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ABSTRACT
Biosorption capacity of three common marine macroalgae viz., Ulva fasciata (green alga), Sargassum wightii (brown alga) and
Gracilaria corticata (red alga) was evaluated with respect to the removal of the heavy metal, Arsenic (As) from aqueous
solution. The influence of various parameters such as pH (2 to 10), biomass weight (0.5 to 3.0 g/L), initial metal ion
concentration (2 to10 ppm/L) and contact time (30 to 150 minutes) on biosorption efficiencies were determined. Results
indicated that the optimum pH was 6 for the removal of Arsenic by U. fasciata and S. wighti, while it was greater than 6 for
G. corticata. The maximum removal of arsenic was 90.2% at biomass weight of 2g/100ml for S. wightii and G. corticata. The
optimum arsenic (As) adsorption percentage was obtained at 90 minutes of contact time for initial metal ion concentration in
all the three macroalgae biomass. The biosorption isotherms studies indicated that the biosorption of Arsenic follows the
Langmuir and Freundlich models. The maximum biosorption capacity, q max, was 2.21mmol/g in G. corticata. The Freundlich
Arsenic adsorption capacity was in the order of U. fasciata < S. wightii < G. corticata, which also suggested about the
coexistence of the monolayer adsorption as well as heterogeneous surface conditions. The FTIR analysis for surface
functional groups of unloaded algal biomass and arsenic loaded biomass revealed that the existence of amino, carboxyl,
hydroxyl and carbonyl groups on the surface of biomass cells and the possible interaction between metal and functional groups.
SEM micrograph of pretreated and Arsenic sorbed algal biomass showed morphological changes due to the exposure of heavy
metal to the algae. These results led to refer that the macroalgal biomass could form a potential, eco-friendly, cost effective and
safe alternative biosorbent for fine tuning of waste water treatment.
Keywords:-Algal biomass, biosorbent, Arsenic removal, FTIR, SEM Micrograph, isotherms, water treatment
1. INTRODUCTION
Heavy metals released into the environment seriously affect the biological system including human physiology [17].
One to the heavy metals, arsenic contaminates the environment through anthropogenic and natural sources. Plants
absorb arsenic fairly easily, which results in food contamination with high ranking concentrations. The World Health
Organization (WHO) declared that inorganic arsenic is a human carcinogen. Various health effects have been observed
both in children and adults when exposed to high amount of arsenic [19]. Consumption of arsenic contaminated fishes
cause irritation of the stomach, intestines and lungs. Also small corns or warts appear on the palms and torso.
Considering such health hazards, several remediation techniques have been developed to remove the arsenic
contaminated problems. It includes soil removal, washing, physical stabilization and use of chemical amendments.
Almost all these techniques are considered as expensive and disruptive [10].
Biosorption is an emerging, economic and eco-friendly process of removing heavy metals from aqueous solution using
biological materials such as algae [11][12], bacteria [13], yeast [9] and fungi [2]. Macroalgal biomass is one of the
most promising types of biosorbents due to the rigid macrostructure, high uptake capacity as well as the ready
abundance of the biomass [7]. Different macroalgae exhibited different affinities towards the same metal which in turn
depends upon the chemical structure of the macroalgae [31]. Electron microscopic analysis of macroalgae revealed the
presence of different metal binding sites of their cell wall (carboxyl, aminoacid, polysaccharides and sulfhydral groups)
which could play an important role in the biosorption process [33].
Macroalgae viz; Cladophora fascicularis, Chaetomorpha sp, Caulerpa, Valoniopsis and Ulva lactuca (Green algae),
Sargassum wightii, a brown algae and Gracilaria edulis a red alga were the typical examples that showed the potential
as biosorbents for efficient removal of heavy metals such as Cd, Hg, Pb, and Chromium V1 from contaminated water
[1], [22], [21]. Considering the arsenic pollution and possibility of utilizing marine macroalgae, the present study was
initiated to evaluate the biosorption potentials of 3 macroalgae viz; Ulva fasciata, Sargassum wightii and Gracilaria
corticata towards Arsenic (As) from aqueous solution.
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biosorption of the positively charged metal ion increased till reaching their maximum biosorption around pH6 for U.
fasciata (84.6%) and S. wightii (87.1%) and pH8 for G. corticata (85.4%). In accordance with our finding, [24]
reported that the maximum up take of cadmium, nickel and zinc by green algae, Codium vermilara, and Spirogyra
insignis, brown algae viz; Fucus spiralis, Ascophyllum nodosum and red algae such as Asparagopsis armata and
Chondrus crispus was at pH6. The increase of biosorption with increasing pH also be related to both Carboxyl and
sulphonate groups on the cell walls of the biomass and to metal chemistry in solution [27], [30], [5].
