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Progress in batch biosorption of heavy metals

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 Journal of Molecular Liquids 209 (2015) 77–86

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Progress in batch biosorption of heavy metals onto algae

Ioannis Anastopoulos a, George Z. Kyzas b,c,⁎
a
Laboratory of Soils and Agricultural Chemistry, Department of Natural Resources and Agricultural Engineering, Agricultural University of Athens, Athens GR-118 55, Greece
b
Division of Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki GR-541 24, Greece
c
Department of Oenology and Beverage Technology, Technological Educational Institute of Kavala, Kavala GR-654 04, Greece

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

Available online 15 May 2015 Biosorption is a promising technology which pays attention to fabricate novel, cheap (low-cost) and highly-
effective materials to apply in wastewater purification technology. Algae belong to a multi applicable group,
Keywords: which can contribute to important sectors. Their major use is to produce a wide range of primary and secondary
Algae metabolites, which applied to food, pharmaceutical and cosmetic industries. Moreover, algae have been sug-
Biosorbents gested as potential feedstock for bioenergy and biofuel production. This review article collects information
Heavy metals
from published works of the last two years (2014 and 2015), discussing about the alternative use of different
Modeling isotherms
Kinetics
algae (micro and macro) in raw or modified form as promising biosorbents for water or wastewater decontam-
Thermodynamics ination. Some important adsorption paths were criticized as the stage of (i) equilibrium (isotherms), (ii) kinetic,
and (iii) desorption. For this purpose, many factors which influence the adsorption process, such as the effect of
solution pH, contact time, temperature and adsorbent's dose, were also discussed.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
The increase of industrial activities led to the production of toxic pol-
lutants (in various amounts) such as heavy metals, dyes, pesticides,
phenols, organic compounds, etc. [1]. Heavy metals are recognized as
one of the most toxic groups which reach in food chain through the dis-
posal of wastes to water receptors or land. Heavy metals are taxed in
causing toxic effects, cancer and diseases because they cannot be de-
graded, [2,3].
Various methods such as adsorption, coagulation, advanced oxida-
tion, and membrane separation have been used for the removal of
heavy metals from wastewaters. However, adsorption is one of the
most effective processes of advanced wastewater treatment [4]. Numer-
ous works have been recently published with primary goal the investi-
gation of removal of different pollutants (either in gas or liquid
medium) using adsorbent materials [5–20]. Some of the widely used
adsorbents materials especially for heavy metals removals from aque-
ous solutions are chitosans [21], nanoadsorbents [22], barks [23], wastes
from olive oil industry [24], coconut based materials [25], agricultural
peels [26,27], zeolites [28], clay soils [29] and betonites and vermiculites
[3]. In this study, the use of algae for heavy metal biosorption is
discussed.
Algae consist of two different types namely micro- and macro-algae.
Macro-algae or “seaweeds” are multi-cellular plants growing in salt or
⁎ Corresponding author at: Laboratory of Soils and Agricultural Chemistry, Department
of Natural Resources and Agricultural Engineering, Agricultural University of Athens,
Athens GR-118 55, Greece.
E-mail address: georgekyzas@gmail.com (G.Z. Kyzas).
fresh water. Macro-algae are generally fast growing and able to reach
up to 60 m (length). According to their pigmentation, they are divided
into three broad groups: (i) brown, (ii) red, and (iii) green seaweed
[30,31]. Micro-algae are photosynthetic unicellar microorganisms that
grow (or exist) in salt or fresh water. There are many characteristics
which affect the classification of micro-algae such as, pigmentation,
arrangements of photosynthetic membranes or other morphological
features. At present, micro-algae are classified to four groups:
(i) diatoms, (ii) green algae, (iii) golden algae and (iv) cyanobacteria
(blue-green algae) [31,32].
Generally micro- and macro-algae are being studied for its multi-
functional utilizations such as food, cosmetics, medicine, energy, etc.
(Fig. 1) [33–36]. Moreover, algae have received a great deal of attention
for decontamination of water by biosorption process. Algal biomass can
be used for live or dead form in a biosorption system. Non-living bio-
mass is more practical and favorable due to the fact that living biomass
cells needs minimum nutrients and environmental conditions, while
dead biomass does not. Moreover, dead biomass is not affected by the
toxicity of metal ions, while they can undergo different chemical and
physical pretreatments to increase their adsorption capacity.
Based on a statistical review on biosorption, algae have been used as
biosorbent material 15.3% more than other kinds of biomass and 84.6%
more than fungi and bacteria [37,38]. Their ability focused on the com-
position of cell wall which includes chitin, lipids, polysaccharides and
proteins. These macromolecules contribute different functional groups
such as carboxyl, hydroxyl, carbonyl, phenolic, etc., which can form co-
ordination complexes with heavy metals. Considering their availability
and low-cost, the rapid biosorption capability, high efficiency, reusabil-
ity, high selectivity, no toxic waste generation, algae could be ideal and

