Journal of Molecular Liquids 229 (2017) 555–565

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Reviews

A review for coffee adsorbents

Ioannis Anastopoulos a,b,⁎⁎, Mina Karamesouti a,⁎⁎, Athanasios C. Mitropoulos c, George Z. Kyzas c,⁎
a
Laboratory of Soils and Agricultural Chemistry, Department of Natural Resources and Agricultural Engineering, Agricultural University of Athens, Athens GR-11855, Greece
b
Department of Agrobiotechnology, Agricultural Research Institute, P.O. Box 22016, 1516 Nicosia, Cyprus
c
Hephaestus Advanced Laboratory, Eastern Macedonia and Thrace Institute of Technology, Kavala GR-654 04, Greece

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

Article history: This review examines the performance of new highly promising materials in water purification industry. Low-
Received 9 November 2016 cost and effective industrial wastes may have ample applications in water decontamination procedures, the
Received in revised form 16 December 2016 most popular of which is the biosorption, a metabolically passive process. Coffee residues are by-products pro-
Accepted 28 December 2016
duced in considerable quantities worldwide. Recently available researches show an expanding applicability of
Available online 29 December 2016
coffee by-products in the wastewater treatment. The food industry, the agriculture and aquaculture, the medicine
Keywords:
and the cosmetics are indicatively some of the industries that discharge significant quantities of toxic substances
Coffee residues through their wastewaters. Dyes and heavy metals are among the most typical chemicals of aforementioned
Biosorbents wastewaters, with various harmful effects on living organisms. The current work collects information from re-
Heavy metals cently published researches discussing the potential of raw or modified coffee residues for wastewater decon-
Dyes tamination. Important adsorption stages such as (i) equilibrium (isotherms), (ii) kinetic, and (iii) desorption
Adsorption isotherms are also compared. Moreover, crucial factors affecting the adsorption process, such as the effect of solution pH,
Kinetics contact time, temperature and adsorbent's dose, are also mentioned.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
2. Isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
2.1. Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
3. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
3.1. Parameters of adsorption processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
3.2. Parameters of characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
3.2.1. FTIR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
3.2.2. BET and pHZPC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
3.2.3. SEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
3.2.4. Composition and functional groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
4. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563

1. Introduction

Water pollution due to industrial activity or hazards has become a

⁎ Correspondence to: G.Z. Kyzas, Hephaestus Advanced Laboratory, Eastern Macedonia
and Thrace Institute of Technology, Kavala GR-65404, Greece.
⁎⁎ Corresponding authors.
E-mail addresses: ianastopoulos@ari.gov.cy (I. Anastopoulos),
minakaramesouti@gmail.com (M. Karamesouti), georgekyzas@gmail.com (G.Z. Kyzas).
global issue of concern. Toxic substances into the water deter human
use, while they impair the beneficial uses of water. Among the numer-
ous chemical pollutants, heavy metals are reported as the most harmful
substances for both flora and fauna, while dyes, produced by a plethora
of manufactories are extremely toxic. The majority of dyes usually orig-
inates from the textile industry, paper and plastic factories, tannery,

http://dx.doi.org/10.1016/j.molliq.2016.12.096
0167-7322/© 2017 Elsevier B.V. All rights reserved.
556 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565
pharmaceutical or food industry etc. [1]. They are organic substances,
and are potentially dissolved in water. Based on their solubility and
chemical characteristics, dyes are categorized into acid, basic, direct,
mordant, vat, reactive, disperse, azo and sulfur dyes. Examples of acid
dyes are the acid violet and the acid brilliant blue, while basic dyes are
Rhodamine B and Methylene blue. Contradictorily, the heavy metals
are not degradable and have a multiplication effect on the majority of
biological species. They are usually disclosed during mining operations,
by agricultural products industries, tanneries, paper industries, etc. [2].
Copper, chromium, cadmium nickel, mercury, lead and zing are the
ones usually contained in untreated industrial waters.
Among the most common methods for the removal of heavy metals
from wastewaters include ion-exchange, filtration, chemical precipita-
tion, electrochemical treatment, chemical precipitation and adsorption
[2]. For both types of aforementioned substances, adsorption is the
most widely used method for water purification, due to the low cost,
the effectiveness in a wide range of pollutants and the undemanding ap-
plicability [3–27]. Several materials have been tested for their adsorp-
tion capacity such as the activated alumina, the silica gel, zeolites and
the most popular the activated carbon [28]. Despite their satisfactory
performance, industries are prohibited to use them extensively, due to
their considerable cost. For this reason, scientific community incessantly
investigates for new, low cost, effective and environmentally friendly
materials.
The agricultural by-products are another cause of environmental
awareness, since their disposal require careful treatment as well. A liter-
ature survey reveals that coffee was the primary agricultural export for
twelve countries in 2004 and “the second most valuable commodity
exported by developing countries” from 1970 to circa 2000 [29]. More-
over, the coffee industry has almost doubled its production during the
last decades skyrocketing the quantity of coffee wastes [30,31]. Based
on the United States Department of Agriculture (USDA), over 150 mil-
lion of 60 kg bags of coffee were produced during the period 2012–13,
while 1 ton of coffee may yield to N600 kg of residues [31].
The coffee tree or shrub belongs to the family Rubiaceae. The Coffea
arabica (Arabica) and Coffea canephora (Robusta) plant species are pro-
viding the 75 and 25% of the world's production respectively [32,33].
With coffee drinks being one of the most popular beverages worldwide,
a significant quantity of by-products is generated as well (6 Mt/yr) [31].
The main coffee industry by-products are the spent coffee grounds
(SCG), the coffee silverskin (CS) and the coffee husks (CH). CS is a tegu-
ment of coffee beans obtained as a by-product of the roasting process. It
is a residue with high concentration of soluble dietary fiber (86% of total
dietary fiber) and high antioxidant capacity, probably due to the con-
centration of phenolic compounds in coffee beans, as well as to the pres-
ence of other compounds formed by the Maillard reaction during the
roasting process, such as melanoidins [34]. Microscopic examination
shows the presence of fibrous tissues from the surface layers of the CS.
The main components of these fibrous tissues are cellulose and hemicel-
lulose. Glucose, xylose, galactose, mannose, and arabinose are the
monosaccharides present in CS; glucose being found in major amounts.
Proteins and extractives are also fractions present in significant
amounts in this coffee waste.
SCG is a residue with fine particle size, high humidity (in the range of
80 to 85%), organic load, and acidity, obtained during the treatment of
raw coffee powder with hot water or steam for the instant coffee prep-
aration. Almost 50% of the worldwide coffee production is processed for
soluble coffee preparation [35]. Therefore, SCG is generated in large
amounts, with a worldwide annual generation of 6 million tons [36].
Numerically, 1 ton of green coffee generates about 650 kg of SCG, and
about 2 kg of wet SCG are obtained to each 1 kg of soluble coffee pro-
duced [37].
The coffee companies, in an attempt to reduce their costs and avoid
environmental pollution, focus on alternative and profitable uses for a
suppositional useless waste. Several researchers have investigated the
treated or untreated coffee wastes and have concluded that it is a
material with a remarkable adsorptive efficiency. Their researches re-
veal how operating conditions such as temperature, contact time, pH,
initial substance concentration, biosorbent's dose and particle size affect
the sorption procedure. Current review article compares the adsorptive
capacity of the various forms of coffee wastes, discussing the most fa-
vorable conditions for the decontamination process, separately for
each hazardous substance.
2. Isotherms
It is necessary to form the most appropriate adsorption equilibrium
correlation in the attempt to discover innovative adsorbents in gain ac-
cess to an ideal adsorption system [38], which is vital for consistent pre-
diction of adsorption parameters and quantitative comparison of
adsorbent behavior for various adsorbent systems (or for varied exper-
imental conditions) [39,40]. Adsorption isotherms, which is a common
name of equilibrium relationships, are essential for optimization of the
adsorption mechanism pathways, expression of the surface properties
and capacities of adsorbents, and productive design of the adsorption
systems since they explain how pollutants interrelate with the adsor-
bent materials [41,42].
Explaining the phenomenon through which the preservation (or re-
lease) or mobility of a substance from the aqueous porous media or
aquatic environments to a solid-phase at a persistent temperature and
pH takes places, in broad-spectrum, an adsorption isotherm is an in-
valuable curve [43,44]. The mathematical association which establishes
a significant role towards the modeling analysis, operational design and
applicable practice of the adsorption systems is normally represented
by plotting a graph between solid-phase and its residual concentration
[45].
When the concentration of the solute remains unchanged as a result
of zero net transfer of solute adsorbed and desorbed from sorbent sur-
face, a condition of equilibrium is achieved. These associations between
the equilibrium concentration of the adsorbate in the solid and liquid
phase at persistent temperature are defined by the equilibrium sorption
isotherms. Linear, favorable, strongly favorable, irreversible and unfa-
vorable are some of the isotherm shapes that may form. Understanding
of the mechanism of adsorption, surface properties, along with the ex-
tent of affinity of the adsorbents are delivered by the physicochemical
parameters accompanied by the fundamental thermodynamic supposi-
tions [46].
In terms of three basic approaches, an extensive diversity of equilib-
rium isotherm models (Langmuir, Freundlich, Langmuir-Freundlich
Brunauer-Emmett-Teller, Redlich-Peterson, Dubinin-Radushkevich,
Temkin, Toth, Koble-Corrigan, Sips, Khan, Hill, Flory-Huggins and
Radke-Prausnitz isotherm), have been framed in the past [47]. The
first approach to be mentioned is kinetic consideration, while thermo-
dynamics being the second one. A state of dynamic equilibrium with
both adsorption and desorption rates in a balance is an adsorption equi-
librium and a framework of deriving numerous forms of adsorption iso-
therm models are given by thermodynamics [48,49]. The key idea in the
generation of characteristic curve is generally given by the third ap-
proach which is potential theory [50]. The alteration in the physical in-
terpretation of the model parameters compels us to follow an
interesting trend in the isotherm modeling which is the derivation in
more than a single approach [51]. Nowadays, the most widely used
models are Langmuir, Freundlich and Langmuir-Freundlich (Table 1).
The amount of pollutant's uptake at equilibrium Qe (mg/g) is calcu-
lated using the mass balance equation:
ðC0 ‐Ce ÞV
Qe ¼ ð1Þ
m
where C0 and Ce (mg/L) are the initial and equilibrium pollutant's con-
centration, respectively; V (L) is the volume of adsorbate (solution); m
(g) is the mass of adsorbent.
 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 557

