Accepted Manuscript

Multivariate and multiobjective optimization of tannery industry effluent treatment

using Musa sp flower extract in the coagulation and flocculation process

Maria Bernadete Pinto, Gisella Rossana Lamas Samanamud, Eduardo Prado Baston,
Alexandre Boscaro França, Luzia Lima Rezende Naves, Carla Cristina Almeida
Loures, Fabiano Luiz Naves
PII: S0959-6526(19)30439-1
DOI: https://doi.org/10.1016/j.jclepro.2019.02.060
Reference: JCLP 15790

To appear in: Journal of Cleaner Production

Received Date: 9 November 2018

Revised Date: 17 December 2018
Accepted Date: 6 February 2019

Please cite this article as: Pinto MB, Samanamud GRL, Baston EP, França AB, Naves LLR, Loures
CCA, Naves FL, Multivariate and multiobjective optimization of tannery industry effluent treatment
using Musa sp flower extract in the coagulation and flocculation process, Journal of Cleaner Production
(2019), doi: https://doi.org/10.1016/j.jclepro.2019.02.060.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT
Multivariate and multiobjective optimization of tannery industry effluent
treatment using Musa sp flower extract in the coagulation and flocculation process

Maria Bernadete Pintoa, Gisella Rossana Lamas Samanamudb, Eduardo Prado Bastona,
Alexandre Boscaro Françaa, Luzia Lima Rezende Navesa, Carla Cristina Almeida
Louresc, Fabiano Luiz Navesa,*

PT
a
Chemical Engineering Department, Federal University of São João Del Rei, São João Del Rei, MG,

RI
Brazil

SC
b
Department of Civil and Environmental Engineering, University of Texas at San Antonio, UTSA, San

Antonio, Texas 78249

U
c
Department of Mechanical Engineering (DEPMC), Federal Center for Technological Education, Angra
AN
dos Reis, RJ, Brazil
M

* Corresponding author at: Department of Chemical Engineering Federal University of Sao Joao Del Rei,
D

Brazil.
TE

E-mail address: fabianonavesengenheiro@ufsj.edu.br (F. L. Naves).

Phone number: +55 31 3741 5281

C EP
AC
 ACCEPTED MANUSCRIPT
Multivariate and multiobjective optimization of tannery industry effluent treatment
using Musa sp flower extract in the coagulation and flocculation process

Abstract

Several studies have focused in the tannery industry due to the high polluting potential
of the effluent generated in leather processing; high concentrations of total chromium
and organic load. However, the high costs attributed to the treatment of tanning residues

PT
explains why this material is not treated within the tannery industry. The extract from
the flower of Musa sp, condensed and hydrolisable tanins, yet to be explored in
literature was applied to remove organic matter from chemically enhanced primary

RI
treatment (CEPT) of total solids, turbidity and total chromium from a tanning industry
and leather processing. The use of the flower extract of Musa sp. proposed in this study
does not require flocculant polymers after the coagulation step. A central composite

SC
design response surface (CCD) was modelled by the factors: coagulant volume, pH and
rotation. The optimization was performed according to the NBI algorithm in a mixed
arrangement to determine optimal weights. The modelling from CCD and minimization

U
of Global Standard Error determines the optimized conditions, turbidity removal, total
cromium, hexavalent chromium and trivalente chromium of 78% and 65.4%, 39.43%
AN
and 61.02%, respectively, increasing the biodegradability from the ratio biochemical
oxygen demand (COD) and chemical oxygen demand (COD) of 0.12 to 0.63.
M
D
TE
C EP
AC

Keywords: tannery; coagulation; flower of Musa sp; optimization

 ACCEPTED MANUSCRIPT
1. Introduction

The leather industry occupies a place of prominence in many countries, and animal
leather is a raw material in the production of coats, bags and so on. High amounts of
water are used in the washing and tanning process, generating an average flow of 6000
m3 day-1 of effluent in the process of 45,000 kg of bovine skin (GARROTE et al.,
1995). The generated effluent is loaded with high concentrations of chromium,

PT
suspended solids, salts, acids, bases, solvents, and dyes (Gasemloo et al., 2018).
Inadequate disposal of effluents from the tannery industry can lead to serious

RI
contamination in receptors and consequently to aquatic animals as well as humans.
Guimarães et al., (2019), studied the behavior of the influence of this type of residues in

SC
male species of Swiss mice, showing changes in productive performance. However,
although it was presented in the paper that the characterization of this residue was

U
performed according to APHA, it was not possible to test which of the compounds
present in the medium could lead to greater changes in the reproductive structure of
AN
Swiss mices (Guimarães et al., 2019). The Cr (VI), Cr (III) species, dyes, acids are
species that favor biomagnification, and consequently the exacerbated accumulation of
M

these species in the final consumer. The Cr (VI) species is a species that can cause
cancer in humans (Battaglia and Vignati, 2018). Many researchers have tested the
D

ecotoxicity of these species on organisms such as sea urchin and seaweed (Nicola et al.,
2005). The great amount of residues and treatment conditions used by conventional
TE

methods (biological and physical) makes it difficult to achieve the best final disposal in
water bodies (Jamshidi et al., 2015).
EP

The peculiar characteristic of the type of effluent generated by leather tanning

industries has led to an increase in the number of studies aiming at the development of
C

proper disposal treatment systems within the specific norms discriminated for each
AC

contaminant. Among the studied processes are: biological (Ahmed et al., 2016); Wang
et al., 2014), advanced oxidation (Cruz-Rizo et al., 2017; Sivagami et al., 2017) and
coagulation and flocculation processes (Elabbas et al., 2016; GARROTE et al., 1995;
Gerek et al., 2016; Lefebvre et al., 2006; Song et al., 2004).

One of the main difficulties in the treatment and adequate discharge of industrial
effluents is the transient regimen of contaminant concentration. Functions were used to
model treatment process after optimization (Naves et al., 2017a). Therefore, the Pareto
frontier built from analyzed answers of different setups associated to the minimization
 ACCEPTED MANUSCRIPT
of Global Percentage Error in low-cost CEPT processes is a viable alternative to tanning
process, especially in the use of biocoagulants. Many studies used coagulants and
flocculants in the removal of heavy metals in the effluent (Johnson et al., 2008). A study
using flocculation process with Fe2+ and microfiltration in the removal of Cr (VI)
resulted in an average removal of 97% (Stylianou et al., 2017). One of the questioning
of Stylianou et al., (2017) was the great formation of mud and the high percentage of

PT
Cr(III). Johnson et al., (2008) used ferric chloride and an anionic polymer in the
removal of heavy metals in a synthetic solution which contained total chromium. One of

RI
the great restrictions in the metal capturing from CEPT is the presence of chelating
agents (Ridge and Sedlak, 2004).

SC
Biological and physical chemical treatments have been used to reduce organic
matter as well as to remove color (Cruz-Rizo et al., 2017). However, biological

U
processes have restrictions which, in turn, can lead to the inviability of their application
in treatments where the recalcitrant organic load is high, as it is the case of tannery
AN
effluents. High concentrations of recalcitrant organic compounds may compromise the
efficiency of organic matter removal, conditioned by the reduction in bacteria and
M

protozoa number due to the aggressiveness of the medium. Some species of fungi such
as Actinomycetes have been used in the removal of chromium due to their better
D

resistance to recalcitrant media. However, there are still few studies on the application
of these species (Polti et al., 2007).
TE

The advanced oxidation processes (AOP) consists of a class of methods that are
EP

promising, mainly due to non-selectivity in the decomposition of compounds present in

the medium attributed to the high oxidation potential of the hydroxyl radicals generated
in the process (Wang et al., 2016). Some work uses AOP in the removal of organic load
C

of effluents from tannery, however, the cost of industrial application is still questionable
AC

(Saxena et al., 2018). The restrictions applied to this type of process lead to the
combination/hybrid treatment processes which consist of a pretreatment to increase the
biodegradability of the treatment (Schrank et al., 2004).

