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Adsorption (2015) 21:645–658

DOI 10.1007/s10450-015-9715-3

Characterization of copper (II) biosorption by brown algae


Durvillaea antarctica dead biomass
Héctor Cid1 • Claudia Ortiz1 • Jaime Pizarro2 • Daniel Barros1 • Ximena Castillo2 •

Liliana Giraldo3 • Juan Carlos Moreno-Piraján4

Received: 27 August 2015 / Revised: 20 October 2015 / Accepted: 4 November 2015 / Published online: 14 November 2015
Ó Springer Science+Business Media New York 2015

Abstract In this study we analyze the Cu(II) biosorption the biomass, characterized as an physisorption phenomena
characteristics of the dead biomass of the Chilean brown in a multilayer heterogeneous system.
macroalgae Durvillaea antarctica as a function of initial
metal ion concentration and pH. We determined an equi- Keywords Biosorption  Copper  Brown algae  Ion
librium time of 120 min and a maximum biosorption per- exchange  FTIR
formance at pH 5.0. The isotherms data at optimum pH
best fitted with the Dubinin–Radushkevish model, showing
a maximum capacity for Cu(II) biosorption of 1 Introduction
1.44 mmol g-1. A quantitative analysis by potentiometric
titrations was performed to determine different acid–base Biosorption is a sorption process, where a biomaterial or a
properties of the biomass surface and a FTIR analysis was biopolymer is engaged as sorbent. The phenomenon of
performed to identify the key functional groups present on biosorption was observed in early 1970s when radioactive
the biomass. We found characteristic peaks corresponding elements (also heavy metals) present in wastewaters released
mainly to amine, carboxylate, hydroxyl and sulphonate from a nuclear power station were found to be concentrated
moieties. A time course FTIR analysis of interaction by several algae (Davis et al. 2003). Research and laboratory
between the biomass and Cu(II) in aqueous solution was studies have demonstrated that biosorption is a promising
performed to estimate sequential steps of functional groups and cost-effectiveness technology for the removal of heavy
interactions, and a SEM analysis was performed to observe metals from aqueous solutions (He and Chen 2014). Com-
the textural properties of D. antarctica biomass surface. pared with conventional methods to treat wastewaters like
The value of the total cation exchange capacity supports an chemical reduction, ion exchange, precipitation, and mem-
ion exchange mechanism for the adsorption of Cu(II) by brane separation; biosorption technology possesses several
advantages: low operating cost, high efficiency in detoxify-
ing low concentrations of heavy metals, less amount of spent
biosorbent for final disposal, and no nutrient requirements
& Claudia Ortiz (Sheng et al. 2004). Many studies have shown that dead
claudia.ortiz@usach.cl biomass (metabolically inactive) may be even more effective
1
Departamento de Biologı́a, Facultad de Quı́mica y Biologı́a,
than living one in sequestering heavy metals (Huang and Lin
Universidad de Santiago de Chile, Santiago, Chile 2015). An intense effort has been made to identify readily
2
Departamento de Ingenierı́a Geográfica, Facultad de
available non-living biomass with high performance for
Ingenierı́a, Universidad de Santiago de Chile, Santiago, Chile removing heavy metals. These biosorbents typically include
3 algae (Davis et al. 2003), fungi (Fomina and Gadd 2014),
Departamento de Quı́mica, Facultad de Ciencias, Universidad
Nacional de Colombia, Bogotá, Colombia bacteria (Wang and Chen 2009), and agricultural waste (Sud
4 et al. 2008). Among various biosorbents reported in the lit-
Departmento de Quı́mica, Facultad de Ciencias, Grupo de
Investigación en Sólidos Porosos y Calorimetrı́a, Universidad erature, marine algal biomass is identified as a promising one
de Los Andes, Bogotá, Colombia due to their high uptake capacities, low cost, renewability as

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646 Adsorption (2015) 21:645–658

well as the ready abundance of the biomass in many parts of Analytical grade reagents or superior grade, were used in
the world’s oceans (Davis et al. 2003). The cell wall extra- all experiments. Multielement Standard for ICP calibration
cellular matrix of brown algae generally contains three (1.000 mg L-1), HCl 37 %, HCl 30 %, HNO3 65 %,
mayor components: cellulose as structural support, alginic anhydrous methanol, NaOH, NH3NO3, KCl and CuSO4
acids and polymers (e.g., manuronic and guluronic acids) 2H2O were obtained from Merck Chemicals (Germany).
complexed with light metals such as sodium, potassium,
magnesium and calcium, and other polysaccharides (e.g.,
sulphated) (Davis et al. 2003; Romera et al. 2007). Alginates 2.2 Biomass preparation
and sulphate polysaccharides have been reported as the
predominant molecular components with active groups in Fresh seaweed samples were washed with distilled water to
brown algae (Sheng et al. 2004). Biosorption of heavy metals remove salt and impurities, and then were dried at 40 °C in
involves several mechanisms that differ qualitatively and an oven (Memmert, Germany) for 72 h. The dry material
quantitatively according to the chemical species used, the was then cut into small pieces before being ground using a
origin of the biomass, and its processing procedure (Holan hammer mill. Dry grounded biomass was sieved at
and Volesky 1995). Algae biomass possesses several 500–1000 lm of particle size, and the material was used
chemical groups that can attract and sequester metals: acet- for all the experiments.
amide, amine, amide, sulfhydryl, sulphate, and carboxyl
(Davis et al. 2003). This chemical diversity originates a 2.3 Determination of optimum pH
combination of mechanisms for the capture of the metals,
including electrostatic attraction, complexation, ion In order to investigate the effect of pH on Cu(II)
exchange, covalent binding, Van der Waals attraction, biosorption, solutions of 50 mg L-1 Cu(II) at different
adsorption and microprecipitation (Raize et al. 2004). The initial pH values (2, 3, 4, 5 and 5.5) were prepared using
scarce information about metal biosorption mechanisms of CuCl22H2O. The pH was adjusted with 0.1 M NaOH or
brown algae biomass reduces the chances of using this 0.1 M HCl. 50 mg of biomass were added to flasks and
material as a competitive product when compared to tradi- mixed with 50 mL of Cu(II) solution at different pH. The
tional well-known metal-removal processes (Fourest and flasks were shaken for 4 h at 160 rpm at room temperature
Volesky 1996). (20 ± 1 °C) with a rotatory shaker (Cole Parmer, USA).
Durvillaea antarctica is a brown macroalgae of the Then 5 mL of each sample was filtered with a PVDF
order of the fucals, highly represented in the South Pacific 0.45 lm membrane and was poured into a propylene tube
Chilean coast (Vasquez 2008). D. antarctica is a main before adding 10 mL of an acid solution (7,5 %
component of complex environments for the development hydrochloric acid and 6 % nitric acid). The acid treated
of many marine species, and represent a potential bioma- samples were analyzed by Atomic Absorption Spectrom-
terial for biosorption processes. The biomass of D. etry (FA-AAS) (Thermo Solar 5, Thermo Scientific,
antarctica is highly available. Its current use is mainly USA).
culinary and for the production of alginates extracts. The
purpose of this study is to understand the mechanisms
underlying Cu(II) biosorption by the dead biomass of the 2.4 Determination of equilibrium time
brown macroalgae D. antarctica. We characterized the
biosorption kinetics, pH influence, equilibrium isotherms, 50 mg of biomass was weighted in a propylene tube and
general acid–base properties, ion exchange properties and 50 mL of a 50 mg L-1 Cu(II) solution adjusted to pH 5
the key functional groups that interact with Cu(II), in order was added. Flasks were shaken at 160 rpm at room tem-
to establish the critical parameters that influence the pro- perature (20 ± 1 °C). Samples were taken at 5, 10, 30, 60,
cess as a first approach to elucidate the Cu(II) biosorption 120 and 240 min. Samples were analyzed in the same way
mechanism in D. antarctica dead biomass. as mentioned in Sect. 2.3.
The metal uptake equilibrium qe (mmol g-1) was cal-
culated according to Eq. 1:
2 Experimental VðCi  Ce Þ
qe ¼ ð1Þ
1000ms
2.1 Biomass and materials
where V is the volume of the copper solution (mL),
Durvilaea antarctica brown seaweed biomass was freshly Ci and Ce are the initial and equilibrium concentration of
collected directly from the Chilean coast (33°230 S 71° copper in solution (mmol L-1) and ms is the biomass
410 O, El Tabo, V region, Chile) in September 2013. (g).

