processes

Article
Coffee Pulp: A Sustainable Alternative Removal of Cr
(VI) in Wastewaters
Dora Luz Gómez Aguilar 1, *, Juan Pablo Rodríguez Miranda 2 , Javier Andrés Esteban Muñoz 1
and Jhon Fredy Betancur P. 3
1 Chemistry Department, National Pedagogical University, Bogotá 110231, Colombia
2 Engineering Department, University Distrital Francisco José de Caldas (UDFJC), Bogotá 110231, Colombia
3 Manizales University, Manizales 170003, Colombia
* Correspondence: [email protected]; Tel.: +57-5941894




Received: 11 April 2019; Accepted: 5 June 2019; Published: 1 July 2019


Abstract: Currently, agricultural waste is proposed as a sustainable alternative in the removal of

heavy metals present in industrial wastewater, to fulfill some of the goals proposed in the Sustainable
Development Goals stated for the 2030 Agenda, in particular in Sections 3.9 and 6.9. Considering this
context, the coffee pulp (Castilla variety) of Caldas municipality (Colombia) was used in study for the
removal of one of the most toxic chemical species of chromium: Cr (VI). Therefore, the agricultural
residue was subjected to a bromatological characterization, determination of the lignocellulosic
composition and elucidation of characteristic organic functional groups by IR spectrophotometry.
Additionally, the optimal parameters for contaminant removal were identified, regarding particle
size, biomass quantity, optimum pH, stirring time, temperature, adsorption kinetics, zero charge
potential (pHpzc ) and adsorption isotherms, to analyze the kinetic model that fitted the process, the
explanation of the possible adsorption mechanism between the contaminant, the surface of the coffee
pulp and the capacity of maximum adsorption, respectively. Finally, the innovation of the research is
discussed considering two criteria: First, when a mixture was made in different proportions between
two agricultural residues (coffee pulp and plantain pseudostem) to show if there was an increase
in the removal of the contaminant under the same optimal conditions found experimentally; and
the second criterion, the comparison of the maximum adsorption capacity, with the percentages of
removal carried out by other authors using the pulp of unmodified coffee.

Keywords: industrial wastewater (IWW); heavy metals; coffee pulp (CP); agricultural residues;
plantain pseudo stem (PP); Sustainable Development Goals (SDG); hexavalent chromium

1. Introduction
Water as one of the natural resources that promotes a sustainable development of the countries
has multiple applications at the domestic, agricultural and industrial levels. In the development of
this type of activity, usually the discharged pollutants type: Organic (organic waste, surfactants, fats
and oils, fertilizers and pesticides, microorganisms) and inorganic (heavy metals, radionuclides). In
relation to the latter, they are the ones most produced by activities such as agriculture and livestock,
electronics, electroplating, painting, metallurgy, mining and tanneries [1].
In the case of inorganic contaminants, specifically heavy metals (Mn+ ), they are chemical elements
with an atomic density greater than 5 g × cm−3 , atomic mass between 63,5 and 200.6 g × mol−1 and
atomic number greater than 20 [2], which can be chemically classified as light, heavy or metalloid
and which, in terms of their toxicity, are classified as toxic (they exert a negative impact on the
ecosystem, due to their high persistence and concentrations, it bioaccumulated and biomagnified) and
non-toxic (essential micronutrients for life) [3]. Similarly, they are considered prior environmental

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Processes 2019, 7, 403 2 of 12