One of the disadvantages attributed to advanced oxidation processes in the

treatment of tannery effluents found in the literature was the difficulty in breaking down
the organic chains of acids with high molecular weight, such as humic and fulvic acids
(Chong et al., 2010; Matilainen and Sillanpää, 2010; Wang et al., 2018). The
configuration of the carbon chains leads to a steric effect, which prevents the oxidant
 ACCEPTED MANUSCRIPT
from acting on smaller organic molecules. For instance, Schrank et al., (2004) used
molecular ozone in the study of the degradation of effluents from leather industry and
obtained COD removals of around 21%. Thus, preliminary removal of such long and
branched chain compounds may lead to improved efficiency of the oxidative processes.

Preliminary removal steps may include the coagulation and flocculation

processes, as proposed in this work with the use of biocoagulants present in the flower

PT
of Musa sp (BRAGA et al., 2018). This polymer extracted from the flower of Musa sp.
is composed of functional groups of coumaric and gallic acids that composse the

RI
condensed and hydrolysable tanins. This application is more feasible when compared to
other processes such as membrane separation (Fettig et al., 2017).

SC
The use of coagulants and flocculants is relatively usual in primary treatments
designed to remove recalcitrant compounds that are not easily removed by other

U
methods (NAVES et al., 2017). However, the use of specific coagulants form great
AN
loads of mud (Mazloomi et al., 2018). Mazloomi et al., (2018) used polyaluminium
chloride in the removal of suspended particles and organic matter. Usually, a great part
of the coagulants has aluminium as a main element due to charge stabilization. As well
M

as the aluminium, many other elements are used in the composition of coagulants that
can be harmful to health depending on the concentration present in the environment.
D

Therefore, many studies have been applied in the use of biocoagulants due to the
TE

capacity of stabilization with reduction of sulfates in the final mud generating a more
biodegradable aspect. The tannin is one of the most common biocoagulant used in the
EP

treatment process and it can be extracted from many renewable sources such as the seed
of Moringa Oleifera (Moreira Braga et al., 2018). The presence of phenolic groups in
the structure of tanin indicates its anionic nature characterized by a proton donor. The
C

tannin present in the extract of flower of Musa sp, was characterized as condensed and
AC

hydrolyzable with traces of gallic and coumaric acid (Moreira Braga et al., 2018). The
great advantage in relation to the other biocoagulants is the viability of being used
concomitantly to coagulation and flocculation, dismissing the use of polymers (Vaz et
al., 2018a).

The coagulation and flocculation processes studied focus in the use of inorganic
coagulants such as salts of iron and aluminium (Song et al., 2004) or using alkalis
(Dandan Wang et al., 2018). These compounds are responsible for stabilizing the
electric charges present on the surface of the colloids, which contextualizes the
 ACCEPTED MANUSCRIPT
coagulation process. For a flocculation process to occur unnaturally, organic
compounds should generally be inserted in the medium. The use of iron and aluminium
salts favor large sludge production at the end of the process. The polymer extracted
from the Musa sp flower acts directly in the process of coagulation and flocculation
simultaneously eliminating the need of additional inputs (Vaz et al., 2018b).

The use of the polymer extracted through the flower of Musa sp, has a capacity

PT
to act directly in the coagulation process, due to its hydrolyzable part, besides favoring
the flocculation process, due to its high molecular weight of its polyphenolic structure.

RI
This Musa sp flower extract was previously studied under better extraction conditions
and the present compounds identified by high performance liquid chromatography

SC
(Moreira Braga et al., 2018). From the chromatograms, it was possible to identify the
peaks corresponding to 8.379 and 11.242 which imply the presence of gallic acid

U
(hydrolyzable) and quercetin (non-hydrolyzable) (Moreira Braga et al., 2018). Many
papers in the literature have evaluated the efficiency of coagulation processes through
AN
the use of coagulants and artificial flocculants such as aluminum sulfate (Khayet et al.,
2011), ferric chloride (Bakraouy et al., 2017), these being the most common coagulants
M

applied. The literature presents references with the use of biocoagulants applied to
coagulation processes, fomented mainly due to the low cost of production and
D

efficiency when compared with other artificial coagulants (Pardede and Budihardjo,
2018). The cost of using coagulants and synthetic flocculants applied to particle
TE

separation in industrial processes, usually averaging US $ 4.00 per kilogram of

coagulant. In contrast, the much lower cost of the Musa sp flower extract, of US $ 0.53
EP

per kilogram, favors a cost reduction of approximately 86%. In addition to the effective
cost reduction, the properties of coagulant and flocculant in the treatment of tannery
C

effluent, its biodegradability is another factor that promotes its use. Another factor for
AC

the use of Musa sp flower extract is sedimentation velocity. In synthetic polymers

generally the satisfactory settling velocity in real processes is 10 m.h-1, the extract used
in the optimized operating conditions presented in this paper provides a settling velocity
of 9.7 m.h-1.

Thus, the aim of this work is the use of a polymer composed of hydrolysable and
condensed tannins (Moreira Braga et al., 2018) from the Musa sp flower, and test the
efficiency of the treatment in terms of turbidity, total solids and sedimentation velocity.
 ACCEPTED MANUSCRIPT
Under the optimized conditions, the COD ratio is verified in terms of BOD for
biodegradability, as well as the determination of the total chromium content.

2. Materials and Methods

The effluent of this study was collected directly from the last stage of the leather

PT
processing prior to the treatment plant in a tannery industry located in the city of Dores
de Campos, in the state of Minas Gerais, Brazil. This industry has an average leather

RI
production of 200 kg day-1 and a generation of 30 m3 day-1 of effluent. A corresponding
volume of 100 liters was collected in a high-density polyethylene vessel and stored

SC
under 4°C as established by the (American Public Health Association et al., 2012). All
effluent used during the experiments was raised to the temperature of 18 ± 5°C, in order
to avoid possible experimental errors. This temperature was used in order to maintain

U
the natural properties of the effluent. Equipment Jar-test model JT-102/6 with six vats
AN
for simultaneous testing was used in the study.

The following chemicals: 98% sulfuric acid (CAS 7664-93-9), and sodium
M

hydroxide (CAS 1310-73-2) acquired from Sigma Aldrich were used in order to correct
pH during the experiments. Phmeter bench model pH 21 from Hanna was used to
D

monitor the acidity and alkalinity of the medium. The coagulant used was extracted
TE

from the Musa sp flower, as established by Moreira Braga et al., (2018). A Hanna brand
HI93414-01 benchtop turbidimeter was also used. Chromium was determined according
to methodology 3500 A referring to the (American Public Health Association et al.,
EP

2012). The total solids analysis was performed according to the direct method by a
multiparameter probe series u-50 - Horiba.
C

All the experiments were carried out in the jar test and can be described in three
AC

stages. The first stage corresponded to the stabilization process of electric charges
through coagulation with the insertion of coagulant and rotation volumes established by
experimental planning. The second stage referred to the flocaulation process under the
established rotation process of 40 rpm (Vaz et al., 2018a). The last stage related to the
sedimentation process, where the suspended solids together with organic matter and
chromium occurred (Malafaia et al., 2015; Mendes et al., 2017; Oliveira et al., 2016).
All steps took place simultaneously inside the jar. The determination of total Cr was
carried out by the method of atomic absorption spectrophotometry. The determination
 ACCEPTED MANUSCRIPT
of Cr(VI) was carried out by the method of 1,5- diphenylcarbazide DR/200, in which
the difference from the concentration of total chromium and of Cr(VI) resulted in the
concentration of chromium (III).

