Chromium biosorption using the residue of alginate extraction from Sargassum filipendula
Introduction
Chromium can exist in oxidation numbers ranging from −2 to +6. However, chromium is stable only under the +3 and +6 oxidation states [1]. The differences in the oxidation state of chromium influence differences in the toxicity and the chemical properties of the metal in water. Hence, trivalent chromium is approximately 300-fold less toxic than the hexavalent form, but according to Suwalsky et al. [2], Cr(III) ions can cause more structural disturbances in erythrocyte membranes than Cr(VI). Hexavalent chromium is part of the United States Environmental Protection Agency (EPA) list, being one of the 129 most critical pollutants [3]. Cr(VI) is both carcinogenic and mutagenic [4], and it may cause damages to the kidney, lungs and ulcerations to the skin [5]. According to the World Health Organization (WHO) drinking water guidelines, the maximum allowable limit for total chromium is 0.05 mg L−1 [6].
The major sources of chromium released into the environment are water streams from electroplating, welding, production of chromium–iron alloys, tannery, metal plating, production of chromates, dichromate, dyes and varnishes, as well as the use in electronic and metallurgy industries [7]. Several technologies are available to remove chromium species from wastewater before it can be launched into water bodies: coagulation–flocculation [8], flotation [9], membrane separation [10], ionic exchange resins [11] and biological treatments. The first processes can present a high cost due to the equipment and monitoring systems used, while the biological treatment is much more sensitive to the characteristics of the wastewater, such as pH and concentration [12].
Different seaweed species, especially brown seaweed, have been studied as alternative adsorbents for the removal of heavy metals from contaminated water by adsorption, including chromium, both in its trivalent and hexavalent forms [13], [14], [15], [16]. Brown seaweed contains alginate biopolymer, the main component of its cellular wall, responsible for its mechanical resistance and significant sorption capacity [17], [18]. Alginate is used in food, textile, cosmetic and pharmaceutical industries due to its jellification, viscosity and stability properties. The use of alginate as biosorbent has also been investigated by several researchers [19], [20], [21].
The residue originated from alginate extraction is discarded or used for the production of animal feed, and it has not yet been exploited as a biosorbent. Even after the extraction of alginate, it contains many of the constituents of the raw seaweed, presenting, therefore, potential for the sorption of heavy metals. The functional groups present in Sargassum biomass are alginate carboxyls, phosphate, sulfate, amino and hydroxyl groups: they are responsible for physical and chemical interactions of heavy metals with the biosorbent [22]. They are supposed to contribute to metal sorption on alginate–extraction residue. In addition, the use of alginate–extraction residue as a biosorbent is economically interesting, since it valorizes the waste from biopolymer production.
The main objective of this study was to characterize the residue from the extraction of alginate from a Brazilian seaweed, a natural renewable resource, and evaluate its capacity for separation and recovery of trivalent and hexavalent chromium ions from aqueous solutions. The study investigates the sorption isotherms at different temperatures, the uptake kinetics for both Cr(VI) and Cr(III); in addition, the materials are characterized using FT-IR spectrometry and SEM-EDX analysis for identifying metal distribution in the biosorbent and its interactions with the biomass.
Section snippets
Material and methods
The brown seaweed Sargassum filipendula was collected from the coast of northern São Paulo, at Cigarra beach (São Sebastião) during the spring (November 21st, 2010), supposed to correspond to the maximum production of biomass. Schenkman [23] observed maximum biomass late spring (November and December) and minimum values during winter (July) for Sargassum cymossum from Praia Grande, Ubatuba, São Paulo, Brazil. The average length of seaweed branches was of approximately 50 cm. The seaweed was
Results and discussion
The extraction yield of alginate from the seaweed S. filipendula was 17.2 ± 0.3%, in agreement with the range of alginate present in brown seaweed (10–40%) [22], [35] and used in industry (13–38%) [36]. Seaweed residue resulting from the extraction of alginate corresponds to 39% of the initial seaweed matter. This high percentage incentives its use as adsorbent, enabling the addition of value to a processing waste material. The high percentage of matter loss (about 45%) during extraction is due
Conclusion
The alginate–extraction residue showed a good affinity for both Cr(VI) and Cr(III). The maximum sorption capacities given by the Langmuir model were 0.635 mmol g−1 for Cr(III) and 0.819 mmol g−1 for total Cr. The SEM-EDX analysis shows that the metal was homogeneously sorbed in the biosorbent. The Cr(VI) biosorption is a complex process, in which carboxyl, amino and sulfonic groups are involved; hexavalent chromium ions are simultaneously sorbed and reduced (to trivalent chromium ions). Uptake
Acknowledgements
Caroline Bertagnolli acknowledges her Doctoral fellowship supported by CNPq – Brazil. Authors also thank Jean-Marie Taulemesse (C2MA) for SEM-EDX analyzes.
