve
the quality of the biodigested CPW, and therefore allowing its
recirculation back to the digester, subsequent post-treatment
strategies must be considered.
Previous studies have been successfully focused on advanced
oxidation processes, such as Fenton oxidation, for the treatment of
different effluents containing biologically recalcitrant compounds,
providing biodegradability improvement at low treatment cost
(Lucas and Peres, 2009; Nieto et al., 2011; Yalfani et al., 2009). This
oxidation process involves different species of iron (namely ferrous
ion) reacting with H2O2 to generate other reactive oxygen species,
especially the hydroxyl radical (HO) (Eq. (1)) (Gil Pavas et al., 2019;
Kantar et al., 2019; Pignatello et al., 2006), which oxidizes organics
contained in the effluent and generates intermediate compounds
(Eq. (2)) that are further converted, hopefully to carbon dioxide and
water (complete mineralization e Eq. (3)) (Guerreiro et al., 2016).
Fe2þ þ H2O2 / Fe3þ þ HOþ OH (1)
HOþ organics /H2O þ intermediates (2)
HOþ intermediates /H2O þ CO2 (3)
During the oxidation process, Fe2þ regeneration occurs through
the reaction of Fe3þ with H2O2 (Eq. (4)) to give continuity to the
previous reactions. In addition, other competitive and undesirable
reactions between the hydroxyl radical and excess of oxidant and/
or catalyst can occur in parallel (Eqs. (5) and (6)) (Kantar et al.,
2019; Walling, 1975), whereby a less amount of hydroxyl radicals
is present in solution to oxidize the organic compounds (Rodrigues
et al., 2017a).
Fe3þ þ H2O2 / Fe2þ þ HO2þ Hþ (4)
HOþ H2O2 / H2O þ HOO (5)
HOþ Fe2þ / Fe3þþ OH (6)
The Fenton process is considered to be environmentally friendly
because non-toxic reagents are employed; in addition, it operates
at ambient temperature and atmospheric pressure, is easy to
operate and implies low capital cost. In addition, it is effective in
removing the organic pollutants or reducing their toxicity and
increasing the biodegradability of effluents allowing the
combination with biological degradation (Rodrigues et al., 2017a),
as mentioned below.
The coagulation/flocculation (C/F) process can be applied alone
or coupled to Fenton’s oxidation. This process is relatively mature,
cost-effective and user-friendly (GilPavas et al., 2017; Guerreiro
et al., 2016), and consists in the destabilization of the colloidal
particles, which is achieved by using a coagulant (Sharp et al.,
2006). The destabilization of the colloidal particles can occur by
four different mechanisms: i) inclusion in a precipitate, when a
high concentration of metal is added to an alkaline medium
forming an hydroxide that traps the colloidal particles, ii) adsorp-
tion and neutralization of charge that occurs when using positively
charged coagulants that have a high affinity to colloid surfaces, iii)
double layer compression resulting from the addition of salts to the
solution, which increases the ionic strength that leads to a double
ion bed compression of the colloids, thereby reducing the repulsion
potential allowing them to aggregate, and iv) adsorption and
bridging between particles by the addition of polyelectrolytes to
the solution, which can adsorb the colloids and form bridges with
each other (Duan and Gregory, 2003). Usually, in wastewater
treatment by coagulation, the destabilization of colloidal particles
occurs by adsorption and neutralization of charge and/or inclusion
in a metal precipitate.
The microflocs formed are aggregated by the addition of a
flocculant, generating particles with large size that can be removed
by sedimentation, flotation or filtration. In this process, aluminum
and iron salts are the most widely used as coagulants. However,
aiming at reducing costs with chemicals, the application of iron
salts is advantageous when dissolved iron resulting from C/F acts as
a catalyst in a subsequent Fenton process (Rodrigues et al., 2017a).
The main goal of this work was to assess some possibilities of
biodigested CPW treatment in order to reduce the concentration of
recalcitrant organic compounds, thus improving the biodegrad-
ability and reducing the toxicity, making possible the recirculation
of the treated wastewater to the anaerobic reactors (this way
increasing the methane production). For that, three strategies were
adopted, namely Fenton’s oxidation (Approach 1), coagulation/
flocculation (C/F) - (Approach 2), and combination of C/F plus
Fenton’s oxidation (Approach 3). Up to the author’s knowledge, in
the scientific literature there are no reports on biodigested CPW
treatment by Fenton’s oxidation and C/F, as well as by the combi-
nation of both processes. Moreover, the treatment costs, which is a
crucial issue for industrial application, were never taken into ac-
count when selecting the best treatment approach.
2. Materials and methods
2.1. Biodigested coffee processing wastewater
The raw coffee processing wastewater (CPW) used in this study
was collected in a coffee-producing farm in the Sa ~o Paulo State,
Pedregulho (Brazil), during the harvest period (AprileJuly) of 2017
and the respective characteristics are shown in Table 1. After pH
adjustment to ~7.0, the influent (with COD ¼ 28500 mg O2 L1) was
treated in a 20 L capacity continuously operated up-flow anaerobic
sludge blanket (UASB) reactor with the dimensions presented
elsewhere (Villa-Montoya et al., 2017) e see UASB1), fed at an
organic loading rate of 18.2 g COD (L d)1, operating at a hydraulic
retention time of 30 h and up-flow velocity of 0.038 m h1. Oper-
ating this way, stable conditions were achieved in the anaerobic
digestion process and the methane production rate was 2.2 L CH4
d1. The volatile solids content in the sludge was 40 g L1, with a
sludge loading rate of 0.2 g COD (g VS d)1.
The discharge effluent of this reactor (biodigested CPW) was
treated using three different approaches: i) Fenton’s oxidation, ii)
 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796 3

Table 1
Characteristics of raw and biodigested CPW, after Fenton’s oxidation (Approach 1), C/F process (Approach 2) and C/F followed by Fenton’s process (Approach 3) - removal
efficiencies are shown between brackets e and global removals for the combined processes (Approach 3) with standard errors for a confidence level of 95% and, the respective
operating costs.

