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Physicochemical studies of cadmium(II) biosorption by the invasive alga in Europe, Sargassum muticum.

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 CaCl2 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.

Biosorption of Cadmium by Fucus spiralis

Environmental Context. Conventional processes for the removal of heavy metals from wastewaters generally involves chemical precipitation of metals (changing the pH) followed by a period to allow the metal precipitates to settle and be separated. These processes are inefficient when the metals are at a low concentration and still demand handling and disposal of toxic metal sludges. An alternative method for heavy metal removal is adsorption onto a biological material, biosorption. The biological materials, including agricultural byproducts, bacteria, fungi, yeast, and algae, all which take up heavy metals in substantial quantities, are relatively inexpensive, widely available, and from renewable sources. However, biological materials are complex and the active mechanisms often unclear. Abstract. Cadmium biosorption properties of nonliving, dried brown marine macroalga Fucus spiralis from Galician coast (northwest Spain) have been investigated. The biosorption capacity of the alga strongly depends on solution pH; the uptake is almost negligible at pH ≤ 2 and reaches a plateau at around pH 4.0. Cadmium biosorption kinetics by F. spiralis is relatively fast, with 90% of total adsorption taking place in less than one hour. A pseudo second order mechanism has been proved to be able to predict the kinetic behaviour of the biosorption process. The effect of initial cadmium ion concentration, alga dose, solution pH, and temperature on the biosorption kinetics has been studied. The Langmuir, Freundlich, Langmuir–Freundlich, and Toth isotherms were used to fit the experimental data and to find out the adsorption parameters. Acid–base properties of the alga have been studied potentiometrically in order to calculate the number of acidic groups and the apparent pK value by using Katchalsky model. The pK obtained is comparable with typical values associated to the ionization of carboxyl groups of alginates, supporting the implication of these groups in the biosorption process.

Thermodynamic and Kinetic Aspects on the Biosorption of Cadmium by Low Cost Materials: A Review

Environmental Context. The toxicity of cadmium in waters can be decreased by using a wide variety of low-cost biomaterials. A number of such investigations are reviewed here and the models used to describe the process of biosorption discussed. Fundamental investigations that probe the thermodynamics and kinetics of the biosorption process are essential for a strong understanding of all biosorption processes. Areas that still need addressing are highlighted, in particular with regard to cadmium biosorption, some models for which are ready to be tested in pilot plants. Abstract. Cadmium is internationally recognized as an important pollutant in the environment, and different methods for its removal from wastewaters (chemical precipitation being the most commonly used) have been reported in the literature. Those methods are in most cases oriented to situations with high concentrations of the pollutant. Thus, alternative removal and recovery methods are being considered for removing very low concentrations of cadmium. These methods are all based on biosorption, the passive adsorption and sequestration of metals by several natural materials of biological origin. In this review we have considered the biosorption of cadmium onto biomaterials from a physicochemical, thermodynamic, and kinetic perspective. The thermodynamic perspective is based on the characterization of the interactions of the binding sites of the biosorbents with cadmium species in aqueous solution. Traditionally, this approach has been quantified using different kinds of isotherms. In addition, the description is completed by taking into account electrostatic effects, and the influence of pH and ionic strength, which are associated with the negative charge developed, in most cases, by the biomaterial. The other point of view in this review is the kinetic one, which is necessary for a full physicochemical description of the sorbate–biosorbent system. Consequently, an updated description of the various approaches commonly employed in kinetic studies in biosorption has been carried out.

