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Current Research in Microbiology and Biotechnology

Vol. 2, No. 6 (2014): 513-518


Research Article
Open Access

ISSN: 2320-2246

Adsorption of mercury (Hg II) by three different algae


species: Potential use as biosorption materials
K. Lyamlouli*, M. Blaghen and N. Takati
Laboratory of Microbiology, Pharmacology, Biotechnology and Environment, Faculty of Sciences Ain-Chock, route El Jadida, B.P.
5366, Casablanca, Morocco.
* Corresponding author: K. Lyamlouli; email: karim-2l@hotmail.fr
Received: 22 October 2014

ABSTRACT

Accepted: 12 November 2014

Online: 16 November 2014

The ability of three different algal biomass (Sphaerococcus coronopifolius, Ulva lactuca and Jania rubens) to remove
mercury from aqueous solutions was investigated. The mercury biosorption process was studied through batch
experiments at 25 C with regard to the influence of contact time, initial mercury concentration, pH and salinity. The
maximum adsorption capacity was registered at pH 6, Sphaerococcus cornopifolius being the most efficient specie
(0,674 mmol/g regarding adsorbed mercury). The kinetics of adsorption was fast and a high capacity of adsorption
occurred within only 60 min. The presence of Na+ interfered significantly with the binding of mercury.

Keywords: Mercury, Biosorption, Algae, Adsorption, Isotherm.


INTRODUCTION

Many chemical substances are water soluble and


therefore easy to gain access to various water systems
forming a threat for the fauna and flora in these
systems. Pollutants can be transported by water at all
stages of the water cycle. The fauna and flora are also
affected by the accumulation of pollutants in the tissues
of plants and other terrestrial and aquatic animals, and
more generally along the food chain, which is seriously
prejudicial to the natural balance of various
ecosystems.

Removal of heavy metals is undoubtedly one of the


most demanding environmental issues, although some
heavy metals at low concentration are essential to life
such as zinc, copper and cobalt, others are superfluous
and are known to cause serious damages in living
organisms [1]. Mercury is a global threat to human and
environmental health, its toxicity in both organic and
inorganic form results from the strong affinity for
sulphur of organic compounds which can lead to the
inactivation of vital cell functions [2].
The conventional treatments used to remove heavy
metals consist of physicochemical techniques such as
filtration, acid leaching, electrochemical processes or

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ion exchange, rather expensive methods and restricted


due to technical constraints [3, 4].

In the bioremediation field, biosorption is an innovative


technology that exploits inactive and dead biomass for
the recovery of heavy metals from aqueous solutions,
although other biomass sources such as bacteria or
yeast has proven their ability to adsorb metal ions [5,
6], algae due to their high sorption capacity and their
availability in almost unlimited amounts are still a first
choice regarding the instauration and the development
of new and efficient biosorbent materials [7, 8].

Green algae contain cellulose and a high percentage of


cells wall are proteins bonded to polysaccharides thus
forming glycoprotein. These compounds contain
several functional groups (amino, carboxyl, sulphate,
hydroxyl) which could be an essential part in the
biosorption process. Red algae also contain cellulose
but their convenience lies in the presence of sulphated
polysaccharides made of galactanes (agar and
carragenates).
The main objective of this work is to study the ability of
algal biomass from three different species,
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K. Lyamlouli et al. / Curr Res Microbiol Biotechnol. 2014, 2(6): 513-518

Sphaerococcus coronopifolius, Ulva lactuca and Jania


rubens, to remove mercury from aqueous solutions.
Basic parameters such as contact time, initial mercury
concentration, pH and salinity of mercury biosorption
equilibrium were determined in batch stirred reactor.

MATERIALS AND METHODS

Biosorbent preparation
Fresh algal biomass was gathered from Moroccan
Atlantic coast (Casabalnca region). The algal samples
were washed with double distilled water to remove salt
and extraneous particles, then air dried. The
protonated biomass was prepared by cleaning the algae
with 0.3N H2SO4 for 3h, then rinsed with distilled water
and dried at 50 C for 24h.