Table 1
Lists of adsorption isotherms mostly discussed in the present study.

Isotherm Non-linear form Ref

Langmuir Qe ¼ Q m KL C e [52]
1þKL Ce
Freundlich Qe = KF(Ce)1/n [53]
Langmuir-Freundlich Q e ¼ Q m KLF C1=n
e
1=n
[54]
1þKLF Ce

Table 2
Lists of kinetic equations.

Equation Equation form Ref

Pseudo-first order (non-linear) Qt¼ Q e ð1‐e−k l t Þ [58]

Pseudo-first order (linear) 1n(Qe‐Qt) = 1n(Qe)‐K1t [58]
Pseudo-second order (non-linear) k Q2t
Q t ¼ 1þk2 2 Qe e t [59]

Pseudo-second order (linear) t

¼ 1
þ ðQ1e Þt [60]
Qt k2 Q 2e

2.1. Kinetics The physicochemical properties of the adsorbent basically corre-

Kinetic studies are important for the prediction of optimum condi-
tions in full-scale batch adsorption processes [55]. Kinetic modeling
gives information about adsorption mechanisms and possible rate-con-
trolling steps such as mass transport or chemical reaction processes
[55–57]. Several kinetic models as pseudo-first and pseudo-second
order (linear or non-linear forms), intraparticle diffusion and Elovich
are available. The most prevalent are the pseudo-first and the pseudo-
second order kinetic equations. The linear and non-linear forms of pseu-
do-first and pseudo-second order kinetic models are presented in Table
2.
3. Discussion
3.1. Parameters of adsorption processes
Adsorption is a process occurring on the surface of almost all solids.
However, the adsorption capacity of solid materials is dependent on
several highly interrelated factors, which can be classified into four
main categories/domains: (i) the physicochemical properties of the ad-
sorbent, (ii) the chemical characteristics of the adsorbates, (iii) the pre-
vailing experimental conditions and d) the affinity between adsorbent
and the adsorbate.
spond to particle diameter, the cation exchange capacity the zeta poten-
tial, the pH value at the point of zero change (pHPZC) and the functional
groups (verified by FTIR spectra), which affect the adsorptive efficiency
of solids. Generally, low particle diameter suggests greater surface area,
which in turn enhances adsorption. Moreover, cation exchange capacity
as well as higher zeta potential measurements also increase adsorptive
capacity of solids.
Among the most significant chemical characteristics of adsorbates
affecting adsorption, the pKa, the ionic radius, the electronegativity
and the free energy of dehydration can also be considered. In the case
of ions, the greater the atomic weight, the electronegativity and the
ionic size, the greater the affinity for the sorption. On the contrary, the
higher the values of the free energy of hydration, the more ion metals
tend to remain to the solute phase, instead of being adsorbed. Addition-
ally, the lower the pKa value, the higher the adsorption.
But, the prevailing experimental conditions are very important for
the adsorption evaluation. The critical experimental conditions affecting
the adsorption capacity of a solid are the initial concentration, the pH of
the aqueous solution, the contact time, the temperature, the biomass
dosage and the co-existence of other pollutants.
The initial concentration and the adsorption capacity are generally
positively correlated, however in cases of extreme increase of the initial
concentration, the aforementioned assumption is not valid [61].

250
Synthetic sample
225 250

200
175 200
Q e (mg/g)

150
Q e (mg/g)

150
125
100
100
75
50 o o
25 C - pH=2 o o
25 C - pH=10 50 BB - 25 C RB - 25 C
o o
25 45 C - pH=10 45 C - pH=2 o
BB - 45 C
o
RB - 45 C
o o
65 C - pH=10 65 C - pH=2 o
BB - 65 C
o
RB - 65 C
0 0
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900
Ce (mg/L)
Ce (mg/L)

(a) (b)
Fig. 1. Effect of temperature in dyes removal ((a) synthetic mixtures; (b) single-component dye solutions) after adsorption onto coffee wastes. Reprinted with permission [66,67].
558 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

Table 3
Adsorption parameters (experimental conditions) for the removal of heavy metals.