contaminants [4] and an indicator of one of the dimensions of sustainable development “Environmental
Health” in the Environmental Performance Indicators (EPI), which measure the sustainability of the
countries; these parameters were established by Yale University [4].
The previous one has led to the search for new alternatives in the removal of the mentioned
pollutants, which may be present in the case of industrial wastewater (IWW). Among the techniques that
have been used for removing these pollutants are conventional and advanced; among the conventional
ones, adsorption with activated carbon and chemical precipitation are found; and between advanced
technologies they are membrane as: ultrafiltration, microfiltration, nanofiltration, reverse osmosis,
electrodialysis; electrocoagulation, and photocatalysis [5]. It should be added that one of the advantages
of these methods is their high efficiency when the metal concentration is higher than 100 mg × L−1 ,
among the disadvantages are the generation of sludge and the high cost for implementation and
maintenance [5].
Therefore, since 1990 there have been proposed new methods that are less expensive in their
implementation and maintenance, more efficient for removal of contaminant concentrations below
1 mg × L−1 to µg × L−1 [5], environmentally friendly and with less sludge production. This type
of technology were known as unconventional or green, as a sustainable alternative in the treatment
of these waters, among which include bioremediation (fungi, bacteria, yeast and green, brown and
red algae), phytoremediation, hydrogels, fly ash and adsorption with agricultural residues [5]. Some
of the heavy metals that have been investigated by some authors and, in contrast to the World
Health Organization (WHO) are considered for their importance in human and environmental health
correspond to: arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg),
manganese (Mn), nickel (Ni), lead (Pb), tin (Sn) and titanium (Ti) [6].
Therefore, among the heavy metals mentioned, the one that has caused the greatest negative
impact in the ecosystem and health, is the chromium. This chemical element of atomic number 24 and
atomic density 7.19 g × cm−3 (at 20 ◦ C), which in addition to being used in activities such as electrolytic
chrome-plating, tanning of skins, biochemical techniques (characterization of carbohydrates, marker of
different cell types and proteins), production of dyes and pigments, has several oxidation states being
the most stable trivalent (Cr (III)) and hexavalent (Cr (VI)) [7]; this element can be present in rocks and
that at the level of minerals present in the earth’s crust, there are more than 103 [8].
According to Coreño-Alonso, Tomasini & Reyna (2010) [7], compounds containing chromium with
an oxidation state 3+, generally have a green color and are not considered mutagenic or carcinogenic,
unlike 6+ that in addition to occurring in the yellow-orange coloration, can cause the mentioned
characteristics at the level of human health. Similarly, Cr (III) is considered an essential micronutrient
(as it occurs in foods such as lentils, egg yolks, nuts, chicken, red meat, among others), but can become
toxic when presented in high concentrations; in comparison to Cr (VI), which can be toxic by any route
of ingestion; at the level of the respiratory system causes damage to the nasal septum, deformation of
the nose, bronchitis, pulmonary fibrosis, lung cancer, nasal cavity, laryngitis; in relation to the digestive
system, it causes hepatitis, gastrointestinal ulcer; and on the skin, original sores, dermatitis and ulcer;
it should be added that in relation to the toxicity of Cr (VI), being high, and to reduce the chemical
species to a less toxic one, in this case to Cr (III), Álvarez, García & Querol (2007) [9] state that Cr (VI)
must first be reduced with sodium metabisulfite to convert it to Cr (III), to then precipitate it in the
form of Cr(OH)3(s) or Cr2 (SO4 )3(s) .
According to the previous context, in contrast to the use of clean technologies for the removal
of this pollutant, present in industrial wastewaters (IWW), fungi (Paecilomyces sp.), Macrophytic
plants (Lemna minor), algae bacterium (Bostrychia calliptera-Rhodomelaceae), biological systems and
bio-adsorbents such as agricultural or lignocellulosic residues were used [10]. Regarding the latter,
besides being considered as liquid or solid products obtained in agroindustrial process, which not
have been an specific use in the production chain, it seeks to give an application in terms of the
IWW treatment, since they have a bad disposition which has led to environmental problems such
as the generation of greenhouse gases (GHG), bad odors (produced by the hydrogen sulfide H2 S(g)
Processes 2019, 7, 403 3 of 12

generated and in mantles aquifers form hydrogen sulfide) and emerging pollutants in waters for
human consumption [11].
It should be added that, in terms of the chemical constitution of these residues, lignin, cellulose
and hemicellulose represent the highest percentage in their composition [12,13]. Therefore, one of this
type of waste corresponds to the coffee pulp, which is obtained as a by-product of the pulping of the
coffee bean, and which, in the context of Colombia, has been used in lombriculture [14], as a culture of
edible mushrooms (Pleurotus ostreatus) [15].
According to the presented panorama, the present investigation had similar to objective the
application of a clean technology, in this case the use of an agricultural waste (coffee pulp, Castilla
variety) such as bioadsorbent, in the removal of Cr (VI) in Synthetic Residual Waters; so that this
technology is implemented in industrial wastewater treatment systems (IWWTS) presenting in its
activities the use of chemicals that have the contaminant described, so that their discharges comply
with environmental regulations in force (that in the context of Colombia, it applies Resolution 631
of 2015 of the Ministry of Environment and Sustainable Development, MADS), as well as to comply
with the goals set out in the Sustainable Development Goals Agenda 2030, in particular paragraphs
3.9 and 6.9.

2. Materials and Methods

2.1. Collection Site and Treatment of Agricultural Residues Coffee Pulp (CP) and Plantain Pseudostem (PP)
The agricultural residues corresponding to the coffee pulp (Castilla variety) and the plantain
pseudostem (Dominico-Harton variety) were collected from a coffee farm “El Bosque” (Maracas lane,
black broken—municipality of Neira) located at coordinates 5.140579 ◦ N–75.484538 ◦ W (Manizales,
Colombia), which were dried at 60 ◦ C and comminuted in a mill to a particle fixing of 0.180 mm.