Equilibrium sorption experiments


Stock Solutions of Hg2+ were prepared by dissolving
HgCl2 in distilled water. 100 mg of dried biomass was
mixed with 100 ml of metal solution in 250 ml
Erlenmeyer flasks. The flasks were agitated at 100 rpm
and left to attain equilibrium for 2h at 25 C. Mercury
uptakes were determined by reckoning the variation of
metal concentration regarding both initial and final
solutions. The pH before and in the course of the
sorption tests, was adjusted with 1 mM NaOH and 1
mM H2SO4.
Aliquots were collected at pre-defined time intervals
and centrifuged. Mercury concentration in the
supernatant was evaluated using a flameless atomic
absorption spectrophotometer MAS 50 (Mercury
Analyzer System, Bacharach, USA).

Batch biosorption studies


Regarding this experiment, three parameters were
taking into consideration: pH; salinity and metal
concentration.
To investigate the pH effect, mercury solutions at
various pH were prepared. The algal biomass (100 mg)
was added into flasks containing metal solutions (100
ml) of known mercury concentration (500 M). The
flasks were agitated for 2h at 100 rpm and at 25 C.

In the Salinity case, various initial concentrations of


NaNO3 were prepared. 100mg of biomass was added
and pH was maintained at 6.0. All flasks contained 500
M of mercury and were shacked at 100 rpm, 25C.
Finally, the same principle was applied to the
adsorption isotherm experiment. 100 mg of biomass
was added to solutions with various mercury
concentrations, and then agitated at 100 rpm, 25 C.
The pH was maintained at 6.0.

RESULTS AND DISCUSSION

The effect of algae pre-treatment on mercury


biosorption
Table 1 shows the significant ability of the three tested
species to fix mercury. According to the obtained
results, it appears clearly that the sulfuric acid
treatment increased relatively the adsorption capacity
(from 70 to 90%, from 60 to 86% and from 54 to 71%
for Sphaerococcus coronopifolius, Ulva lactuca and Jania
rubens, respectively). This can be explained by the fact
that the acid treatment allows the impurity riddance
and thus the liberation of more biosorption surfaces
and binding sites for the complexation of mercury ions
such as Ca2+, Mg2+ and Na+ [9, 10].
Table 1: Effect of algae pre-treatment (100mg) on the
removal of mercury (500M) at pH 6 and 25C
Algae species
Ulva Lactuca
Jania Rubens
Sphaerococcus Coronopifolius

Raw
60%
54%
70%

Removal (%)
Pre-treated
86%
71%
90%

The effect of biosorption time


As shown in Figure 1, the equilibrium biosorption (time
needed to attain an equilibrium concentration) was
reached within 60 min only. More than 70%, 65% and
60% of mercury were eliminated regarding,
Sphaerococcus coronopifolius, Ulva lactuca and Jania
rubens respectively.

Figure1: Effect of contact time on the adsorption of mercury (500g) at pH 6 and 25C
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The effect of pH on biosorption


Biosorption is highly reliant on pH value; in fact the pH
of solutions has a direct impact on the surface charge of
adsorbent and affects the metal ions solubility [11].
Therefore the effect of initial pH on the removal of
mercury using various species of algae was studied
(Figure 2). The highest removal value was achieved at
pH 6 for all three species (95%, 90% and 70% for

Sphaerococcus coronopifolius, Ulva lactuca and Jania


rubens, respectively). This behavior can be explained by
the nature of the biosorption at different pH, the ionic
state of functional group of sorbent and the metal
chemistry [12]. At a pH value below 4, the active
surface sites could be ether protonated or dissociated
[13, 14].

Figure 2: Effect of pH on the removal of mercury (500g)

The effect of Salinity


The influence of salinity on the biosorption equilibrium
has been studied within a concentration range of
NaNO3 of 0.1-1000 mM. Figure 3 shows that the
presence of Na+ affects the sorption of mercury by
establishing a competition on par with the ions fixation
sites, available on the algal biomass.

