A low-cost biosorbent obtained from the Palomino Fino grape seed, a Sherry wine industry by-product, has been proposed as a way of valorising this material. The biomass was characterised obtaining values of 0.68 ± 0.05 g mL−1 for bulk density, 1.02 ± 0.09 g mL−1 for apparent density and 33.3% for porosity. The pHpzc was 5.2 and the surface negative charge value was 2.4 ± 0.2 mmol g−1. The analysis of surface morphology showed differences due to the sorption. The results showed a promising potential for chromium(VI) removal from aqueous solutions. The studies were carried out in batch scale and a 23 factorial design was applied for the optimisation of the process. A percentage of 91.7 ± 0.6% was achieved for the biosorption of Cr(VI) under optimal conditions using pH 5.5, 15 g/L of biosorbent and 8 h of contact time. The biosorption capacity showed a remarkable linearity from 0 to 2 mmol L−1 Cr(VI) and a precision of 0.64% for the removal of 1 mmol L−1 of metal. Langmuir, Freundlich and Temkin isotherm equations and the parameters of six kinetic models were used in the equilibrium modelling and identifying the mechanism of the biosorption. The combination of physical and chemical sorption mechanisms was proposed for the chromium removal with a high maximum sorption capacity (qmax = 208.3 mg g−1). Thermodynamic parameters indicated the spontaneous and endothermic nature of the chromium removal. The successful biosorption was based on the special grape seed components with a relevant content in antioxidant and lignocellulosic compounds.
A disposable colour-changeable optical sensor based on an interesting polymer inclusion-membrane (PIM) was designed to determine Cd(II) ions in aqueous medium. The Schiff base 2-acetylpyridine benzoylhydrazone (2-APBH) immobilised on the polymer membrane was used as a sensing molecule. The amounts of the PIM components were optimised by a 32 fractional factorial design with two central points and two blocks. The best optical sensor composition consisted of 2.5 g of poly(vinylchloride) (PVC) as a base polymer, 3 mL of tributyl phosphate (TBP) as a plasticiser, and 0.02 g of 2-APBH as a reagent. The sensor showed a good linear response in the range from 0.02 mg L−1 (limit of detection) to 1 mg L−1 of Cd(II) under the following experimental conditions: pH 9.5 (adjusted using ammonium chloride buffer solution at 0.337 mol L−1), 60 min of exposure time plus 2 min of sonication (pulses at 2 s intervals), and 10 min of short-term stability. The relative standard deviation of the method was determined to be 4.04% for 0.4 mg L−1 of Cd(II). The optical sensor was successfully applied to the determination of Cd(II) in natural-water and art-paint samples.
We evaluated the potential use of agri-food waste for the removal of heavy metal ions from aqueous solutions and its application in different processes (e.g., water remediation, in the production of biomass enriched in nutritionally significant elements, etc.). Biomasses from grape seed, grape pomace, loquat seed, Calabrese broccoli stem, empty pods of carob and broad bean pods, unripe bitter orange peel, kumquat, orange pulp and Canary Island banana pulp were prepared. The percentages and biosorption capacities were evaluated and compared with those refe-renced using Valencia orange peel (Citrus sinensis Valencia late). These studies allow for easily providing added value to different agri-food wastes. The results show that the proposed biomasses were able to retain the studied metal ions and obtained different percentages, being in some cases above 90%. The highest values were obtained using broad bean pod (Pb(II) (91.5%), Cd(II) (61.7%), Co(II) (40.7%) and Ni(II) (39.7%)). Similar values were observed using grape seed, broccoli stem, carob pod and unripe bitter orange peel. Carob pod for biosorption of Cd(II) is also of great interest. These studies suggest that the agri-food residues evaluated can be applied to prepare effective biosorbents of divalent metal ions from aqueous solutions.
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