References (64)
- et al.
Aqueous geochemistry of chromium: a review
Water Res.
(1991) - et al.
Cr(III) exerts stronger structural effects than Cr(VI) on the human erythrocyte membrane and molecular models
J. Inorg. Biochem.
(2008) - et al.
Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water
J. Hazard. Mater.
(2006) - et al.
Removal of chromium(VI) from aqueous solutions by polymer inclusion membranes
Water Res.
(2002) - et al.
Kinetics of removal of chromium from water and electronic process wastewater by ion exchange resins: 1200H, 1500H and IRN97H
J. Hazard. Mater.
(2003) - et al.
Cr(VI) and Cr(III) removal from aqueous solution by raw and modified lignocellulosic materials: a review
J. Hazard. Mater.
(2010) - et al.
Biosorption of hexavalent chromium onto raw and chemically modified Sargassum sp
Bioresour. Technol.
(2008) - et al.
Comparative study of chromium biosorption by red, green and brown seaweed biomass
Chemosphere
(2008) - et al.
Three phase partitioning of carbohydrate polymers : separation and purification of alginates
Carbohydr. Polym.
(2002) - et al.
Heavy metal uptake of alginate gels studied by NMR microscopy
Colloids Surfaces A Physicochem. Eng. Asp.
(1996)
Copper adsorption on calcium alginate beads: equilibrium pH-related models
Hydrometallurgy
Heavy metal sorption by calcium alginate beads from Laminaria digitata
J. Hazard. Mater.
A review of the biochemistry of heavy metal biosorption by brown algae
Water Res.
Influence of the extraction-purification conditions on final properties of alginates obtained from brown algae (Macrocystis pyrifera)
Int. J. Biol. Macromol.
Biosorption of metals in brown seaweed biomass
Water Res.
Biosorption of lead(II) and copper(II) from aqueous solutions by pre-treated biomass of Australian marine algae
Bioresour. Technol.
Pseudo-second order model for sorption processes
Process Biochem.
Sorption of lead, copper, cadmium, zinc, and nickel by marine algal biomass: characterization of biosorptive capacity and investigation of mechanisms
J. Colloid Interface Sci.
Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction
Chemosphere
A novel study of hexavalent chromium detoxification by selected seaweed species using SEM-EDX and XPS analysis
Chem. Eng. J.
Removal of Cr(VI) from aqueous solutions by low-cost biosorbents: marine macroalgae and agricultural by-products
J. Hazard. Mater.
A preliminary study on the adsorptive removal of Cr(VI) using seaweed, Hydrilla verticillata
J. Hazard. Mater.
Piecewise linear regression: a statistical method for the analysis of experimental adsorption data by the intraparticle-diffusion models
Chem. Eng. J.
Adding value to marine macro-algae Laminaria digitata through its use in the separation and recovery of trivalent chromium ions from aqueous solution
Chem. Eng. J.
Zinc and cadmium biosorption by untreated and calcium-treated Macrocystis pyrifera in a batch system
Bioresour. Technol.
Comparative study of the biosorption of Pb(II), Ni(II) and Cr(VI) ions onto S. cerevisiae: determination of biosorption heats
J. Hazard. Mater.
Process development for the removal of lead and chromium from aqueous solutions using red mud an aluminium industry waste
Water Res.
Chromium (III) uptake by agro-waste biosorbents: chemical characterization, sorption–desorption studies, and mechanism
J. Hazard. Mater.
Determination of kinetic and equilibrium parameters of the batch adsorption of Co(II), Cr(III) and Ni(II) onto coir pith
Process Biochem.
Adsorption of Cr(III) from wastewater by wine processing waste sludge
J. Colloid Interface Sci.
Reduction and removal of Cr(VI) from aqueous solutions using modified byproducts of beer production
J. Hazard. Mater.
Batch Cr(VI) removal by polyacrylamide-grafted saw-dust: kinetics and thermodynamics
Water Res.
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