http://dx.doi.org/10.1016/j.molliq.2015.05.023
0167-7322/© 2015 Elsevier B.V. All rights reserved.
78 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86
Nomenclature
BET Brunauer–Emmett–Teller
D–R Dubinin–Radushkevich isotherm equation
ELV Elovich kinetic equation
F Freundlich isotherm equation
FP Fractional power
F–S Fritz–Schlunder isotherm equation
L Langmuir isotherm equation
L–F Langmuir–Freundlich isotherm equation
PS1 Pseudo-first order kinetic equation
PS2 Pseudo-second order kinetic equation
R–P Redlich–Peterson isotherm equation
S Sips isotherm equation
T Temkin isotherm equation
promising biosorbents. Algae can be considered as low-cost biosorbent
materials, because no special treatment is needed (apart from acid or
base modification). Herrera et al. found that an approximate cost of
biosorption 10 g of Ag(II) onto cellulose phosphate was about 2$ USD
[39]. Additionally, low-cost biosorption process using algae as adsor-
bent has lately been introduced as an alternative (unit cost of virgin
algae is approximately ranging from 1$ USD to 3/kg) [40].
The composition of the cell wall of algae plays a significant role in the
biosorption process [31]. The cell wall of algae consists of different com-
ponents such as polysaccharides, proteins and lipids. Moreover it con-
tains a number of many functional groups, which also play a key role
in the biosorption of metals from aqueous solutions. Regarding macro-
algae, brown algae cell walls are composed mainly from cellulose,
alginic acid, polymers complexed with light metals such as sodium, po-
tassium, magnesium, calcium, and polysaccharides. The predominant
active groups are alginates and sulfate [41]. Green algae have mainly
cellulose, while high percentage of the cell wall is protein bonded to
polysaccharides. Proteins contain functional groups such as amino, car-
boxyl, sulfate, and hydroxyl, which participate significantly to
biosorption process [42]. Red algae contain cellulose in cell wall, but
their biosorption capacities can be mainly attributed to the presence
of sulfated polysaccharides made of galactans [41].
Micro-algal cell wall consisted mainly of polysaccharides, proteins,
and lipids, which offer several functional groups (i.e., –COOH, –OH,
–PO3, –NH2, –SH). The latter confers a net overall negative charge
to the cell surface, and concomitantly a high binding affinity for metal
cations via counterion interactions. The cell walls of micro-algae consti-
tute proteins, which are made up of amino acids, that provide groups
(i.e., –NH2), facilitating metal binding [43]. Additionally, the polysac-
charides of the cell wall also provide amino and carboxyl groups, as
well as sulfate ones. Chojnacka et al. confirmed the latter by stating
that algal cell wall components such as peptidoglycan, teichuronic
Fig. 1. General uses of algae: (a) fertilizers; (b) cosmetics; (c) animal feed; (d) biofuels; (e) medicine; (f) human food.
acid, teichoic acid, polysaccharides and proteins, are polyelectrolytes
carrying charged groups (such as carboxyl, phosphate, hydroxyl or
amine) [44].
There are a few review articles focused on the use of algae for remov-
al of heavy metal ions from water media [31,41,45]. To our knowledge,
there is a lack of updated application-trends for algae utilized as
biosorbents. For this purpose, in this review article, fabricated (raw
or treated) novel algae biosorbents are summarized and discussed,
but only for the very last time period (only 2014–2015). Isotherm, ki-
netic, and equilibrium modeling were discussed in details. Moreover pa-
rameters which affect the biosorption process, such as the effect of
solution pH, contact time, temperature and biosorbent's dose are also
commented.
2. Biosorption modeling
In order to develop an effective and accurate design model for the re-
moval of pollutants from aqueous media, biosorption kinetics and equi-
librium data are required.
2.1. Isotherm models
It is necessary to form the most appropriate biosorption equilibrium
correlation in the attempt to discover innovative adsorbents in gain ac-
cess to an ideal biosorption system [46] which is vital for consistent pre-
diction of biosorption parameters and quantitative comparison of
biosorbent behavior for various biosorbent systems (or for varied ex-
perimental conditions) [47,48]. Adsorption isotherms, which is a com-
mon name of equilibrium relationships, are essential for optimization
of the biosorption mechanism pathways, expression of the surface
properties and capacities of biosorbents, and productive design of the
biosorption systems since they explain how pollutants interrelate with
the biosorbent materials [49,50].
Explaining the phenomenon through which the preservation (or
release) 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 [51,52]. The mathematical association which establishes
a significant role towards the modeling analysis, operational design and
applicable practice of the biosorption systems is normally represented
by plotting a graph between solid-phase and its residual concentration
[53].
When the concentration of the solute remains unchanged as a result
of zero net transfer of solute biosorbed and desorbed from biosorbent
surface, a condition of equilibrium is achieved. These associations be-
tween the equilibrium concentration of the adsorbate in the solid and
liquid phase at persistent temperature are defined by the equilibrium
biosorption isotherms. Linear, favorable, strongly favorable, irreversible
and unfavorable are some of the isotherm shapes that may form.
 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86 79

Understanding of the mechanism of biosorption, surface properties, Table 2

along with the extent of affinity of the biosorbents are delivered by the Lists of kinetic equations used.