2.2. Bromatological Analysis, Lignocellulosic Content and Infrared Spectrum (IR)

In the bromatological analysis, the parameters of percentage of humidity, ash, crude fiber, total
protein, crude ether extract and carbohydrate were determined using the methodology reported by
the AOAC (Association of Official Analytical Chemistry), while for the quantification of lignin and
cellulose, the ANSI (American National Standards Institute)/ASTM standards (American Society for
Testing and Materials) were used.
The IR spectrum for each agricultural residue before the removal of the Cr (VI) contaminant was
carried out using an IR AFFINITY-1S equipment Shimadzu brand with the Attenuated Total Reflection
ATR technique.

2.3. Quantification of Cr (VI)

To determine the concentration of Cr (VI) in the Synthetic Residual Water the reference method 3111
B standard methods (Atomic Absorption Spectrophotometry—AAS, direct flame method air-acetylene
(oxidant is employed); slit 0.2 nm) with the VARIAN AA 140 spectrophotometer. We used 2.8411 g of
analytical reagent of K2 Cr2 O7 99.5% purity, for the realization of a stock solution of 1000 mg × L−1
in Cr (VI) in a volume of 1000 mL; from this, the Cr (VI) standards of concentrations of 1, 5, 10 and
15 mg × L−1 in a volume of 25 mL were made to perform the calibration curve.

2.4. Determination of the Optimum pH of Adsorption with CP

It was prepared by 25 mL of Synthetic Residual Water of Cr (VI), at a concentration of 100 mg × L−1 ,
using a stock solution of 1000 mg × L−1 Cr (VI). Then, the pH of each solution was adjusted to 1, 2, 3, 4,
5 with HNO3 0.100 M and pH 9 with NaOH 0.100 M. Later, 0.500 g of agricultural residue (CP) was
added and stirred for 60 min at 100 RPM with a magnetic stirrer at room temperature 18 ◦ C. After
this time, they were filtered on qualitative filter paper and with the supernatant determined its final
Processes 2019, 7, 403 4 of 12

concentration by AAS. It should be noted that this experimental procedure was performed in triplicate
for each pH.

2.5. Kinetic Adsorption with CP

It was prepared by a volume of 25 mL of a Synthetic Residual Water of Cr (VI) at a concentration
of 100 mg × L−1 , using a stock solution of 1000 mg × L−1 Cr (VI) and adjusted to the optimum pH of the
contaminant adsorption determined according to number 2.4. Subsequently, 0.500 g was added of the
agricultural residue (CP) and placed on a magnetic stirrer at 100 RPM at different contact times (5, 10, 15,
30, 45, 60, 75, 90, 105 and 120 min). Subsequently, they were filtered on qualitative filter paper and with
the supernatant their final concentration in the AAS was determined using the methodology described
in Section 2.3. It should be noted that this experimental procedure was performed in duplicate for each
contact time.

2.6. Isotherm Adsorption with CP

It was prepared by 25 mL of a Synthetic Residual Water of Cr (VI) at different concentrations
(20, 50, 100, 150, 250 and 500 mg × L−1 ), from a stock solution of 1000 mg × L−1 , were adjusted to the
optimum pH of adsorption determined according to numeral 2.4. Subsequently, they were added
a mass of 0.500 g of CP with an agitation of 100 RPM and allowed to optimum contact time found
in Section 2.5. It should be noted that this experimental procedure was performed in duplicate for
each concentration.

2.7. Determination of the Zero Charge Point (pHpzc ) and Active Sites
For the determination of pHpzc the mass titration method reported by Rodríguez-Estupiñan,
Giraldo, Moreno-Piraján (2010) was used [16]; for this, were weighed 0.500 g; 0.600 g; 0.700 g; 0.800 g;
0.900 g and 0.100 g of agricultural residue (CP or PP); subsequently, 15 mL NaCl 0.100 M were added,
they were left stirring in a magnetic stirrer at 100 RPM at a temperature of 18 ◦ C, the containers were
covered for a time of 48 h and after this time the pH of each mix were read.
Regarding the determination of active sites present on the surface of coffee pulp, the Boehm
methodology exposed by Boehm (1994, cited in Segovia et al., 2018) was used [17], in which we seek to
quantify the concentration (µmol × g−1 o mmol × g−1 ) of the basic sites and total acids by volumetric
acid base by regression. Therefore, to neutralize the total active sites of basic character, 0.100 g of
agricultural residue (CP or PP) in a beaker was weighed and added 25 mL of a HCl solution 0.010 M;
in relation to the neutralization of the total acid-active sites, these exclusively quantified the carboxylic,
phenolic and lactonic groups, which were determined by measuring the previous amount of the residue
and 25 mL of a 0.010 M NaOH solution was added.
To quantify carboxylic active sites, 0.100 g of the respective agricultural residue was weighed
in beakers and 25 mL of a 0.010 M NaHCO3 solution was added; in relation to the quantification of
carboxylic and lactonic active sites, the same mass of the residues respectively was measured and
25 mL of 0.010 M Na2 CO3 solution was added; finally, the concentration of active phenolic sites was
obtained by subtraction of the total acidic active sites and the sum of the carboxylic and lactonic sites.
Finally, tests were left in a thermostat bath at 25 ◦ C for seven days and after time; the base acid
titration was carried out with 0.010 M HCl to titrate the aliquots of NaOH, NaHCO3 and Na2 CO3 and
for the values of the aliquot of HCl was used NaOH 0.010 M.