Raw CPW Biodigested After Fenton (Approach Approach 3 Discharge

Parameter CPW 1) Limits
After C/F (Approach 2) After Fenton Global Removal
(%)

pH 4.3 ± 0.3 6.9 ± 0.1 7.0 ± 0.2a 7.0 ± 0.1a 7.0 ± 0.2a n.d. 6.0e9.0 b

COD (mgO2 L1) 28500 ± 1780 4263 ± 170 1889 ± 85 (55.7 ± 0.5%) 2613 ± 100 1003 ± 80 76.5 ± 0.3 180 b
(38.7 ± 0.2%) (62.2 ± 0.3%)
BOD5 (mgO2 L1) 13000 ± 700 1387 ± 31 816 ± 25 (39.7 ± 1.8%) 846 ± 24 (39.0 ± 1.0%) 467 ± 10 (44.9 ± 0.6%) 66.3 ± 0.8 10 c

TOC (mgC L1) n.d. 1447 ± 5 706 ± 6 (51.3 ± 1.2%) 907 ± 8 (37.3 ± 0.6%) 345.2 ± 7 76.2 ± 0.7
(61.8% ± 0.8)
BOD5:COD 0.46 ± 0.01 0.34 ± 0.02 0.44 ± 0.01 0.32 ± 0.02 0.47 ± 0.01 n.d.
b
Turbidity (NTU) n.d. 506 ± 6.0 n.d. 21.4 ± 2.0 n.d. n.d. 100
V. fischeri inhibition (%), 5 min n.d. 11 ± 1.0 0.0 ± 0.5 0.0 ± 0.3 0.0 ± 0.5 n.d.
V. fischeri inhibition (%), n.d. 14 ± 0.5 0.0 ± 0.6 1.6 ± 0.4 0.0 ± 0.3 n.d.
15 min
V. fischeri inhibition (%), n.d. 20 ± 1 0.0 ± 0.4 3.3 ± 0.5 0.0 ± 0.6 n.d.
30 min
Operating costd (R$ m3/V - e 74.1/16.5 3.4/0.76 70.8/15.8 74.2/16.6
m3)
a
- after neutralization, n.d. - Not determined.
b
CONAMA No. 357/2005 (Art. 16) (Brazil, 2005).
c
Commission for Environmental Policy of Minas Gerais, (COPAM, 2008).
d
Operating costs are related with consumption of chemicals (it was not considered the costs of treatment/processing of sludge generated). The costs of reagents were those
given by BAUMINAS Química and Pero
xidos do Brasil (Brazil): H2O2 (50.0% (w/v), density at 25  C ¼ 1.2 g mL1) e 2.30 R$ per kg; FeCl3 (38% (w/w)) e 1.78 R$ per kg. For
converting from Brazilian Real to Euro, it was used the exchange rate of 4.48 R$/V - European Central Bank and Portugal Bank, August 20, 2018 (www.bportugal.pt).

coagulation/flocculation (C/F) and iii) combination of both pro- oxidation experiments, only replacing the biodigested CPW by
cesses in series. distilled water. The residual concentration of oxidant (H2O2) and
the presence of hydroxyl radicals were evaluated along the reaction
time.
2.2. Fenton’s oxidation procedure