physicochemical parameters accompanied by the fundamental thermo- Isotherm Equation Reference

dynamic suppositions [54]. A special mention should be done for ion-

Pseudo-first order (non-linear) Q t ¼ Q e 1−e−k1 t [75]
exchange [55–57]. Several biosorption studies were done to develop a Pseudo-first order (linear) ln(Qe − Qt) = ln(Qe) − k1t [75]
mathematical equilibrium sorption models and to verify their suitability Pseudo-second order (non-linear) k2 Q e t 2
[76]
Q t ¼ 1þk 2Qe t
for describing biosorption of heavy metals by algae biomass. These stud-  
Pseudo-second order (linear) t
¼k 1
þ 1 [77]
ies concluded that the biosorption mechanisms involving algae are an Qt 2Qe
2 Qe t

ion-exchange reaction type between cations (light metals: Ca2 +, Elovich Qt ¼ 1

βel ln ða  βel Þ þ 1
βel ln ðtÞ [78,79]

Mg2+, Na+ and K+) already bound to the algae and the others present
in the aqueous solution. In this case, light metal ions are initially at-
tached to the sorbent binding sites (the functional groups) and the
heavy metals ions are present in solution. It has been demonstrated
that the binding of metals by algal biomass from aqueous solutions
can be described by ion-exchange reaction [58].
[72–74]. Several kinetic models as pseudo-first and pseudo-second
order (linear or non-linear forms) 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 pseudo-first and
pseudo-second order kinetic models are presented in Table 2.

M2þ þ ðL−BiomassÞ↔ðM−BiomassÞ þ L2þ ð1Þ

2+ 2+
where M and L represent the divalent metal cations biosorbed and
released from the biomass.
In terms of three basic approaches, an extensive diversity of
equilibrium isotherm models (Langmuir, Freundlich, Brunauer–
Emmett–Teller, Redlich–Peterson, Dubinin–Radushkevich, Temkin,
Sips, Khan isotherms), has been framed in the past [59] (See Table 1).
The first approach to be mentioned is kinetic consideration, while ther-
modynamics being the second one. A state of dynamic equilibrium with
both biosorption and desorption rates in a balance is an adsorption
equilibrium and a framework of deriving numerous forms of adsorption
isotherm models is given by thermodynamics [60,61]. The key idea in
the generation of characteristic curve is generally given by the third
approach which is potential theory [62]. The alteration in the physical
3. Micro-algae
The utilization of Spirulina platensis was investigated in order to
biosorb Cu2+ by Al-Homaidan et al. [80]. Experiments were carried
out at initial Cu2+ concentration of 100 mg/L, as a function of biomass
dose (0.02–1.5 g/L), contact time (30–180 min), temperature (20–
60 °C) and pH (2–10). Maximum biosorption (90.6%) was found to be
for 0.05 g dose, 90 min of contact time, at 37 °C and pH = 7. The
biosorption percentage was found to increase from 47.65 to 90.61%
with the increase of the initial concentration from 10 to 100 mg/L. The
opposite effect was observed at 150 and 200 mg/L, suggested the full
cover of binding sites after certain concentrations.
Cr3+ was removed from water media by Chlorella miniata [81]. For
this purpose, batch experiments in the presence of NO− −
3 , Cl and SO4
2−

interpretation of the model parameters compels us to follow an inter-
esting trend in the isotherm modeling which is the derivation in more
than a single approach [63].
The amount of metal's uptake at equilibrium Qe (mg/g) is calculated
using the mass balance equation:
ðC0 −Ce ÞV
Qe ¼
m due to the formation of Cr(OH)SO4(aq) and the decrease of Cr(OH)2+
where C0 and Ce (mg/L) are the initial and equilibrium metal's con-
were investigated. It is noted that the addition of salts in solution
could increase the ionic strength and resulted in hindering the uptake
of target metal. In all cases (with or without anions), an increase of
biosorption capacity was observed as the pH increased from 3 to 4.5.
Comparing to control system, anion systems appeared to have lower
biosorption capacity, while the inhibitory order was SO− 4
2
N Cl−
− −2
N NO3 . In the case of SO4 , the decrease of biosorption capacity was
ð2Þ
and Cr3+ in solution. In the other cases, the formation of inner-sphere
surface complex (NO− 3 ) and the outer-sphere surface complex (Cl )
−

centration, respectively; V (L) is the volume of adsorbate (solution); were the basic reasons for the reduction of biosorption capacity.
m (g) is the mass of adsorbent. S. platensis extract (SPE) beads were fabricated and were examined
as novel biosorbent for the sanitation of polluted waters from Cr6 +
2.2. Kinetic equations [82]. SPE beads showed maximum biosorption at pH = 2 at pH range
of 1–5. Among the desorption eluants tested (distilled water, 0.1 M
Kinetic studies are important for the prediction of optimum condi- NaOH, 0.1 M EDTA, 0.1 M HCl, 0.1 M HNO3), NaOH was found to be
tions in full-scale batch adsorption processes [72]. Kinetic modeling the most efficient. Following biosorption–desorption process for 5 re-
gives information about adsorption mechanisms and possible rate- peated cycles, SPE beads maintained about 70% of their initial capacity
controlling steps such as mass transport or chemical reaction processes (that of the 1st cycle). Fig. 2 shows surface images of SPE beads prepared
using different coagulants. The methanol- or ethanol-coagulated SPE
beads have much better compressive strength than the propanol- or
Table 1 butanol-coagulated beads. In general, the coagulation mechanism of
Lists of adsorption isotherms (non-linear forms).
the polymer is the exchange of the solvent and the non-solvent. The sol-
Isotherm Equation Reference vent will diffuse out and the non-solvent will diffuse in. In the case of
Langmuir Q m KL Ce [64] SPE beads that coagulated in propanol or butanol, a flat region could
Qe ¼ 1þKL Ce
Freundlich Qe = KF(Ce)1/n [65]
be observed on the surface of the bead. This flat region is the result of
Dubinin–Radushkevic Q e ¼ ðQ s Þe−kDR ε
2
[66] temporary adhesion between insufficiently coagulated SPE beads in
 