2.8. Determination of the Removal Percentage with Mixtures of Lignocellulosic Residues (CP and PP)
The mixtures between lignocellulosic residues (CP and PP) were made with the purpose of
determining if the percentages of Cr (VI) removal increased, with respect to the use of lignocellulosic
residues in an independent way. To stop this, three mixtures were prepared, in the mixture one was
used a ratio 1:1 CP and PP (0.250 g:0.250 g), the two mixtures were made in a ratio of 2:1 CP and
PP (0.250 g:0.125 g) and three mixtures were made in a ratio of 3:1 CP and PP (0.250 g:0.0825 g).
Processes 2019, 7, 403 5 of 12

Subsequently, each of the mixtures were placed in 25 mL of the solutions that had a concentration of
100 mg × L−1 Cr (VI), were shaken at 100 RPM, the pH was adjusted as determined in Section 2.4 and
was left in the contact time obtained according to number 2.5. Finally, they were filtered on qualitative
filter paper and with the supernatant their final concentration in the AAS was determined.

3. Results and Discussion

3.1. Bromatological Analysis and Lignin and Cellulose Percentage

Table 1 presents the results of bromatological analysis, cellulose and lignin present in the coffee
pulp (CP) and plantain pseudostem (PP), for each of these parameters, the respective analyzes were
performed in triplicate.

Table 1. Data of bromatological analysis, cellulose and lignin in agricultural residues.

AGRICULTURAL RESIDUALS
PARAMETER
PLANTAIN
COFFEE PULP (CP) METODOLOGY USED
PSEUDOSTEM (PP)
AOAC 7.003/84,
% Humidity 12.40 ± 0.00 13.40 ± 0.64 930.15/90 Adapted [18]
(p. 47)
AOAC 7.009/84,
% Ashes 10.43 ± 0.18 10.61 ± 0.24 942.05/90 Adapted [18]
(p. 47)
AOAC 7.060/84,
% Fats and Oils (F and
1.85 ± 0.08 1.00 ± 0.25 920.39/90 Adapted [18]
O)
(p. 48)
Kjeldahl
Method-Gunning-Arnold
%Protein 10.53 ± 0.64 3.73 ± 0.18
Adapted-Griffin-1995
[19] (p. 51)
AOAC 7.066/84,
% Raw fiber 16.29 ± 0.50 16.71 ± 0.11 962.09/90 Adapted [18]
(p. 48)
Found between the
difference of the
% Carbohydrates 48.50 ± 0.00 54.55 ± 0.00 parameters (humidity,
ash, crude fiber, ether
extract and total protein)
ANSI/ASTM D1103-60
% Cellulose 29.93 ± 0.21 49.20 ± 2.65
[19]
ANSI/ASTM D1106-56
% Lignin 19.25 ± 0.16 5.49 ± 0.25
[20].

When analyzing the data in Table 1, it is observed that between the two lignocellulosic residues
(CP and PP) the parameter that differs most in the bromatological analysis was the protein percentage,
being higher in the CP with a value of 10.53% with respect to the PP of 3.73%, which is significant,
because according to the exposed by the authors mentioned in the introductory section, the CP is very
used in the lombriculture, in the obtaining of edible fungi and as a raw material in the production of
animal concentrates.
On the other hand, at the level of the lignocellulosic composition, the CP presented a lower
cellulose value of 29.93% with respect to that of PP, which was 49.20%; while, in lignin, the highest
percentage was presented by the CP of 19.25% in relation to the PP of 5.49%. These two parameters are
very important since, these compounds are those that occur externally in the cell wall of the plants
Processes 2019, 7, 403 6 of 12

and are responsible for providing the functional groups that allow carrying out the adsorption of the
removal of heavy metals, in this case the Cr (VI).

3.2. Infrared (IR) Spectrum of the CP and PP

The reading of the infrared spectrum was performed in the range of the middle IR region
(400–4000 cm−1 ); this was done in order to observe and analyze the absorption bands characteristic of
the functional groups associated with agricultural residues (CP and PP) that could intervene in the Cr
(VI) bioadsorption process, as well as the lignin and cellulose chemical structure, which mainly make
up the waste. Therefore, the obtained spectra are illustrated in Figures 1 and 2, respectively:

Figure 1. Infrared spectrum of the coffee pulp before the application of the bioadsorption process of
chromium (Cr) (VI).