% adsorption by
100
Macroalgae
90
Concentration
80 of
Ulva
Sodium arsenate
70
fasciata
(ppm)
69.5
2 60
76.2
4 50
84.6
6 40
82.1
8 30
72.5
10
20
Sargass Gracilar
um
ia
wightii corticata
75.4
72.1
83.5
75.3
87.1
82.5
82.7
85.4
67.8
76
10
0
2
10
pH values
Fig. 1. Influence of pH on Arsenic adsorption by macroalgae
3.2 Influence of biosorbent dosage
The pattern of influence of macroalgal biomass dosage on the biosorption of Arsenic from aqueous solution is shown in
Fig.2. As observed from Fig.2, a steep increase in the Arsenic uptake took place as the biomass of S. wightii and G.
corticata was increased from 0.5g to 2g/100 ml dosage. The biomass concentration of 2g/100ml has shown maximum
removal of 90.2% of Arsenic from the aqueous solution. In contrast, U. fasciata biomass at concentration 3g/100ml
showed maximum removal of 80.4% Arsenic from aqueous solution. Above the optimum biomass dosage, the
percentage uptake of Arsenic was decreasing gradually with the increase in concentrations. This effect could be
explained by the formation of aggregates of biomass at higher doses which decreases the surface area of biomass
adsorption [15]. These results coincided with the findings of [29] in the uptake of lead from aqueous solution by brown
algae Sargassum myriocystum and biosorption of Pb(II) and Cd(II) from aqueous solution using green alga Ulva lactuta
biomass [25]. Similarly [24] suggested that the electrostatic interactions between cells could function as a significant
factor in the relationship between biomass concentration and metal biosorption.
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Agitation time
80
mts 70
30 60
60 50
90 40
30
120
20
150
10
Ulva
fasciata
79.4
81.1
82.6
68.5
62.2
Sargass Gracilar
um
ia
wightii corticata
79.2
81.2
84.6
87.5
85.1
85.4
75.4
72.3
64.2
65.6
0
30
60
90
120
150
Ulva fasciata
Sargassum wightii
Gracilaria corticata
90
80
Concentration of
70
Ulva
Sodium arsenate
fasciata
(ppm)
60
60.1
2 50
63.5
4
40
67.2
6
56.5
8 30
52.3
10 20
Sargass Gracilar
um
ia
wightii corticata
65.8
63.7
66.7
65.2
69.5
71.3
70.2
75.5
75.1
77.4
10
0
2
10
Ulva fasciata
Sargassum wightii
Gracilaria corticata
Page 97
qmax(mmol g-1)
b (L mmol -1)
r2
Ulva fasciata
1.820.34
1.120.22
0.98
Sargassum wightii
1.310.16
2.290.31
0.97
Gracilaria corticata
2.210.26
2.120.12
0.98
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structures were fewer and less pronounced. In the arsenic loaded G. corticata, Fig. 16(b) the surface was apparently
smoother with mount like structures. This result coincided with earlier studies by [20] on the heavy metal Cu II and Cr
III binding on the surface of Palmaria palmate, red alga. Electron Microscopic studies on the structure of G. corticata
thallus by [28] revealed the presence of high content of sulphur with metals like zirconium, chromium, zinc, iron and
potassium could produced in the changes in surface morphology of G. corticata.
Fig. 14( a)
EM Micrograph of U.fasciata (control)
Fig. 15 (a)
SEM Micrographs of S. wightii (control)
Fig . 16 (a)
SEM Micrographs of G. corticata (control)
Fig. 14(b)
SEM Micrograph of Arsenic loaded U. fascia
Fig. 15 (b)
SEM Micrographs of Arsenate loaded S. wightii
4.CONCLUSION
Results of experiments could lead to the conclusion that the dried algal biomass effectively removed the arsenic from
aqueous solution. This has tremendous potential as an economic, effective, safe alternative to existing commercial
adsorbents. It is easy and effective technique for fine tuning of waste water treatment and removal of heavy metals
from the various industrial wastes containing heavy metals
Page 102
Acknowledgements
The authors express sincere thanks to Dr. Shakina, Assistant Professor, Dept of Chemistry, Sara Tucker College,
Palayamkottai for her valuable guidance throughout the tenure of this work. The first author gratefully acknowledge
the Director, CMFRI, Cochin and Scientist In charge and staff of Vizhinjam Research Centre of CMFRI, Vizhinjam for
the facilities provided to carry out this work. Thanks are extended to Dr. Sarika, Scientist, Mr. Shine, CMFRI,
Vizhinjam and Dr. K. Paulraj, H.O.D. Dept. of Botany N.M.C.College, Marthandam for their valuable suggestions
during the preparation of MS of this paper.
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