Temkin Q e ¼ RT ln ðAT Ce Þ [67] the coagulant, which indicates a slow solvent exchange speed. In addi-
bT
tion, cracks were observed in these beads, and these cracks may act as
Redlich–Peterson Qe ¼ KR C e [68]
1þaR Cge weak points during real applications. However, the methanol- and
β
Sips KS Ce S [69]
Qe ¼ β ethanol-coagulated SPE beads exhibited denser and smoother surfaces
1þaS Ce S
Khan Q s bK Ce
Q e ¼ ð1þb [70] and had better compression strength than the propanol or butanol co-
C ÞaK
K e

BET Q s CBET Ce [71] agulated SPE beads. In further studies, the methanol-coagulated SPE
Qe ¼ ðCs −Ce Þ½1þðCBET −1ÞðCe =Cs Þ
beads were used.
80 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86
Fig. 2. FE-SEM images of dried SPE beads using various coagulants: (a) methanol, (b) ethanol, (c) 1-propanol, and (d) 1-butanol with magnification: 200× and insert panel: 500×.
Reprinted with permission by Elsevier [82].
Chlorella vulgaris was also investigated for the adsorption of Cr6+
[83]. The maximum adsorption obtained at pH = 3, while the equilibri-
um attained at 120 min for all the studied concentrations (C0,Cr = 20–
120 mg/L). The surface morphology of biosorbent using scanning elec-
tron microscopy (SEM) demonstrated rough surface area with definite-
ly detectable micropores.
Another research team also examined the uptake of Cr6+ by lipid-
extraction residue of C. vulgaris from aqueous solutions [84]. The lipid-
extraction led to increase of surface area (from 0.56 to 1.71 m2/g) and
pore volume (from 0.0079 to 0.0214 mL/g). One possible explanation
was that during the extraction procedure, a potential disruption of
cells was noticed. The increase of biosorption capacity was achieved
by reducing the solution pH from 4 to 0.5 and increasing the tempera-
ture form 15 to 45 °C. The morphological observation of the cells by
SEM (Fig. 3) shows that the surface of the cells became wrinkled, porous
and had more cracks after lipid extraction, thereby leading to an en-
hancement in surface area and pore volume, which indicates the poten-
tial higher adsorption capacity of the biomass. The algal cells subjected
to elemental analysis show that the C and H contents decreased slightly
after extraction. These results suggested that most lipids were success-
fully extracted. (See Fig. 4.)
Scenedesmus quadricauda was another algae which was sufficiently
applied for the sequestration of Cr3 + and Cr6 + [85]. Maximum
biosorption for Cr3+ (pH = 1–6) and Cr6+ (pH = 1–9) was found at
pH = 6 and pH = 1, respectively. FTIR spectra before and after metal
biosorption showed that sulfoxide and hydroxyl functional groups con-
tribute to adsorption. Kinetic data showed that 120 min of contact time
was enough for equilibration. Desorption studies demonstrated that
0.1 M HNO3 and 0.1 M NaOH was the best eluent studied in order to re-
cover Cr3+ (85%) and Cr6+ (60%), respectively.
The biosorption of Cu2 + and Cr2 + from aqueous media by
immobilized algae (S. platensis and C. vulgaris) was examined by
Hadiyanto et al. [86]. Compared to Chlorella, Spirulina appeared to
biosorb higher amounts of metals. The explanation can be attributed
to the cell size of the biosorbents; Spirulina sp. has larger size cells
(more than 200 μm) than Clorella sp., supporting the above results. In
both biosorbents the uptake of Cr2 + (0.63 Å) was more than Cu2 +
(0.96 Å), indicating that size plays a significant role. These results are
in accordance with many studies which found that the smaller ionic ra-
dius of a metal, the higher the biosorption rate is [87,88].
Chlorella vulgaris and S. platensis were also tested from another team
for their ability to biosorb Zn2+ [89]. At the studied pH range (3–6), the
maximum biosorption was at pH = 5–6. Kinetic studies were conduct-
ed using 50 mg Zn2+/L and revealed that 30 min was sufficient to equil-
ibrate. The mean biosorption energies (E) for C. vulgaris, and S. platensis
were evaluated to be 2.7 and 2.8, respectively. Values of E b 8 kJ/mol led
to conclusion that main mechanism of biosorption was physisorption
[28].
The potential of four types of Arthrospira platensis (TDB-typical dry
biomass, CDB-carbohydrate-enriched dry biomass, TLB-typical living
biomass and CLB-carbohydrate-enriched living biomass) was evaluated
for the uptake of Cu2+ and Ni2+ from aqueous solutions [90]. In the case
of Cu2+, the accumulation of carbohydrates in dry types significantly
enhanced the adsorption capacity (TDB: 17.3 mg/g, CDB: 33.44 mg/g),
while the opposite effect was observed in living biomass (TLB:
40.65 mg/g, CLB: 35.59 mg/g). In the case of Ni2+, in living forms the ac-
cumulation of carbohydrates led to an important reduction of adsorp-
tion capacities (TLB: 90.91 mg/g, CLB: 63.29 mg/g), while no serious
effect was presented on dry types (TDB: 52.63 mg/g, CDB: 56.82 mg/g).
In all studied cases, Ni2 + appeared to have a higher biosorption ca-
pacity than Cu2 +. According to mean free energy of sorption obtain-
ed from D–R isotherm model, all calculated values were in the range
7.9–12.7 kJ/mol, implying that the phenomenon belongs to chemi-
sorption (8–16 kJ/mol).
The utilization of Dunaliela algae as biosorbent for the removal of
Cd2+, Pb2+, Ni2+, Cr2+, Zn2+ and Cu2+ from wastewaters was tested
 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86 81