Figure 2. Infrared spectrum of the plantain pseudostem before the application of the bioadsorption
process of Cr (VI).
Processes 2019, 7, 403 7 of 12

At the level of the interpretation of the absorption bands of the infrared spectra exposed in Figures 1
and 2, concerning the residues of coffee pulp and plantain pseudostem, respectively, a broad band in
common around the region can be observed of 3320 cm−1 , which is attributed to the stretching of the
hydroxyl group (OH); similarly, a band in common is observed around 2924–2960 cm−1 associated
with the symmetric stretching of the C-H bond, coming from saturated chain alkyl compounds and in
the region of 2820 cm−1 associated with the voltage vibration coming from the CH2 [21].
The absorption bands in common in the region of 1725 cm−1 are associated with the C=O stretching
from the carbonyl group, as well as the 1250 cm−1 that indicates an asymmetric stretching of the C-O-C
bond associated with an aromatic ether; finally, the band presented at 1050 cm−1 is confirmatory for
Processes 2019, 7, x FOR PEER REVIEW 7 of 12
the hydroxyl group [21].
According to
According to the
the elucidation
elucidation of
of the
the absorption
absorption bands
bands carried
carried out,
out, in
in relation
relation to
to the
the chemical
chemical
structure of lignin and cellulose are illustrated in Figure 3a,b respectively:
structure of lignin and cellulose are illustrated in Figure 3a,b respectively:

(a) (b)
Figure
Figure 3.
3. Chemical
Chemicalstructures
structuresof:
of: (a)
(a)Lignin
Lignin[22];
[22];(b)
(b)cellulose
cellulose[22].
[22].

As seen
As seen inin Figure
Figure 3a,b,
3a,b, the
the hydroxyl
hydroxyl group
group is is present
present in in the
the chemical
chemical structures
structures of
of lignin
lignin and
and
cellulose, which
cellulose, whichisis bound
bound to to the
the aromatic
aromatic ringring and
and saturated
saturated chains,
chains, respectively;
respectively;in inthe
the case
case of
of the
the
stretching of the carbonyl group, it can be inferred that it is associated with lignin,
stretching of the carbonyl group, it can be inferred that it is associated with lignin, since it is attachedsince it is attached
to the
to the aromatic
aromatic rings.
rings. InInthe
thesame
sameway, way, the
the ethers
ethers are
are present
present in in the
the chemical
chemical composition,
composition, with with aa
structure C=C-O-R
structure C=C-O-Rattached
attachedto tothe
thearomatic
aromaticring;
ring;ititshould
shouldbe benoted
notedthat
thatthe
theabsorption
absorptionband
bandof of1190
1190
−1
cm present
presentininthe
thePP PPspectrum
spectrumisisassociated
associatedwith
withthethevibration
vibrationof ofananacetal,
acetal,which
whichisisassociated
associatedwith
with
cm −1

the chemical
the chemical structure
structure of of cellulose.
cellulose.
According to
According to the
the present
present context,
context, itit can
can bebe inferred
inferred that
that according
according to to the
the absorption
absorption bandsbands
characterized in
characterized inrelation
relationto the
to functional groups,
the functional those that
groups, can probably
those that can intervene
probablyinintervene
the bioadsorption
in the
process of the process
bioadsorption contaminant,
of theare the hydroxyl
contaminant, areandthecarbonyl
hydroxylgroups. These can
and carbonyl be attributed
groups. These can to the
be
chemical structure of lignin and cellulose, which are the major components
attributed to the chemical structure of lignin and cellulose, which are the major components according to the proximal
analysis performed
according and described
to the proximal analysis in Section 3.1.
performed and described in Section 3.1.

3.3. Determination
3.3. DeterminationofofOptimal
OptimalpH
pHofofAdsorption
Adsorptionin
inthe
theCP
CP
The XLSTAT
The XLSTAT software
software free
free version
version was
was used
used for
for 15
15 days,
days, with
with the
the objective
objective of
of observing
observing the
the
optimum pH of adsorption of the contaminant, in which in the “y” axis was plotted
optimum pH of adsorption of the contaminant, in which in the “y” axis was plotted the removal the removal
percentage (this
percentage (this obtained
obtained between
between thethe ratio
ratio of
of the
the initial
initial and
and final
final concentration
concentration andand the
the initial
initial
concentration)and
concentration) andononthe
the“x”
“x” axis
axis the
the pH
pH units,
units, with
with which
which obtain
obtain the
the box
box plots
plots graphic
graphic illustrated
illustratedinin
Figure 4:
Figure 4:
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Processes 2019, 7, x FOR PEER REVIEW 8 of 12

Figure
Figure 4.
4. Box
Boxplots
plotsof
ofCr
Cr(VI)
(VI)at
atdifferent
different pH,
pH, obtained
obtained from
from XLSTAT software.
XLSTAT software.