The Fenton’s reactions were performed in batch mode using a
250 mL-capacity glass batch reactor. The reactor was equipped with
a water recirculation jacket connected to a water thermostatic bath
(Huber, polystat cc1) to maintain the temperature constant. A
volume of 150 mL of biodigested CPW was put into the reactor and,
after reaching the required temperature, the pH was adjusted to the
desired value with 1 M H2SO4 or 1 M NaOH. Subsequently, the
required amount of iron (as ferric chloride - FeCl3.6H2O, from
Labchem®) was added, and when the pH became steady, H2O2 (30%
w/v, from Carlo Erba®) was put into the reactor, this corresponding
to the initial instant of the oxidation runs (t ¼ 0 in the figures
below), which were extended for 3 h. As the effluent from the
Fenton reaction was intended to be subjected to anaerobic diges-
tion, the reaction was catalyzed with FeCl3 instead of FeSO4 (nor-
mally used). On the one hand, the sulfates are reduced to hydrogen
sulfide by action of anaerobic microorganisms, which present s
toxic effects and generate odors and, on the other hand, it generates
sulfuric acid by the action of oxygen, which can induce corrosion.
The homogenization into the reactor was achieved by stirring at
200 rpm, using a bar and a magnetic plate (Falc®).
Along time, the temperature and pH values were recorded, and
samples were collected to measure the total organic carbon (TOC),
after adding an excess of sodium sulfite to eliminate the residual
hydrogen peroxide and stop the reaction in the sampling vial. In the
last samples, collected after 180 min, BOD5, COD and toxicity
(evaluated by the inhibition of Vibrio fischeri) were measured in the
effluent, after increasing the pH until ~12 (this way precipitating
the iron and eliminating the residual oxidant present) with 10 M
NaOH and further neutralization to pH ~7.0 with concentrated
H2SO4. The samples for toxicity assessment were neutralized using
1 N HCl, as proposed by the analytical methodology
(Standardization, 2005).
The blank runs were performed the same way as the Fenton’s
2.3. Chemical coagulation/flocculation procedure
Coagulation/flocculation was carried out in a jar test apparatus
(VELP Scientifica, model JLT6). In each beaker, 200 mL of bio-
digested CPW was placed and the pH adjusted to the desired value
with 10 M NaOH or 1 M H2SO4; then, FeCl3 (Labchem®) solution
(12 g L1) was added and the pH immediately readjusted (if
necessary). All runs were performed at room temperature (~28  C).
The coagulation step comprised high stirring speed (150 rpm)
during 3 min and, for the flocculation stage, the stirring was slowed
down to 15 rpm for a period of 20 min. These operating conditions
were established according to data reported in the literature
(Eckenfelder , 2000; Poland and Pagano, 2010; Rodrigues et al.,
2014a). In the flocculation step no flocculant was added because
in previous studies it was verified that it did not increase the
organic load reduction (Karthik et al., 2008; Nandy et al., 2003;
Rodrigues et al., 2013).
In order to separate the flocs from the clarified effluent, sedi-
mentation was carried out for 20 h and then a portion of super-
natant was taken to determine turbidity, BOD5, COD, TOC, toxicity
and biodegradability (expressed as BOD5:COD ratio).
2.4. Analytical methods
The chemical oxygen demand was determined according to
Method 5220D (APHA, 2005). Firstly, the samples were digested at
150  C for 2 h in closed reflux (termoreactor Merck, model 420) and
then the amount of potassium dichromate not consumed was
determined, measuring the absorbance at 605 nm (photometer
Merck, model Nova 60 Spectroquant). The dissolved COD (CODdiss.)
was determined in the same way as described for COD, after
filtration on a glass microfiber filter GF/D from Whatman.
BOD5 corresponds to oxygen consumption in 5 days by
4 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796
microorganisms in the organic matter biodegradation process
(Method 5210 D (APHA, 2005)). The samples were placed in a BOD
analysis apparatus (Velp Scientifica, model BOD EVO) and incu-
bated (Velp Scientifica, model FOC 215 E incubator) at 20  C for
assessing the dissolved oxygen consumption.
The total organic carbon was measured in a TOC analyzer (Shi-
madzu, model TOC- L) equipped with an autosampler (Shidmazu,
model ASI-L). In the analytic procedure the samples are subjected
to catalytic combustion at 680  C and the concentration of the
formed CO2 is measured in an infrared detector (Method 5310 D
(APHA, 2005)).
The turbidity was determined using a HI88703 turbidimeter
from Hanna Instruments, following the Method 2130 B (APHA,
2005).
The inhibition of Vibrio fischeri (V. fischeri) was the selected
method to evaluate the acute toxicity of the wastewater. The
respective determination was carried out according to ISO 11348e3
(Standardization, 2005), comparing the luminescence intensity
emitted by the bacteria before and after the V. fischeri exposure to
the samples for 5, 15 and 30 min at 15  C. For this purpose, a
Microtox analyzer (ModerWater, model 500) was used.
The concentration of hydrogen peroxide was measured ac-
cording to the method developed by Sellers (1980), which is based
on the measurement at 400 nm of the absorbance of the yellow
color developed by the reaction of hydrogen peroxide with tita-
nium oxalate (Thermo Unicam spectrophotometer, model Helios g).
The presence of hydroxyl radicals was evaluated by measuring
the absorbance at 563 nm of the brown color of 1,5-
diphenylcarbazone formed by oxidation of 1,5-diphenylcarbazide
by the hydroxyl radicals (Wang et al., 2011).
Three-dimensional fluorescence excitation-emission matrix (3D
EEM) spectra were obtained using a JASCO spectrofluorometer (FP-
8300). Samples were diluted with Milli-Q water in order to avoid
inner filter effect and analyzed in a 1 cm quartz cuvette. Excitation
wavelength range varied from 200 to 500 nm with 2 nm steps
increment while the emission spectrum was recorded between 250
and 750 nm with 1 nm steps. The scan speed was fixed at
1000 nm min1 and the slit width was fixed at 5 nm and 10 nm in
excitation and emission, respectively. Milli-Q water blanks were
analyzed in the same conditions as the samples and the respective
spectrum was subtracted to samples spectra in order to minimize
Raman scattering. The 1st and 2nd order Rayleigh scattering lines
were removed using internal filter.
All analytical determinations were performed in duplicate and
the coefficients of variation were less than 7.0% for pH, 9.0% for
BOD5, 6.0% for COD, 2.0% for TOC and hydrogen peroxide concen-
tration, 3.0% for absorbance at 530 nm (indirect measurement of
the hydroxyl radicals), 8.0% for turbidity and 10.0% for V. fischeri
inhibition.
3. Results and discussion
3.1. Characteristics of biodigested CPW
The physicochemical characteristics of the biodigested CPW
used in this work are reported in Table 1. In general, the effluent is
characterized by the presence of a high amount of organic com-
pounds, since it presents high concentrations of BOD5, TOC and
COD (the concentration of dissolved organic matter, expressed as
dissolved COD, represents 95% of the total COD) and low biode-
gradability (BOD5:COD <0.4), which suggests difficult stabilization
by biological degradation. As expected from the anaerobic diges-
tion of CPW, the pH is neutral and high turbidity levels were found.
The biodigested CPW has low toxicity as indicated by V. fischeri