HATCH.

The effluent was characterized according to Table 1.

PT
Table 1.
Characterization of effluent from the leather industry collected in the finishing step

RI
Parameters Measured values Method Permissible discharge Regulation
concentration
pH 10.66 Electrometric 5.0 – 9.0 CONAMA 430
(APHA, AWWA,

SC
WEF, 1998) nº
4.500-H+ B

Chemical Demand Oxygen 3229 Open reflux– CONAMA 430

U
(COD) [mgO2L-1] APHA, AWWA, 60 - 80
WEF (1998)
AN
n° 5220 B
Biochemical Oxygen Demand 387 5th day assay – 120 CONAMA 430
-1
(BOD) [mgO2L ] APHA, AWWA,
WEF (1998)
M

n°5210 B
Total Cr [mgL-1] 6.2 Chroma Ver method 1.1 CONAMA 430
– Hach
D

Sedimentary solids [mgL-1] 10.5 Chroma Ver method 20% removal CONAMA 430
– Hach
TE

Turbidity [NTU] 690 Chroma Ver method NT _________

– Hach
EP

The first step was performed under 3 minutes, the second step under 12 minutes
and the last step, 15 minutes (Vaz et al., 2018a). A volume of two liters of effluent at
C

room temperature of 23 ± 5 ˚C was inserted into each of the wells from the jar test at the
AC

beginning of the experiments. The pH was measured according to each experiment.

During the third sedimentation stage, the height of separation of the phases of the solids
and clarified water was measured at intervals of 3 minutes each to determine the
sedimentation rate. After each batch of experiments, 50 mL aliquots were drawn via
volumetric pipette at the same depth of the jar without altering the stability of the solids
deposited in the lower part. Samples were analyzed in terms of total turbidity and solids.
The COD and BOD analysis were performed according to (APHA et al., 1998).
 ACCEPTED MANUSCRIPT
The modeling of the coagulation and flocculation process was performed by a
response surface methodology (CCD) and the optimization was performed according to
the algorithm Normal Boundary Intersection (NBI) (Das and Dennis, 1998), along with
a mixed array composed of a simplex Lattice with a fit of an 8-degree polynomial and
spacing between the points in the triangular arrangement of 12.5% (De Freitas Gomes et
al., 2012).

PT
The construction of the Pareto frontier through the NBI algorithm has as its first
step the determination of the elements of the Payoff matrix Φ , which represents the

RI
optimal values of the multiple objective functions minimized individually. The solution

vector that minimizes the i-th objective function individually f i (x ) is represented by

SC
, with a minimum value of f i (x ) this point is f i (xi ) . When replacing the individual
xi* * *

U
optimum point xi obtained in the optimization of objective function in the other
( ) which is, therefore, a non-optimal value of this function.
AN
f i xi*
functions, we have
M

( )
 f1* x1* L ( )
f1 xi* L f1 xm*( )

 M O M
D


( )
Φ =  f i x1* L *
fi x ( )
*
i L ( )
f i xm*
*
TE

 M O M
 m 1( )
 f x* L fm x ( )
*
i L f xm*
*
m ( )
EP

In the NBI method, the values presented in the payoff matrix can be used to
C

normalize the objective functions, especially when there is a need to compare responses
AC

at very different scales. In a similar way, writing the set of individual optimums in a
U * *
[
vector, we have f = f1 (x1 ) K , ( )
f i * xi* K, ( )]
f m* xm*
T
. This vector is called Utopia
Point. In the same way, by grouping the maximum (non-optimal) values of each

objective function we have f

N
[
= f1N K, fi N K, f mN ].
T
This vector is called
Nadir Points. Using these two sets of extreme points, the normalization of the objective
functions can be obtained as:
 ACCEPTED MANUSCRIPT
f i ( x ) − f iU
f (x ) = i = 1,K, m (1)
f i N − f iU

The convex combinations of each line of the Payoff matrix form the CHIM
(Convex Hull of Individual Minima), or the Utopia Line.

PT
RI
U SC
AN
M
D

Figure 1 - Pareto frontier constructed from the NBI algorithm

TE

Fig. 1 represents each of the points associated with the Pareto Frontier, where a, b

and e are calculated from the scaloned payoff matrix,

Φ wi . Considering the set of
EP

convex values for the weights, w, it follows that

Φwi will represent a point on the utopia

Φwi in the
C

line. Making n̂ denote a unit vector normal to the utopia line at points
direction of origin, we can write that Φw+Dnˆ , with D∈R , will represent the set of points
AC

in that normal (Naves et al., 2017b). The point of intersection of this normal with the
boundary in the nearer viable region of origin will correspond to the maximization of
the distance between the utopia line and the Pareto Border. Thus, the NBI method can
be written as a constrained nonlinear programming problem such that:
 ACCEPTED MANUSCRIPT
Max D
(x, t )
subject to : Φ w + Dnˆ = F (x ) (2)

x∈Ω

This type of statistical modeling was used due to the greater comprehensiveness
of the response surface model composed of the constraint referring to the condition xTx.

PT
The composition of this arrangement was based on 23 factorial experiments, 2x3
experiments in the axial conditions and 6 central points used to determine the variance

RI
within the experimentation (Myers et al., 2013). The Box-Bekhen arrangement
generates fewer experiments and has a lower coverage area of the model since there are

SC
no axial points to the model. The factors and levels that were used to compose the
response surface model are presented in Table 2.

Table 2.

U
AN
Levels and factors for the experimental arrangement Central Composite Design (CCD)

Coded Levels
M

Factors -1.68 -1.00 0.00 1.00 1.68

Real Levels
Coagulant 4.0 5.0 6.0 7.0 8.0
D

volume (mL)
(x1)
TE

pH 4.0 5.0 6.5 8.0 9.0

(x2)
Rotation (rpm) 80.0 85.0 92.0 100 105.0
EP

(x3)
C

Levels were chosen according to the literature (Vaz et al., 2018b). Due to the
AC

high processing cost of the total chromium analysis, they were performed only at two
points, referring to the untreated effluent and the optimized conditions of the
coagulation, flocculation and sedimentation process. The level of significance of 95%
was chosen according to work developed in the field (Naves et al., 2017b). The Global
Percentage Error, in which optimal weight are determined and, therefore, the most
suitable experimentat conditions of the process were calculated according to Equation 3.
∗
=∑ −1 (3)
 ACCEPTED MANUSCRIPT
In which GPE is the global percentage error of optimal Pareto responses in
relation to the goals

∗
Values of optimal responses;

Defined goals;

m Number of goals

PT
RI
3. Results and Discussion

3.1. Process modeling

SC
The curvature of the model was tested before the axial experiments on the
experimental matrix of the CCD which was a quadratic model (Myers et al., 2013). The

U
presence of curvature in the model can be verified by the p-value lower than the level of
AN
significance (5%) for both answers in terms of curvature. In this context, the next step
was to carry out the axial experiments and the definition of the CCD, as presented in
Table 3.
M
D

Table 3.
Percent removals of the parameters: Turbidity, total solids and settling velocity for each experiment
TE

-1 -1
StdOrder X1 X2 X3 Turbidity [NTU] Total Solids [mg L ] Sedimentation Speed [m min ]
1 -1 -1 -1 378 24700 0.143
EP

2 1 -1 -1 269 24300 0.164

3 -1 1 -1 484 22700 0.095
4 1 1 -1 438.8 22300 0.100
C

5 -1 -1 1 655 24500 0.141

AC

6 1 -1 1 665 24300 0.123

7 -1 1 1 247.9 23100 0.103
8 1 1 1 245.9 22700 0.101
9 -1.68 0 0 454 23100 0.134
10 1.68 0 0 374.4 23700 0.142
11 0 -1.68 0 654 23823 0.134
12 0 1.68 0 378.4 22000 0.108
13 0 0 -1.68 216 23600 0.192
14 0 0 1.68 255 24920 0.157
 ACCEPTED MANUSCRIPT
15 0 0 0 232 23600 0.097
16 0 0 0 205 22800 0.135
17 0 0 0 248 23500 0.095
18 0 0 0 198 22345 0.134
19 0 0 0 250 23300 0.089
20 0 0 0 213 22900 0.106

PT
Analysis of variance for the complete quadratic model and Regression analysis
using the Ordinary Least Square (OLS) algorithm were performed to verify the

RI
influence of the factors on the responses analyzed, as presented in Tables 4-6.