According
According to
to Figure 4, the optimum pH of adsorption
adsorption of Cr (VI) was 2.0, due to the presented
higher percentage of removal of contaminant.

3.4. Determination
3.4. Determination pH
pHpzc andActive
pzcand ActiveSites
Sitesofofthe
theSurface
Surfaceofofthe
theCP
CP
Table 22 reports
Table reports the
thevalues
valuesobtained
obtainedfrom
fromthethetotal
totalactive
activesites
sitesofofacid
acidand
andbasic
basiccharacter present
character in
present
the surface of the CP and the potential of zero charge pH
in the surface of the CP and the potential of zero charge pHpzc.
pzc .

Table Quantification
2. 2.
Table of of
Quantification thethe
total acidic
total and
acidic basic
and groups
basic onon
groups thethe
surface ofof
surface thethe
coffee pulp
coffee (CP)
pulp and
(CP)
zero charge potential (pHpzc ). and zero charge potential (pHpzc).

Total Active
Total ActiveSites
Sites pHpzc pHpzc
Acids (mmol
Acids×(mmol
g ) × g−1 )
−1 Basics
Basics (mmol × g(mmol
−1 ) × g−1)
0.28 0.28 0.17 0.17 3.95 3.95

In Table 2 it observed that predominantly the acid sites upon the basics on the surface of the CP,
In Table 2 it observed that predominantly the acid sites upon the basics on the surface of the CP,
allowing establish that the pHpzc of the bioadsorbent is acid and that the hydroxyl groups present in
allowing establish that the pHpzc of the bioadsorbent is acid and that the hydroxyl groups present in
the lignin and cellulose of the CP (see Table 1 and numeral 3.2) are responsible for the adsorption of
the lignin and cellulose of the CP (see Table 1 and numeral 3.2) are responsible for the adsorption of
Cr (VI) in the agricultural waste, in contrast to what was exposed by Leyva (2007, cited in Moreno,
Cr (VI) in the agricultural waste, in contrast to what was exposed by Leyva (2007, cited in Moreno,
2007) [23].
2007) [23].
On the other hand, with the above data we propose the adsorption mechanism to explain the
On the other hand, with the above data we propose the adsorption mechanism to explain the
removal of Cr (VI) in the Synthetic Residual Waters. For this, it should be noted that the optimum pH
removal of Cr (VI) in the Synthetic Residual Waters. For this, it should be noted that the optimum
obtained for this removal according to number 3.3 was 2.0 pH units, in this condition the species of
pH obtained for this removal according to number 3.3 was 2.0 pH units, in this condition the species
Cr (VI), according to Rollinson (1973, cited in Acosta et al., 2010) [24] is in the aqueous solution as
of Cr (VI), according to Rollinson (1973, cited in Acosta et al., 2010) [24] is in the aqueous solution as
(HCrO4)−−, (Cr2O7)−2−2
, (CrO4)− and that the pHpzc was 3.95 indicating that the load of the surface of the
(HCrO4 ) , (Cr2 O7 ) , (CrO4 )− and that the pHpzc was 3.95 indicating that the load of the surface of the
CP is positive with respect to the optimum pH of 2.0, which is lower than the zero load point of the
CP is positive with respect to the optimum pH of 2.0, which is lower than the zero load point of the
CP [17]; for this reason, the removal occurs by electrostatic interactions, as illustrated in Figure 5:
CP [17]; for this reason, the removal occurs by electrostatic interactions, as illustrated in Figure 5:

OH: coming from

the lignin and
cellulose

Figure 5. Cr (VI) adsorption mechanism with CP surface proposed by authors.

removal of Cr (VI) in the Synthetic Residual Waters. For this, it should be noted that the optimum pH
obtained for this removal according to number 3.3 was 2.0 pH units, in this condition the species of
Cr (VI), according to Rollinson (1973, cited in Acosta et al., 2010) [24] is in the aqueous solution as
(HCrO4)−, (Cr2O7)−2, (CrO4)− and that the pHpzc was 3.95 indicating that the load of the surface of the
CP is positive with
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2019, 7, 403 to the optimum pH of 2.0, which is lower than the zero load point of the 9 of 12
CP [17]; for this reason, the removal occurs by electrostatic interactions, as illustrated in Figure 5:

OH: coming from

the lignin and
cellulose

Figure
Processes 2019,5.7,Cr (VI) PEER
x Figure
FOR adsorption
(VI)mechanism
REVIEW
5. Cr with CP surface
adsorption mechanism withproposed byproposed
CP surface authors. by authors. 9 of 12