123
Adsorption (2015) 21:645–658 647

2.5 Biosorption experiments assumptions, Langmuir are represented by the following


equations:
The biosorption experiments were carried out in 50 mL qm  bL  C e
flasks containing 50 mL of Cu(II) solutions at different qe ¼ ð2Þ
1 þ bL  Ce
concentrations, and 50 mg of algae biomass. The initial
concentrations of Cu(II) ranged between 7.5 and 300 mg Rearranging the Eq. 2, a linear expression can be derived
L-1 at pH 5. The solutions were maintained in agitation at as function of Ce:
160 rpm during the time required to reach the equilibrium    
1 1 1 1
(previously determined as described in Sect. 2.4) at ¼  þ ð3Þ
qe bL  qm Ce qm
20 ± 1 °C. After reaching the equilibrium, the solutions
were filtered through a 0.45 lm PVDF membrane. The where qm (mmol g-1) is the maximum sorption capacity,
filtrate was analyzed to determine the Cu(II) concentration qe (mmol g-1) and Ce (mmol L-1) the equilibrium copper
at the end of the process. The equilibrium data were concentration, respectively, in the solid and in the liquid
adjusted to Langmuir, Freundlich, Dubinin–Radushkevich phase, and bL the equilibrium constant related to the energy
and Elovich isotherm models to determine the maximum of sorption (L mmol-1).
capacity of the biomass to adsorpt Cu(II) and to describe The essential features of the Langmuir isotherm may be
the biosorption phenomena on D. antarctica. The selection expressed in terms of equilibrium parameter RL, a dimen-
of this particular models were based on the need to explain sionless constant, referred to as separation factor or equi-
the complex phenomena of biosorption, to describe the librium parameter (Zheng et al. 2009).
process in terms of the nature of the interactions (physical 1
or chemical, Dubinin–Radushkevich model) the way of RL ¼ ð4Þ
1 þ bL  Co
depleting binding sites and the heterogeneity of the sorbent
(Langmuir, Freundlich and Elovich models). The selected where C0 is the adsorbate initial concentration (mmol L-1),
isotherm models are commonly applied to the biosorption bL is the constant related to the energy of adsorption
characterization on algae biomass (Davis et al. 2003; (Langmuir constant). RL value indicates the adsorption
Fomina and Gadd 2014; Hanbali et al. 2014). Biosorption nature of unfavorable if RL [ 1, linear if RL = 1, favorable
often need than one more model to describe the sorption if 0 \ RL \ 1 and irreversible if RL = 0.
process (Loukidou et al. 2004; Gautam et al. 2015).
Equations and models are described as follows: 2.5.2 The Freundlich isotherm model

The Freundlich equilibrium isotherm equation is an


2.5.1 Langmuir isotherm model empirical equation used for the description of multilayer
adsorption with interaction between adsorbed molecules.
This model describes quantitatively about the formation of The model is applicable to the adsorption on heterogeneous
a monolayer adsorbate on the outer surface of the adsorbent surfaces by a uniform energy distribution and reversible
and after that no further adsorption takes place. The adsorption. The Freundlich equation implies that adsorp-
Langmuir represents the equilibrium distribution of tion energy exponentially decreases on the finishing point
adsorbate between the solid and liquid phases. The Lang- of adsorptional centres of an adsorbent. The Freundlich
muir adsorption isotherm the most widely used isotherm constants are empirical constants depends on many envi-
for the biosorption of pollutants from a liquid solution ronmental factors. The value of 1/n ranges between 0 and 1
based on the following hypotheses. (1) Monolayer indicates the degree of non-linearity between solution
adsorption. (2) Adsorption takes place at specific homo- concentration and adsorption. If the value of 1/n is equal to
geneous sites on the adsorbent. (3) Once a pollutant 1, the adsorption is linear (Yu and Liu 2008).
occupies in a site; no further adsorption can take place in 1=n
that site. (4) Adsorption energy is constant and does not qe ¼ KF  Ce ð5Þ
depend on the degree of occupation of an adsorbent’s Rearranging the Eq. 5, a linear expression can be derived
active centers. (5) The strength of the intermolecular as function of Ce (5):
attractive forces is believed to fall off rapidly with distance.
(6) The adsorbent has a finite capacity for the pollutant. (7) 1
log qe ¼ log KF þ  log Ce ð6Þ
All sites are identical and energetically equivalent. (8) The n
adsorbent is structurally homogeneous. (9) There is no where KF is the Freundlich constant (mmol g-1 (L
interaction between molecules adsorbed on neighboring mmol-1)1/n) representing the maximum capacity of
sites (Rangabhashiyam et al. 2014). Based upon these biosorption and Ce (mmol L-1) the equilibrium copper