The factors influenced each one of the final answers in a significant way

SC
considering the perspectives of p-values which were smaller than the level of
significance. In addition, a fit with the respective R2_adj values was verified. Models

U
also had a satisfactory fit, and could faithfully represent the process of coagulation,
AN
flocculation and sedimentation. Fig. 2 shows the Pareto charts for the standardized
effects of each of the responses evaluated, along with the standardized residuals for each
of the responses.
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Fig. 2. Pareto Charts for standadized effects for turbidity removal; total solids; sedimentation speed.

The residues corresponding to each of the responses were distributed following a

EP

normal behavior, which shows the good adjustment obtained through ANOVA from the
good fit check (p-value> 0.05). The lack of fit of the model can be associated with
C

errors to type I, usually presented in the form of noises (Myers, R.H.; Montgomery,
AC

2009). Therefore, the analysis of the lack of fit of the model, together with R2_adj value
and the residuals, form a database that attest to the good approximation of the predicted
model with experimental model presented here for the removal of turbidity, solids and
sedimentation velocity. Only the ANOVA check, may not be sufficient to check the
problem presented (Montgomery, 2013).

3.2. Analysis of the main effects

 ACCEPTED MANUSCRIPT
Because the models associated with the responses and the factors were
satisfactory, and all factors were significant, it was necessary to study the behavior of
each of the responses rather than varying the levels of each of these factors. In this
context, Fig. 3 and Fig. 4 show the effect behavior on each of the factors of the
analyzed responses.

PT
RI
U SC
AN
M
D

Fig. 3. Main effects and interactions for sedimentation velocity

TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 4. Principal effects and interactions for total solids and turbidity
M

An increase in coagulant concentration (x1) during the experimentation reflected

an increase in settling velocity. With the increase of the concentration of tannin in the
D

solution, there is a considerable increase in positive charges as well. In a region

TE

considered acid, even small concentrations can be enough to compress the double layer,
the bridge mechanism forms bigger flocs. The use of higher tannin concentrations can
lead to the change in the main mechanism of the process. In regions in which the pH is
EP

more alkaline, the concentration of NaOH solution is enough to initiate the process of
coagulation which in turn dismisses the coagulant to initiate the flocculation process.
C

The relationship between the coagulant volume and pH became the most evident in
AC

terms of efficiency. When the tannin-based coagulant was inserted into aqueous
medium, its ionization occurred, releasing hydronium cations to the medium. Thus,
when the pH was lower represented by the coded level (-1), there was a high
concentration of H+ cations, which might contribute to the stabilization of the colloids
present in the medium.

Even though the charges on the colloids were stabilized by the hydronium
cations present in the solution, the formation of flakes was compromised; it requires a
large molecule, a coagulant. When the solution was at the most basic pH, the H+ cations
 ACCEPTED MANUSCRIPT
released from the ionization of the coagulant were rapidly stabilized by the OH- rich
medium. Overall, increasing the pH and increasing the coagulant insertion decreased the
sedimentation velocity.

The Brownian motion imparted in small particles through the bombardment of

water molecules naturally occurs in systems such as the coagulation process. However,
an additional energy portion is usually required so that the increase of entropy, the

PT
stabilization of the surface charges can take place effectively during the coagulation
process. When at this stage, the agitation process is not enough to lead to effective

RI
coagulant dispersion, a coagulant dosage may be poorly dispersed, leading to a
recombination of the charges in some particles (Ghernaout, 2017). Thus, the frequency

SC
and number of collisions between the particles are important effects for the coagulation
process (Ghernaout, 2014), which indicates an optimal rotation frequency for the
analyzed responses to be potentiated.

U
The formation of flakes is directly related to the first stage of coagulation,
AN
associated with the stabilization of colloid charges. Thus, when coagulation is not
effective, it may lead to the formation of small flakes, which leads to lower
M

sedimentation rates. Particle size, concentration and shear stress are the main factors
that directly influence the separation efficiency. When the mixture is intense with a
D

shear stress imparted by blades of the low equipment, there may be formation of
compact flakes, but with a slow growth rate (Ghernaout, 2017). When the shear is
TE

increased by the action of the blades, it favors the occurrence of conical flocculation
which, in turn, increases the flocculation rate through the formation of large flakes
EP

(Ghernaout, 2017). Thus, there is an intense interaction between the factors analyzed as
presented in the analysis of variance, demonstrating the need to evaluate the parameters
C

related to the interactions.

AC

Despite the low frequency of agitation, at the highest levels in the CCD, the
volume of coagulant in the medium increases, due mainly to the magnitude of its
molecules (Moreira Braga et al., 2018), which leads to an increase in the frequency of
agitation favoring the dispersion of the coagulant and avoiding recombinations
(Ghernaout, 2017). This phenomenon also occurs when analyzing the concentration of
coagulant and pH effect. An increase in the volume of coagulant and an increase of the
pH leads to higher levels and, consequently, it favors the stabilization of coagulant
loads.
 ACCEPTED MANUSCRIPT
The sedimentation rate decreases inversely proportional to the coagulant
concentration at a more acidic pH, represented by lower levels. The ionization of the
coagulant in water, generates a hydronium cation, represented in a generic way by the
reaction presented in Eq. 4.

+ → + (4)

The coagulant was characterized as a polyphenolic polymer of gallic acid and

PT
coumaric acid (Moreira Braga et al., 2018). During the increase of coagulant
concentration in solution with acidic characteristic, the ionic strength increases

RI
considerably according to Eq. 5.

= ∑

SC
(5)

'I' is the ionic strength that represents the measurement of the concentration of

U
the ions present in the medium, 'C' the ionic concentration and 'Z' the ion charge present
in the medium. The increase in the concentration of H+ cations in the solution may favor
AN
the recombination of the phenoxy ion and consequently the recombination of the phenol
molecule. In this sense, when we analyzed the influence of the coagulant concentration
M

on neutral pH, we observed a higher demand of coagulant required for a higher

sedimentation rate, characterized by the greater stabilization of the negative charges of
D

the colloids (Ghernaout, 2017). Thus, validating the need to obtain optimal values of
TE

each of the levels of the factors.

The mechanism of reduction of total chromium in the process of

coagulation/flocculation can be related to the capacity of formation of complexes
EP

between the Cr (III) and Cr (IV) in solution, mainly gallic acid, part of the molecule of
tanin (Fazary et al., 2011). According to Fazary et al., (2011), the gallic acid had the
C

capacity of forming complexes of type L2M with the species Cu (III), Cr (III) and Fe
AC

(III).