inhibitions of 11.0e20.0%.
The 3D-EEM spectrum provides information about several dis-
solved organic compounds that might be present, such as aromatic
proteins (EM < 380 nm and EX < 250 nm), fulvic-like compounds
(EM and EX of >380 nm and <250 nm, respectively), microbial
metabolic by-products (EM < 380 nm and EX > 250 nm) and humic
acid-like compounds (EM > 380 nm and EX > 250 nm) (Chen et al.,
2003; Kang et al., 2015). The results showed that the presence of
fluorescence in CPW corresponds to humic acid-like compounds,
once only one fluorescence center was observed in the region of
such substance (see Fig. 1a).
The biodigested CPW is not suitable for direct discharge into
water bodies because, except for pH, all parameters are above the
legislated values (CONAMA Resolution No. 357/2005 (Brazil, 2005)
or Normative COPAM No.01/2008 (COPAM, 2008) - cf. Table 1. On
the other hand, the recirculation to anaerobic reactors (which is a
common approach to increase the alkalinity of the raw effluent fed
to the reactors) or the treatment by another biological process
should be not feasible, considering the low biodegradability (and
some toxicity) of the biodigested CPW. So, this effluent needs a
subsequent treatment for degradation of the recalcitrant com-
pounds, biodegradability improvement and toxicity reduction, thus
allowing its recirculation to the anaerobic digester. In this study,
three strategies were considered for that purpose: Fenton process
(Approach 1), chemical coagulation/flocculation (C/F) (Approach 2)
and combination of C/F and Fenton reaction (Approach 3).
3.2. Optimization of Fenton process (approach 1)
The Fenton process is influenced by several operating condi-
tions, namely: catalyst dose (Fe3þ), initial pH, initial oxidant (H2O2)
concentration and temperature. A parametric study was carried out
to evaluate the effect of each variable on organic compounds
removal, improvement of the biodegradability (assessed in terms of
the BOD5:COD ratio) and reduction of the toxicity. The obtained
results are presented and discussed in the following sections.
3.2.1. Effect of the catalyst dose
The effect of iron dose was evaluated in the range
0.90e2.70 g L1 (corresponding to Fe3þ:H2O2 ratios (w/w) of
0.1e0.3, close to the typical ratios reported for the Fenton process -
between 0.05 and 0.2 (USP Technologies, 2019)), and the remaining
variables, H2O2 concentration, initial pH and temperature, respec-
tively, were fixed at 9.0 g L1, 3.0 and 30  C. The TOC reduction is
fast in the first 60e90 min of reaction, then the removal rate decays
up to 150 min and TOC remains approximately constant for higher
reaction times e see Fig. 2a. A similar trend was observed for pH
evolution (Fig. 2b), which decreases from the beginning of the re-
action (t ¼ 0) up to 60 min, being the variation attenuated after-
ward. The decrease of pH for t < 0 is caused by the addition of the
Fenton’s reagents (particularly the iron salt) and during the reac-
tion (t > 0) is commonly attributed to the carboxylic acids (inter-
mediate compounds) formed, as reported in other studies (Lima
et al., 2018; Rodrigues et al., 2018; Rodrigues et al., 2017b; Soares
et al., 2019).
The maximum TOC removal (43.1% after 180 min) was obtained
for the catalyst dose of 1.8 g L1. The greatest overall COD (49.4%)
and BOD5 (30.4%) removals were also observed for this catalyst
dose, along with the maximum BOD5:COD ratio (0.45), as shown in
Table 2. Higher Fe3þ concentrations caused a decrease in the pro-
cess efficiency, probably due to the fact that the iron in excess reacts
with HO (Eq. (6)) (Walling, 1975), thereby decreasing the hydroxyl
radical concentration in solution. This fact is corroborated by the
decay of HO formation when [Fe3þ] increases from 1.8 to 2.7 g L1
in the blank tests (Fig. 3a) whereas a rapid hydrogen peroxide
consumption is observed (Fig. 3b).
 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796
Fig. 1. 3D EEM fluorescence spectra of biodigested CPW (a), after Fenton’s oxidation alone (b), after coagulation/flocculation (c) and after C/F followed by Fenton’s process (d).
Regarding the acute toxicity, only the Fe3þ dose of 0.9 g L1
originated some toxicity, but the inhibition of V. fischeri (2.4e6.9% -
Table 2) was less than that obtained for the initial biodigested CPW
(11.0e20.0% - Table 1).
3.2.2. Effect of the initial pH
The effect of pH was assessed in the range of 2e7, keeping
constant the temperature at 30  C, the H2O2 concentration at
9.0 g L1 and the Fe3þ at the previously obtained optimal dose
(1.8 g L1). This range of pH values was selected to encompass the
commonly reported values (2e5) as optimal for the Fenton process
(Pignatello, 1992; Rivas et al., 2001; Zhang et al., 2019). The highest
mineralization was reached at initial pH of 5.0, corresponding to
46.5% TOC reduction (see Fig. 2c). In addition, this pH value led to
the highest removals of BOD5 (33.6%) and COD (51.7%) and biode-
gradability improvement (BOD5:COD ratio increased from 0.34 to
0.45) whereas generating a non-toxic effluent as shown in Table 2.
The optimal pH for treating the biodigested CPW was not very
acidic as typically reported for other treatments by the Fenton
process (pH 2.5e3.0). This fact was associated to the decay of pH
from 5.0 to near 2.5 as shown in Fig. 2d, due to the addition of FeCl3
with the simultaneous formation of the above-mentioned carbox-
ylic acids. This aspect is advantageous for the industrial application
of the Fenton process in the treatment of this type of effluent since
it allows reducing the costs associated with the consumption of
acid for the preliminary acidification.
The existence of an optimum pH is justified by the fact that, on
5
the one hand, at very high pH occurs the decomposition of
hydrogen peroxide into water and oxygen (Szpyrkowicz et al.,
2001) and the formation of iron hydroxide (Pignatello, 1992),
which is therefore not solubilized and available to catalyze the
reaction. On the other hand, at very acidic pH (<2.0) H2O2 reacts
with the Hþ in solution and forms H3Oþ 2 ; moreover, the Fe
3þ
con-
centration, responsible for ensuring the continuity of the reaction,
decreases because in such conditions the Fe(OH)2þ and Fe(OH)þ 2
species prevail (Pignatello, 1992). Thus, both the amount of oxidant
and the catalyst available to generate the hydroxyl radicals
decrease, which leads to a reduced efficiency of the process.
3.2.3. Influence of initial hydrogen peroxide concentration
Four runs were carried out to determine the effect of the initial
H2O2 dose by varying its concentration in the range of 4.5 g L1 to
18.0 g L1 (corresponding to 0.5e2.0 times the stoichiometric dose
based on the COD value); usually, higher amounts are required for
the complete removal of COD since part of the H2O2 decomposes
into oxygen and water (Southworth and Voelker, 2003) and it is
also consumed in scavenging reactions. The concentration of Fe3þ
(1.80 g L1), initial pH (5.0) and temperature (30  C) were kept
constant. In Fig. 2e one can see that, for all H2O2 concentrations
tested, the TOC removal increases rapidly in the first 30 min of
reaction, which coincides with the higher pH decay during the
reaction (see Fig. 2f), and still increases but at a lower rate up to
150 min and afterward is approximately constant. The maximum
TOC removal was achieved for [H2O2] ¼ 9.0 g L1, corresponding to
6 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796