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648 Adsorption (2015) 21:645–658

concentration, respectively, in the solid and in the and 1/n biomass) was quantitatively expressed in a measured
the Freundlich parameter. property known as the cation exchange capacity (CEC).
The CEC was measured by cation displacement as
2.5.3 The Dubinin–Radushkevich isotherm model described by Hawari and Mulligan (2006). 20 mL of 1 mol
L-1 of potassium acetate was added to 1.0 g of the algal
The Dubinin–Radushkevich isotherm can be applied for biomass in a 50 mL centrifuge conical tube. Samples were
the estimation of apparent free energy and the character- shaken for 30 min at 75 rpm and then were centrifuged for
istics of adsorption (Nguyen and Do 2001). This isotherm 10 min at 65039g. The supernatant was discarded, and the
model is temperature dependent, when the adsorption data process was repeated. 20 mL of distilled water was added
at different temperatures plotted as a function of logarithm to the algal material of each sample, and then were shaken
of amount adsorbed versus the square of potential energy, for 30 min at 75 rpm. The samples were centrifuged for
all suitable data will lie on the same curve: 10 min at 65039g and the supernatant was discarded. This
ðKe Þ 2 process was performed twice before adding ammonium
qe ¼ qm ð7Þ
acetate (25 mL, 1 mol L-1) to the material. After that, the
where K is the Dubinin–Radushkevich isotherm constant samples were shaken for 30 min at 75 rpm and then cen-
related to the adsorption energy (mol2 J-2), qm is the the- trifuged for 10 min at 65039g. The clear supernatant was
oretical isotherm saturation capacity (mmol g-1), e is the collected in a clean 50 mL centrifuge tube. This process
Polanyi potential, calculated from Eq. 8: was repeated twice by pouring the clear supernatant into
1 the same centrifuge tube. The concentration of potassium
e ¼ R  T  lnð1 þ Þ ð8Þ was measured by FA-AAS. The value for the concentration
Ce
of potassium was equal to the CEC. In order to investigate
where R is the gas constant (8.314 J mol-1K-1) and T is which intrinsic cations were significantly released when the
the temperature (K). The mean free energy E (kJ mol-1) of biomass is in contact with Cu(II) in solution, the dynamics
sorption can be found by using K values represented in of Cu(II) biosorption and release of the biomass intrinsic
Eq. 9. cations Ca(II), K(I), Mg(II) and Na(I) was evaluated. The
1 tracking of cation released and copper adsorbed was
E ¼ pffiffiffiffiffiffi ð9Þ determined as follows: samples of 50 mg of the biomass
2K
was weighted on 50 mL propylene flasks and 50 mL of
Values of qm and K are calculated from the intercept and Cu(II) solutions at different concentrations (7.5–300 mg
slope of the plot by plotting ln qe versus e2. L-1) pH 5, were added to the flasks. The flasks were
shaken at 160 rpm and room temperature (20 ± 1 °C) and
2.5.4 The Elovich isotherm model the saturation time was determined. The samples taken at
different times: 5, 10, 30, 60, 120 and 240 min were acid
The Elovich model is based on a kinetic principle assuming treated (as described in Sect. 2.3) for elemental analysis by
that the adsorption sites increase exponentially with ICP-OES (Optima 2000DV, Perkin Elmer, USA). Samples
adsorption, which implies a multilayer adsorption (Ham- were analyzed in the same way as mentioned in Sect. 2.3.
daoui and Naffrechoux 2007). It is expressed by the fol- All experiments were carried out in triplicate.
lowing equation:
qe ð qe Þ 2.7 Biomass carboxyl blocking treatment
¼ KE  Ce qm ð10Þ
qm
A portion of 5 g of D. antarctica biomass was suspended in
where KE is the Elovich equilibrium constant (L mmol-1) 250 mL of anhydrous methanol and 1.2 mL concentrated
and qm is the Elovich maximum adsorption capacity hydrochloric acid was added to the suspension. The reac-
(mmol g-1). If the adsorption obeys Elovich equation, tion mixture was stirred a magnetic agitation plate for 6 h
Elovich maximum adsorption capacity and Elovich con- at 250 rpm. After the agitation, the treated biomass was
stant can be calculated from the slopes and the intercepts of washed 20 times with milliQ water. Then the biomass was
the linear plot ln (qe/Ce) versus qe. dried for 72 h at 40 °C in an oven. This treatment causes
esterification of the carboxylic acids present on the biomass
2.6 Cation exchange capacity and light metal
surface. The reaction occurs as follows: RCOOH þ
intrinsic ion mobilization Hþ
CH3 OH ! RCOOCH3 þ H2 O: The metal binding ability
The exchange capacity of the biomass to hold cations (i.e. of carboxyl groups should be significantly reduced as a
the number of negatively charged sites per gram of result of esterification (Gardea et al. 1990).

