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Laboratory of Microbiology, Pharmacology, Biotechnology and Environment, Faculty of Sciences Ain-Chock, route El Jadida, B.P.
5366, Casablanca, Morocco.
ABSTRACT
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.
INTRODUCTION
Many chemical substances are water soluble and ion exchange, rather expensive methods and restricted
therefore easy to gain access to various water systems due to technical constraints [3, 4].
forming a threat for the fauna and flora in these
systems. Pollutants can be transported by water at all In the bioremediation field, biosorption is an innovative
stages of the water cycle. The fauna and flora are also technology that exploits inactive and dead biomass for
affected by the accumulation of pollutants in the tissues the recovery of heavy metals from aqueous solutions,
of plants and other terrestrial and aquatic animals, and although other biomass sources such as bacteria or
more generally along the food chain, which is seriously yeast has proven their ability to adsorb metal ions [5,
prejudicial to the natural balance of various 6], algae due to their high sorption capacity and their
ecosystems. availability in almost unlimited amounts are still a first
choice regarding the instauration and the development
Removal of heavy metals is undoubtedly one of the of new and efficient biosorbent materials [7, 8].
most demanding environmental issues, although some
heavy metals at low concentration are essential to life Green algae contain cellulose and a high percentage of
such as zinc, copper and cobalt, others are superfluous cells wall are proteins bonded to polysaccharides thus
and are known to cause serious damages in living forming glycoprotein. These compounds contain
organisms [1]. Mercury is a global threat to human and several functional groups (amino, carboxyl, sulphate,
environmental health, its toxicity in both organic and hydroxyl) which could be an essential part in the
inorganic form results from the strong affinity for biosorption process. Red algae also contain cellulose
sulphur of organic compounds which can lead to the but their convenience lies in the presence of sulphated
inactivation of vital cell functions [2]. polysaccharides made of galactanes (agar and
carragenates).
The conventional treatments used to remove heavy
metals consist of physicochemical techniques such as The main objective of this work is to study the ability of
filtration, acid leaching, electrochemical processes or 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 In the Salinity case, various initial concentrations of
rubens, to remove mercury from aqueous solutions. NaNO3 were prepared. 100mg of biomass was added
Basic parameters such as contact time, initial mercury and pH was maintained at 6.0. All flasks contained 500
concentration, pH and salinity of mercury biosorption M of mercury and were shacked at 100 rpm, 25C.
equilibrium were determined in batch stirred reactor.
Finally, the same principle was applied to the
MATERIALS AND METHODS adsorption isotherm experiment. 100 mg of biomass
Biosorbent preparation was added to solutions with various mercury
Fresh algal biomass was gathered from Moroccan concentrations, and then agitated at 100 rpm, 25 C.
Atlantic coast (Casabalnca region). The algal samples The pH was maintained at 6.0.
were washed with double distilled water to remove salt
and extraneous particles, then air dried. The RESULTS AND DISCUSSION
protonated biomass was prepared by cleaning the algae The effect of algae pre-treatment on mercury
with 0.3N H2SO4 for 3h, then rinsed with distilled water biosorption
and dried at 50 C for 24h.
Table 1 shows the significant ability of the three tested
Equilibrium sorption experiments species to fix mercury. According to the obtained
Stock Solutions of Hg2+ were prepared by dissolving results, it appears clearly that the sulfuric acid
HgCl2 in distilled water. 100 mg of dried biomass was treatment increased relatively the adsorption capacity
mixed with 100 ml of metal solution in 250 ml (from 70 to 90%, from 60 to 86% and from 54 to 71%
Erlenmeyer flasks. The flasks were agitated at 100 rpm for Sphaerococcus coronopifolius, Ulva lactuca and Jania
and left to attain equilibrium for 2h at 25 C. Mercury rubens, respectively). This can be explained by the fact
uptakes were determined by reckoning the variation of that the acid treatment allows the impurity riddance
metal concentration regarding both initial and final and thus the liberation of more biosorption surfaces
solutions. The pH before and in the course of the and binding sites for the complexation of mercury ions
sorption tests, was adjusted with 1 mM NaOH and 1 such as Ca2+, Mg2+ and Na+ [9, 10].
mM H2SO4.