3.3. Multiobjective optimization

The multiobjective optimization was performed according to the algorithm NBI,

described by Das and Dennis (1998). However, problems that have a greater number of
two responses (biobjective), the Pareto surface analysis becomes quite complex due to
the transposition of the coordinate plane. Thus, there is a possibility of determining the
 ACCEPTED MANUSCRIPT
optimal weight that potentiates the three responses concomitantly. In order to describe
the optimization process, the flowchart represented by Fig. 5 shows the entire
development.

PT
RI
U SC
AN
M
D

Fig. 5. Flowchart for modeling, and optimization for process of treatment of effluent of tannery
TE

Therefore, the optimized values were first determined from the NBI, but the
EP

weights for each of the responses were taken from a Lattice simple mixing arrangement,
with a spacing between the weights used of 12.5%, consequently a model that should fit
a polynomial of degree 8 (Gomes et al., 2013). A total of 49 random combinations of
C

weights were generated as shown in Table 7.

AC

From the formulation initially developed by Das and Dennis (1998), it was
possible to determine the optimal responses: F1(x*), F2(x*) e F3(x*)

Fig. 6 and Fig. 7 represent the behavior of each of the responses within the
pyramidal region in terms of weight variation.
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
f(x1*) – removal of turbidity in the optimal condition; f(x2*) – removal of solids in the optimal contion

Fig. 6. Response surface and contour plots for responses:

M
D
TE
C EP
AC

f(x3*) – Sedimentation rate in the optimal condition;

Fig. 7. Response surface and contour plots for responses

The change in the values of the weights affects a change in the behavior of the
objective function represented by the optimal values for each one of the analyzed
answers. This fact is noted from Figs. (5, 6), where the different regions in the graphs,
characterized by a triad of combinations of weights have different answers. Fig. 8
 ACCEPTED MANUSCRIPT
shows the individual behavior of each of the optimized responses over the variation of
the weights.

PT
RI
U SC
AN
M

x1, x2 and x3 weight

Fig. 8. Main effects for the three optimized responses

D

The turbidity responses F1(x*) and settling velocity F2(x*) have very similar
TE

behaviors in which increasing the weight to the coagulant volume prevents turbidity
removal. As discussed earlier in the main effects section, an exaggerated increase in
EP

coagulant concentration may lead to electrical recombination and consequently

reduction of floc size (Ghernaout, 2014). Therefore, the concentration of coagulant
C

should be sufficient for the stabilization of the charges on the surface of the colloids.
AC

Increasing the weights for the factors: pH and agitation, leads to a decrease in
the number of solids. This increase, however, leads to a greater entropy of the aqueous
medium, since the repulsion of the colloids by the negative charges present by the
hydroxyl groups favors the stabilization from the positive charges generated by the
coagulant. However, an expressive increase in weight relative to pH can lead to the
stabilization of the cations generated by the coagulant, preventing solid removal. An
analysis of the rotation verifies that the effect may be contrary to the sedimentation
 ACCEPTED MANUSCRIPT
velocity response, since an exacerbated increase can lead to a decrease in the size of the
flakes, and consequently the reduction of the sedimentation velocity.

Finally, it is important to determine the best weight that will lead to the
concomitant optimization of both responses. Therefore, the determination of the best
combination of weights, as previously mentioned, directly influences the analyzed
responses and it was determined by global standard error (GSE) (Gomes et al., 2013).

PT
Fig. 9 shows the response surface as well as the contour plot for the GSE function.

RI
U SC
AN
M
D

Fig. 9. Surface and contour plot for GSE

TE

The minimization of the GSE-related function leads to a better combination of

weights, which consequently leads to the best value of the answers. The function
EP

representing the GSE was minimized according to Generalized Reduced Gradient

(GRG) algorithm. As a response we obtained the weights: β1 = 0.54, β2 = 0.17 and β3 =
C

0.28, shown in Fig. 10.

AC
 ACCEPTED MANUSCRIPT

PT
RI
SC
Fig. 10. Better weights for each of the factors, which minimize the EPG

U
AN
3.4. Validation of experiments

Validation of experimental conditions were determined from the NBI-Simplex

M

Lattice algorithm. The factors were coagulant volume, pH and rotation and the
optimized level conditions were 6.3 mL, 6.8 and 87 rpm respectively.
D

The validation was performed with 13 experiments determined from the power
sample size test in the region of the central points. Table 8 shows the values of the
TE

responses in the experimental conditions compared to values estimated by the NBI

algorithm in the weights of Table 8.
EP

The means comparison test showed that all means of the experimental responses
C

were statistically equal to the empirical values determined from the NBI algorithm in
AC

the optimal weights.

3.5. Analysis of Cr(III) and BOD / COD ratio

The optimized conditions allowed us to determine the removal of total
chromium and the degree of biodegradability of the effluent. These parameters were
measured in the effluent in natura and after the treatment in the optimized conditions.
Table 9 presents these values, as well as the experimental conditions.
 ACCEPTED MANUSCRIPT
In addition to the optimization of the responses already mentioned in this work,
there was a good removal of total chromium, which is one of the refractory
contaminants with high polluting potential when inserted into recipient water bodies.
The biodegradability ratio was also very satisfactory. The effluent in natura presented
values to a ratio of 0.12, which eliminates the possibility of biological treatment due to a
high degree of recalcitrance. After treatment, the ratio increased to 0.58 likely to be

PT
used in a biological treatment. This hybrid system can be considered of lower cost than
physical chemical processes, for instance.

RI
4. Conclusion

SC
Overall, the use of tannin, extracted from the flower of Musa sp is a likely
source of coagulation and flocculation effective in the removal of turbidity, solids,

U
chromium and the increase in biodegradability that can be used as a pre-treatment in the
AN
biological process. The treatment can be applied to effluents of high non-biodegradable
organic matter content. However, with certain limitations, which imply the removal of
M

several other composites present in the effluent from the tannery. In addition, statistical
modeling methods as well as multivariate and multiobjective optimization determined
D

optimal conditions (levels) besides the optimal weights within the NBI algorithm. The
process can be considered multivariate and multiobjective because of the difficulty
TE

associated to the treatment with the chemical composition of leather tanning effluent.
The minimization of GPE associated to the NBI algorithm solves the problem of finding
EP

setups referring to levels of each one of the factors (pH, rotation and coagulant volume)
to the maximization of removal of response parameters (turbidity, total chromium,
C

hexavalent chromium and trivalent chromium) with higher stability of response. Thus,
this research showed that the modeling and optimization tools were adequate to predict
AC

optimal parameters for the treatment of leather tanning effluent.

5. References

Ahmed, E., Abdulla, H.M., Mohamed, A.H., El-Bassuony, A.D., 2016. Remediation
and recycling of chromium from tannery wastewater using combined chemical–
biological treatment system. Process Saf. Environ. Prot. 104, 1–10.
 ACCEPTED MANUSCRIPT
https://doi.org/10.1016/j.psep.2016.08.004

American Public Health Association, American Water Works Association, Water

Environment Federation, 2012. Standard Methods for the Examination of Water
and Wastewater, Standard Methods. https://doi.org/10.2105/AJPH.51.6.940-a

APHA, AWWA, WEF, 1998. Standard Methods for the Examination of Water and
Wastewater, 21 th. ed. American Public Health Association, New York.

PT
Bakraouy, H., Souabi, S., Digua, K., Dkhissi, O., Sabar, M., Fadil, M., 2017.