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Adsorption (2015) 21:645–658 649

2.8 Acid–base characterization 2.10 Scanning electron microscopy (SEM)

The pretreatment of samples and titration procedures were SEM analyses were performed on an environmental SEM
based on Murphy et al. (2007), with modifications: D. (JEOL JSM-6490LV, Jeol Ltd, Tokio, Japan). The ana-
antarctica dried biomass (5 g) was treated with 250 mL of lytical conditions were: backscattered electrons mode
0.1 M of HCl and maintained in agitation (250 rpm) for (BSE), magnification of 50 to 92000, electron beam
6 h at room temperature. Then the biomass was filtered and voltage of 20 kV, work distance of 10.0–10.4 mm, spot
washed 20 times with distilled water. The obtained proto- size of 4.0–4.8 nm, pressure of 0.90 Torr, and temperature
nated biomass was oven dried at 40 °C for 72 h. For each of 20 °C. The biomass samples were raw native biomass,
titration, 100 mg of protonated biomass was dispersed in protonated biomass (see Sect. 2.8 to see the description of
100 mL of NaCl solution at different concentrations (1, 10 preparation of this sample) and protonated biomass treated
and 100) and agitated at 250 rpm for 15 min. The NaCl with 100 mg L-1 of Cu(II) for 4 h. This technique was
solutions were made with boiled distilled water to elimi- used to examine the algae cell surface changes.
nate diluted CO2. The titration and pH measurements were
performed by an automatic titrator (TitroLine Alpha Plus
20, Schott, Germany). After the titration begun, the sus- 3 Results and discussion
pension was maintained 3 min under a nitrogen steam and
2 min with agitation. The titration was carried out by 3.1 Determination of optimum pH and equilibrium
stepwise addition of 0.01 mL of standardized NaOH 0.1 M time for Cu(II) biosorption
to the suspension stirring under a nitrogen atmosphere.
Titrations were performed under three different concen- The study of biosorption at different pH showed that the
trations of NaCl (1, 10 and 100) to determinate the Point of best performance was achieved at pH 5.0 (Fig. 1). At this
Zero Net Proton Charge (PZNPC) to estimate different pH the Cu(II) cations are soluble, and the observed phe-
acidities at the biomass surface and to determine apparent nomena is totally associated to a sorption phenomena. In
pKa’s of the biomass. The concentration of acidic func- this experiment is possible to observe that D. antarctica
tional groups was extrapolated from the combination of the biomass has a better performance at pH 2.0 than at pH 3.0.
titration curve of protonated biomass and the Gran curve as This can be explained by the fact that sulphonate groups
previously proposed (Brunelot et al. 1989). Apparent pKa’s usually contribute to metal binding at a pH nearly 1.0–2.5
were extrapolated from first derivative of the titration curve (Sheng et al. 2004). Initial pH values of 2.01 and 3.02
and the titration curve (Murphy et al. 2007). A sample of increase to 2.36 and 3.59 at equilibrium, respectively. pH
protonated biomass presaturated with 100 mg L-1, and the values of 4.00, 5.00 and 5.51 decreased at equilibrium to
biomass treated for carboxyl blocking were titrated on 3.94, 4.81 and 4.43 respectively. A more detailed discus-
1 mM of NaCl to analyze the reduction of acid groups after sion on pH changes and their relationship with intrinsic
the biosorption phenomena and to analyze the reduction of cations is presented in Sect. 3.7. Equilibrium experiments
acid groups after carboxyl blocking. All potentiometric were carried out at pH 5.0, where maximum uptake
titrations were carried out in triplicate. capacity was achieved and metal precipitation was

2.9 Fourier-transform infrared spectroscopy 0.3

(FTIR) analysis

Durvillaea antarctica biomass samples without any


qe (mmol g-1)

0.2
treatment (raw biomass), were treated with HCl 0,1 M
(protonated) and samples preprotonated were treated with
100 mg L-1 of Cu(II) solutions and prepared in pellets of
KBr at 5 %. After the preparation, the pellets were 0.1

examined with a Diffuse Reflectance Fourier Transform


Infrared Spectrometer (DRIFTS) (Nicolet Impact 410,
Thermo Electronic Corporation, USA). The measurements 0.0
were taken in a range of 400–4000 cm-1 at 32 scans.
5
2

5.
pH

pH

pH

pH

pH

This technique was used to elucidate the chemical char-


acteristics relevant to metallic ion sorption by the algal Fig. 1 Effect of pH on Cu(II) biosorption on D. antarctica dead
biomass. biomass. Data represent an average of the experiments (n = 3)

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650 Adsorption (2015) 21:645–658

0.20 obtained by this model was 1.44 mmol g-1. The maximum
capacity obtained from the Dubinin–Radushkevish was
coherent with the experimental observations of maximum
0.15
biosorption at maximum concentration (1.34 mmol g-1).
qe (mmol g-1)

The constant for the adsorption energy at 20 °C was


0.10 6.09 9 108 mol2 J-2. The value of the mean sorption
energy (E) gives information about chemical and physical
sorption phenomena. The E value ranges from 1 to
0.05
8 kJ mol-1 they are associable to physical sorption and
from 8 to 16 kJ mol-1 for chemical sorption (Zheng et al.
0.00 2009). In the case of D. antarctica, the E value found was
0 100 200 300 2.87 kJ mol-1 indicating that a physisorption process
Time (min) occur when Cu(II) cations interact with the biomass. The
Elovich isotherm model was the second best-fit model
Fig. 2 Kinetics of Cu(II) biosorption on D. antarctica dead biomass.
Data represent an average of the experiments (n = 3) obtaining an r2 value of 0.930. The good fitting of Elovich
model partially explain the interaction between Cu(II)
cations and D. antarctica biomass in terms of the com-
avoided. The time needed to reach the equilibrium in the plexity of the matrix on the distribution of interaction sites,
system was 120 min approximately. Figure 2 shows that describing the system as a multilayer adsorption system
the aqueous system start with a rapid initial sorption in and not a monolayer as the Langmuir model explain. The
which after 10 min, a 91.6 % (0.14 mmol g-1) of the total interpretation obtained by the two models indicates that the
Cu(II) biosorbed at 240 min (0.15 mmol g-1) is achieved, Cu(II) biosorption on D. antarctica biomass responds as a
followed by a period of much slower uptake at the final physisorption phenomena in an heterogeneous multilayer
time studied. system. A comparison between the results of this work and
the literature shows that D. antarctica has a higher sorption
3.2 Biosorption isotherms capacity to Cu(II) cations. The maximum capacity to bio-
sorpt Cu(II) by D. antarctica biomass obtained from the
The biosorption experiments were carried out at pH 5.0 and Dubinin–Radushkevish model (1.44 mmol g-1) is one of
the results are shown in Fig. 3. The equilibrium data were the highest values observed when the result is compared
analyzed using the four proposed models and fitted to their with copper biosorption capacities of other brown algae
corresponding linearized forms. The calculated isotherms (Table 2).
parameters are given in Table 1. The best fit equilibrium
model was determined based on the linear regression cor- 3.3 Potentiometric titrations
relation coefficient r2.
The Dubinin–Raduskevish model (Fig. 4) fits well to the The various amounts of acidic groups in the biomass and
data, with an r2 value of 0.974. The maximum capacity their corresponding pKa values were evaluated identifying
the inflection points of the titration curves and the first
1.5
derivative plots. The amount of strong acidic groups
(0.03 mmol g-1) was determined from the first peak in the
first derivative plot (results not shown) while the total
amount of acidic groups was determined from the final
1.0 peak (0.45 mmol g-1). The quantity of weak acidic groups
qe (mmol g-1)