Cr III binding by surface polymers in natural biomass: the role of carboxylic groups

Environmental context. Large quantities of chromium are discharged into the environment as a result of its widespread use in modern industries, and consequently, chromium could constitute a serious pollution problem. Adsorption onto natural biomass offers real potential as a way of removing chromium from the environment, because such adsorbents contain biopolymers with particular chemical stability and selectivity towards metals. In addition, natural biomass constitutes an eco-friendly and cost-effective alternative to the existing methods. Here, specific interactions between chromium and the biomass are investigated. Abstract. The chromium(III)-binding capacity of several biomaterials has been described under fixed conditions of pH (4.5) and initial metal concentration (100 mg L–1). Three of these materials (Sargassum muticum, orange peel and bracken fern) have been selected and subjected to different studies. Fourier transform infrared and scanning electron microscopy techniques were used to describe the structure of the biomaterials, supporting the hypothesis of a mechanism of metal complexation via carboxylic groups. Potentiometric titrations revealed the quantity of carboxyl groups present in S. muticum, orange peel and bracken fern: 1.78, 0.49 and 0.67 mmol g–1, respectively. Moreover, a model considering different types of binding sites was used to simulate the process and determine the apparent pK values of the main functionalities. The number of carboxylic groups was clearly correlated with the maximum amount of CrIII binding by the materials. A Langmuir competitive model was used to determine the complexation constants for chromium, log KCr, which are very close (~3), supporting the idea of the implication of essentially one acid functionality. Desorption studies were conducted for different times employing H2SO4 and sodium citrate.

A dynamic proof of mercury elimination from solution through a combined sorption-reduction process.

Physico-chemical factors affecting mercury elimination from solution using fern as sorbent have been analysed. It was demonstrated that interaction of mercury with this biomass follows two processes, adsorption by the functional groups in the biopolymers of the cell wall and reduction by easily oxidized compounds of the biomass. Batch experiments have been done to analyse the effect of pH, ionic strength of the media or competition with other metals. Ionic strength did not show a significant influence in the process, but mercury speciation with the formation of negatively charge complexes represented an important drawback in metal elimination. Continuous flow conditions were also analysed since many industrial applications will require them. These studies allowed distinguishing the two processes: mercury sorption was observed but also reduction of this metal occurs. Reduction to mercury (I) and metallic mercury has been confirmed by scanning electron microscopy analysis of the column filling after the continuous flow experiments.

Experimental evidences for a new model in the description of the adsorption-coupled reduction of Cr(VI) by protonated banana skin

This work reports experimental evidences, not previously considered, to evaluate the Cr(VI) removal by protonated banana skin biomass. Variations in the number of hydroxyl groups, quantified by potentiometric titrations, and CO2 evolution during experiments, were attributed mainly to the oxidation of hydroxylic entities present in the studied material. The results indicate that these groups together with the carboxylic moieties are the main functionalities involved on the adsorption-coupled reduction process. The column experiment carried out provides a new approach to obtain the maximum reduction capacity of the material (3.72 mmol g(-1)). Moreover, we hereby propose a model that reports the first evidence for the instant bound of Cr(III) species to the material used, formed after the reduction of Cr(VI) present in solution. The removal process was quantified carrying out experiments under various pHs, biomass doses and Cr(VI) concentrations, and the mechanism underlying chromium removal was identified.

Silver nanoparticles coated with natural polysaccharides as models to study AgNP aggregation kinetics using UV-Visible spectrophotometry upon discharge in complex environments

This study provides quantitative information on the aggregation and dissolution behaviour of silver nanoparticles (AgNPs) upon discharge in fresh and sea waters, represented here as NaCl solutions of increasing ionic strength (up to 1M) and natural fjord waters. Natural polysaccharides, sodium alginate (ALG) and gum Arabic (GA), were used as coatings to stabilize the AgNPs and the compounds acted as models to study AgNP aggregation kinetics. The DLVO theory was used to quantitatively describe the interactions between the AgNPs. The stability of AgNPs was established using UV-Visible spectrophotometry, including unique information collected during the first seconds of the aggregaton process. Alginate coating resulted in a moderate stabilization of AgNPs in terms of critical coagulation concentration (~82mM NaCl) and a low dissolution of <10% total Ag in NaCl solutions up to 1M. Gum Arabic coated AgNPs were more strongly stabilized, with ~7-30% size increase up to 77mM NaCl, but only when the silver ion content initially present in solution was low (<10% total Ag). The ALG and GA coated AgNPs showed a strongly enhanced stability in natural fjord waters (ca. 5h required to reduce the area of the surface plasmon resonance band (SPRB) by two fold) compared with NaCl at an equivalent ionic strength (1-2min period for a two fold SPRB reduction). This is ascribed to a stabilizing effect from dissolved organic matter present in natural fjord waters. Interestingly, for AgNP-GA solutions with 40% of total silver present as unreacted silver ions in the NP stock solution, fast aggregation kinetics were observed in NaCl solutions (SPRB area was reduced by ca. 50% within 40-150min), with even more rapid removal in fjord waters, attributed to the high amount of silver-chloride charged species, that interact with the NP coating and/or organic matter and reduce the NPs stabilization.