Fig. 3. SEM-EDX spectra of C. vulgaris biomass. (a) and (b) before lipid extraction; (c) and (d) after lipid extraction; (e) and (f) after reaction with Cr(VI).
Reprinted with permission by Elsevier [84].

[91]. Kinetic studies revealed two stages; a rapid stage in which
the metals biosorbed on surface of algae and a slow one in which
the metal ions transported across the cell into the cytoplasm. In the
first 12 min, 74% metal uptake was observed and an equilibration
period was noticed within 24 h (the adsorption percentage was 95%).
Among the tested metals, Pb2+ was found to biosorbed satisfactorily
(0.79 mg/75 algae cells).
A comparative table is given below (Table 3), including all important
biosorption properties and kinetic data about micro-algae discussed in
this section.

Fig. 4. SEM images of (a) before (b) lead-treated C. fastigiata powder.

Reprinted with permission by Springer [98].
82 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86

Table 3
List of models for adsorption isotherms and kinetics for biosorption of heavy metal ions onto microalgae.

Biosorbent (microalgae) Metal Isotherm model Kinetic model Qm Reference

(mg/g)

Spirulina platensis Cu2+ L – 1.64–1.94a [86]

Chlorella vulgaris Cu2+ L – 1.14–1.47a [86]
Arthrospira platensis (typical dry biomass) Cu2+ L PS2 17.3b [90]
Arthrospira platensis (carbohydrate-enriched dry biomass) Cu2+ L PS2 33.44b [90]
Arthrospira platensis (typical living biomass) Cu2+ F PS2 40.65b [90]
Arthrospira platensis (carbohydrate-enriched living biomass) Cu2+ F PS2 35.59b [90]
Spirulina platensis Cr2+ L – 12.3–16.8a [86]
Chlorella vulgaris Cr2+ L – 10.2–13.7a [86]
Chlorella miniata Cr3+ L – 14.7–41.2c [81]
Scenedesmus quadricauda Cr3+ L PS2 58.47b [85]
Scenedesmus quadricauda Cr6+ F PS2 46.51b [85]
Spirulina platensis (extract beads) Cr6+ BET – 52.826d [82]
Chlorella vulgaris Cr6+ L, F, T, R–P – 0.515b [83]
Chlorella vulgaris (lipid-extraction residue) Cr6+ S – 43.3e [84]
Arthrospira platensis (typical dry biomass) Ni2+ L PS2 52.63b [90]
Arthrospira platensis (carbohydrate-enriched dry biomass) Ni2+ L PS2 56.82b [90]
Arthrospira platensis (typical living biomass) Ni2+ F PS2 90.91b [90]
Arthrospira platensis (carbohydrate-enriched living biomass) Ni2+ F PS2 63.29b [90]
Spirulina platensis Zn2+ L, D–R PS1, PS2 2.1f [89]
Chlorella vulgaris Zn2+ L, D–R PS1, PS2 2.2f [89]

Superscripts:
a
Qm obtained at initial concentration range 15–30%.
b
Qm (mg/g) from Langmuir model.
c
Qm (mg/g) obtained at pH = 3, 4, 4.5.
d
Qm (mg/g) obtained from BET isotherm model.
e
Qm (mg/g) obtained from Sips model.
f
Qm (mol/g) obtained from D–R model.