Fig. 2. Effect of Fe3þ dose (a,b), initial pH (c,d), H2O2 concentration (e,f) and temperature (g,h) in TOC removal and evolution of pH, with standard errors for a confidence level of
95%, during the Fenton process alone (experimental conditions were as follows: a,b) pHinitial ¼ 3.0, T ¼ 30  C and [H2O2] ¼ 9.0 g L1; c,d) T ¼ 30  C, [Fe3þ] ¼ 1.8 g L1 and
[H2O2] ¼ 9.0 g L1; e,f) pHinitial ¼ 5.0, T ¼ 30  C, [Fe3þ] ¼ 1.8 g L1; g,h) pHinitial ¼ 5.0, [Fe3þ] ¼ 1.8 g L1 and [H2O2] ¼ 9.0 g L1).
 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796 7

Table 2
Operating conditions used in the Fenton’s oxidation runs (Approach 1), removal efficiencies, BOD5:COD ratio and toxicity reached after 180 min of reaction with standard errors
for a confidence level of 95%. Bold conditions refer to the run providing better efficiencies when each variable was changed in the parametric study.

Parameter [H2O2] (g L1) [Fe3þ] (g L1) Initial pH T (oC) Removal efficiency (%) BOD5:COD Inhibition V. fischeri at 5/15/30 min (%)

TOC COD BOD5

Fe3þ 9 0.9 3.0 30 26.8 ± 0.5 26.8 ± 0.8 18.1 ± 0.8 0.36 ± 0.08 2.4 ± 0.2/3.8 ± 0.4/6.9 ± 0.6
1.8 43.1 ± 0.8 49.4 ± 0.2 30.4 ± 0.3 0.45 ± 0.02 0.0 ± 0.1/0.0 ± 0.3/0.0 ± 0.4
2.25 35.4 ± 0.6 36.9 ± 0.2 25.5 ± 0.2 0.38 ± 0.03 0.0 ± 0.3/0.0 ± 0.4/0.0 ± 0.3
2.7 32.3 ± 1.0 33 ± 0.6 22.9 ± 1.0 0.37 ± 0.01 0.0 ± 0.1/0.0 ± 0.2/0.0 ± 0.4
pH 9 1.8 2 30 18.1 ± 0.5 21.2 ± 0.4 14.6 ± 3.0 0.27 ± 0.05 3.2 ± 0.2/6.2 ± 0.3/10.2 ± 0.5
3 43.1 ± 0.8 49.4 ± 0.2 30.4 ± 0.3 0.45 ± 0.02 0.0 ± 0.1/0.0 ± 0.3/0.0 ± 0.4
5 46.5 ± 0.9 51.7 ± 0.4 33.6 ± 1.2 0.45 ± 0.06 0.0 ± 0.1/0.0 ± 0.2/0.0 ± 0.1
6 41.5 ± 1.2 39.2 ± 0.8 24.5 ± 1.7 0.01 ± 0.02 0.0 ± 0.2/0.0 ± 0.5/0.0 ± 0.6
7 24.8 ± 0.4 28.7 ± 0.05 17.3 ± 0.7 0.01 ± 0.01 2.6 ± 0.3/3.3 ± 0.2/6.8 ± 0.5
H2O2 4.5 1.8 5 30 26.3 ± 0.8 26.5 ± 0.4 20.8 ± 1.5 0.35 ± 0.03 2.9 ± 0.5/4.0 ± 0.4/6.7 ± 0.1
9 46.5 ± 0.9 51.7 ± 0.4 33.6 ± 1.2 0.45 ± 0.06 0.0 ± 0.1/0.0 ± 0.2/0.0 ± 0.1
13.5 38.3 ± 1.3 42.6 ± 2.6 27.6 ± 1.6 0.41 ± 0.03 0.0 ± 0.2/0.0 ± 0.3/0.0 ± 0.1
18 30.9 ± 1.8 35.9 ± 0.1 23.4 ± 1.6 0.39 ± 0.05 0.0 ± 0.4/0.0 ± 0.8/0.0 ± 0.2
T 9 1.8 5 20 34.3 ± 0.5 39 ± 1.2 29.7 ± 2.0 0.37 ± 0.03 0.0 ± 0.4/0.0 ± 0.3/0.0 ± 0.7
30 46.5 ± 0.9 51.7 ± 0.4 33.6 ± 1.2 0.45 ± 0.06 0.0 ± 0.1/0.0 ± 0.2/0.0 ± 0.1
55 51.3 ± 1.2 55.7 ± 0.5 39.7 ± 1.8 0.44 ± 0.01 0.0 ± 0.5/0.0 ± 0.6/0.0 ± 0.4

Fig. 3. Effect of Fe3þ dose on the formation of hydroxyl radicals (by measuring the absorbance at 563 nm in the presence of 1,5-diphenyl carbazide) (a) and in the consumption of
hydrogen peroxide (b), with standard errors for a confidence level of 95%, in blank tests.

