Effect of copper (ii) biosorption over light metal cation desorption in the surface of macrocystis pyrifera biomass
Introduction
Biosorption is a physicochemical process, where biological material or derivate parts from this material (i.e. biopolymers) are capable of binding cations and anions, due to different physicochemical interactions with ions or molecules to their surface. The study of biosorption phenomenon started in the early 1970s, when radioactive elements (also heavy metals) present in wastewaters, coming from a nuclear-powered station, were found to be concentrated by several algae specimens [1]. Since then, several researchers have demonstrated that biosorption with macroalgae is a promising and cost-effectiveness technology for the removal of heavy metals from aqueous solutions [[2], [3], [4], [5], [6], [7], [8], [9], [10]]. By the other side, biosorption seems to be a structural and complementary response of macroalgae to abiotic stress, as seen in Oedogonium sp, where the increase of ocean acidification by CO2 affects the bioremediation capabilities of sporophytes [11] positively, so the biosorption turns in an important parameter as indicator of an extracellular matrix reconfiguration [12].
Compared with traditional methods to treat wastewaters like acid mine drainage, as chemical reduction, ion exchange, precipitation, and membrane separation; technologies based on biosorption of brown macroalgae have several advantages: low operative costs, a comparative efficiency compared with traditional methods to detoxify heavy metals in low to medium concentrations, no nutrient requirements by the use of dead biomass, because it seems more effective than use living biomass [7], and a better circular economy [13].
The cell wall of brown seaweeds, that contains a large extracellular matrix (ECM), generally contains three major components: cellulose (structural support) and phycocolloids as alginic acids complexed with light metals such as sodium, potassium, magnesium and calcium, by their constructing blocks (mannuronic and guluronic acids), and fucoidans (sulphated polyfuranoses) [1,14]. These phycocolloids have been reported as the predominant molecular components with active groups who interact, by different physicochemical mechanisms, with light metals and heavy metals [15]. The seaweed biomass possesses several chemical groups that can attract and sequester metals: acetamide, amino, amide, sulfhydryl, sulfonate, and carboxyl [1,16]. This chemical diversity originates a combination of mechanisms to capture the metals, including electrostatic attraction, complexation, ion exchange, covalent bonding, Van der Waals attraction, adsorption and microprecipitation [17]. These properties allows the brown macroalgae to naturally accumulate light metals from their natural niche in their extracellular matrix, due to the affinity of these light metals with many of their structural macromolecules [18]. Considering the importance of light metals in the natural binding capacities of brown macroalgae, the effect of heavy metals, especially which ones have an anthropogenic origin, over light metal mobility is poorly studied in these phycological organisms. Even though the ion exchange is considered the primary mechanism in brown macroalgae biosorption, the exchange of alkali and alkaline-terrous light metals in the biosorption system is poorly characterized. Since these two groups could be non-covalently bound to the same binding sites, so cation exchange data and better mathematical models to interpret these data are necessary [6]. By the technological side, the scarce of information about the exchange of these two light cation metals, by heavy metal biosorption, reduce the chances to develop new products or materials from raw or modified marine biomass, as a competitive technology when are compared to the traditional well-known metal-removal processes [19,20].
Macrocystis pyrifera is part of the group of brown macroalgae from the order of Laminariales (Kelp), with a high presence in the South Pacific Chilean subtidal zones, being one of the primary fisheries resources exported as raw biomass [21]. This kelp has high importance in the formation of benthonic communities and represents a potential biomaterial for biosorption processes, by the high number of sporophytes in the adult stage, with a high availability of biomass that allows the obtainment of derived products, including biosorbent materials [22]. The present study was focused on the effect of Cu(II) biosorption over light metal cation biosorption naturally present on brown M. pyrifera biomass surface, in order to understand the dynamics of alkaline and alkaline-terreous light metals desorption, to develop biosorbents in a more rational way, using Cu(II) as a model of desorption dynamics. Hence, the novelty of this study is the use of M. pyrifera dried biomass as a biosorbent to remove Cu(II) ions in aqueous solution, with the simultaneous desorption of light metal cations. Data from this single metal biosorption will be useful to further study the biosorption process in multi-metallic systems, as usually can be found in real wastewaters, with the considerations of the light metal cation desorption. Biosorption kinetics and isotherms by non-linear equation models were studied, as the pH influence over Cu(II) biosorption and on the desorption was studied by batch methods. The critical functional groups present in this biomass was also studied. Finally, the morphological changes induced by biosorption over the biomass surface was observed by microscopical methods.
Section snippets
Biomass and materials
We collect M. pyrifera live sporophytes in the subtidal zone (33°23′S 71° 41′O, El Tabo, V Region, Chile). We use only analytical grade and mass spectrometry quality reagents for all experiments. Multielement Standard for ICP calibration (1.000 mg L−1), HCl 37 %, HCl 30 %, HNO3 65 %, anhydrous methanol, NaOH, NH3NO3, KCl, and CuCl2·2H2O were obtained from Merck Chemicals (Germany).
Biomass preparation
Fresh seaweed samples were washed with distilled water to remove salt and impurities and then were dried at 40 °C
Determination of optimum pH and equilibrium time for Cu(II) biosorption
The highest performance on Cu(II) biosorption was achieved at pH 5 (Fig. 1A). Cu(II) ions are soluble at this pH, and since we do not observe precipitation, the process is associated with a physisorption phenomenon. As the pH decrease, a tendency on the reduction of biosorption capacity was observed, except for pH 2. This could be explained due to the presence of chemical moieties which are capable to react at this pH, since it exists a high presence of free hydrogen activity in the
Conclusions
The biomass of M. pyrifera have a good kinetic behaviour that obeys the Pseudo-second order model by a fast chemisorption process. The Langmuir non-linear model fits better to the biosorption isotherms data with a maximum capacity of biosorption of 1.149 mmol g−1. Cation exchange with alkaline-earth metal cations have a primary role in the overall Cu(II) biosorption, been responsible in a 56 % of the total Cu(II) exchanged. The strength of the integration of Cu(II) with the surface and the
Author contribution statement
The author's contributions are stated as follows:
-Dr. Héctor Cid contributes with sample collection, batch experiments, funding from their project FONDEF VIU-16p0070E and as the leading writer of the present manuscript.
-Dr. Claudia Ortiz participates as a mentoring for the development of the experiments, contribute with funding from the project CORFO 13IDL2-18665, and as co-writer and as a revisor of the research manuscript.
-Dr. Jaime Pizarro contributes with mentoring, sample collection,
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the project CORFO13IDL2-18665, Corporación de Fomento de la Producción (CORFO), Ministerio de Economía, Fomento y Turismo, Chile, and project FONDEF VIU-16p0070E.
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