4. Macro-algae
The feasibility of three macroalgae species (Ulva lactuca, Jania rubens,
Sphaerococcus coronopifolius) was examined for Hg2 + removal by
Lyamlouli et al. [92]. The modification of raw algae with 0.3 N H2SO4
was found to increase the biosorption capacity (U. lactuca: from 60 to
86%, J. rubens: 54 to 71%, S. coronopifolius: from 70 to 90%). Some param-
eters such as contact time (0–300 min), initial concentration, salinity
(0.1–100 mM NaNO3) and pH (2–7), were also discussed in details.
Maximum adsorption was achieved at pH 6, while the equilibrium
time after 60 min. It was found that the biosorption percentage of
metal decreased with the increase of salinity due to the competition of
Na+ and Hg2+ for the same binding sites.
Ulva lactuca was also tested for the removal of Cr6+ from water me-
dium [93]. Batch experiments were carried out in order to study the ef-
fect of solution pH (2–7), contact time (15–180 min) and biosorbent
dose (1–8 g of biomass). The biosorption percentage was found to be
96% at pH = 5 (1 g dose and 38.32 mg/L concentration).
Ainane et al. used raw Bifurcation bifurcata (RB) and modified with
1 M HCl (AB) as biosorbents for the uptake of Cr6+ [94]. Kinetic studies
(pH = 5.8, 25 °C, dose = 2 g/L and initial concentration = 50 mg/L) re-
vealed that biosorption capacity of AB (13.35 mg/g) was higher than
that of RB (9.42 mg/g). The kinetic data were better described by Elovich
and fractional power model.
Azolla filiculoides was also tested to adsorb Cr6 + from water [95].
The maximum biosorption capacity (83.34%) was obtained at pH = 2
(studied range 1–6) and the equilibrium was attained after 100 min of
contact time. Mean free energy of adsorption (obtained from D–R iso-
therm model) was 8.494 kJ/mol, indicating that bioadsorption process
was chemisorption. Thermodynamics studies (at a range of 293–
323 K) showed that biosorption of Cr6 + onto A. filiculoides biomass
was spontaneous and exothermic.
Enteromorpha green algae were tested satisfactorily of the removal
of Pb2+ from water [96]. Optimum condition for the highest metal up-
take obtained at pH 3 (pH range 3–7.5), biosorbent's dose of 0.3 g
in 25 mL lead solution (300 mg/L); the equilibrium was determined
after 20 min (contact time range 2–120 min). The modification of
Enteromorpha green algae with sodium silicates caused the increase of
maximum adsorption capacity from 83.82 to 1433.46 mg/g.
Batch experiments were applied to investigate the uptake of Pb2+ by
Sargassum myriocystum [97]. The solution pH, biomass concentration
and contact time varied from 2 to 7, 0.5 to 3.5 g, and 30 to 330 min, re-
spectively. The maximum removal was obtained at pH = 5, 2 g as dose
and 60 min contact time, respectively. The effect of temperature was
also examined; the maximum percentage removal (86.67%) was
found at 25 °C (temperature range 20–50 °C).
Caulerpa fastigiata was also examined for the uptake of Pb2 + by
Sarada et al. [98]. Batch experiments were carried out changing the
initial solution pH (2–8), contact time (5–90 min), biomass dose (2.5–
10 g/L), biosorbent particle size (0.074–0.150 mm) and temperature
(25–40 °C). Optimum adsorption was found at pH = 5 and the removal
capacity decreased increasing the biosorbent's dose (from 6.13 to
4.84 mg/g). Moreover, biosorption percentage was decreased from
82 to 70% (increase of particle size) and from 88.41 to 81.51% (increase
of temperature). Thermodynamic studies demonstrated that the
biosorption process was spontaneous and exothermic.
Raw forms of Hizikia fusiformis and modified ones (washed with
water (HFW), modified with 0.1 N HCl (HFH), and 0.1 M NaOH
(HFN)) were used for the sequestration of Pb2+, Zn2+, Ni2+ and Cd2+
[99]. Modifications were found to improve the biosorptive ability of
raw H. fusiformis (the changes in FTIR spectra also confirmed that).
One possible explanation is that modifications led to the formation of
open surface space with higher pore size. Maximum biosorption was
found at pH = 4–6. Based on maximum monolayer biosorption capacity
(obtained from Langmuir isotherm), the selectivity order was Pb2+ N
Cd2+ N Ni2+ N Zn2+. These results are in agreement with Leusch et al.
[100], who reported that the order of metal removal by Sargassum
fluitans (brown algae) was Pb2+ N Cd2+ N Cu2+ N Ni2+ N Zn2+. In soil
environment, Sposito assumed that the tendency of metals to form co-
valent bonds is related to their ionic radii and ionization potentials
quantified by the Misono softness parameter; thus, he proposed a selec-
tivity sequence of Pb2+ N Cd2+ N Cu2+ N Co2+ N Ni2+ N Zn2+ [101].
The adsorption of Cd2+ and Cu2+ from aqueous medium using red
algae Osmundea pinnatifida was also investigated [102]. Maximum
 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86 83

Table 4
List of models for adsorption isotherms and kinetics for biosorption of heavy metal ions onto macroalgae.

Biosorbent (macroalgae) Metal Isotherm model Kinetic model Qm Reference

(mg/g)

Osmundea pinnatifida Cd2+ L – 10.02a [102]

Hizikia fusiformis (modified with 0.1 M NaOH) Cd2+ L PS2 14.423a [99]
Padina sp. (modified) Cd2+ – PS2 1.7235b [104]
Ulva lactuca Cr6+ L – 1.86a [93]
Bifurcation bifurcata Cr6+ L FP, ELV 23.4c [94]
Bifurcation bifurcata (modified with 1 M HCl) Cr6+ L FP, ELV 29.29c [94]
Azolla filiculoides Cr6+ L, F, D–R PS2 10.638a [95]
Cystoseira indica (modified with 0.1 M NaCl) Co2+ T PS2 54.640–59.524a [103]
Cystoseira indica (modified with 0.1 M NaCl) Cu2+ L PS2 94.339–103.093a [103]
Osmundea pinnatifida Cu2+ L – 6.94a [102]
Ulva lactuca Hg2+ L – 90.9a [92]
Jania rubens Hg2+ L – 90.9a [92]
Sphaerococcus coronopifolius Hg2+ L – 111.11a [92]
Enteromorpha green algae (raw) Pb2+ F PS2 83.82a [96]
Enteromorpha green algae (modified with sodium silicates) Pb2+ F PS2 1433.46a [96]
Hizikia fusiformis (modified with 0.1 M NaOH) Pb2+ L PS1 26.745a [99]
Caulerpa fastigiata Pb2+ F PS2 16.109d [98]
Hizikia fusiformis (modified with 0.1 M NaOH) Ni2+ L PS1 13.898a [99]
Hizikia fusiformis (modified with 0.1 M NaOH) Zn2+ L PS2 10.555a [99]