was then calculated by difference (0.42 mmol g-1). Once


these values were established, the corresponding pKa val-
ues were identified from the original titration curve. The
0.5
pKa values obtained were 3.60, 3.94, 4,31, 4.86, 5.73 and
8.44. Values in the range of 3.5–5.5 may be attributed
mainly to carboxyl groups (Yesim and Tülin 2001). Sul-
0.0 phonate groups usually only contribute to metal binding at
0 1 2 3 4 low pH and their typical pKa values ranged 1.0–2.5 (Sheng
Ce (mmol L-1)
et al. 2004). Apparent pKa values in this range were not
Fig. 3 Biosorption isotherm of Cu(II) on D. antarctica dead biomass detected by titration, but the presence of sulphonate groups
at pH 5.0. Data represent an average of the experiments (n = 3) on the seaweed surface was later confirmed by FTIR

123
Adsorption (2015) 21:645–658 651

Table 1 Calculated parameters from the linearization of isotherms models


Langmuir isotherm Freundlich isotherm
-1 -1 -1 2
qm (mmol g ) bL (L mmol ) RL (range of Co: 7.5–300 mg L ) r 1
n
n KF r2

1.85 0.74 0.153–0.004 0.878 1.24 0.81 3.19 0.883


Elovich isotherm Dubinin–Radushkevich isotherm
-1 1 2
qm (mmol g ) KE (L mmol - ) r qm (mmol g-1) K (9108 mol2 J-2) E (kJ mol-1) r2

1.73 1.06 0.930 1.44 6.09 2.87 0.974

1
role in binding Cu(II) at very high pH values (Davis et al.
2003). Algal proteins have also been known to interact with
0 metal ions, particularly between pH 6–9, and protonated
amino groups have a pKa value of around 8 (Percival and
-1 MacDowell 1968). It was shown that D. antarctica biomass
contained a high number of acidic functionalities (both
Ln qe

-2
total and weak) on the seaweed surface, showing the
-3
complexity in composition of the surface. The point of zero
net proton charge (PZNPC) was calculated as the media
-4 value of the intercepts of the different curves of titration at
different ionic strengths (results not shown), obtaining a
-5 value of 5.54. D. antarctica saturated with 100 mg L-1 of
0 2×107 4×107 6×107 8×107
Cu(II) was titrated to evaluate the availability of acid
ε2 groups after the biosorption, showing a value of
0.2 mmol g-1 of total acid groups, representing a reduction
Fig. 4 Linear expression of Dubinin–Radushkevish isotherm model
for Cu(II) biosorption on D. antarctica dead biomass. Data represent of an 55.6 % in the availability of this chemical groups.
an average of the experiments (n = 3)
3.4 Identification of functional groups by infrared
analysis
analysis (see Sect. 3.4). Hydroxyl groups in seaweed cell
wall polysaccharides are considerably weaker than car- The FT-IR analysis was used for detecting vibration fre-
boxyl groups and therefore they may only interact with quency changes of native moieties in the algal sorbent.
cations at a higher pH that usually occurs at pH over 10. This can be used to identify functional groups present in
Therefore, surface hydroxyl groups only play a significant the surface on the native biomass, comparing treatments

Table 2 Comparison of Cu(II)


Brown algae specie pH qm (mmol g-1) References
biosorption maximum
capacities of brown algae and Ascophyllum nodosum 4.0 0.91 Romera et al. (2007)
D. antarctica biomass
Durvillaea antarctica 5.0 1.44 This work
Fucus serratus 5.5 1.60 Ahmady-Asbchin et al. (2008)
Fucus spiralis 4.0 1.10 Romera et al. (2007)
Fucus vesiculosus 5.0 1.66 Mata et al. (2008)
Padina sp. 5.0 1.14 Sheng et al. (2004)
Sargassum sp. 5.0 0.99 Sheng et al. (2004)
Sargassum sp 5.5 1.13 Karthikeyan et al. (2007)
Sargassum filipendula 4.5 0.89 Davis et al. (2000)
Sargassum filipendula 4.5 1.32 Kleinübing et al. (2011)
Sargassum fluitans 4.5 0.80 Davis et al. (2000)
Sargassum vulgarie 4.5 0.93 Davis et al. (2000)

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652 Adsorption (2015) 21:645–658