Adsorbent Metal Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

Coffee grounds Cu(II) (1) 0.5–3.0 mg/L – – 97%a [71]

(2) b200 μm, N200 μm
(3) 5 g/L
(5) 120–130 rpm
(7) 60 min
Coffee residues (1) 0–150 mg/L LF PS1 70 mg/g [72]
(7) 5–1440 min
(2) 475–525 μm
(4) 2–8
Exhausted coffee grounds (1) 124.7 mg/L – – 16.4% [73]
(2) 0.25–0.45 mm
(4) pH 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 18% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 23.7% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 20.8% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 40.3% [73]
(4) 5
(7) 60 min
Spent coffee grains (1) 0.08–4.72 mmol/L L PS2 0.19 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 0–1440 min
Spent coffee grains (1) 0.08–4.72 mmol/L L PS2 0.45 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 4–5
(7) 7200 min
Spent coffee grains (1) 0.08–4.72 mmol/L L PS2 1.53 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 7200 min
Coffee grounds Pb(II) (1) 0.5–3.0 mg/L – – 96%a [71]
(2) b200 μm, N200 μm
(3) 5 g/L
(5) 120–130 rpm
(7) 60 min
Spent coffee grains (1) 0.01–1.2 mmol/L L PS2 0.42 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 3, 4
(7) 7200 min
Spent coffee grains (1) 0.01–1.2 mmol/L L PS2 0.45 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 7200 min
Spent coffee grains (1) 0.01–1.2 mmol/L L PS2 0.77 mmol/g [74]
(3) 50, 100 mg/40 mL
(4) 2–12
(7) 7200 min
Coffee husks (1) 25 mg/L L PS2 7.2 mg/g [75]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee husks (1) 25 mg/L L PS2 230 mg/g [76]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee residues (1) 20, 80 mg/L – PS2 9.7 mg/g [77]
(2) 0.149 mm
(3) 1, 2 g/L
(4) 3, 5
(7) 0–180 min
Exhausted coffee grounds (1) 19–291 μmol/L L – 18.5–72.4 μmol/ga [78]
(2) 1 mm
(3) 0.388–8.738 g/L
Coffee husks (1) 0–120 mg/L L, F PS2 50.8 mg/g [79]
(3) 0.5–12 g
(4) 2–9
 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 559

Table 3 (continued)

Adsorbent Metal Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

(5) 50–300 rpm

(7) 30–240 min
Exhausted coffee grounds Cr(VI) (1) 98.1, 304.9 mg/L – – 87.93, 88.54%a [73]
(2) 0.25–0.45 mm
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 88.95, 90.38%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 90.21, 91.22%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 90.18, 91.21%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Exhausted coffee grounds (1) 98.1, 304.9 mg/L – – 84.5, 86.63%a [73]
(4) pH 2
(5) 40 rpm
(7) 4 days
Coffee husks (1) 25 mg/L L PS2 5.9 mg/g [75]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee husks (1) 25 mg/L L PS2 220 mg/g [76]
(3) 0–9 g/L
(4) 0.5–9
(6) 0–150 °C
(7) 0–240 min
Coffee husks (1) 20–100 mg/L L PS2 59.54 mg/g [80]
(3) 0.5–5 g
(4) 2–8
(6) 25–55 °C
(7) 30–240 min
Exhausted coffee grounds Ni(II) (1) 124.7 mg/L – – 0% [73]
(2) 0.25–0.45 mm
(4) pH 5
(7) 60 min
Exhausted coffee grounds (1) 124.7 mg/L – – 7.7% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1) 124.7 mg/L – – 6.9% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 7.7% [73]
(4) 5
(7) 60 min
Exhausted coffee grounds (1)124.7 mg/L – – 24.3% [73]
(4) 5
(7) 60 min
Coffee residues Zn(II) (1) 20, 80 mg/L – PS2 4.4 mg/g [77]
(2) 0.149 mm
(3) 1, 2 g/L
(4) 3, 5
(7) 0–180 min

(1) Initial concentration, (2) particle size, (3) adsorbent dosage, (4) effect of pH, (5) agitation speed, (6) effect of temperature, (7) effect of contact time, (8) effect of solution's volume, (9)
effect of ionic strength.
L: Langmuir, F: Freundlich, L-F: Langmuir-Freundlich, PS1: Pseudo-first order, PS2: Pseudo-second order.
a
Calculated from initial concentration study.

The solution pH plays an important role in controlling the surface
charge of the adsorbent, the degree of ionization of the adsorbate in
the solution as well as in the dissociation of various functional groups
on the active sites of the adsorbent [62].
Concerning the contact time, there are always identified two main
stages during sorption process: (i) the rapid and quantitatively predom-
inant and (ii) the slower and quantitatively insignificant. During the
first stage, the sorption process is accelerated due to the high availability
of active sites on the biosorbent, while, in the second stage, the process
is decelerated until an equilibrium is reached [63].
Temperature is also critical to the adsorption process. The reported
positive correlation between the temperature and adsorption is mainly
attributed to the increased numbers of active surface sites and the in-
crease in the porosity, which consequently increases the pore volume
560 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

Table 4
Adsorption parameters (experimental conditions) for the removal of dyes.

Adsorbent Dye Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

Biochar from coffee grounds Rhodamine B (2) 0.3 mm – – 45%a [81]

(3) 0.3–5 g
(4) 1–10
Biochar from coffee grounds (2) 0.3 mm – – 18%a [81]
(3) 0.3–5 g
(4) 1–10
Biochar from coffee grounds (2) 0.3 mm – – 38%a [81]
(3) 0.3–5 g
(4) 1–10
Coffee ground powder (1) 7.18 mg/L L PS1, PS2 2.52 mg/g [82]
(3)1 g/L
(6) 5–19 °C
(7) 0–120 min
(8) 10–200 mL
(9) 0.001–0.1 M K2SO4
Coffee ground powder Rhodamine 6G (1) 6.65 mg/L L PS1, PS2 7.7 mg/g [82]
(3) 1 g/L
(6) 5–19 °C
(7) 0–120 min
(8) 10–200 mL
(9) 0.001–0.1 M K2SO4
Coffee wastes Crystal violet (1) 80–400 mg/L L PS2 125 mg/g [83]
(3) 0.1–10 g/L
(4) 2.3–10.5
(6) 20–50 °C
(7) 0–180 min
(9) 0–30 g/L NaCl
Polyphenol coffee grounds (1) 50, 150, 250 mg/L F PS2 36.82 mg/g [84]
(3) 5, 15, 25 g/L
(4) 3, 6, 9
(5) 200 rpm
(6) 27 °C
(7) 0.5, 5.25, 10 min
Coffee wastes Toluidine blue (1) 80–400 mg/L L PS2 142.5 mg/g [83]
(3) 0.1–10 g/L
(4) 2.3–10.5
(6) 20–50 °C
(7) 0–180 min
(9) 0–30 g/L NaCl
Coffee wastes Methyl orange (1) 20–120 mg/L L PS2 58.82 mg/g [85]
(3) 0.2–20 g/L
(4) 2.7–10.5
(5) 120 rpm
(6) 25–55 °C
(7) 0–240 min
(9) 0–10 g/L NaCl
Coffee wastes (1) 20–120 mg/L L PS2 62.5 mg/g [85]
(3) 0.2–20 g/L
(4) 2.7–10.5
(5) 120 rpm
(6) 25–55 °C
(7) 0–240 min
(9) 0–10 g/L NaCl
Coffee residues Methyl red (1) 5–50 mg/L L, F – 98%a [86]
(2) 0.05–0.25 g/L
(4) 3–10
(7) 10–60 min
Coffee residues (1) 5–50 mg/L L, F – 93.5%a [86]
(2) 0.05–0.25 g/L
(4) 3–10
(7) 10–60 min
Coffee residues (1) 5–50 mg/L L, F – 86.3%a [86]
(2) 0.05–0.25 g/L
(4) 3–10
(7) 10–60 min
Magnetic coffee silverskin Methylene blue (1) 25–1000 mg/L L PS2 556 mg/g [87]
(7) 30–300 min
Magnetic green coffee (1) 50 mg/L – PS2 66.2 mg/gb [88]
(2) b500 μm
(3) 0.5 g/L
(4) 5.5
(6) 20 °C
(7) 30–300 min
Magnetic coffee silverskin (1) 50 mg/L – PS2 99 mg/gb [88]
(2) b500 μm
 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565 561