Superscripts:
a
Qm (mg/g) from Langmuir model.
b
Qe (mg/g) obtained from kinetic studies.
c
Qe (mg/g) obtained from batch studies (biosorbent's dose: 0.5–5.0 g/L (C0,metal = 50 mg/L)).
d
Qe (mg/g) obtained from batch studies at T = 25 °C.

biosorption was found at around pH = 5 (studied pH range 2–9). The
optimum equilibrium time was 60 min. It was also observed that the
biosorption percentage increased with increasing algae dose from 5 to
20 g/L (Cd2+ = 75.36%; Cu2+ = 70.22%) and then decreased. The for-
mer was attributed to the availability of more biosorption sites and
the latter due to the partial aggregation of biomass at higher dose
resulting in decrease of effective surface area.
Akbari et al. used raw and modified (with chemical solutions of NaCl,
CaCl2, HCl) Cystoseira indica biomass as promising adsorbents for the re-
moval of Co2+ and Cu2+ ions [103]. NaCl-treated biomass performed
the highest biosorption capacity for both studied metals. For this pur-
pose, further experiments were conducted by using NaCl-biomass. Ki-
netic studies showed that over 90% of total metal removal was taken
place within the first 70 min. Heavy metal removal was found to in-
crease after temperature increase from 25 to 45 °C. In binary metal sys-
tem, a synergistic effect on biosorption capacity was observed. This can
be explained by the fact that the adsorbed Cu2+ (or Co2+) ions made
the biosorbent surface slightly basic (in nature) and could interact
with the other ions (Co2+ or Co2+, respectively) causing a multi-layer
adsorption. Moreover, electrostatic repulsions between adsorbed Cu2+
and Co2+ could be hindered due to Cu2+–Co2+ interaction.
The uptake of Cd2+ from aqueous solutions by modified Padina sp.
was examined in other work [104]. Based on FTIR spectra (this will
be extensively discussed in Section 5), the pretreatment (with
polyallylamine hydrochloride) solution of biosorbents was found to in-
crease the number of –OH and N–H groups resulting to the enrichment

Table 5
Kinetic parameters for biosorption of heavy metal ions onto algae.

Biosorbent (algae) Metal Experimental conditions Pseudo-first order Pseudo-second order Reference

C0 T Qe Qe,cal,ps1 k1 R2 Qe,cal,ps2 k2 R2
(mg/L) (°C) (mg/g) (mg/g) (min−1) (mg/g) (g/mg min)