46.5% after 180 min of reaction. The same dose also led to the best
COD (51.7%) and BOD5 (33.6%) removal efficiencies, as well as to a
higher BOD5:COD ratio (0.45), as can be seen in Table 2. The exis-
tence of an optimal H2O2 concentration has been reported by other
researchers that treated industrial wastewater by Fenton’s oxida-
tion (GilPavas et al., 2017; Guerreiro et al., 2016) and can be
explained by the scavenging of hydroxyl radicals by excess of H2O2,
generating HOO species with a lower oxidation potential (Eq. (5))
(Walling, 1975).
As regards acute toxicity (evaluated by inhibition of Vibrio
fischeri), only the sample corresponding to the lowest H2O2 con-
centration (4.5 g L1) inhibits the bacterial growth, but the inhi-
bition values (2.9e6.7% e Table 2) were smaller than those
obtained for the initial biodigested CPW (11e20% - Table 1). For
higher oxidant doses, no toxicity was detected in the final effluent.
3.2.4. Effect of temperature
The influence of the temperature on the process efficiency was
evaluated by carrying out three runs at 20  C, 30  C and 55  C,
respectively. These values are practically inside the optimal range
(20e50  C) reported in the literature for the best performance of
Fenton’s oxidation (Parmar, 2014). Still, the minimum temperature
has been established considering the weather conditions in S~ ao
Paulo State (Brazil) during the coffee harvest period (AprileJuly)
and when CPW is produced, at an ambient temperature never
below 20  C; the maximum value corresponds to the temperature
of the effluent discharged from the anaerobic reactors (55  C), and
therefore there are no additional costs associated with heating the
effluent. Furthermore, it is known that for temperatures above
60e70  C the thermal decomposition of hydrogen peroxide in
water and oxygen can occur.
As shown in Fig. 2g and Table 2, overall TOC removals raised
significantly when increasing the temperature from 20 to 30  C,
however, a smaller increase was achieved between 30 and 55  C.
Again, a pH decay was observed during the oxidative process,
which was most noticeable for the assay at 55  C as shown in
Fig. 2h. The positive effect of temperature on the process efficiency
is associated with the increase of the kinetic constants of the re-
actions, as expressed by the Arrhenius law. For the temperature
leading to the best efficiency (55  C), removals of 51.3, 55.7 and
39.7% for TOC, BOD5 and COD, respectively, were obtained (see
Table 2). Moreover, the biodegradability was improved and the
toxicity of wastewater was totally eliminated (Table 2).
The effect of temperature on the process efficiency found in the
present work has been early reported by other authors when
treating biodigested sugarcane vinasse (Guerreiro et al., 2016), real
paper wastewater (Torrades et al., 2003) and textile dyeing efflu-
ents (Rodrigues et al., 2014b; Rodrigues et al., 2013), who also
observed a positive effect of temperature on the Fenton’s oxidation
efficiency.
The biodigested CPW treated by Fenton’s oxidation, using the
optimal conditions previously found (9 g L1 of H2O2, initial pH of 5,
8 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796
1.8 g L1 of Fe3þ and temperature of 55  C), shows only humic acid-
like compounds as fluorescent dissolved organic matter as
observed for biodigested CPW; however, the fluorescence center
decreased when compared to that obtained for the wastewater
before Fenton’s oxidation (see Fig. 1).
The treated biodigested CPW shows a high organic content
(COD ¼ 1889 mg O2 L1; TOC ¼ 706 mg C L1 and BOD5 ¼ 816 mg O2
L1 e see Table 1). The concentrations of COD and BOD5 are clearly
above the discharge limits established in Brazilian legislation
(COD ¼ 180 mg O2 L1 and BOD5 ¼ 10 mg O2 L1), so the effluent
cannot be discharged into water bodies. Considering that a signif-
icant increase in biodegradability (BOD5:COD raised from 0.34 to
0.44) and decrease in toxicity were observed (see Table 1), it is
anticipated that the proposed treatment by the Fenton process can
allow to recirculate the effluent (which still contains a considerable
content of organic matter) back to the anaerobic reactor.
The operating cost of this treatment process is considerable
(74.1 R$ m3/16.5 V m3 cf. Table 1). Therefore, another strategy
was sought, starting with the more conventional stage of coagu-
lation/flocculation, aiming at a better efficiency of the organic
matter removal and at a reduction of costs.
3.3. Chemical coagulation/flocculation (approach 2)
3.3.1. Effect of pH
The influence of pH on TOC, COD and BOD5 removals, as well as
on turbidity and toxicity reduction during the coagulation/floccu-
lation process, was assessed by performing a number of experi-
ments varying this parameter in the range 2e11. The selection of
this range took in account the pH values reported in the literature
for the best performance of coagulation using ferric salts (Eck-
enfelder Jr., 2000). The highest removal efficiencies were obtained
at high pH values (10e11), i.e., removals of 19e22% (Fig. 4a) were
achieved. Coagulation/flocculation allows suspended, colloidal and
dissolved material to be removed through the formation of flocs
(Ghernaout and Ghernaout, 2012), but a significant proportion of
organic matter can still remain in the effluent after this process.
Coagulation/flocculation was not satisfactory to enhance the
effluent biodegradability (assessed in terms of BOD5:COD ratio),
which remained invariable at ca. 0.33 (Fig. 4a). However, the pro-
cess led to a significant reduction of the effluent turbidity, up to 92%
(Fig. 4c). In addition, a reduction of the inhibition of Vibrio fischeri
also occurred (Fig. 4c). Taking into account the results obtained, a
pH of 10 was selected as the best one for operating the coagulation/
flocculation process. At this pH value, the anionic forms of iron
(Fe(OH)-4) and Fe(OH)3 become dominant, consequently the coag-
ulation/flocculation process occurs probably by the mechanism of
inclusion in a precipitate (Duan and Gregory, 2003; Ghernaout and
Ghernaout, 2012), i.e. the colloidal organic matter is trapped during
the formation of Fe(OH)3.
3.3.2. Effect of Fe3þ dosage
The concentration of Fe3þ was assessed within the range of
62.5e1000 mg L1 at pH 10. It was found that the organic matter
removal increased with the coagulant dose until 250 mg L1;
higher doses did not provide any efficiency improvement (Fig. 4b).
For the optimal dose of coagulant (250 mg Fe3þL1) a significative
reduction in the organic matter content was achieved
(COD ¼ 38.7%, BOD5 ¼ 39.0%, TOC ¼ 37.3%) (see Table 1 and Fig. 4b).
The turbidity of the effluent significantly decreased up to
[Fe3þ] ¼ 125 mg L1, but a lower decrease occurred when the dose
was increased to 250 mg L1 and finally remained at an approxi-
mately constant value (27 NTU) for the higher doses (Fig. 4d).
Although the acute toxicity for a contact time of 5 min has been
initially reduced to 1.6%, it disappeared for [Fe3þ] > 125 mg L1; for
[Fe3þ]  250 mg L1, a residual inhibition around 1.6% and 3.4% was
observed for contact times with the bacteria of 10 and 15 min,
respectively.
As regards biodegradability, Fig. 4b shows that the BOD5:COD
ratio remained approximately constant (0.32e0.34) whatever the
iron dose employed and very similar to that obtained for the raw
biodigested CPW.
The existence of a plateau when changing the coagulant dose
can be explained by the fact that the colloidal particles get desta-
bilized when the coagulant added to the biodigested CPW interacts
with negative colloids and neutralizes their charges. However,
when coagulant is in excess, it can be adsorbed by the colloids, so
these become positively charged and electrostatic repulsion occurs,
which leads to re-stabilization of the colloids, thus impairing the
coagulation (Verma et al., 2010).
The coagulation/flocculation process improves the effluent
quality at a much lower operating cost (3.4 R$ m3 z 0.76/V m3 -
Table 1) as compared to the Fenton process, only associated with
the iron chloride consumption because the costs of acid and base
for pH adjustment are negligible. The 3D EEM spectrum points out
again to the presence of humic acid-like compounds (Fig. 1 c), but
the fluorescence center is below that observed for biodigested CPW.
The effluent still presents a high organic load (COD ¼ 2613 mg O2
L1; TOC ¼ 907 mg C L1 and BOD5 ¼ 846 mg O2 L1), which means
that it does not meet the discharge limits (see Table 1). Thus, a
subsequent treatment is required; however it cannot be a biological
degradation because the effluent generated after C/F presents some
toxicity and low biodegradability (not reaching the BOD5:COD
threshold ratio of 0.4 that is the value reported in the literature for
easily biodegradable wastewaters (Pulgarin et al., 1999; Zaghdoudi
et al., 2017)). Therefore, its recirculation to the anaerobic digestor is
not an option either.
An alternative approach for biodigested CPW treatment, as re-
ported by Guerreiro et al. (2016), is coagulation/flocculation as a
pretreatment step upstream from the Fenton process (which con-
stitutes the Approach 3 in this study). This strategy aims to reduce
the costs associated with chemicals consumption in the second
process. On the one hand, a less amount of hydrogen peroxide is
consumed because the organic content is reduced in the coagula-
tion/flocculation step and, on the other hand, the iron salt still
remaining in solution after coagulation/flocculation will be used as
catalyst in the chemical oxidation step.
3.4. Chemical coagulation/flocculation plus Fenton’s oxidation
(approach 3)
In order to increase the mineralization and/or biodegradability
and to reduce the toxicity of CPW at the lowest treatment cost, the
strategy of combining coagulation/flocculation (C/F) with Fenton’s
oxidation was adopted. Thus, the effluent is first treated by C/F
under the best operating conditions reached in Approach 2
(pH ¼ 10.0 and [Fe3þ] ¼ 250 mg L1) and, afterward submitted to
Fenton’s oxidation. In the second treatment step the optimal con-
ditions of pH and temperature previously found when testing
Approach 1 (pH ¼ 5.0, T ¼ 55  C) were selected, only evaluating the
effect of the initial concentrations of catalyst and oxidant, as pre-
sented below. In Fenton’s oxidation the optimal iron and hydrogen
peroxide concentrations found in Approach 1 were not used
because the organic load is lower since part of it was removed in
the first treatment step (i.e. in the coagulation/flocculation process)
3.4.1. Influence of Fe3þ concentration
The dose of Fe3þ was varied in the range 0.55e2.2 g L1, main-
taining [H2O2] ¼ 5.6 g L1 (corresponding to the stoichiometric
amount of COD of the effluent after C/F - 2613 mg O2 L1, as shown
 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796
Fig. 4. Effect of pH and Fe3þ concentration on the removals of TOC, COD and BOD5 and on biodegradability expressed as BOD5:COD ratio (a,b) and turbidity and acute toxicity of the
effluent (c,d), with standard errors for a confidence level of 95%, after the coagulation/flocculation process (vcoagulation ¼ 150 rpm, tcoagulation ¼ 3 min, [Fe3þ]a,c ¼ 62.5 mg L1,
pHb,d ¼ 10, T ¼ ~28  C, vflocculation ¼ 20 rpm, tflocculation ¼ 15 min).
in Table 1). As can be seen in Fig. 5a and Table 3, the removals of
TOC, BOD5 and COD increased with the catalyst dose up to 1.8 g L1
and decreased for higher concentrations. This iron concentration
also leads to one of the largest pH decreases during the Fenton
reaction (Fig. 5b). The optimal Fe3þ dose reached was the same
observed when treating biodigested CPW only by Fenton’s oxida-
tion. The existence of an optimal catalyst dose results from the fact
that the excess of ferric iron in solution reacts with the hydroxyl
radical (Eq. (6)), as mentioned above.
The biodegradability increased from 0.34 for the raw bio-
digested CPW to 0.43 after C/F plus Fenton’s oxidation and a non-
toxic effluent was reached (see Table 3).
3.4.2. Effect of initial H2O2 concentration
The influence of the initial H2O2 concentration was evaluated in
the range 5.6e11.2 g L1, setting the catalysts dose at the optimal
value previously determined (1.8 g L1). As shown in Fig. 5c and
Table 3 the mineralization increased with the oxidant concentra-
tion up to 8.4 g L1, corresponding to TOC, COD and BOD5 removals
of 61.8, 62.2 and 44.9% after 180 min of reaction, respectively.
Moreover, the pH decreased during the reaction, more pro-
nouncedly for such oxidant dose (see Fig. 5d), the biodegradability
of the effluent was further improved, and its toxicity was null for all
H2O2 concentrations tested.
The combination of the two processes (coagulation/flocculation
followed by Fenton’s reaction) reached global removals of 76.2, 76.5
and 66.3% for TOC, COD and BOD5, respectively - Table 1 - and,
again, only the presence of humic acid-like fluorescent compounds
was observed but with a decrease in the fluorescence center
compared to the effluent before treatment (see Fig. 1). The Fenton’s
oxidation alone (Approach 1) or combined with C/F (Approach 3)
implies similar operating costs (~74.0 R$ m3/~17.0 V m3). Both
treatment strategies are the best ones to treat the biodigested CPW,
9
once they allow higher organic matter removals as compared with
the C/F process alone (see Table 1). Despite the reduction of the
organic content, COD and BOD5 remain above the discharge limits
imposed by the Brazilian legislation (see Table 1). Thus, the treated
biodigested CPW cannot be discharged into water bodies, but
considering the elimination of the toxicity and the strong biode-
gradability improvement, the wastewater can be recirculated to the
anaerobic reactor; this will be the aim of future work, in order to
assess the impact on bio-methane production.
3.5. Comparison with literature data
Some reports on the treatment of raw coffee wastewaters are
available in the open literature. Anaerobic digestion has shown be
efficient in the removal of organic load (COD removals between 60
and 86%) with high methane production (Battista et al., 2016;
Beyene et al., 2014; Cruz-Salomo
n et al., 2018; Fia et al., 2012; Villa-
Montoya et al., 2017). In a system composed by two anaerobic UASB
reactors in series treating CPW and operating at high organic
loading rate (18.2 g COD (L d)1), the organic matter removal
(expressed as COD) attained 84%, which is within the range above
mentioned, along with high methane production (2.2 L CH4 d1
(Su