Table 4 (continued)

Adsorbent Dye Experimental conditions Isotherm Kinetic Qm or removal (%) Ref

(3) 0.5 g/L

(4) 5.5
(6) 20 °C
(7) 30–300 min
Magnetic spent coffee grounds (1) 50 mg/L – PS2 78.1 mg/gb [88]
(2) b500 μm
(3) 0.5 g/L
(4) 5.5
(6) 20 °C
(7) 30–300 min
Coffee residues (1) 10–100 mg/L L – 4.68 mg/g [89]
(2) b0.595 mm
(3) 20–60 g/L
(4) 3–10
(5) 100 rpm
(6) 30 °C
(7) 0–20 min
Coffee residues (3) 0.5–1 g/L L PS2 112 mg/g [1]
(4) 7.5
(6) 25 °C
(7) 0–1440 min
Pyrolized coffee residues (3) 0.5–1 g/L L PS2 132 mg/g [1]
(4) 7.5
(6) 25 °C
(7) 0–1440 min
Coffee residues (1) 5–60 mg/L F PS2 6.69 mg/gb [90]
(2) b0.5 mm
(3) 7 g/L
(5) 120 rpm
(6) 27 °C
(7) 10–180 min
Coffee husks Brilliant yellow 3G-P (1) 15–550 mg/L L – 24.04–35.04 mg/g [91]
(4) 2–12
(6) 20, 30, 40 °C
Coffee wastes Remazol red 3BS (1) 0–1000 mg/L L, L-F PS1 179–241 mg/g [92]
Remazol yellow 3RS (2) 475–525 μm PS2
Remazol blue RN (3) 0–15 g/L PS3
(4) 2–12
(5) 60–180 rpm
(6) 25–65 °C
(7) 0–1440 min
Coffee husks Fast green (3) 0.5 to 5 mg/L L, F PS1 96.6 mg/g [93]
(4) 2–5
(5) 120 rpm

(1) Initial concentration, (2) particle size, (3) adsorbent dosage, (4) effect of pH, (5) agitation speed, (6) effect of temperature, (7) effect of contact time, (8) effect of solution's volume, (9)
effect of ionic strength.
L: Langmuir, F: Freundlich, L-F: Langmuir-Freundlich, PS1: Pseudo-first order, PS2: Pseudo-second order, PS3: Pseudo-third order.
a
Calculated from initial concentration study.
b
Calculated from kinetic study.

of the adsorbent. Aksu reported an increase of the activated carbon's ca-
pacity, by increasing the temperature from 25 to 45 °C [64]. Additional-
ly, the increase of temperature decreases the thickness of the boundary
layer surrounding the sorbent, enhancing the adsorption as well. More-
over, higher temperature increases the kinetic energy of the dye mole-
cules, enhancing the rate of intraparticle diffusion of the sorbate. Alpat
et al. [65] reported an increase in the Ni(II) biosorption within the tem-
peratures 20 to 40 °C, while in temperatures from 40 to 60 °C a decrease
was reported. This decrease is possibly attributed to the deactivation of
the biosorbent surface or the destruction of some active sites on the
biosorbent's surface. Contrary results were presented by Kyzas, who
found that the increase of temperature caused an increase in adsorption
capacity for dyes removal [66,67] (Fig. 1a, b).
Horsfall and Spiff [68] concluded that at high temperatures there is
noted a decrease in the thickness of the boundary layer due to the in-
creased tendency of the metal ion to escape from the biomass surface,
while the metal is in solution phase, limiting the adsorption process.
The decrease in the adsorption, resulting from the increasing tempera-
ture, occurs due to the weak interaction between the biomass surface
and the metal ion, implying that a physisorption process take place. In
other bio-materials, the temperature increase affects the texture of bio-
mass, reducing the sorption capacity. Based on Qaiser et al. [69], the
overall metal uptake by biomass is significantly affected by the temper-
ature, due to the high variability of potential binding sites.
The biomass dosage is positively correlated to the adsorptive capac-
ity due to the fact that the greater the surface area the greater the avail-
ability of the adsorption sites [70]. However, after a certain point, it is
found that the uptake capacity drops, due to the aggregation/agglomer-
ation of adsorbent particles, leading to a decrease in the available sur-
face area [70]. Table 3 indicates the initial experimental conditions
from the biosorption experiments of heavy metals using coffee resi-
dues/wastes as biosorbent material, while the respective Table 4 is for
dyes removal.
3.2. Parameters of characterization
3.2.1. FTIR
There are many analytical techniques to characterize the coffee res-
idues. Fourier transform analysis is a useful tool, which reveals the pos-
sible functional groups which are able to interact with target pollutant.
562 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565