RI
Optimization of the treatment of an anaerobic pretreated landfill leachate by a
coagulation–flocculation process using experimental design methodology. Process

SC
Saf. Environ. Prot. 109, 621–630. https://doi.org/10.1016/j.psep.2017.04.017

Battaglia, E., Vignati, D.A.L., 2018. Chromium Hazard and Risk Assessment : New

U
Insights from a Detailed Speciation Study in a Standard Test Medium 37, 983–992.
https://doi.org/10.1002/etc.4044
AN
BRAGA, W.L.M., ROBERTO, J.A., VAZ, C., SAMANAMUD, G.R.L., LOURES,
C.C.A., GRANÇA, A.B., LOFRANO, R.C.Z., NAVES, L.L.. R., GOMES, J.H.F.,
M

NAVES, F.L., 2018. Extraction and optimization of the Musa sp flower extract
applied to the treatment of iron ore dump. J. Environ. Chem. Eng.
D

https://doi.org/10.1016/j.jece.2018.05.058
TE

Chong, M.N., Jin, B., Chow, C.W.K., Saint, C., 2010. Recent developments in
photocatalytic water treatment technology: a review. Water Res. 44, 2997–3027.
EP

https://doi.org/10.1016/j.watres.2010.02.039

Cruz-Rizo, A., Gutiérrez-Granados, S., Salazar, R., Peralta-Hernández, J.M., 2017.

C

Application of electro-Fenton/BDD process for treating tannery wastewaters with

AC

industrial dyes. Sep. Purif. Technol. 172, 296–302.

https://doi.org/10.1016/j.seppur.2016.08.029

Das, I., Dennis, J., 1998. Normal-Boundary Intersection: An alternate method for
generating pareto optimal points in multicriteria optimization problems. Soc. Ind.
Appl. Math. J. Optim. 631–657.
https://doi.org/http://dx.doi.org/10.1137/S1052623496307510

De Freitas Gomes, J.H., Júnior, A.R.S., De Paiva, A.P., Ferreira, J.R., Da Costa, S.C.,
 ACCEPTED MANUSCRIPT
Balestrassi, P.P., 2012. Global Criterion Method based on principal components to
the optimization of manufacturing processes with multiple responses. Stroj.
Vestnik/Journal Mech. Eng. 58, 345–353. https://doi.org/10.5545/sv-jme.2011.136

Elabbas, S., Ouazzani, N., Mandi, L., Berrekhis, F., Perdicakis, M., Pontvianne, S.,
Pons, M.N., Lapicque, F., Leclerc, J.P., 2016. Treatment of highly concentrated
tannery wastewater using electrocoagulation: Influence of the quality of aluminium

PT
used for the electrode. J. Hazard. Mater. 319, 69–77.
https://doi.org/10.1016/j.jhazmat.2015.12.067

RI
Fazary, A.E., Hernowo, E., Elisa, A., Chou, A.T., Hung, C., Mohamed, L., Ju, T.Y.,
2011. Complex Formation Between Ferric ( III ), Chromium ( III ), and Cupric ( II

SC
) Metal Ions and ( O , N ) and ( O , O ) Donor Ligands with Biological Relevance
in Aqueous Solution 1965–1986. https://doi.org/10.1007/s10953-011-9768-1

U
Fettig, J., Pick, V., Oldenburg, M., Phuoc, N. V., 2017. Treatment of tannery
AN
wastewater for reuse by physico-chemical processes and a membrane bioreactor. J.
Water Reuse Desalin. 7, 420–428. https://doi.org/10.2166/wrd.2016.036
M

GARROTE, J.I., BAO, M., CASTRO, P., BAO, M.J., 1995. Step
coagulation/flocculation process. Water Res. 29.
D

Gasemloo, S., Khosravi, M., Sohrabi, M.R., Dastmalchi, S., Gharbani, P., 2018.
TE

Response surface methodology (RSM) modeling to improve removal of Cr (VI)

ions from tannery wastewater using sulfated carboxymethyl cellulose nanofilter. J.
EP

Clean. Prod. https://doi.org/10.1016/j.jclepro.2018.10.177

Gerek, E.E., Yılmaz, S., Yavuz, Y., Koparal, A.S., 2016. Toxicity analysis of tannery
C

wastewater treatment using chemical coagulation. Toxicol. Lett. 258, S193.

AC

https://doi.org/10.1016/j.toxlet.2016.06.1708

Ghernaout, D., 2017. Entropy in the Brownian Motion ( BM ) and Coagulation

Background Email address : Colloid surfaces Sci. 2, 143–161.
https://doi.org/10.11648/j.css.20170204.14

Ghernaout, D., 2014. The hydrophilic/hydrophobic ratio vs. dissolved organics removal
by coagulation - A review. J. King Saud Univ. - Sci. 26, 169–180.
https://doi.org/10.1016/j.jksus.2013.09.005
 ACCEPTED MANUSCRIPT
Gomes, J.H.F., Paiva, a. P., Costa, S.C., Balestrassi, P.P., Paiva, E.J., 2013. Weighted
Multivariate Mean Square Error for processes optimization: A case study on flux-
cored arc welding for stainless steel claddings. Eur. J. Oper. Res. 226, 522–535.
https://doi.org/10.1016/j.ejor.2012.11.042

Guimarães, A.T.B., de Oliveira Ferreira, R., de Souza, J.M., da Costa Estrela, D.,
Talvani, A., Souza, D.M.S., Rocha, T.L., Malafaia, G., 2019. Evaluating the

PT
reproductive toxicology of tannery effluent in male SWISS mice. Sci. Total
Environ. 648, 1440–1452. https://doi.org/10.1016/j.scitotenv.2018.08.253

RI
Jamshidi, M., Ghaedi, M., Dashtian, K., Hajati, S., 2015. New ion-imprinted polymer-
functionalized mesoporous SBA-15 for selective separation and preconcentration

SC
of Cr(iii) ions: Modeling and optimization. RSC Adv. 5, 105789–105799.
https://doi.org/10.1039/c5ra17873h

U
Johnson, P.D., Girinathannair, P., Ohlinger, K.N., Ritchie, S., Teuber, L., Kirby, J.,
AN
2008. Enhanced Removal of Heavy Metals in Primary Treatment Using
Coagulation and Flocculation. Water Environ. Res. 80.
M

https://doi.org/10.2175/106143007X221490

Khayet, M., Zahrim, A.Y., Hilal, N., 2011. Modelling and optimization of coagulation
D

of highly concentrated industrial grade leather dye by response surface

TE

methodology. Chem. Eng. J. 167, 77–83. https://doi.org/10.1016/j.cej.2010.11.108

Lefebvre, O., Vasudevan, N., Torrijos, M., Thanasekaran, K., Moletta, R., 2006.
EP

Anaerobic digestion of tannery soak liquor with an aerobic post-treatment. Water

Res. 40, 1492–1500. https://doi.org/10.1016/j.watres.2006.02.004
C

Malafaia, G., Estrela, C., Tiago, A., Guimarães, B., Godinho, F., Araújo, D., Mozena,
AC

W., Sueli, A., Rodrigues, D.L., 2015. Vermicomposting of different types of

tanning sludge ( liming and primary ) mixed with cattle dung. Ecol. Eng. 85, 301–
306. https://doi.org/10.1016/j.ecoleng.2015.10.010

Matilainen, A., Sillanpää, M., 2010. Removal of natural organic matter from drinking
water by advanced oxidation processes. Chemosphere 80, 351–365.
https://doi.org/10.1016/j.chemosphere.2010.04.067

Mazloomi, S., Ghodsei, S., Amraei, P., 2018. Data in Brief Data on the removal of
turbidity from aqueous solutions using polyaluminum chloride. Data Br. 20, 371–
 ACCEPTED MANUSCRIPT
374. https://doi.org/10.1016/j.dib.2018.08.024

Mendes, B.D.O., Souza, J.M. De, Sueli, A., Rodrigues, D.L., Malafaia, G., 2017. Short-
term dermal exposure to tannery effluent does not cause behavioral changes in
male Swiss mice Curto período de exposição dérmica à efluente de curtume não
provoca alterações comportamentais em camundongos Swiss machos.
https://doi.org/10.4136/1980-993X

PT
Montgomery, D.C., 2013. Design and Analysis of Experiments Eighth Edition.