arez et al., 2018)).
Besides the application of anaerobic biological processes, there
are some studies reported in the literature where physical/chemical
processes, such as coagulation/flocculation, photo-Fenton oxida-
tion, electrochemical advanced oxidation and adsorption, were
adopted to treat raw CPW. COD removal efficiencies of 67% and 63%
were obtained for coagulation/flocculation and photo-Fenton
oxidation of CPW, respectively (Zayas et al., 2007). The treat-
ability of coffee processing wastewater was also evaluated by
anodic oxidation with electrogenerated H2O2 and TOC and color
removals of 73e84% and 89e93%, respectively, were achieved
10 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796

Fig. 5. TOC removal and evolution of pH along reaction time for different Fe3þ doses (a,b) and H2O2 concentrations (c,d), with standard errors for a confidence level of 95%, in CPW
previously treated by coagulation/flocculation (experimental conditions were as follows: a,b) pHinitial ¼ 5.0, T ¼ 55  C and [H2O2] ¼ 5.6 g L1; c,d) pHinitial ¼ 5.0, T ¼ 55  C and
[Fe3þ] ¼ 1.8 g L1).

Table 3
Operating conditions used in Fenton’s oxidation of biodigested CPW after treatment by C/F, respective removal efficiencies, along with BOD5:COD ratio and toxicity achieved
after 180 min of reaction with standard errors for a confidence level of 95%. Bold conditions refer to the run providing better efficiencies when each variable was changed in the
parametric study.