Aliquots were collected at pre-defined time intervals Table 1: Effect of algae pre-treatment (100mg) on the
and centrifuged. Mercury concentration in the removal of mercury (500M) at pH 6 and 25C
supernatant was evaluated using a flameless atomic Removal (%)
absorption spectrophotometer MAS 50 (Mercury Algae species Raw Pre-treated
Analyzer System, Bacharach, USA). Ulva Lactuca 60% 86%
Jania Rubens 54% 71%
Sphaerococcus Coronopifolius 70% 90%
Batch biosorption studies
Regarding this experiment, three parameters were The effect of biosorption time
taking into consideration: pH; salinity and metal As shown in Figure 1, the equilibrium biosorption (time
concentration. needed to attain an equilibrium concentration) was
reached within 60 min only. More than 70%, 65% and
To investigate the pH effect, mercury solutions at 60% of mercury were eliminated regarding,
various pH were prepared. The algal biomass (100 mg) Sphaerococcus coronopifolius, Ulva lactuca and Jania
was added into flasks containing metal solutions (100 rubens respectively.
ml) of known mercury concentration (500 M). The
flasks were agitated for 2h at 100 rpm and at 25 C.
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 Sphaerococcus coronopifolius, Ulva lactuca and Jania
Biosorption is highly reliant on pH value; in fact the pH rubens, respectively). This behavior can be explained by
of solutions has a direct impact on the surface charge of the nature of the biosorption at different pH, the ionic
adsorbent and affects the metal ions solubility [11]. state of functional group of sorbent and the metal
Therefore the effect of initial pH on the removal of chemistry [12]. At a pH value below 4, the active
mercury using various species of algae was studied surface sites could be ether protonated or dissociated
(Figure 2). The highest removal value was achieved at [13, 14].
pH 6 for all three species (95%, 90% and 70% for
Figure 3: Effect of the initial concentration of Na+ on the removal of mercury (500g) at pH 6 and 25C.
Adsorption equilibrium registered lower value, for exemple, in some studies it
The experiment results are show in Figure 4. The was found that the fixation of mercury on the poly-
maximum adsorption capacity was obtained for (glycidylmethacrylate-co-divinylbenzene) and N-
Sphaerococcus Coronopifolius (0,674 mmmol/g) in hydroxymethyl-thioamide was at value equal to 0.2 and
comparison with Ulva Lactuca and Jania Rubens (0,419 0.36 mmol/g, respectively [16].
and 0,399 mmol/g, respectively). Some author
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. Where:
KF (mg1-n g-1 Ln) represents the sorption capacity and
Freundlich isotherm n the Empirical parameter, depicting the energetic
The Freundlich isotherm although criticized for lacking heterogeneity.
a fundamental thermodynamic basis, is often used to
reckon the adsorption on heterogeneous surfaces and it The curve y = ax+b, where y = Log Qe and x = 1/n
is not restricted to monolayer formation. It is expressed (Figure 5), enable to calculate the various constants
by the following equation: (slope and intercept of the linear plot).
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 Where:
liquid solution [17]. The data may be represented as
follows:
Qm (mg/g) is the maximum adsorption capacity and KL
(L/mg) is the Langmuir constant referring to
adsorption energy. Like stated previously for Data analysis
Freundlich model, data can be determined exploiting Table 2 represents the obtained data following
the linear curves (Figure 6). Freundlich and Langmuir models. For all experimental
systems, the RL value was between 0 and 1 which
Moreover, Langmuir model parameters can be used to confirms a favorable uptakes, a value exceeding 1
predict the affinity between the sorbate and sorbent would indicate an unfavorable uptake, and an
using a dimensionless constant called the equilibrium irreversible state if RL = 0. Taking into consideration
parameter RL, which is expressed as follows: 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.
With C0 being the absorbate initial concentration.