It is also interesting to note that the effect of Na+ is


observable only from a Na+ concentration of 1 mM, a
value from which the rate of Na+ ions is higher than that
of mercury. Beyond 1mM of Na+, the quantity of fixed
mercury decreased distinctly thus strengthening the
occurrence of a competition phenomenon. Similar
results were obtained for sawdust using NaCl as salt
source [15].

Figure 3: Effect of the initial concentration of Na+ on the removal of mercury (500g) at pH 6 and

Adsorption equilibrium
The experiment results are show in Figure 4. The
maximum adsorption capacity was obtained for
Sphaerococcus Coronopifolius (0,674 mmmol/g) in
comparison with Ulva Lactuca and Jania Rubens (0,419
and 0,399 mmol/g, respectively). Some author

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25C.

registered lower value, for exemple, in some studies it


was found that the fixation of mercury on the poly(glycidylmethacrylate-co-divinylbenzene)
and
Nhydroxymethyl-thioamide was at value equal to 0.2 and
0.36 mmol/g, respectively [16].
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Figure 4: Biosorption capacity versus the concentration of mercury at pH 6 and 25C.

In-depth study
For a more substantial study and in order to investigate
the sorption isotherm, the obtained data were analyzed
referring to Freundlich and Langmuir models.

Freundlich isotherm
The Freundlich isotherm although criticized for lacking
a fundamental thermodynamic basis, is often used to
reckon the adsorption on heterogeneous surfaces and it
is not restricted to monolayer formation. It is expressed
by the following equation:

Where:
KF (mg1-n g-1 Ln) represents the sorption capacity and
n the Empirical parameter, depicting the energetic
heterogeneity.

The curve y = ax+b, where y = Log Qe and x = 1/n


(Figure 5), enable to calculate the various constants
(slope and intercept of the linear plot).

Figure 5: Freundlich isotherm model

Langmuir isotherm
Developed by Langmuir in 1916, it is probably the best
known and the most applied regarding sorption
isotherm, it is widely used for solute adsorption from a
liquid solution [17]. The data may be represented as
follows:
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Where:

Qm (mg/g) is the maximum adsorption capacity and KL


(L/mg) is the Langmuir constant referring to
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adsorption energy. Like stated previously for


Freundlich model, data can be determined exploiting
the linear curves (Figure 6).
Moreover, Langmuir model parameters can be used to
predict the affinity between the sorbate and sorbent
using a dimensionless constant called the equilibrium
parameter RL, which is expressed as follows:

With C0 being the absorbate initial concentration.

Data analysis
Table 2 represents the obtained data following
Freundlich and Langmuir models. For all experimental
systems, the RL value was between 0 and 1 which
confirms a favorable uptakes, a value exceeding 1
would indicate an unfavorable uptake, and an
irreversible state if RL = 0. Taking into consideration
the correlation coefficient (R2), the obtained values
prove that the adsorption data are well depicted by
Langmuir model which indicate the formation of
monolayer coverage of the adsorbate on the outer
surface.

Figure 6: Langmuir isotherm model

Algae
Species
Jania rubens
Ulva lactuca
Sphaerococcus coronopifolius

Table 2: Isotherms parameters

Langmuir parameters
Qm (mg.g-1) KL (L.mg-1)
90,9
0,24
90,9
0,1
111,11
0,27

RL
0,06
0,14
0,05

CONCLUSION

The study revealed that the pre-treated biomass can be


used to develop an efficient biosorption material
aiming to remove mercury from wastewater streams.
The adsorption capacity was pH dependent with 6.0 as
an optimal value. Furthermore, the equilibrium data of
adsorption are in good agreement with the Langmuirs
model. The kinetics of adsorption was fast and the
presence of Na+ interfered significantly with the
binding of mercury.

REFERENCES
1.
2.