Parameter [H2O2] (g L1) [Fe3þ ] (g L1) Initial pH T (oC) Removal efficiency (%) BOD5:COD Inhibition V. fischeri at 5/15/30 min (%)

TOC COD BOD5

Fe3þ 5.6 0.55 5.0 55 43.4 ± 0.6 40.3 ± 0.2 21.4 ± 2.0 0.42 ± 0.07 0.0 ± 0.9 / 0.0 ± 0.4 / 0.0 ± 0.6
1.12 49.3 ± 0.9 47.7 ± 0.5 30.3 ± 1.4 0.42 ± 0.04 0.0 ± 0.2 / 0.0 ± 0.4 / 0.0 ± 0.3
1.8 52.5 ± 0.5 54.9 ± 0.9 38.5 ± 0.5 0.43 ± 0.02 0.0 ± 0.6 / 0.0 ± 0.5 / 0.0 ± 0.3
2.2 50.6 ± 1.0 48.6 ± 0.2 34.4 ± 2.4 0.41 ± 0.03 0.0 ± 0.2 / 0.0 ± 0.4 / 0.0 ± 0.3
H2O2 5.6 1.8 5 55 52.5 ± 0.5 54.9 ± 0.9 38.5 ± 0.5 0.43 ± 0.02 0.0 ± 0.6 / 0.0 ± 0.5 / 0.0 ± 0.3
8.4 61.8 ± 0.8 62.2 ± 0.3 44.9 ± 0.6 0.47 ± 0.01 0.0 ± 0.5 / 0.0 ± 0.3 / 0.0 ± 0.6
9.6 57.9 ± 0.7 57.5 ± 0.2 40.7 ± 0.7 0.44 ± 0.04 0.0 ± 0.5 / 0.0 ± 0.7 / 0.0 ± 0.2
11.2 55.4 ± 1.2 55.9 ± 0.7 38.8 ± 1.0 0.44 ± 0.08 0.0 ± 0.8 / 0.0 ± 0.4 / 0.0 ± 0.6

(Villanueva-Rodríguez et al., 2014). High removals of COD and BOD
(>98%) were also reached by using commercial activated carbon,
avocado peel carbon and avocado seed carbon as adsorbents (Devi,
2009; Devi et al., 2008).
Few investigations were performed on the treatment of anaer-
obic digested CPW, which is the goal of the present study.
Selvamurungan et al. (2010) studied the integration of anaerobic
biodigestion in a UASB with aerobic biodegradation to treat bio-
digested CPW. The authors achieved overall removals of 68.6 and
74.6% for COD and BOD, respectively. A similar study was carried
out Rossmann et al. (2013) and similar removals (87 and 84% for
BOD and COD) were achieved with and without the aeration step. A
different work was performed by Sanabria et al. (2012) that applied
a post-treatment consisting of wet peroxidation using AleCeeFe-
PILC as catalyst to the anaerobically digested effluent and obtained
removals of 50 and 66% for TOC and COD, respectively. The overall
COD removal efficiency, corresponding to anaerobic digestion plus
wet peroxidation, was 97%.
In the present study, Fenton oxidation per se or combined with
coagulation/flocculation proved to be promising strategies for
biodigested CPW treatment, allowing COD removals above 93e96%
when considering the previous anaerobic digestion. These effi-
ciencies are higher than those obtained by Selvamurungan et al.
(2010) and Rossmann et al. (2013) using combined anaerobic and
aerobic degradation. However, they are similar to that reached by
Sanabria et al. (2012) when employing anaerobic digestion fol-
lowed by wet peroxidation.
 V. Gomes de Barros et al. / Environmental Pollution 259 (2020) 113796
4. Conclusions
In this study it was evaluated the treatment of biodigested CPW
by Fenton and coagulation/flocculation processes, alone and com-
bined, to obtain an effluent with characteristics allowing its recir-
culation back to anaerobic digesters. It was found that:
i) The Fenton’s oxidation per se (Approach 1) represents an
efficient strategy for improving the biodegradability (from
0.34 to 0.44) and eliminating the toxicity of the biodigested
CPW while obtaining a considerable organic matter removal
(55.7%, 39.7% and 51.3% for COD, BOD5 and TOC removals,
respectively).
ii) The Coagulation/flocculation alone (Approach 2) showed
lower levels of organic matter removal (~37%e~39%), did not
increase the biodegradability and generated an effluent that
maintained some toxicity, although showing lower inhibi-
tion of V. fischeri than the biodigested CPW.
iii) The combination of the two processes (C/F plus Fenton’s
oxidation) allowed to make the wastewater more biode-
gradable and non-toxic, like the Fenton process alone, and to
obtain the highest global removals of TOC (76.2%), COD
(76.5%) and BOD5 (66.3%).
Taking in account that it is intended to recirculate the bio-
digested CPW back to the anaerobic reactor, the strategies sug-
gested are the Fenton process (Approach 1) or the combination of C/
F plus Fenton’s oxidation (Approach 3), with similar operating costs
(~74 R$ m3/~17 V m3), once both approaches reduce the content
of refractory organic compounds making the effluent more biode-
gradable and non-toxic. However, the effect of the recirculation on
biogas production has to be evaluated. Still, for the application of
such treatment industrially, the study will have to proceed for
larger laboratory and/or pilot facilities (scale-up).
Declaration of competing interest
The authors declare that there is no conflict of interest regarding
the publication of this article.
Acknowledgments
This work was financially supported by Projects UID/EQU/
00511/2019 - Laboratory for Process Engineering, Environment,
Biotechnology and Energy - LEPABE - and by Associate Laboratory
LSRE-LCMdUID/EQU/50020/2019 funded by national funds
through FCT/MCTES (PIDDAC). We would also like to thank the
scientific collaboration under project “AIProcMat@N2020 -
Advanced Industrial Processes and Materials for a Sustainable
Northern Region of Portugal 2020” (NORTE-01-0145-FEDER-
000006, NORTE 2020, Portugal 2020 Partnership Agreement,
through FEDER). Valciney Gomes de Barros is grateful to the Bra-
zilian Coordination for the Improvement of Higher Education
Personnel (CAPES) for his Sandwich Doctorate scholarship (Process
88881.132416/2016e01). The authors are thankful to the WWTP of
Parada for providing the aerobic biological sludge for BOD analyses.
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