Table 5 cationic species while at pH values lower than pHPZC, the solid surface
Interactions of functional groups of coffee adsorbents and their shifts in FTIR spectra. has a positive charge and could interact with ionic species [98]. Τhe
Adsorbent Wavenumber Assignment Ref knowledge of pHPZC could be useful to understand the protonation/de-
(cm−1) (functional groups) protonation behavior of sorbent materials for explaining the adsorption
Coffee wastes 3446 Bonded O\ \H [83] mechanism [97]. Besides the pHPZC, adsorption also depends on the sur-
2924 C\\H face area. The amount of material adsorbed is directly proportional to
2852 CH2 the specific surface. The more the surface area the more adsorbed
1728 C_O stretching vibration
amount [99].
1658 COO
1535 N\\H
1454 C_O 3.2.3. SEM
1382 COO\ \ The morphology of coffee adsorbents varies due to the treatment of
1165 C\\O\\C stretching vibration them (washing etc.) before adsorption use. Azouaou et al. showed the
1029 C\\O stretching vibration
Spent coffee 3473 Bonded O\ \H, N\\H [94,95]
structure of coffee grounds indicating that the coffee grounds had a po-
grounds 2925 Aliphatic\\CH rous and homogenous structure with deep pores [100] (Fig. 2a, b). On
2854 Aliphatic\\CH the other hand, in the case of untreated coffee materials the surface
1741 C_O stretching was not smooth, but scraggy with a variety of cavities [67,101] (Fig.
1641 C_O stretching, N\ \H, secondary
2c, d). These cavities can be characterized as channels onto the surface
amine
1543 Secondary amine group of untreated coffee materials instead of pores, given the small surface
1462 Symmetric banding of CH3 area calculated from BET analysis.
1377 N\\H,\\OH stretching
1246 Symmetric banding of CH3 3.2.4. Composition and functional groups
1165 C\\O\\C vibration
The most usual way to determine the surface functional groups onto
1088 Stretching vibration of C\
\OH
613 Stretching vibration of\\CN coffee adsorbents is based on the Boehm titration method [102]. Aque-
Coffee residues 3390 Stretching vibration of bonded O\\H [96] ous solutions of NaHCO3 (0.10 mol/L), Na2CO3 (0.05 mol/L), NaOH
2924 Asymmetrical stretch vibration\ \CH3 (0.10 mol/L), and HCl (0.10 mol/L) were prepared. 50 mL of these solu-
2854 Symmetrical stretch vibration\\CH2
tions were added to vials containing 1 g of dry coffee samples, let to be
1651 Stretching vibration of C_O
1463 Symmetric bending of\ \CH3 shaken (~140 rpm) until equilibrium (24 h), and then filtered. Five so-
1377 Asymmetrical bending vibration of lution blanks (without the adsorbent) were also prepared. In this way,
\\CH3,\ \CH2 the number of the basic sites was calculated from the amount of HCl
that reacted with the coffee adsorbents. The various free acidic groups
were derived using the assumption that NaOH neutralizes carboxyl, lac-
Many researchers applied this technique before (pure) and after (load- tone and phenolic groups, Na2CO3 neutralizes carboxyl and lactone and
ed material) adsorption to find changes in absorption of different bands. NaHCO3 neutralizes only carboxyl groups. The excess of base or acid was
Α detailed description about different functional groups is listed in Table then determined by back titration using NaOH (0.10 mol/L) and HCl
5. Imessaoudene et al. [94] observed that after cobalt by spent coffee the (0.10 mol/L) solutions [103]. Based on the above, Kyzas found that the
infrared bands 3473, 1641, 1543, 1377, 1088 and 613 cm−1 were slight- composition of coffee residues was 44% water, 12% protein, 14% lipids,
ly shifted to 3465, 1635, 1520, 1379, 1068 and 609 cm−1, respectively, 25% carbohydrates and 5% ash [72]. According to Boehm method
suggested that\\OH, C_O and amino groups may be participate in ad- [102], the functional groups at the surface of adsorbents were carboxylic
sorption process. Nitayaphata et al. [89] concluded that after methylene 0.97 mmol/g and basic 0.93 mmol/g, followed by phenolic 0.14 mmol/g
blue adsorption by coffee residues the bands shifted from 3390 and and 0.11 lactonic mmol/g. In another study [67], the respective compo-
1651 cm−1 to 3396 and 1627 cm−1, respectively demonstrated that sition was determined as 41% water, 9% protein, 20% lipids, 27% carbo-
carbonyl and hydroxyls group could be ideal actives sites for methylene hydrates and 3% ash, while the results from Boehm method showed
blue adsorption. Based on another study, before and after adsorption of that the coffee surface was carboxylic 0.94 mmol/g and basic
crystal violet cationic dye by polyphenol-extracted coffee grounds, the 0.91 mmol/g, followed by phenolic 0.16 mmol/g and 0.12 lactonic
bands went from 2924 to 2920 cm−1 attributed to C\\H asymmetric mmol/g. Franca et al. [104] found different results for the composition
and symmetric stretch of methyl and methylene groups get involved (47% water, 7% protein, 17% lipids, 28% carbohydrates and 1% ash),while
in adsorption. the results from Boehm method showed that the coffee surface was ap-
proximately neutral (carboxylic 0.80 mmol/g and basic 0.78 mmol/g,
3.2.2. BET and pHZPC followed by phenolic 0.12 mmol/g and 0.07 lactonic mmol/g). Oliveira
Another significant material characteristics of that governed the ad- et al. found different results [105]; the proximate composition of the
sorption phenomenon are the pH and surface area (Table 6). In sorption coffee husks employed was 10% water, 11% protein, 2% lipids, 70% car-
processes, the pH plays a significant role due to the fact that it affects the bohydrates and 7% ash. The functional groups at the surface of the
ionization of active sites and it influences the surface charge. The pH at husks were predominantly phenolic (2.24 mmol/g), followed by lacton-
which the sorbent surface charge takes a zero value is defined as point ic (1.05 mmol/g), carboxylic (0.60 mmol/g) and basic (0.49 mmol/g)
of zero charge (pHPZC) [97]. For pH values higher than pHPZC, the sor- groups. All above clearly indicate the differentiation of surface chemis-
bent has a negative sorbent surface charge and could interact with try of coffees which is directly related with the treatment before the ad-
sorption use.

Table 6 4. Concluding remarks

BET and pHPZC parameters of various coffee adsorbents.