RI
Moreira Braga, W.L., Roberto, J.A., Vaz, C.A.S., Samanamud, G.R.L., Loures, C.C.A.,
França, A.B., Lofrano, C.Z., Naves, L.L.R., De Freitas Gomes, J.H., F., N.L.,

SC
2018. Extraction and optimization of the Musa sp flower extract applied to the
treatment of iron ore dump. J. Environ. Chem. Eng. 6, 0–1.
https://doi.org/10.1016/j.jece.2018.05.058

U
Myers, R.H.; Montgomery, D.C., 2009. Response Surface Methodology: Process and
AN
Product Optimization Using Designed Experiments, second ed. ed. New York.

Myers, R.H., Montgomery, D.C., Anderson-Cook, C.M., 2013. Response Surface

M

Methodoly: Process and Product Optimization Using Designed Experiments,

Journal of Chemical Information and Modeling.
D

https://doi.org/10.1017/CBO9781107415324.004
TE

Naves, F.L., de Paula, T.I., Balestrassi, P.P., Moreira Braga, W.L., Sawhney, R.S., de
Paiva, A.P., 2017a. Multivariate Normal Boundary Intersection based on rotated
EP

factor scores: A multiobjective optimization method for methyl orange treatment.

J. Clean. Prod. 143, 413–439. https://doi.org/10.1016/j.jclepro.2016.12.092
C

Naves, F.L., de Paula, T.I., Balestrassi, P.P., Moreira Braga, W.L., Sawhney, R.S., de
AC

Paiva, A.P., 2017b. Multivariate Normal Boundary Intersection based on rotated

factor scores: A multiobjective optimization method for methyl orange treatment.
J. Clean. Prod. 143, 413–439. https://doi.org/10.1016/j.jclepro.2016.12.092

NAVES, F.L., VAZ, C., ALMEIDA, M., GONÇALVES, P., 2017. Process for the
benefit of iron ore using natural polymer for coagulation and flocculation. BR 10
2017 024105 0.

Nicola, E. De, Iaccarino, M., Gallo, M., Di, A., Morrone, G., Warnau, M., Belgiorno,
 ACCEPTED MANUSCRIPT
V., Pagano, G., 2005. Toxicity of leather tanning wastewater effluents in sea
urchin early development and in marine microalgae 61, 208–217.
https://doi.org/10.1016/j.chemosphere.2005.02.037

Oliveira, R. De, Martins, L., Costa, B., Moreira, J., Souza, D., Alves, W., Pessoa, I.,
Menezes, P. De, Sueli, A., Rodrigues, D.L., Gontijo, B., Ribeiro, D., Costa, D.O.,
Pereira, I., Rodrigo, A., Malafaia, G., 2016. Chemosphere The C57BL / 6J mice

PT
offspring originated from a parental generation exposed to tannery ef fl uents
shows object recognition de fi cits Abra a 164, 593–602.

RI
https://doi.org/10.1016/j.chemosphere.2016.08.144

Pardede, A., Budihardjo, M.A., 2018. The Removal of Turbidity and TSS of the

SC
Domestic Wastewater by Coagulation-Flocculation Process Involving Oyster
Mushroom as Biocoagulant 05007.

U
Polti, M.A., Amoroso, M.J., Abate, C.M., 2007. Chromium(VI) resistance and removal
AN
by actinomycete strains isolated from sediments. Chemosphere 67, 660–667.
https://doi.org/10.1016/j.chemosphere.2006.11.008
M

Ridge, A.C., Sedlak, D.L., 2004. Effect of ferric chloride addition on the removal of Cu
and Zn complexes with EDTA during municipal wastewater treatment 38, 921–
D

932. https://doi.org/10.1016/j.watres.2003.10.004
TE

Saxena, S., Saharan, V.K., George, S., 2018. Enhanced synergistic degradation
efficiency using hybrid hydrodynamic cavitation for treatment of tannery waste
EP

effluent. J. Clean. Prod. 198, 1406–1421.

https://doi.org/10.1016/j.jclepro.2018.07.135
C

Schrank, S.G., José, H.J., Moreira, R.F.P.M., Schröder, H.F., 2004. Elucidation of the
AC

behavior of tannery wastewater under advanced oxidation conditions.

Chemosphere 56, 411–423. https://doi.org/10.1016/j.chemosphere.2004.04.012

Sivagami, K., Sakthivel, K.P., Nambi, I.M., 2017. Advanced oxidation processes for the
treatment of tannery wastewater. J. Environ. Chem. Eng.
https://doi.org/10.1016/j.jece.2017.06.004

Song, Z., Williams, C.J., Edyvean, R.G.J., 2004. Treatment of tannery wastewater by
electrocoagultion. Desalination 164, 249–259. https://doi.org/10.1016/S0011-
9164(04)00193-6
 ACCEPTED MANUSCRIPT
Stylianou, S., Simeonidis, K., Mitrakas, M., Ernst, M., 2017. Reductive precipitation
and removal of Cr ( VI ) from groundwaters by pipe flocculation-microfiltration.
https://doi.org/10.1007/s11356-017-9967-4

Vaz, C., Almeida, M., Gonçalves, P., Roberto, J., França, A.B., Lofrano, R.C.Z.,
Fabiano, D., Naves, L.L.R., Milagres, K., Naves, F.L., 2018a. Use of the extract of
the flower of Musa sp, in the treatment from coagulation - flocculation, of iron ore

PT
fines Carlos Vaz. J. Environ. Chem. Eng. 6, 1155–1160.
https://doi.org/10.1016/j.jece.2018.01.047

RI
Vaz, C., Almeida, M., Gonçalves, P., Roberto, J., França, A.B., Lofrano, R.C.Z.,
Fabiano, D., Naves, L.L.R., Milagres, K., Naves, F.L., 2018b. Use of the extract of

SC
the flower of Musa sp, in the treatment from coagulation - flocculation, of iron ore
fines Carlos Vaz. J. Environ. Chem. Eng.

U
Wang, B., Wu, Y., Jiang, B., Song, H., Li, W., Jiang, Y., Wang, C., Sun, L., Li, Q., Li,
AN
A., 2016. Optimized degradation removal of 2-nitrotoluene by combination of
cathodic reduction and electro-oxidation process. Electrochim. Acta 219, 509–515.
M

https://doi.org/10.1016/j.electacta.2016.10.001

Wang, D., Guo, F., Wu, Y., Li, Z., Wu, G., 2018. Technical, economic and
D

environmental assessment of coagulation/filtration tertiary treatment processes in

TE

full-scale wastewater treatment plants. J. Clean. Prod. 170, 1185–1194.

https://doi.org/10.1016/j.jclepro.2017.09.231
EP

Wang, D., Ye, Y., Liu, H., Ma, H., Zhang, W., 2018. Chemosphere Effect of alkaline
precipitation on Cr species of Cr ( III ) -bearing complexes typically used in the
tannery industry 193, 42–49.
C
AC

Wang, K., Li, W., Gong, X., Li, X., Liu, W., He, C., Wang, Z., Minh, Q.N., Chen, C.L.,
Wang, J.Y., 2014. Biological pretreatment of tannery wastewater using a full-scale
hydrolysis acidification system. Int. Biodeterior. Biodegrad. 95, 41–45.
https://doi.org/10.1016/j.ibiod.2014.05.019
 ACCEPTED MANUSCRIPT
Table 4.