Hizikia fusiformis (modified with 0.1 M NaOH) Cd2+ 5 20 ± 0.5 4.46 4.477 0.074 0.974 4.739 8.259 0.996 [99]
Padina sp. (modified) Cd2+ 50 – 1.4167 5.1780 0.1660 0.866 1.7235 0.2052 0.999 [104]
Cystoseira indica (modified with 0.1 M NaCl) Co2+ 100 25 – 54.59 0.1367 0.592 59.17 0.00306 0.999 [103]
Cystoseira indica (modified with 0.1 M NaCl) Cu2+ 100 25 – 76.11 0.1141 0.889 80 0.00293 0.999 [103]
Arthrospira platensis (typical dry biomass) Cu2+ 100 26–28 22.73 – – 0.769 21.93 0.0101 0.974 [90]
Arthrospira platensis (carbohydrate-enriched dry biomass) Cu2+ 100 26-28 23.53 – – 0.136 23.24 0.028 0.991 [90]
Arthrospira platensis (typical living biomass) Cu2+ 100 26-28 32.15 – – 0.656 31.27 0.0104 0.986 [90]
Arthrospira platensis (carbohydrate-enriched living biomass) Cu2+ 100 26-28 37.88 – – 0.231 37.84 0.1936 0.999 [90]
Scenedesmus quadricauda Cr3+ 100 – 35.09 10.69 0.019 0.989 35.58 0.006 0.999 [85]
Scenedesmus quadricauda Cr6+ 100 – 15.69 11 0.016 0.989 15.79 0.004 0.997 [85]
Azolla filiculoides Cr6+ 20 – 5 3.698 0.0253 0.989 5.88 0.00862 0.998 [95]
Enteromorpha green algae (raw) Pb2+ 200 25 14.49 – – – 14.95 0.605 1.000 [96]
Hizikia fusiformis (modified with 0.1 M NaOH) Pb2+ 5 20 ± 0.5 4.52 4.533 0.058 0.998 4.823 11.0936 0.975 [99]
Caulerpa fastigiata Pb2+ 59.304 25 16.109 1.775 0.022 0.933 16.447 0.0319 0.999 [98]
Arthrospira platensis (typical dry biomass) Ni2+ 100 26-28 40.65 – – 0.869 40.43 0.0385 0.999 [90]
Arthrospira platensis (carbohydrate-enriched dry biomass) Ni2+ 100 26-28 11.76 – – 0.097 11.53 0.0211 0.991 [90]
Arthrospira platensis (typical living biomass) Ni2+ 100 26-28 45.45 – – 0.798 45.42 0.2547 0.998 [90]
Arthrospira platensis (carbohydrate-enriched living biomass) Ni2+ 100 26-28 27.47 – – 0.066 27.38 0.0908 0.994 [90]
Hizikia fusiformis (modified with 0.1 M NaOH) Ni2+ 5 20 ± 0.5 4.36 4.382 0.054 0.999 4.663 11.704 0.979 [99]
Hizikia fusiformis (modified with 0.1 M NaOH) Zn2+ 5 20 ± 0.5 3.94 4.037 0.022 0.975 4.448 32.405 0.987 [99]
Spirulina platensis Zn2+ 50 22 32.6 31.5 0.53 0.980 – 0.051 0.990 [89]
Chlorella vulgaris Zn2+ 50 22 37.8 38.2 0.58 0.990 – 0.070 0.990 [89]
84 I. Anastopoulos, G.Z. Kyzas / Journal of Molecular Liquids 209 (2015) 77–86
Table 6
FTIR peaks for different algae after biosorption.
Algae Peak Functional group
(cm−1)
Caulerpa 3305 –OH, –NH
fastigiata 2936 C–H (stretching vibrations)
1549 N–H (amide)
2175 –C≡N (polyacrylonitrile)
1655 –C=O (carboxylic acid)
792 Si–C (siliceous from diatomaceous earth)
Scenedesmus 3311 O–H, N–H (stretching vibrations)
quadricauda 2900 C–H (stretching vibration)
1655 C=O (stretching of typical amide)
1542 C–N (amide)
1256 P=O (phosphate ester)
1082 sulfoxides
of metal binding sites. It also showed that the highest biosorption was
achieved using 1 g as adsorbent dose (0.1–1.0) after 60 min of contact
time.
Sulaymon et al. evaluated the competitive biosorption of lead, cad-
mium, copper, and arsenic ions by using native algae [40]. A series of ex-
periments were carried out in a batch reactor to obtain equilibrium data
for adsorption of single, binary, ternary, and quaternary metal solutions.
The biosorption of these metals is based on ion exchange mechanism
accompanied by the release of light metals such as calcium, magnesium,
and sodium. The optimum pH found for removal was 5 for Cd2+ and
As3 + and 3 and 4 for Pb2 + and Cu2 +, respectively. Based on FTIR
characterization, Pb2+ made a greater change in the functional groups
of algal biomass due to high affinity to this metal. An ion exchange
model was found suitable for describing the biosorption process.
The affinity constant sequence calculated for single system was
KPb N KCu N KCd N KAs; these values reduced in binary, ternary, and qua-
ternary systems.
A comparative table is given below (Table 4), including all important
biosorption properties discussed in this section, while all above
commented about kinetic approaches were summarized in tabular
form in Table 5.
5. FTIR spectroscopy
There are many analytical techniques to characterize the algae.
Fourier transform analysis is a useful tool which reveals the possible
functional groups which are able to interact with metal ions. Α detailed
description about different functional groups is listed in Table 6. Many
researchers applied this technique before (pure material) and after
(metal-loaded material) adsorption to find changes in absorption of dif-
ferent bands in order to understand which functional groups are in-
volved in biosorption process. Khoubestani et al. observed minor shifts
for the peaks at 1082 and 3311 cm−1, suggesting the potential partici-
pation of sulfoxide and hydroxyl functional groups in biosorption of
Cr3+ and Cr6+ by S. quadricauda [85]. Also, FTIR could be used to under-
stand the alterations or the creation of new bands in the case of fabricate
modified algae. Shin and Kim found that the peaks of the case of
H. fusiformis (after base treatment) increased from 2.80 to 3.13 (unit
amount of carboxylate), indicating that the modification with NaOH
could increase the number of carboxylate ester units and carboxylic
groups, which are more effective to biosorb heavy metals from aqueous
solution [99]. Padina sp. was modified via PAA/HCl (allyamine hydro-
chloride) solution by Naspu et al. [104]. FTIR analysis showed that
PAA/HCl solution led to biosorbents with increasing number of O–H
and N–H groups.
6. Conclusions
In this work, micro- and macro-algae appear to be promising
biosorbents for the removal of heavy metals from wastewater.
Biosorption was controlled by contact time, biomass dose, initial con-
centration, solution pH and temperature. Among tested isotherm and
Reference kinetic models, Langmuir and pseudo-second order were found to fit
well the experimental data. Future work must give emphasis on the
[98] preparation of algae biosorbents via physical and chemical treatments
in order to improve the adsorption capacity. Moreover, more realistic
conditions by using real wastewater including different pollutants are
necessary. Desorption studies and multiple biosorption–regeneration
cycles must follow every batch equilibration approaches for better un-
[85] derstanding the biosorptive characteristic of materials.
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