Adsorbent BET surface area (m2/g) pHPZC Ref Current work reviews the most recent researches on wastewater pu-
Coffee residues 0.19 3.9 [77] rification using the widely available coffee by-products. Scientists main-
Coffee husks 0.41 5.2 [91] ly focus on the adsorption of heavy metals and dyes, since they are
Coffee wastes ~2.3 3.3–3.5 [92] considered as the most common chemical pollutants, threatening
Coffee residues 187 – [89] water resources and the ecosystem. The researchers applied the tech-
Coffee wastes – 5.5 ± 2 [83]
nique of the adsorption, since it is acknowledged as the most effective
 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565
Fig. 2. SEM images for different coffee adsorbents. Reprinted with permission by Elsevier [67,100,101].
and inexpensive methodology in water purification, while it proves to
be suitable for the vast majority of pollutants.
Despite the significant amount of available literature, comparative
analysis between studies is intricate due to the absence of a process pro-
tocol. Harmonization of experimental processes can be significantly
useful during the juxtaposition of the performance of variable adsor-
bents for variable pollutants. The study of adsorption mechanism is a
complex issue and it is usually poorly discussed, mainly based only on
model implementation, (i.e. kinetics, thermodynamics etc.). Although
many researchers use batch experiments, column studies are necessary
for better understanding coffee waste practical applicability in pilot-,
and full-scale operations. Evidently, the chemical modification of natu-
ral by-products improves their sorptive ability, however, the sorptive
capacity of raw materials should be included in the study, as a reference
base point, as well. Moreover, testing repetitive adsorption – desorption
cycles is critical for material reusability assessment, while testing the
material in real wastewaters is necessary for estimating its the actual ef-
ficiency. Finally, apart from the material FTIR analysis and BET surface
area estimation, the initial presence of heavy metals in the original
raw materials is another very important information for the scientist.
Future work should focus on the estimate of the potential cost of the
adsorption process. Alternative techniques for the improvement of the
materials' adsorptive capacity, such as composting, should be consid-
ered. Finally, adsorption generates large amount of wastes and conse-
quently their disposal suggests a crucial environmental issue.
References
[1] A. Orfanos, I.D. Manariotis, H.K. Karapanagioti, Sorption of methylene blue onto
food industry byproducts, Int. Biochar Initiat (2015), Article ID 7046. .
[2] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, J. Envi-
ron. Manage. 92 (2011) 407–418.
563
[3] I. Anastopoulos, G.Z. Kyzas, Agricultural peels for dye adsorption: a review of re-
cent literature, J. Mol. Liq. 200 (2014) 277–285.
[4] I. Anastopoulos, G.Z. Kyzas, Progress in batch biosorption of heavy metals onto
algae, J. Mol. Liq. 209 (2015) 77–86.
[5] I. Anastopoulos, G.Z. Kyzas, Composts as biosorbents for decontamination of vari-
ous pollutants: a review, Water Air Soil Pollut. 226 (2015), Article ID 61. .
[6] I. Anastopoulos, I. Massas, C. Ehaliotis, Use of residues and by-products of the olive-oil
production chain for the removal of pollutants from environmental media. A review
of batch biosorption approaches, J. Environ. Sci. Health., Part A 50 (2015) 677–718.
[7] G.Z. Kyzas, D.N. Bikiaris, Recent modifications of chitosan for adsorption applica-
tions: a critical and systematic review, Mar. Drugs 13 (2015) 312–337.
[8] G.Z. Kyzas, J. Fu, N.K. Lazaridis, D.N. Bikiaris, K.A. Matis, New approaches on the re-
moval of pharmaceuticals from wastewaters with adsorbent materials, J. Mol. Liq.
209 (2015) 87–93.
[9] G.Z. Kyzas, K.A. Matis, Nanoadsorbents for pollutants removal: a review, J. Mol. Liq.
203 (2015) 159–168.
[10] I. Anastopoulos, I. Massas, C. Ehaliotis, Composting improves biosorption of Pb2+
and Ni2+ by renewable lignocellulosic materials. Characteristics and mechanisms
involved, Chem. Eng. J. 231 (2013) 245–254.
[11] I. Anastopoulos, M. Panagiotou, C. Ehaliotis, P.A. Tarantilis, I. Massas, NaOH pre-
treatment of compost derived from olive tree pruning waste biomass greatly im-
proves biosorbent characteristics for the removal of Pb2+ and Ni2+ from
aqueous solutions, Chem. Ecol. 31 (2015) 724–740.
[12] Y. Zhang, L. Yan, W. Xu, X. Guo, L. Cui, L. Gao, Q. Wei, B. Du, Adsorption of Pb(II) and
Hg(II) from aqueous solution using magnetic CoFe2O4-reduced graphene oxide, J.
Mol. Liq. 191 (2014) 177–182.
[13] B. Yahyaei, S. Azizian, Rapid adsorption of binary dye pollutants onto the
nanostructred mesoporous alumina, J. Mol. Liq. 199 (2014) 88–95.
[14] X. Tang, Q. Zhang, Z. Liu, K. Pan, Y. Dong, Y. Li, Removal of Cu(II) by loofah fibers as
a natural and low-cost adsorbent from aqueous solutions, J. Mol. Liq. 191 (2014)
73–78.
[15] A. Shamsizadeh, M. Ghaedi, A. Ansari, S. Azizian, M.K. Purkait, Tin oxide nanoparti-
cle loaded on activated carbon as new adsorbent for efficient removal of malachite
green-oxalate: non-linear kinetics and isotherm study, J. Mol. Liq. 195 (2014)
212–218.
[16] T.A. Saleh, A.A. Al-Saadi, V.K. Gupta, Carbonaceous adsorbent prepared from waste
tires: experimental and computational evaluations of organic dye methyl orange, J.
Mol. Liq. 191 (2014) 85–91.
[17] L. Qian, M. Ma, D. Cheng, The effect of water chemistry on adsorption and desorp-
tion of U(VI) on nano-alumina, J. Mol. Liq. 197 (2014) 295–300.
[18] P. Li, Z. Du, X. Ma, G. Wang, G. Li, Synthesis, adsorption and aggregation properties
of trisiloxane room-temperature ionic liquids, J. Mol. Liq. 192 (2014) 38–43.
564 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565
[19] C. Li, Y. Dong, J. Yang, Y. Li, C. Huang, Modified nano-graphite/Fe3O4 composite as
efficient adsorbent for the removal of methyl violet from aqueous solution, J.
Mol. Liq. 196 (2014) 348–356.
[20] E.G. Lemraski, E. Kargar, Standard Gibbs energy of adsorption and surface proper-
ties for ionic liquids binary mixtures, J. Mol. Liq. 195 (2014) 17–21.
[21] R. Hosseini Nia, M. Ghaedi, A.M. Ghaedi, Modeling of reactive orange 12 (RO 12)
adsorption onto gold nanoparticle-activated carbon using artificial neural network
optimization based on an imperialist competitive algorithm, J. Mol. Liq. 195 (2014)
219–229.
[22] Y.F. Hao, L.G. Yan, H.Q. Yu, K. Yang, S.J. Yu, R.R. Shan, B. Du, Comparative study on
adsorption of basic and acid dyes by hydroxy-aluminum pillared bentonite, J. Mol.
Liq. 199 (2014) 202–207.
[23] D. Gusain, F. Bux, Y.C. Sharma, Abatement of chromium by adsorption on nanocrys-
talline zirconia using response surface methodology, J. Mol. Liq. 197 (2014)
131–141.
[24] A.A. El-Bindary, M.A. Hussien, M.A. Diab, A.M. Eessa, Adsorption of Acid Yellow 99
by polyacrylonitrile/activated carbon composite: kinetics, thermodynamics and
isotherm studies, J. Mol. Liq. 197 (2014) 236–242.
[25] A.A. El-Bindary, A.Z. El-Sonbati, A.A. Al-Sarawy, K.S. Mohamed, M.A. Farid, Adsorp-
tion and thermodynamic studies of hazardous azocoumarin dye from an aqueous