ANOVA for Turbidity

Source DF Adj SS Adj MS F-Value P-Value

Model 9 468412 52046 75.02 0.000

Linear 3 88035 29345 42.30 0.000

PT
X1 1 5744 5744 8.28 0.016

X2 1 75273 75273 108.50 0.000

RI
X3 1 7018 7018 10.12 0.010

Square 3 224953 74984 108.08 0.000

SC
2
X1 1 75262 75262 108.48 0.000
2
X2 1 169119 169119 243.77 0.000

U
2
X3 1 1190 1190 1.72 0.220
AN
2-Way Interaction 3 155425 51808 74.68 0.000

X1 x2 1 335 335 0.48 0.503

M

X1 x3 1 3289 3289 4.74 0.055

X2 x3 1 151800 151800 218.81 0.000

D

Error 10 6938 694

TE

Lack-of-Fit 5 4464 893 1.80 0.266

Pure Error 5 2473 495

EP

Total 19 475350
2 2
R = 0.9854 R _adj = 0.9723
C
AC
 ACCEPTED MANUSCRIPT
Table 5.

ANOVA for Total Solids

Source DF Adj SS Adj MS F-Value P-Value

Model 9 24078898 2675433 33.74 0.000

Linear 3 15889572 5296524 66.79 0.000

PT
X1 1 469094 469094 5.92 0.035

X2 1 13006293 13006293 164.02 0.000

RI
X3 1 2414186 2414186 30.44 0.000

Square 3 3853083 1284361 16.20 0.000

SC
2
X1 1 1619 1619 0.02 0.889
2
X2 1 2045213 2045213 25.79 0.000

U
2
X3 1 1426824 1426824 17.99 0.002
AN
2-Way Interaction 3 4336243 1445414 18.23 0.000

X1 x2 1 1064341 1064341 13.42 0.004

M

X1 x3 1 1152162 1152162 14.53 0.003

X2 x3 1 2119741 2119741 26.73 0.000

D

Error 10 792984 79298

TE

Lack-of-Fit 5 386901 77380 0.95 0.521

Pure Error 5 406083 81217

EP

Total 19 24871883
2 2
R = 0.9681 R _adj = 0.9394
C
AC
 ACCEPTED MANUSCRIPT
Table 6.

ANOVA for sedimentation speed

Source DF Adj SS Adj MS F-Value P-Value

Model 9 0.047157 0.005240 146.35 0.000

Linear 3 0.016858 0.005619 156.95 0.000

PT
X1 1 0.001633 0.001633 45.61 0.000

X2 1 0.013893 0.013893 388.04 0.000

RI
X3 1 0.001332 0.001332 37.20 0.000

Square 3 0.010304 0.003435 95.93 0.000

SC
2
X1 1 0.001611 0.001611 44.99 0.000
2
X2 1 0.004007 0.004007 111.91 0.000

U
2
X3 1 0.003785 0.003785 105.72 0.000
AN
2-Way Interaction 3 0.019996 0.006665 186.16 0.000

X1 x2 1 0.018974 0.018974 529.93 0.000

M

X1 x3 1 0.001017 0.001017 28.41 0.000

X2 x3 1 0.000005 0.000005 0.14 0.714

D

Error 10 0.000358 0.000036

TE

Lack-of-Fit 5 0.000244 0.000049 2.15 0.210

Pure Error 5 0.000114 0.000023

EP

Total 19 0.047516
2 2
R = 0.9925 R _adj = 0.9857
C
AC
 ACCEPTED MANUSCRIPT

Table 7.
NBI optimization with Misture arrangement
n Weight Optimal Responses
β1 β2 β3 F*1(x) F*2(x) F*3(x)
1 1 0 0 213.060 22910.000 0.124
2 0.875 0.125 0 239.390 23072.840 0.135
3 0.875 0 0.125 219.336 23089.228 0.127
4 0.75 0.25 0 246.415 22384.678 0.136

PT
5 0.75 0.125 0.125 238.235 22881.183 0.134
6 0.75 0 0.25 251.088 22449.245 0.137
7 0.625 0.375 0 263.940 22637.175 0.140

RI
8 0.625 0.25 0.125 276.792 22825.105 0.142
9 0.625 0.125 0.25 289.644 23496.140 0.145

SC
10 0.625 0 0.375 268.972 23200.965 0.147
11 0.5 0.5 0 263.097 23388.895 0.140
12 0.5 0.375 0.125 257.069 23576.825 0.141

U
13 0.5 0.25 0.25 261.800 23764.755 0.136
14 0.5 0.125 0.375 266.140 23342.270 0.143
AN
15 0.5 0 0.5 241.303 22850.015 0.144
16 0.375 0.625 0 254.155 22494.099 0.138
17 0.375 0.5 0.125 267.007 22682.029 0.140
M

18 0.375 0.375 0.25 279.860 22929.872 0.143

19 0.375 0.25 0.375 273.297 23057.889 0.145
20 0.375 0.125 0.5 267.588 23245.819 0.148
D

21 0.375 0 0.625 261.670 23433.749 0.151

TE

22 0.25 0.75 0 220.816 23116.940 0.130

23 0.25 0.625 0.125 231.518 23380.528 0.133
24 0.25 0.5 0.25 244.370 22425.661 0.136
EP

25 0.25 0.375 0.375 257.223 22538.953 0.138

26 0.25 0.25 0.5 270.075 22726.883 0.141
27 0.25 0.125 0.625 282.927 23150.027 0.143
C

28 0.25 0 0.75 271.957 23102.743 0.146

29 0.125 0.875 0 220.138 23091.824 0.128
AC

30 0.125 0.75 0.125 221.733 23111.415 0.131

31 0.125 0.625 0.25 234.586 23418.885 0.134
32 0.125 0.5 0.375 247.438 22794.869 0.136
33 0.125 0.375 0.5 260.290 22583.807 0.139
34 0.125 0.25 0.625 273.142 22771.737 0.141
35 0.125 0.125 0.75 218.460 23095.706 0.134
36 0.125 0 0.875 220.428 23097.286 0.129
37 0 1 0 199.350 22994.000 0.125
38 0 0.875 0.125 237.653 22568.276 0.134
39 0 0.75 0.25 250.505 22770.066 0.137
40 0 0.625 0.375 225.250 23666.722 0.124
41 0 0.5 0.5 219.145 23090.056 0.127
42 0 0.375 0.625 220.642 23105.052 0.130
 ACCEPTED MANUSCRIPT
43 0 0.25 0.75 227.868 23334.906 0.132
44 0 0.125 0.875 207.830 23632.024 0.122
45 0 0 1 190.960 23323.000 0.125
46 0.333333 0.333333 0.333333 261.650 23088.865 0.140
47 0.666667 0.166667 0.166667 259.000 23612.226 0.140
48 0.166667 0.666667 0.166667 238.590 23641.152 0.135
49 0.166667 0.166667 0.666667 239.400 23604.623 0.135

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Table 8.
Verification of validation from experimental and empirical responses

F1(x*) Exp F2(x*) Exp F3(x*) Exp F1(x*) Emp F2*(x) Emp F3*(x) Emp
237.12 22586.3 0.1359 237.6 22568.28 0.134
Exp: Experimental Emp: Empirical

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Table 9.
Verification of optimized conditions for chrome removal and biodegradability

Factors Unit Better Optimal Removal Removal Removal Ration

6+ 3+
Levels Weight [%] Cr [%] Cr [%] Cr BOD/COD
(NBI) (Simplex) total
x1 mL 6.3 0.54

PT
x2 ------ 6.8 0.17 65.4% 39.43% 61.02% 0.58
x3 Rpm 87 0.28

RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC