Elsevier

Chemical Engineering Journal

Volume 197, 15 July 2012, Pages 261-271
Chemical Engineering Journal

Batch cadmium(II) biosorption by an industrial residue of macrofungal biomass (Clitopilus scyphoides)

https://doi.org/10.1016/j.cej.2012.04.106Get rights and content

Abstract

An industrial waste of Clitopilus scyphoides (Pleurotus mutilus) fungal biomass collected from an antibiotic production plant was tested as a biosorbent for Cd(II) cations. The residue was first characterized by SEM observations, TGA and XRF analyses, and acid–base potentiometric titration. It contained 13.5% (w/w) mineral matter in which Ca, Si and P elements prevailed. Modeling of the potentiometric data showed that amino, phosphate and carboxyl groups were the main functional groups present in the biosorbent. Batch biosorption experiments were then performed to assess the optimal pH for cadmium(II) removal and the biosorption efficiency at varying biosorbent (X) and metal (C0) concentrations. Cadmium uptake by fungal particles was fast, equilibrium being reached within 15 min. The biosorption capacity increased and the biosorption yield decreased with increasing C0/X ratio. A maximum capacity around 200 mg metal g−1 residue was obtained at optimal pH and high C0/X ratio. The biosorption kinetics obeyed the pseudo-first and -second order models as well as the intraparticle diffusion model. Metal biosorption data at equilibrium were well fitted by a 3-parameter equation derived from the BET isotherm model characterizing a multilayer adsorption process. Metal recovery and biosorbent reusability were also investigated using acidic eluent.

Highlights

► Cadmium removal by abundant, low cost and easily collected macrofungal biomass. ► Exhaustive biosorbent characterization (SEM, TGA, XRF, IR, potentiometric titration). ► Fast metal uptake (<15 min) and high biosorption capacity (up to 200 mg g−1). ► Data best fitted by the pseudo-first-order kinetic and the BET isotherm models. ► Biosorbent reusability demonstrated using nitric acid as eluent.

Introduction

Large amounts of metals are released by human activities into aquatic ecosystems. Overabundance of essential metallic elements (e.g. copper, iron, manganese and zinc) may generate toxicity. Non-essential metals (e.g. As, Cr, Se) and the so-called “Big Three” [1], i.e. Cd, Hg and Pb, display acute toxicity. Among these, cadmium, which is used in many industrial processes, e.g. manufacturing of alloys, pigments, alkaline accumulators and phosphate fertilizers, electroplating and, to a lesser extent, nuclear industry, is ubiquitous in the environment and, as such, is currently of particular concern.

Various physico-chemical processes can be applied to the removal of heavy metals from contaminated wastewater, among which chemical precipitation, coagulation–flocculation, flotation, membrane filtration (ultrafiltration, nanofiltration and reverse osmosis), ion exchange and electrodialysis [2]. As a general rule, these treatment techniques suffer from high costs (capital investment, operation and/or maintenance costs) and may be inefficient for the removal of metals from dilute solutions, below 100 mg dm−3 metal. A reliable alternative is offered by adsorption techniques. Activated carbons are efficient sorbents, mainly used in the removal of organic contaminants but also in the treatment of metal-bearing wastewater [3]. These adsorbents are expensive, however, and the search for low-cost materials has become a priority task for those who, in ever-increasing number, are concerned with the treatment of metal-contaminated waters. Thus, a wealth of inexpensive adsorbants has been applied to metal removal over the last twenty years. They include some industrial by-products and natural compounds such as minerals, e.g. zeolite and clay [3], but are mainly materials of biological origin, with emphasis on agricultural/plant waste materials, either raw or chemically modified [4], [5]. Bacterial, fungal and algal biomasses are also promising candidate biosorbents, owing to their abundance and low cost [4], [5], [6]. While both macro- and microalgae have been tested for their metal uptake capacity, most metal biosorption tests with fungal biomass have been performed using filamentous microfungi (molds) such as Aspergillus, Penicillium or Rhizopus species [6]. Studies on utilization of macrofungi (mushrooms) as biosorbents in the treatment of metal-laden aqueous solutions are scarcer [7], [8], [9], [10], [11].

The edible fungus Clitopilus scyphoides (formerly Pleurotus mutilus) is used by the SAIDAL industrial complex in Médéa (Algeria) for the production of pleuromutilin antibiotic. Large amounts of fungal residue (c. 35 tons/year) are produced during the fermentation process and discharged to landfill with no valorization. In a previous study, Chergui et al. presented the main physicochemical features of this waste fungal biomass and tested it as a biosorbent for iron(III)-cyanide complex anion [12]. Later on, Yeddou-Mezenner investigated the ability of the fungal residue to adsorb the cationic dye Basic Blue 41 [13]. Here, additional characteristics of the C. scyphoides residue are given and the evaluation of the biosorption properties of the fungal waste is extended to metal cations, cadmium(II) being chosen as a significant example. Batch experiments were performed in varying operating conditions, i.e. initial pH and metal concentration of the test solution, and biosorbent concentration. The effect of other metal cations on the biosorption capacity of the biomass was also investigated. Experimental data were compared to standard kinetic and equilibrium sorption models.

Section snippets

Biosorbent preparation

The industrial fungal waste, obtained after pleuromutilin extraction from S. scyphoides biomass, was obtained from the SAIDAL antibiotic production complex in Médéa (Algeria). This waste, collected as wet flocs with yellowish color and characteristic odor, was thoroughly washed with distilled water and dried for 24 h at 50 °C in an oven. The dried residue was ground manually in a mortar and sieved to yield particles of 315–400 μm diameter. This particle size was selected by referring to previous

SEM observations

SEM micrographs of dried biosorbent particles showed fairly regular spherical structures with an external surface which, although rather smooth, displayed a number of cracks likely to favor solute adsorption through enhanced diffusion to active sites (Fig. 1).

TGA and XRF analyses

Three main peaks occurred on the thermogram resulting from TGA of dried biosorbent particles (Fig. 2). The first one, appearing as early as a temperature of 50 °C, was due to evaporation of residual physiosorbed water that resulted in about

Conclusion

The C. scyphoides residue displayed promising adsorption characteristics for cadmium recovery from contaminated water, among which a low cost (abundant, easily collected waste material with no pre-treatment needed) together with high biosorption rate and capacity compared to other tested fungal biosorbents (Table 4). In line with previous studies on metal–cyanide complex ion [12] and cationic dye [13] biosorption, the present results confirm the potentialities of this macrofungal biomass for

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