Kaplan D.(2013). Absorption and Adsorption of Heavy Metals


by Microalgae. Handbook of Microalgal Culture: Appl
Phycology Biotechnol, Second Edition.(Handbook).
Muneer B, Iqbal MJ, Shakoori FR et al. (2013). Tolerance and
Biosorption of Mercury by Microbial Consortia: Potential Use

http://crmb.aizeonpublishers.net/content/2014/6/crmb513-518.pdf

3.
4.
5.
6.
7.

8.

R2
0,990
0,947
0,915

Freundlich parameters
KF
1/n
R2
24,3
0,26
0,988
47,7
0,13
0,938
61,6
0,11
0,759

in Bioremediation of Wastewater. Pakistan J. Zool., 45(1):


247-254.
Beccari M, Di pinto AC, Marani D et al. (1986). I metalli nelle
acque: origine, distribuzione, metodi di rimazione, CNR,
instuto di ricerca sulle qcque, Quaderni, 71, Roma. (Italian).
Meghraj H and Daneshwar P. (2013). Isolation and
Identification of Heavy Metals Tolerant Bacteria from
Industrial and Agricultural Areas in Mauritius. Curr Res
Microbiol Biotechnol. 1(3): 119-123.
De J. and Ramaiah N. (2007). Characterization of marine
bacteria highly resistant to mercury exhibiting multiple
resistances to toxic chemicals. Ecological Indic. 7: 511-520.
Chiu HH, Shieh WY, Lin SU et al. (2007). Alteromonas tagae
sp. nov. and Alteromonas simiduii sp. nov., mercury-resistant
bacteria isolated from a Taiwanese estuary. Int. J Sys Evol
Microbiol. 57: 209-1216.
Volesky B and Holan ZR. (1995). Biosorption of heavy metals.
Biotechnol. Prog. 11: 235-250.
Nirmal KJI and Cini O. (2012). Removal of heavy metals by
biosorption using freshwater alga Spirogyra hyaline. J.
Environ. Biol.33: 27-31.

517

K. Lyamlouli et al. / Curr Res Microbiol Biotechnol. 2014, 2(6): 513-518


9.
10.
11.
12.
13.
14.

Yang J and Volesky B. (1999). Cadmium biosorption rate in


protonated Sargassum biomass. Environ. Sci. Technol. 33:
751-757.
Sulaymon AH, Mohammed AA and Al-Musawi TJ. (2013).
Column Biosorption of Lead, Cadmium, Copper, and Arsenic
ions onto Algae. J Bioprocess Biotech. 3:1.
Hossain MA, Ngo HH, Guo WS et al. (2012). Adsorption and
desorption of copper(II) ions onto garden grass. Bioressour
Technol, 121: 386-395.
Yaqub A, Naeem MF, Anjun KM et al. (2009). Biosorption of
mercury (Hg II) by Oedogonium urceolatum: equilibrium and
kinetics. BIOLOGIA (PAKISTAN). 55 (1&2): 99-109.
Lu D, Cao Q, Li X et al. (2009). Kinetics and equilibrium of
Cu(II) adsorption onto chemically modified orange peel
cellulose biosorbents. Hydrometallurgy 95: 145-152.
Lodeiro P, Cordero B, Grille Z et al. (2004). Physicochemical
studies of cadmium(II) biosorption by the invasive alga in
Europe, Sargassum muticum. Biotechnol Bioeng 88: 237-247.

15. Ajmal M, Khan AH, Ahmad S, Ahmad A. (1998). Role of


sawdust in removal of copper(II) from industrial wastes.
Water Res. 32: 3085-3091.
16. Yalcinkaya Y, Arica MY, Soysal L et al. (2002). Cadmium and
mercury uptake by immobilized Pleurotus sapidus. Turk. J.
Chem. 26: 441-452.
17. YS. HO, Porter JF, Mckay G. (2002). Equilibrium isotherm
studies for the sorption of divalent ions onto peat: Copper,
Nickel and Lead single component systems. Water Air and
Soil Pollut. 141: 133.

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