solution onto low cost rice straw based carbons, J. Mol. Liq. 199 (2014) 71–78.
[26] L. Cui, W. Xu, X. Guo, Y. Zhang, Q. Wei, B. Du, Synthesis of strontium hydroxyapatite
embedding ferroferric oxide nano-composite and its application in Pb2+ adsorp-
tion, J. Mol. Liq. 197 (2014) 40–47.
[27] S. Azizian, M. Bagheri, Enhanced adsorption of Cu2+ from aqueous solution by Ag
doped nano-structured ZnO, J. Mol. Liq. 196 (2014) 198–203.
[28] A. Bhatnagar, M. Sillanpää, Utilization of agro-industrial and municipal waste ma-
terials as potential adsorbents for water treatment - a review, Chem. Eng. J. 157
(2010) 277–296.
[29] S. Ponte, The ‘Latte Revolution’? Regulation, markets and consumption in the glob-
al coffee chain, World Dev. 30 (2002) 1099–1122.
[30] J.M.V. Nabais, P. Nunes, P.J.M. Carrott, M.M.L. Ribeiro Carrott, A.M. García, M.A.
Díaz-Díez, Production of activated carbons from coffee endocarp by CO2 and
steam activation, Fuel Process. Technol. 89 (2008) 262–268.
[31] S.I. Mussatto, E.M.S. Machado, S. Martins, J.A. Teixeira, Production, composition,
and application of coffee and its industrial residues, Food Bioproc. Tech. 4 (2011)
661–672.
[32] H.D. Belitz, W. Grosch, P. Schieberle, Coffee, tea, cocoa, Food Chem. 938-951
(2009).
[33] H. Etienne, Somatic embryogenesis protocol: coffee (Coffea arabica L. and C.
canephora P.), Protoc. Somatic Embryogenesis Woody Plants 77 (2005) 167–179.
[34] R.C. Borrelli, F. Esposito, A. Napolitano, A. Ritieni, V. Fogliano, Characterization of a
new potential functional ingredient: coffee silverskin, J. Agric. Food Chem. 52
(2004) 1338–1343.
[35] K. Ramalakshmi, L.J.M. Rao, Y. Takano-Ishikawa, M. Goto, Bioactivities of low-grade
green coffee and spent coffee in different in vitro model systems, Food Chem. 115
(2009) 79–85.
[36] T. Tokimoto, N. Kawasaki, T. Nakamura, J. Akutagawa, S. Tanada, Removal of lead
ions in drinking water by coffee grounds as vegetable biomass, J. Colloid Interface
Sci. 281 (2005) 56–61.
[37] R.A. Pfluger, Soluble coffee processing, Solid Wastes: Origin, Collection, Processing,
and Disposal, 1975.
[38] V.C. Srivastava, M.M. Swamy, I.D. Mall, B. Prasad, I.M. Mishra, Adsorptive removal
of phenol by bagasse fly ash and activated carbon: equilibrium, kinetics and ther-
modynamics, Colloids Surf., A 272 (2006) 89–104.
[39] F. Gimbert, N. Morin-Crini, F. Renault, P.M. Badot, G. Crini, Adsorption isotherm
models for dye removal by cationized starch-based material in a single component
system: error analysis, J. Hazard. Mater. 157 (2008) 34–46.
[40] Y.S. Ho, J.F. Porter, G. McKay, Equilibrium isotherm studies for the sorption of diva-
lent metal ions onto peat: copper, nickel and lead single component systems,
Water Air Soil Pollut. 141 (2002) 1–33.
[41] M.I. El-Khaiary, Least-squares regression of adsorption equilibrium data: compar-
ing the options, J. Hazard. Mater. 158 (2008) 73–87.
[42] G. Thompson, J. Swain, M. Kay, C.F. Forster, The treatment of pulp and paper mill
effluent: a review, Bioresour. Technol. 77 (2001) 275–286.
[43] S.J. Allen, G. McKay, J.F. Porter, Adsorption isotherm models for basic dye adsorp-
tion by peat in single and binary component systems, J. Colloid Interface Sci. 280
(2004) 322–333.
[44] G. Limousin, J.P. Gaudet, L. Charlet, S. Szenknect, V. Barthès, M. Krimissa, Sorption
isotherms: a review on physical bases, modeling and measurement, Appl.
Geochem. 22 (2007) 249–275.
[45] M.C. Ncibi, Applicability of some statistical tools to predict optimum adsorption
isotherm after linear and non-linear regression analysis, J. Hazard. Mater. 153
(2008) 207–212.
[46] E. Bulut, M. Özacar, I.A. Şengil, Adsorption of malachite green onto bentonite: equi-
librium and kinetic studies and process design, Microporous Mesoporous Mater.
115 (2008) 234–246.
[47] A. Malek, S. Farooq, Comparison of isotherm models for hydrocarbon adsorption
on activated carbon, AICHE J. 42 (1996) 3191–3201.
[48] J.H. De Boer, The Dynamical Character of Adsorption, 1953.
[49] A.L. Myers, J.M. Prausnitz, Thermodynamics of mixed-gas adsorption, AICHE J. 11
(1965) 121–127.
[50] M.M. Dubinin, The potential theory of adsorption of gases and vapors for adsor-
bents with energetically nonuniform surfaces, Chem. Rev. 60 (1960) 235–241.
[51] D.M. Ruthven, Principles of Adsorption and Adsorption Processes, 1984.
[52] I. Langmuir, The constitution and fundamental properties of solids and liquids. Part
I. Solids, J. Am. Chem. Soc. 38 (1916) 2221–2295.
[53] H. Freundlich, Over the adsorption in solution, Z. Phys. Chem. 57 (1906) 385–470.
[54] C. Tien, Adsorption Calculations and Modeling, Butterworth-Heinemann, Boston,
U.S.A., 1994
[55] J. Febrianto, A.N. Kosasih, J. Sunarso, Y.-H. Ju, N. Indraswati, S. Ismadji, Equilibrium
and kinetic studies in adsorption of heavy metals using biosorbent: a summary of
recent studies, J. Hazard. Mater. 162 (2009) 616–645.
[56] D. Park, Y.S. Yun, J.M. Park, The past, present, and future trends of biosorption,
Biotechnol. Bioprocess Eng. 15 (2010) 86–102.
[57] G.Z. Kyzas, J. Fu, K.A. Matis, New biosorbent materials: selectivity and bioengineer-
ing insights, Processes 2 (2014) 419–440.
[58] S. Lagergren, About the theory of so-called adsorption of soluble substances,
Handlingar 24 (1898) 1–39.
[59] G. Blanchard, M. Maunaye, G. Martin, Removal of heavy metals from waters by
means of natural zeolites, Water Res. 18 (1984) 1501–1507.
[60] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (1999) 451–465.
[61] R.P.S. Jeyakumar, V. Chandrasekaran, Adsorption of lead(II) ions by activated car-
bons prepared from marine green algae: equilibrium and kinetics studies, Int. J.
Ind. Chem. 5 (2014) 1–9.
[62] S. Banerjee, M.C. Chattopadhyaya, Adsorption characteristics for the removal of a
toxic dye, tartrazine from aqueous solutions by a low cost agricultural by-product,
Arab. J. Chem. (2016) (in press) http://dx.doi.org/10.1016/j.arabjc.2013.1006.1005.
[63] M. Zaheer Aslam, N. Ramzan, S. Naveed, N. Feroze, Ni(II) removal by biosorption
using Ficus religiosa (Peepal) leaves, J. Chil. Chem. Soc. 55 (2010) 81–84.
[64] Z. Aksu, A. Tatlı, Ö. Tunç, A comparative adsorption/biosorption study of Acid Blue
161: effect of temperature on equilibrium and kinetic parameters, Chem. Eng. J.
142 (2008) 23–39.
[65] S. Alpat, S.K. Alpat, B.H. Çadirci, Ö. Özbayrak, İ. Yasa, Effects of biosorption param-
eter: kinetics, isotherm and thermodynamics for Ni(II) biosorption from aqueous
solution by Circinella sp, Electron. J. Biotechnol. 13 (2010) 4–5.
[66] G. Kyzas, A decolorization technique with spent “Greek Coffee” grounds as zero-
cost adsorbents for industrial textile wastewaters, Materials 5 (2012) 2069–2087.
[67] G.Z. Kyzas, N.K. Lazaridis, A.C. Mitropoulos, Removal of dyes from aqueous solu-
tions with untreated coffee residues as potential low-cost adsorbents: equilibrium,
reuse and thermodynamic approach, Chem. Eng. J. 189-190 (2012) 148–159.
[68] M. Horsfall Jnr., A.I. Spiff, Effects of temperature on the sorption of Pb2+ and Cd2+
from aqueous solution by Caladium bicolor (Wild cocoyam) biomass, Electron. J.
Biotechnol. 8 (2005) 43–50.