3.5. Adsorption Kinetics

3.5. Adsorption Kinetics of
of CP
CP
Regarding
Regarding the the kinetics
kinetics of
of adsorption
adsorption obtained
obtained forfor Cr
Cr (VI),
(VI), according
according toto the
the time
time ofof removal,
removal, the
the
optimal time of adsorption of the contaminant was 105 min, because this is the
optimal time of adsorption of the contaminant was 105 min, because this is the highest percentage of highest percentage
of contaminant
contaminant removal
removal andand where
where removal
removal indicating
indicating thatthat it had
it had reached
reached equilibrium
equilibrium between
between thethe
Cr
Cr (VI) with the functional groups of the surface of the CP is kept constant. In
(VI) with the functional groups of the surface of the CP is kept constant. In turn, to determine theturn, to determine the
kinetic
kinetic model
modelthatthatbestbestmatched
matched thethe
behavior of the
behavior data,
of the theythey
data, applied the methods
applied the methodsgraphics zero order,
graphics zero
first
order,order,
first second order, pseudo-first
order, second order and
order, pseudo-first pseudo
order and second
pseudoorder,secondwhere
order,thewhere
selection criterion
the selection
for the model
criterion for thethatmodel
best matched
that bestthe processthe
matched bioadsorption was given inwas
process bioadsorption terms of the
given in coefficient
terms of theof
determination (R 2 ), will approach the value of one.
coefficient of determination (R ), will approach the value of one.
2

Therefore,
Therefore, it it was
was established
established that
that the
the kinetic
kinetic model
model thatthat was
was most
most adjusted
adjusted to to the
the process
process of
of
bioadsorption
bioadsorption of Cr (VI) was the pseudo second order kinetic model of Ho and McKay, since it
of Cr (VI) was the pseudo second order kinetic model of Ho and McKay, since it
obtained
obtained the
the correlation
correlation coefficient
coefficient higher
higher compared
compared to to the
the zero-order
zero-order models
models one,
one, two
two and
and pseudo
pseudo
first
first order
order [25],
[25], obtaining
obtaining Figure
Figure 6:
6:

Figure 6. Pseudo
Pseudo second
second order
order of
of Ho and McKay kinetic model for the removal of Cr (VI) with CP.
CP.

3.6. Adsorption Isotherms

3.6. Adsorption Isotherms of
of the
the CP
CP
To
To identify
identify this
this parameter,
parameter, three
three mathematical
mathematical models
models were
were applied
applied (Langmuir,
(Langmuir, Freundlich
Freundlich and
and
Henry),
Henry), being the linearized model of Langmuir the one that was most adjusted in the removal of Cr
being the linearized model of Langmuir the one that was most adjusted in the removal of Cr
(VI),
(VI), because
because this
this was
was the
the one
one that
that presented
presented the
the highest
highest correlation
correlation coefficient
coefficient in
in comparison
comparison to
to the
the
other two models
other two models [26],
[26], according
accordingto
tothe
thevalues
valuesshown
shownininTable
Table33and
andFigure
Figure7:7:

Table 3. Datos de isotermas de adsorción con CP.

Adsorption Isotherms
Separation Factor (RL) Maximum Adsorption Capacity
Langmuir Freundlich Henry
Model Langmuir (qmáx) (mg × g−1)
R2 R2 R2
0.9869 0.8420 0.7180 0.12–0.77 13.48
Processes 2019, 7, 403 10 of 12

Table 3. Datos de isotermas de adsorción con CP.

Adsorption Isotherms Separation Factor (RL) Maximum Adsorption Capacity

Model Langmuir (qmáx ) (mg × g−1 )
Langmuir R2 Freundlich R2 Henry R2
0.9869 0.8420 0.7180 0.12–0.77 13.48
Processes 2019, 7, x FOR PEER REVIEW 10 of 12

Figure 7. Linearized
Linearized Langmuir
Langmuir Model
Model for
for Cr
Cr (VI)
(VI) with CP.

The Langmuir isotherm has three assumptions: The The first

first indicates that the the adsorption
adsorption of of Cr
Cr (VI)
(VI)
only occurs at specific sites located on the surface of the CP (see mechanism mechanism adsorption
adsorption in in Figure
Figure 5);
5);
the second establishes that each metal is adsorbed only on each active site of the CP surface; and the
third assumption
assumption suggests
suggeststhat
thattherethereisisnonointeraction
interaction between
between adsorbed
adsorbed metals Cr Cr
metals (VI)(VI)
adjacent to the
adjacent to
surface
the of the
surface of CP
the [23].
CP [23].
Additionally, in
Additionally, inTable
Table33ititisisobserved
observedthat thatthe
theseparation
separationfactor
factorRLRLwaswas found
foundin in
a range
a rangeof of
0.12 to
0.12
0.77
to indicating
0.77 thatthat
indicating the the
adsorption
adsorption of Crof(VI)
Cr on
(VI)the
onsurface of theof
the surface CPthe
was CPfavorable [27]; and
was favorable finally,
[27]; and
according
finally, to the maximum
according adsorption
to the maximum capacity of
adsorption the CPof
capacity (qmax
the ),CP
it is
(qdeduced that 13.48that
max), it is deduced mg of Cr (VI)
13.48 mg
is adsorbed for each gram of agricultural residue (CP).
of Cr (VI) is adsorbed for each gram of agricultural residue (CP).