with Cu(II) solutions at different concentrations or differ- bands of proteins, polymeric compounds and carboxylic
ent times of contact with the metal. It is well known that acid groups, which are able to react with cations in aqueous
the cell wall extracellular matrix composition of algal solutions.
biomass contains a large number of complex organic
components such as proteins, lipids, carbohydrate polymers 3.5 Time course infrared analysis
(cellulose, xylane, mannan, alginic acid, fucoidans, etc.)
and inorganic ions (Ca2?, Mg2?, K?, Na?, etc.) (Davis The time course IR analysis of the interactions of Cu(II)
et al. 2003). The IR characterization of protonated biomass ions with the protonated biomass gives information to
made possible to found the functional groups and made a establish the relative sequential order of the interactions
comparison with the metal loaded biomass, without inter- of the different moieties in the algal biomass surface with
ference of the intrinsic inorganic ions. The corresponding the metal. A band shifting superior than 10 cm-1 (both
FTIR spectrum of D. antarctica protonated dead biomass is left and right shifts) in wave number of dominant peaks
presented in Fig. 5. The most specific peaks found are a can be associated with the loaded metal and this shift in
broad band centered at 3424 that can be attributed to the wavelength showed that there was a metal binding
stretching modes of amino (–NH2) and alcohol groups process taking place on the surface of the algae and the
(–OH), respectively (Kleinübing et al. 2010). According to particular functional group (Kleinübing et al. 2010).
Svecova et al. (2006), the presence of amine groups is Different band shifting’s was observed. At 5 min of
usually confirmed by the presence of a shoulder around interaction, the stretching band of –NH and –OH did not
3265 cm-1, this peak is frequently hidden by vibrations of shown changes, but at 10 min the band shifts from 3424
–OH groups and appeared at 3255 cm-1 in D. antartica to 3435 cm-1 and maintain the same value up to the last
biomass. The signal at 2926 cm-1 is related to C–H point of the kinetics (240 min). The other –NH stretching
stretching modes and the asymmetric stretching of car- band (1530 cm-1) shifted at 10 min to 1520 cm-1 and
boxylate O–C–O vibration at 1625 cm-1. The band at maintained this value until the last point. This two bands
1383 cm-1 may be due to C–OH deformation vibration shifts show that the amine moieties at 10 min interact
with contribution of O–C–O symmetric stretching vibration with Cu(II) ions. The band corresponding to O–C–O
of carboxylate group (Mathlouthi and Koenig 1986). The (1625 cm-1) change at 30 min (1634 cm-1) and was
bands at 1530–1560 cm-1 can be assigned to amino groups maintained to the end of the run. The flexion of the –OH
(NH stretching) (Chen and Yang 2006). A band at group of the COOH moieties (1384 cm-1) has a shift at
1530 cm-1 was found for D. antarctica. The bands at 5 min and maintained its value of 1374 cm-1. This two
about 1253 cm-1 representing –SO3 stretching are mainly shifts of carboxyl moieties may be seen at 30 min,
present in sulfonic acids of polysaccharides, such as probably because the two oxygen of the COO- moieties
fucoidans (Sheng et al. 2004). The band at 1030 cm-1 is works as a bidentate group to interact with Cu(II) ions
assigned to the C–O stretching of alcohol groups (Sheng (Fourest and Volesky 1996). This can be interpreted as
et al. 2004). The results of FT-IR spectrum confirm the the carbonyl oxygen in the COO- playing a mayor role at
presence of different functional groups and characteristic a later times (30 min) compared with the hydroxyl group
which interacts in the first 5 min, giving evidence of a
bidentate interaction at short times. The band corre-
sponding to C–OH stretching changes at 5 min from 1030
100 at 1041 cm-1 and increases the shift at 1052 cm-1 to the
end, supporting the fact that hydroxyl groups of the car-
boxyl group start to work at the beginning of the
90
Transmitance (%)

biosorption. The band corresponding to –SO3 groups


1253
change at 10 min from 1253 to 1241 cm-1 showing an
2926 interaction of this functional moieties at early times. It
80
1383 1030 can be deduced that the Cu(II) biosorption by D.
3255 1625 antarctica biomass depends on the chemical groups pre-
70 sent in the surface of the matrix that will be available to
3424 sequester Cu(II) cations. These groups initially involve
hydroxyl groups, then carboxyl groups and lately amine
60 and sulphonate groups. No significant band movement
4000 3000 2000 1000
was observed after 30 min in all shifts, which is corre-
Wavenumber (cm-1)
lated with the saturation equilibrium observed (see
Fig. 5 FTIR spectrum of D. antarctica protonated dead biomass Sect. 3.1).

123
Adsorption (2015) 21:645–658 653

3.6 Carboxyl blocking effect on biosorption 0.8

Since it is consider that carboxyl groups (weak acid group)


0.6
are primarily responsible for metal sorption in several

qe (mmol g-1)
brown seaweeds, it was expected that D. antarctica would
exhibit less biosorption if this functionality was blocked. 0.4
Despite this fact, the complexity of alginates polysaccha-
rides structures in brown algae could be different in a
0.2
particular brown algae respect to the availability of car-
boxyl moieties, because the main constitution of this kind
of polysaccharides is by blocks of guluronic acids and 0.0
manuronic acids (Davis et al. 2003). Haug (1961) found 0 100 200 300

when more guluronic acid is present in alginate polysac- Time (min)


charides, more affinity exist to divalent cations, because Raw biomass Carboxyl blocking treated
they generate more sites to scavenging cations. Consider- biomass
ing this information, it was interesting to demonstrate the
Fig. 6 Effect on biosorption kinetics of carboxyl blocking treatment
contribution of carboxyl groups as the main responsible for on D. antarctica biomass at pH 5.0. Data represent an average of the
the biosorption of Cu(II) cations and how the biosorption experiments (n = 3)
of the element was affected after blocking experiments.
The blocking treatment applied to D. antarctica biomass
metallic cations and biosorption of them onto the cell
generated a reduction in the Cu(II) biosorption capacity
surface (Yun et al. 2001). We investigated the effect of pH
from 0.97 ± 0.01 to 0.55 ± 0.01 mmol g-1, representing
on the quantity of light metal ions released from the bio-
a 43.3 % of biosorption reduction. This result is coherent
mass during the biosorption process. The influence of pH
with results published by Fourest and Volesky (1996), who
on the Cu(II) biosorption capacity of the biomass and the
showed that Sargassum fluitans biomass reduce in 45.3 %
quantity of light metal ions released are shown in Fig. 7.
the Cd(II) biosorption at pH 4.5 when carboxyl moieties
The biosorption capacity of Cu(II) cations increased with
were blocked. The potentiometric titrations showed that the
the pH. The initial concentration of Cu(II) for all the
total acid groups were significantly reduced after the
experiments was 0.78 mmol L-1. The changes in Cu(II)
blocking treatment, from 0.45 to 0.34 mmol g-1, repre-
biosorbed and the light metal cations amount released are
senting a 24 % approximately of reduction in the avail-
summarized in Table 3.
ability of acid groups. As seen in other brown algae,
carboxyl groups play an important role in the biosorption
of heavy metals in brown algae (Davis et al. 2003). The
adsorption kinetics of native and the treated D. antarctica
biomass were compared at pH 5.0. It seems that the native
0.2
biomass is rapidly depleted by Cu(II) almost in the same
way as treated biomass, but after 20 min the treated bio-
qe (meq g-1)

mass is saturated slowly and with a final lower capacity in


0.0
reducing Cu(II) concentration (Fig. 6). This result is cor-
related with the time course FTIR studies (see Sect. 3.5), in
relation with two signals of the oxygen in the COO-
-0.2
moieties, where the carbonyl oxygen was shifted at 30 min.