[69] S. Qaiser, A.R. Saleemi, M.M. Ahmad, Heavy metal uptake by agro based waste ma-
terials, Electron. J. Biotechnol. 10 (2007) 409–416.
[70] K. Belay, A. Hayelom, Removal of methyl orange from aqueous solutions using
thermally treated egg shell (locally available and low cost biosorbent), Chem.
Mater. Res. 6 (2014) 31–39.
[71] J. Seniūnaitė, R. Vaiškunait, V. Bolutien, Coffee grounds as an adsorbent for copper
and lead removal form aqueous solutions, In: The 9th International Conference
“ENVIRONMENTAL ENGINEERING”, VGTU Press, 2014 (22–23 May 2014, Vilnius,
Lithuania).
[72] G.Z. Kyzas, Commercial coffee wastes as materials for adsorption of heavy metals
from aqueous solutions, Materials 5 (2012) 1826–1840.
[73] C. Liu, D. Pujol, M.À. Olivella, F. De La Torre, N. Fiol, J. Poch, I. Villaescusa, The role of
exhausted coffee compounds on metal ions sorption, Water Air Soil Pollut. 226
(2015), Article ID 289. .
[74] F.J. Cerino-Córdova, P.E. Díaz-Flores, R.B. García-Reyes, E. Soto-Regalado, R. Gómez-
González, M.T. Garza-González, E. Bustamante-Alcántara, Biosorption of Cu(II) and
Pb(II) from aqueous solutions by chemically modified spent coffee grains, Int. J. En-
viron. Sci. Technol. 10 (2013) 611–622.
[75] H.G. Alemayehu, A.K. Burkute, A.G. Ede, Adsorptive removal of Pb(II) and Cr(VI)
from wastewater using acid untreated coffee husk, Interlink Continental J. Environ.
Sci. Toxicol. 1 (2014) 9–16.
[76] A.G. Ede, H.G. Alemayehu, A.K. Burkute, Adsorptive removal of Pb(II) and Cr(VI)
from wastewater using acid untreated and acid treated coffee husks: comparative
study, Int. J. Res. Chem. Environ. 4 (2014) 26–31.
[77] C.-H. Wu, C.-Y. Kuo, S.-S. Guan, Adsorption kinetics of lead and zinc ions by coffee
residues, Pol. J. Environ. Stud. 24 (2015) 761–767.
[78] H.D. Utomo, Lead adsorption onto various solid surfaces, Nat. Resour. 6 (2015) 152.
[79] S. Berhe, D. Ayele, A. Tadesse, A. Mulu, Adsorption efficiency of coffee husk for re-
moval of lead(II) from industrial effluents: equilibrium and kinetic study, Int. J. Sci.
Res. Publ. 5 (2015) 1–8.
[80] A.G. Ede, Adsorptive removal of Cr (VI) ion from wastewater by activated coffee
husk and banana peel: comparative study, World J. Pharm. Res. 4 (2014) 212–225.
[81] K. Chinmai, B.C. Hamsa, K.D. D'souza, B.R. Mahesh Chandra, B.S. Shilpa, Feasibility
studies on spent coffee grounds biochar as an adsorbent for color removal, Int. J.
Appl. Innov. Eng. Manag. 3 (2014), Article ID 10. .
[82] K. Shen, M.A. Gondal, Removal of hazardous Rhodamine dye from water by ad-
sorption onto exhausted coffee ground, J. Saudi Chem. Soc., (in press), DOI: 10.
1016/j.jscs.2013.1011.1005.
[83] R. Lafi, A.B. Fradj, A. Hafiane, B.H. Hameed, Coffee waste as potential adsorbent for
the removal of basic dyes from aqueous solution, Korean J. Chem. Eng. 31 (2014)
2198–2206.
[84] M.D. Pavlović, A.V. Buntić, K.R. Mihajlovski, S.S. Šiler-Marinković, D.G. Antonović, Z.
Radovanović, S.I. Dimitrijević-Branković, Rapid cationic dye adsorption on poly-
phenol-extracted coffee grounds-a response surface methodology approach, J. Tai-
wan Inst. Chem. Eng. (2014).
 I. Anastopoulos et al. / Journal of Molecular Liquids 229 (2017) 555–565
[85] R. Lafi, A. Hafiane, Removal of methyl orange (MO) from aqueous solution using
cationic surfactants modified coffee waste (MCWs), J. Taiwan Inst. Chem. Eng. 58
(2016) 424–433.
[86] H.S. Jahin, Adsorption of methyl red from aqueous solutions using activated carbon
prepared from coffee residue, Int. J. Environ. Pollut. 3 (2014) 126–132.
[87] A. Zuorro, A.D. Battista, R. Lavecchia, Magnetically modified coffee silverskin for the
removal of xenobiotics from wastewater, Chem. Eng. Trans. 35 (2013) 1375–1380.
[88] A. Zuorro, R. Lavecchia, S. Natali, Magnetically modified agro-industrial wastes as
efficient and easily recoverable adsorbents for water treatment, Chem. Eng.
Trans. 38 (2014) 349–354.
[89] W. Nitayaphat, T. Jintakosol, K. Engkaseth, Y. Wanrakakit, Removal of methylene
blue from aqueous solution by coffee residues, Chiang Mai J. Sci. 42 (2015)
407–416.
[90] M.D. Pavlović, I.R. Nikolić, M.D. Milutinović, S.I. Dimitrijević-Branković, S.S. Šiler-
Marinković, D.G. Antonović, Plant waste materials from restaurants as the adsor-
bents for dyes, Chem. Ind. 69 (2015) 667–677.
[91] I.I. Fasfous, N.A. Farha, Removal of Cibacron Brilliant Yellow 3G-P dye from aqueous
solutions using coffee husks as non-conventional low-cost sorbent, World Acade-
my of Science, Engineering and Technology, International Journal of Chemical, Mo-
lecular, Nuclear, Materials and Metallurgical Engineering, 6, 2012, pp. 908–914.
[92] G.Z. Kyzas, N.K. Lazaridis, A.C. Mitropoulos, Optimization of batch conditions and
application to fixed-bed columns for a sequential technique of total color removal
using “greek coffee” residues as materials for real dyeing effluents, J. Eng. Sci.
Technol. Rev. 5 (2012) 66–75.
[93] N. Ahalya, M.N. Chandraprabha, R.D. Kanamadi, T.V. Ramachandra, Adsorption of
fast green onto coffee husk, J. Chem. Eng. Res. 2 (2014) 201–207.
[94] D. Imessaoudene, S. Hanini, A. Bouzidi, A. Ararem, Kinetic and thermodynamic
study of cobalt adsorption by spent coffee, Desalin. Water Treat. 57 (2016)
6116–6123.
565
[95] D. Imessaoudene, S. Hanini, A. Bouzidi, Biosorption of strontium from aqueous so-
lutions onto spent coffee grounds, J. Radioanal. Nucl. Chem. 298 (2013) 893–902.
[96] W. Nitayaphat, T. Jintakosol, K. Engkaseth, Y. Wanrakakit, Removal of methylene
blue from aqueous solution by coffee residues, Chiang Mai J. Sci. 42 (2015)
407–416.
[97] N. Fiol, I. Villaescusa, Determination of sorbent point zero charge: usefulness in
sorption studies, Environ. Chem. Lett. 7 (2009) 79–84.
[98] V. Dulman, S.M. Cucu-Man, Wood sawdust, tree bark and wood chips: waste ligno-
cellulosic materials for dye removal, in: G. Crini, P.M. Badot (Eds.), Sorption Pro-
cesses and Pollution: Conventional and Non-conventional Sorbents for Pollutant
Removal from Wastewaters, Presses Univ. Franche-Comté, Paris, France 2010,
pp. 233–267.
[99] K.H. Tan, Principles of Soil Chemistry, Taylor & Francis, CRC press, Boca Raton, Flor-
ida, USA, 2010.
[100] N. Azouaou, Z. Sadaoui, A. Djaafri, H. Mokaddem, Adsorption of cadmium from
aqueous solution onto untreated coffee grounds: equilibrium, kinetics and ther-
modynamics, J. Hazard. Mater. 184 (2010) 126–134.
[101] W.E. Oliveira, A.S. Franca, L.S. Oliveira, S.D. Rocha, Untreated coffee husks as
biosorbents for the removal of heavy metals from aqueous solutions, J. Hazard.
Mater. 152 (2008) 1073–1081.
[102] H.P. Boehm, Chemical identification of surface groups, Adv. Catal. 16 (1966)
179–274.
[103] H. Valdés, M. Sánchez-Polo, J. Rivera-Utrilla, C.A. Zaror, Effect of ozone treatment
on surface properties of activated carbon, Langmuir 18 (2002) 2111–2116.
[104] A.S. Franca, L.S. Oliveira, M.E. Ferreira, Kinetics and equilibrium studies of methy-
lene blue adsorption by spent coffee grounds, Desalination 249 (2009) 267–272.
[105] L.S. Oliveira, A.S. Franca, T.M. Alves, S.D.F. Rocha, Evaluation of untreated coffee
husks as potential biosorbents for treatment of dye contaminated waters, J. Haz-
ard. Mater. 155 (2008) 507–512.