3.7. Mixtures
3.7. Mixtures of
of more
more Efficient
Efficient Bio
Bio Adsorbents
Adsorbents for
for the
the Removal
Removal of
of Chromium
Chromium (VI)
(VI) in
in Synthetic
Synthetic Wastewater
Wastewater
Table 44 reports
Table reports the
the data obtained from
data obtained from the
the mixtures
mixtures in
in different
different proportions
proportions between
between the CP and
the CP and
the PP.
the PP.
Table 4. Results of the mixtures in different proportions between the CP and PP for the removal of
Table 4. Results of the mixtures in different proportions between the CP and PP for the removal of Cr
Cr (VI).
(VI).
Mixture Ratio (g) Optimum pH of
Mixture Ratio (g) Agricultural Optimum pH of
Mixture Agricultural Waste Adsorption (pH Vol. (mL) Vol. % Removal
%
Mixture Waste(PP:CP) Adsorption
Units) (mL) Removal
(PP:CP) (pH Units)
1 0.250:0.250 59.13
1 2 0.250:0.250
0.125:0.250 2.0 25 59.13
59.28
2 3 0.125:0.250
0.0825:0.250 2.0 25 59.28
58.86
3 0.0825:0.250 58.86
According to the data shown in Table 4, it is observed that by varying the ratio between CP and
According to the data shown in Table 4, it is observed that by varying the ratio between CP and
PP to increase the removal of Cr (VI) in the Synthetic Residual Waters, there was no improvement
PP to increase the removal of Cr (VI) in the Synthetic Residual Waters, there was no improvement in
in the percentages of removal of the contaminant, allowing inferring that this type of methodology
the percentages of removal of the contaminant, allowing inferring that this type of methodology
would not be feasible to implement it in a Wastewater Treatment Plant System (WWTPS).
would not be feasible to implement it in a Wastewater Treatment Plant System (WWTPS).

4. Conclusions
The coffee pulp becomes a sustainable alternative to be used as a bioadsorbent in the Wastewater
Treatment Plant Systems (WWTPS) for the removal of Cr (VI), since, it is easy to acquire, its cost of
implementation and maintenance would be economical, it does not generate sludge in the treatment
Processes 2019, 7, 403 11 of 12

4. Conclusions
The coffee pulp becomes a sustainable alternative to be used as a bioadsorbent in the Wastewater
Treatment Plant Systems (WWTPS) for the removal of Cr (VI), since, it is easy to acquire, its cost of
implementation and maintenance would be economical, it does not generate sludge in the treatment
and it is of high efficiency 87.94%. A cost level is lower compared to conventional technologies, in
the case of chemical precipitation would be necessary to use a reducing agent (sodium metabisulfite)
to convert the Cr (VI) to Cr (III) and then prepare it with the addition of NaOH and in the case of
adsorption, the material that is most used is activated carbon, which in the market is high cost. With
the above, it is proposed to promote this type of technology, so that industries that generate dumping
with Cr (VI) are used to comply with both the regulations and the market that prevails in each country,
so that our system of this type of pollutants continues to be negatively impacted even more negatively
and to meet the goals in numbers 3.9 and 6.9 in the Sustainable Development Goals of the 2030 Agenda.
On the other hand, when comparing the data obtained from the coffee pulp for the removal of Cr
(VI), with those reported by other authors using optimal conditions of adsorption, it was found that
linearized models of Langmuir are those that have always been presented as a behavior of the data in
the isotherms. Regarding the interpretation of the mathematical models of adsorption kinetics, the
one that best fits is the behavior of the pseudo second order of Ho and McKay. While, the capacity of
maximum adsorption has varied, the main difference is found in the initial dose of contaminant. The
reported results are: 5.90 mg × g−1 [28], 44.95 mg × g−1 [29], 59.54 mg × g−1 [30] and 220 mg × g−1 [31],
and that found in the present study was 13.48 mg × g−1 , being observed that this result is shown
among those previously reported.

Author Contributions: D.L.G.A. performed the experimental methodology, the systematization and analytical
treatment of the experimental data obtained; J.P.R.M. and J.F.B.P. guided the research conducted, and revised
the manuscript; J.A.E.M. and D.L.G.A. drafted the manuscript. Finally, all the authors discussed the results and
contributed to the final version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: We thank the Pontificia Javeriana University, which allows us to develop the experimental
work of the present investigation.
Conflicts of Interest: The authors declare no conflict of interest.

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