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Five different brown seaweeds, Bifurcaria bifurcata, Saccorhiza polyschides, Ascophyllum nodosum, Laminaria ochroleuca and Pelvetia caniculata were studied for their ability to remove cadmium from aqueous solution. Kinetics of cadmium adsorption by all the algae were relatively fast, with 90% of total adsorption occurring in less than 1h. These experiments could be accurately described by a pseudo-second-order rate equation, obtaining values between 1.66x10(-3) and 9.92x10(-3) g/mgmin for the sorption rate constant k. Several equilibrium adsorption isotherms were obtained for the quantitative description of cadmium uptake. The use of the Langmuir isotherm led to values between 64 and 95 mg/g for qmax and between 0.036 and 0.094 L/mg for b. The effect of pH on biosorption was also studied. Acid-base properties of algae were studied by potentiometry to determine pK values (from 3.54 to 3.98) and the total number of acid groups.

In recent years, there has been a significant increase in the studies concerning brown seaweed as biosorbents for metal removal owing to their high binding ability and low cost. This work reports the results of a study regarding the cadmium binding equilibria of dead biomass from the seaweed Sargassum muticum; this alga is a pest fouling organism that competes with the local fucalean species and may also interfere with the "sea industry"; therefore, it would constitute an ideal material to be used as biosorbent. Seven different treatments were tested in order to obtain a stable biomass that could be suitable for industrial use under a broad range of operational conditions. The treatments employed were protonation, chemical cross-linking with formaldehyde, KOH, Ca(OH)(2) and CaCl(2) or physical treatments with acetone and methanol. The equilibrium adsorption isotherms of Langmuir, Freundlich, and Langmuir-Freundlich were obtained for the quantitative description of the cadmium uptake. The effect of pH on biosorption equilibrium was studied at values ranging from 1 to 6, demonstrating the importance of this parameter for an accurate evaluation of the biosorption process. Maximum biosorption was found pH higher than 4.5. The maximum biosorption uptake for the raw biomass was 65 mg g(-1), while for formaldehyde cross-linking biomass the uptake increases to 99 mg g(-1) and for protonated biomass to 95 mg g(-1). Potentiometric titrations were carried out to estimate the total number of weak acid groups and to obtain their apparent pK value, 3.85, using the Katchalsky model. Kinetic studies varying cadmium concentration, algal dose, and ionic strength were carried out. Over 95% of the maximum cadmium uptake was achieved within 45 min, so the process can be considered relatively fast. A pseudo-second-order model, for the kinetics of cadmium biosorption, was shown to be able to reproduce experimental data points with accuracy.

Abstract: Samples of dead biomass from the marine brown algae Fucus ceranoides, Fucus vesiculosus and Fucus serratus were studied for their ability to remove cadmium from aqueous solutions. The metal sorption process is rapid, with 90% of the metal uptake completed within the first 25 min of contact. The kinetic data was described successfully by a pseudo second order chemical sorption process with rate constants of ca. 0.6 g mmol−1 min−1. At pH 4.5, the raw biomass of the three species exhibited equilibrium uptake capacities for Cd as high as 0.8 mmol g−1 (90 mg g−1), on a dry weight basis, without chemical pretreatment. These sorption capacities are much higher than those reported for activated carbon and chitin. The sorption of Cd was found to increase as pH increases, reaching a plateau at pH 5. Batch sorption experiments and continuous potentiometric titrations of acid-treated biomass samples in 0.05 M NaNO3 were used to derive thermodynamic binding parameters according to the NICCA model. The total amount of acid sites was 2.4–2.9 mmol g−1, with median values of the affinity distribution for protons and cadmium ions, log K˜ H and log K˜ Cd, of 3.7 and 2.69, respectively (conditional values). The apparent heterogeneity of the sorbent was successfully taken into account by the empirical NICCA isotherm, which described very well the competition between protons and metal ions, in contrast with a simpler discrete competitive Langmuir model. The experimental results demonstrate that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for cadmium removal from wastewaters. This use would represent an example of exploitation of a renewable marine resource in water treatment technologies for the prevention of heavy metal pollution in the environment. [Copyright &y& Elsevier]