3.7 Ion exchange with alkali and alkaline earth


metal ions at different pH -0.4
2.0 3.0 4.0 5.0 5.5
pH
As it was mentioned before, the pH is one of the most Mg (meq g) Ca (meq g) K (meq g)
important parameters affecting biosorption. At low pH, a Na (meq g) Cu (meq g)
high concentration of protons in the solution competes with
metal cations in forming bonds with the active sites (the Fig. 7 Alkali and alkaline earth metal ions desorption and simulta-
neous Cu(II) biosorption for D. antarctica biomass at different initial
functional groups) on the algal surface. As pH increases,
pH. The initial concentration for all experiments was 50 mg L-1.
more ligands with negative charges (carboxyl, hydroxyl Positive values represent sorption of the correspondent cations and
groups, etc.) are exposed with a subsequent attraction of negative values represent desorption phenomena

123
654 Adsorption (2015) 21:645–658

Table 3 Effect of pH in Cu(II) biosorption on D. antarctica biomass and light metal cations released at different initial pH
pH Cu(II) biosorbed Light metal ion released (meq g-1) Order of cation released
(meq g-1)
K(I) Na(I) Ca(II) Mg(II) Sum of
cations

2.0 0.03 ± 0.01 0.36 ± 0.01 0.21 ± 0.00 0.08 ± 0.00 0.12 ± 0.00 1.35 ± 0.02 K(I) [ Na(I) [ Mg(II) [ Ca(II)
3.0 0.01 ± 0.00 0.07 ± 0.00 0.03 ± 0.00 0.13 ± 0.00 0.09 ± 0.00 0.41 ± 0.00 Ca(II) [ Mg(II) [ K(I) [ Na(I)
4.0 0.10 ± 0.00 0.11 ± 0.00 0.15 ± 0.01 0.05 ± 0.00 0.11 ± 0.00 0.68 ± 0.02 Na(I) [ K(I) [ Mg(II) [ Ca(II)
5.0 0.26 ± 0.00 0.04 ± 0.00 0.12 ± 0.00 0.03 ± 0.00 0.07 ± 0.00 0.44 ± 0.01 Na(I) [ Mg(II) [ K(I) [ Ca(II)
5.5 0.08 ± 0.04 0.11 ± 0.01 0.23 ± 0.01 0.04 ± 0.01 0.09 ± 0.03 0.82 ± 0.07 Na(I) [ K(I) [ Mg(II) [ Ca(II)
Coefficient of 103.7 90.3 53.6 56.2 22.3 55.9
variation (%)
All experiments were performed at the same initial Cu(II) concentration (0.78 meq g-1). The coefficient of variation was calculated considering
the experimental values at all pH for both, cation released and copper biosorbed

During the biosorption process of Cu(II), at pH 2.0, 4.0 biosorption process to 3.94, 4.81 and 4.43, causing the
and 5.5 alkaline metals (K(I) and Na(I)) was mainly des- increase of H30? ions in the solution, which favored the
orbed than alkaline earth metals (Ca(II) and Mg(II)) and, at cation exchange with microelement cations (Fig. 8). At
pH 3.0, the opposite occurs. At pH 5.0 no clear predilection low pH, the biosorption occurs to a very low extent because
to alkaline or alkaline earth metal desorption was see it. At the functional groups are protonated. As the pH increases,
high pH’s, Na(I) was clearly the main ion desorpted from more functional groups become deprotonated and thus
the biomass. In a general context, the sum of Na(I), K(I), available for binding metal cations or to exchange with
Ca(II), and Mg(II), released from the biomass has a ten- intrinsic cations. At pH 5,0 the bonds of the protons with
dency to decrease with an increase of the pH (Table 3). functional groups are weaker and the groups easily release
This result shows that at pH 2.0 and 3.0 (higher H30? the protons into the solution, which favors the binding of
content) the biomass release between 40 and = 48 times the metal cations. It could be deduced that the ion exchange
more light metal cations than the Cu(II) ions bounded, between the copper ion and the intrinsic cations occurs
seven times more at pH 4.0, an almost equal proportion at more favorably at pH nearly 5.0.
pH 5.0 (1.7 times) and eleven times more at pH 5.5. There
is no clear explanation to describe why a mayor release of 3.8 Ion exchange with alkali and alkaline earth
total cations is observed at pH 5.5 compared with pH 5.0 metal ions at different Cu(II) initial
(where the maximum biosorption capacities were concentrations
observed). In order to check if the mass of Cu(II) cations
bound and light metal cations released from the biomass In the literature is reported that metal cations from aqueous
differ significantly at the pHs values examined, coefficients solutions (e.g. Cu(II), Mn(II), Zn(II), and Co(II)) are bound
of variation were calculated. The differences were statis- to algae biomass by ion exchange, whereby acidic func-
tically significant since the variation coefficients values tional groups in the biomass exchange protons and/or
were higher than 10 % (Michalak and Chojnacka 2010) cations of alkaline earth metals (Ca(II), Mg(II)) and alkali
showing that the initial pH is an important factor in metals (Na(I), K(I)) with metal ions from the solutions
releasing the intrinsic cations (Table 3) for each light metal (Kratochvil et al. 1998). Light metals, which are present in
studied and the sum of light metal cations released. Mg(II) marine and freshwater environments, are naturally bound
was the cation released with less variation, which can be by functional groups on the surface of the algal cell wall. In
interpreted as Mg(II) was the light metal cation desorpted Sect. 3.7, the effects of pH (2.0, 3.0, 4.0, 5.0, and 5.5) on
less affected by the initial H30?concentration, followed by the mass of Cu(II) cations bound (with an initial concen-
Na(I), Ca(II) and finally K(I). During the biosorption of tration of 50 mg L-1) and light metal cations from the
Cu(II) cations, changes in the initial pH were also biomass were investigated. In the next experiment, the
observed. The initial pH values of 2.01 and 3.02 increased biosorption of Cu(II) cations by D. antarctica was studied
to 2.37 and 3.61, respectively. This means that the con- in the concentration range between 7.5 and 300 mg L-1 at
centration of H30? ions decreased in the solution (were pH 5.0. It was found that the mass of Cu(II) cations bound
strongly bound to the biomass), whereas the initial pH by the biomass of D. antarctica, qe (bound), and the mass
values of 4.00, 5.00 and 5.51 decreased after the of light metal cations (K(I), Na(I), Ca(II) and Mg(II))