Aluminium removal from wastewater by refused beach cast seaweed. Equilibrium and dynamic studies.

Aluminium removal has been investigated in synthetic and real wastewaters provided by an aluminium surface treatment plant. Marine algae, obtained as beach cast seaweed (a refuse substance) were used as adsorption material. The influence of pH, metal concentration and time for aluminium elimination was studied by use of synthetic solutions. The optimum pH value was 4.0, which provided a maximum adsorption capacity of 22.5 mg g(-1). The adsorption percentage surpassed 80% in less than 30 min of contact time. Real solutions from the industrial unit were fully characterized and tested in two different fixed-bed columns. One column was filled with 27.5 g of dried beach cast seaweed. Three cycles of adsorption and two of desorption were carried out. The first cycle (12 mg g(-1) maximum sorption capacity) was enough to reach the maximum adsorption capacity at 15 mL min(-1) flow rate. The second column was packed with 1100 g of seaweed and its behaviour was compared to another column filled with activated charcoal, following both the same experimental procedure. Maximum sorption capacity was 14 mg g(-1) for seaweed, whereas the activated charcoal only reached 1.6 mg g(-1) (flow rate of 250 mL min(-1)).

Full description of copper uptake by algal biomass combining an equilibrium NICA model with a kinetic intraparticle diffusion driving force approach

In this work kinetic and equilibrium studies related to copper binding to the protonated macroalga Sargassum muticum are reported. An intraparticle-diffusion linear driving force (LDF) model has been chosen for the quantitative description of the kinetics at several initial metal concentrations. Copper intraparticle homogeneous diffusion coefficient (D(h)) obtained is in the range 0.2-0.9×10(-10) m(2) s(-1). NICA isotherm is demonstrated to constitute a substantial improvement with respect to a simpler Langmuir competitive equation. The binding parameters were chosen to provide the best simultaneous description of the equilibrium experiments. Values of log K(Cu) (4.3), n(Cu) (1) and p (0.31) in NICA isotherm, and log K(Cu) (3.5-5) in Langmuir competitive model, have been obtained. These parameters have been also used to predict the competition between copper and cadmium for binding sites. Two acids, HNO(3) and HCl, have been tested to evaluate their effectiveness to release copper from the metal-laden biomass.

Physicochemical characterisation of the ubiquitous bracken fern as useful biomaterial for preconcentration of heavy metals.

Batch experiments with dry bracken fern have been done to determine cadmium and lead sequestering capacity of this biomaterial. Biomass characterisation was done by infrared spectroscopy and potentiometric analysis. The effect of pH of the metal containing solution, contact time and initial metal concentration has been studied, together with the acid-base properties of the biomaterial. Results obtained have been analysed using mathematical and modelling techniques. Effect of pH on metal sequestration has been correlated with observed acid-base properties of the natural substrate. Kinetic data analysis provided relevant information about metal sequestration rate, showing important differences between lead and cadmium. Maximum uptake was found to be the same for both metals 0.410 mmol/g. This value was also clearly correlated to the number of acidic groups determined for this material which was found to be 0.432 mmol of acidic groups per gram of fern. Results obtained indicate that acidic groups are the functional groups responsible of the sequestration of metal ions and that bracken fern is a promising material for metal preconcentration.