123
Adsorption (2015) 21:645–658 655

0.15 6 capacity constants of the metal and on their concentrations


qH (meq g -1)
in the solution. If the concentration of a microelement ion
pH eq
0.10
that is supposed to be bound by the biomass is in excess in
q H+ (meq g-1)

comparison with the remaining ions, this ion will be

pH in eq
4 dominant in binding to the functional groups. In the case of
0.05
D. antarctica, among all light metal cations Na(I) was the
principal cation displaced, with a quantity of 0.47 meq g-1
0.00 released (representing an 33.5 % of total cation released).
2
Following a decreasing order, Mg(II) was the second
highest, followed by Ca(II) and K(I), with released
-0.05
2 4 6 amounts of 0.39 meq g-1 (28.1 %), 0.28 meq g-1
pH (initial) (20.2 %) and 0.16 meq g-1 (11.8 %), respectively. Despite
Fig. 8 Effect of initial pH on proton sorption and desorption on D.
this observations, the linear tendencies between the initial
antarctica biomass. The initial Cu(II) concentration was Cu(II) concentration range studied and the individual
0.78 mmol g-1. The data were obtained from batch experiments at intrinsic cation released show a better correlation and a
the equilibrium increased slope to the alkaline earth metal ions Ca(II) and
Mg(II). There is a better correlation in the release of this
released per gram of the biomass a (released) in the process cations when more Cu(II) ions are available in solution,
of biosorption was correlated, obtaining an r2 value of with the alkaline cations K(I) and Na(I) in solution, that are
0.984 for the sum of light metal ion released (Fig. 9). The released more slowly. This result show a more relevant role
same criteria is applied to the individual light metal cations of the alkaline earth metal in the ion exchange at all range
released, obtaining R values for K(I), Na(I), Ca(II) and of Cu(II) initial concentrations. The intrinsic ions constitute
Mg(II) corresponding to 0.867, 0.910, 0.938 and 0.959 93.5 % (1.31 ± 0.03 meq g-1 as the sum of the four
respectively. Therefore, the quantity of light metal ions cations) of all light metal ions released during the
released as we expect will tend to be equal to the equiva- biosorption process of Cu(II) at the maximum concentra-
lents of bound microelement ions at the maximum capacity tion of the cation. It can be said that, for D. antarctica
obtained (pH 5.0). biomass, Mg(II) cations followed by Ca(II) cations, play a
The explanation is that protons also influence the equi- dominant role in the cation exchange for the biosorption
librium of the process. Different metal ions are bound to process. The intrinsic ions constitute 93.5 %
the functional groups in the equilibrium state. The type of (1.31 ± 0.03 meq g-1 as the sum of the four cations) of all
metal ion bound to the groups depends on the values of the light metal ions released during the biosorption process of

1.0
Mg+2

Ca+2

K+
qe Cu+2 (meq g -1)

Na+

0.5 Σ(K+ , Na+ , Ca+2 , Mg+2 )

0.0
0.0 0.2 0.4 0.6
α intrinsic light metal ions released (meq g -1)

Fig. 9 Alkali and alkaline earth metal ions desorption and simulta- are represented by the a value (abscise axis) and the Cu(II)
neous Cu(II) biosorption on D. antarctica biomass. The experiment biosorption is represented in the ordinate axis. Linear regression
was performed at an initial pH 5.0 and Cu(II) concentrations ranging express the correlation of increments on Cu(II) concentration and the
between 0.12 and 4.71 mmol L-1. Every cation released and the sum release of the light metal cations
of total cations released at the different initial Cu(II) concentrations

123
656 Adsorption (2015) 21:645–658

Fig. 10 SEM microphotography of D. antarctica dead biomass. a Raw biomass. b Acid treated biomass c. Acid treated biomass loaded with
100 mg L-1 of Cu(II). Magnification of 9200 is shown for all samples

Cu(II) cations at the maximum concentration of initial 3.9 Scanning electron microscopy (SEM)
Cu(II). It can be assumed that, in the case of D. antarctica,
Mg(II), followed by Ca(II) cations, played a dominant role The textural properties of D. antarctica biomass surface
in the cation exchange in the biosorption process. The were observed with SEM analyses, before and after the
amounts of cations released, and the good correlation for elimination of intrinsic cations and Cu(II) loading. In all
the dependence of the average a (released) on the average samples, a characteristic form of the sample showing a
qe (bound), suggest that cation exchange is the main plain surface and no apparent porosity can be seen. Also, it
mechanism taking place for Cu(II) biosorption at pH 5.0 is possible to appreciate another type of surface, with a
(Fig. 9). Cation exchange capacity value (CEC) obtained smoother appearance and some porosity (Fig. 10a–c). The
for D. antarctica was 0.90 ± 0.04 meq g-1. This value is surface of the algae was more amorphous in not-acid
certainly minor than the sum of total cations released which treated biomass (Fig. 10a) and did not show as many
can be explained because the assay only included K(I) as cavities as the sample after an acid wash (Fig. 10b). The
the cation studied, and probably they do not occupy all acid wash removes intrinsic cations, and is useful to see the
sites previously occupied by another intrinsic light metal effect of these elements on the surface structure (Fig. 10b).
cations. Despite the discrepancy in the CEC value After the acidic treatment, the portions of smoother surface
obtained, if one considers this value as the total of dis- presented more porosity. This could be due to the
placed cations and is related to the maximum capacity of crosslinking generated between the intrinsic light metal
biosorption of Cu(II) ions observed (1.4 meq g-1), the cations and the surface polysaccharides (Davis et al. 2003).
percentage attributable to ion exchange would correspond The protonated sample loaded with Cu(II) presents a more
to 64.2 %, supporting the idea that the cation exchange regular structure (Fig. 10c), with more porosity, probably
would be the main mechanism of biosorption for D. because the Cu(II) ions generate a rearrangement of the
antarctica. polysaccharides by crosslinking. The SEM analyses show

123
Adsorption (2015) 21:645–658 657

that the raw biomass did not present an important surface Acknowledgments This work was supported by the project
porosity, and the loss of intrinsic cations on the biomass CORFO 13IDL2-18665, Corporación de Fomento de la Producción
(CORFO), Ministerio de Economı́a, Fomento y Turismo, Chile.
surface tends to generate porosity. The presence of Cu(II)
cations clearly generates a textural change, making the
surface more regular and with more porosity. References

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