José L. Barriada

Dissolved silver in European estuarine and coastal waters

Silver is one of the most toxic elements for the marine microbial and invertebrate community. However, little is known about the distribution and behaviour of dissolved silver in marine systems. This paper reports data on dissolved and sediment-associated silver in European estuaries and coastal waters which have been impacted to different extents by past and present anthropogenic inputs. This is the first extended dataset for dissolved silver in European marine waters. Lowest dissolved silver concentrations were observed in the Gullmar Fjord, Sweden (8.9 +/- 2.9 pM; x +/- 1sigma), the Tamar Estuary, UK (9.7 +/- 6.2 pM), the Fal Estuary, UK (20.6 +/- 8.3 pM), and the Adriatic Sea (21.2 +/- 6.8 pM). Enhanced silver concentrations were observed in Atlantic coastal waters receiving untreated sewage effluent from the city of A Corũna, Spain (243 +/- 195 pM), and in the mine-impacted Restronguet Creek, UK (91 +/- 71 pM). Anthropogenic wastewater inputs were a source of dissolved silver in the regions studied, with the exception of the Gullmar Fjord. Remobilisation of dissolved silver from historically contaminated sediments, resulting from acid mine drainage or sewage inputs, provided an additional source of dissolved silver to the estuaries. The ranges in the log particle-water partition coefficient (K(d)) values of 5-6 were similar for the Tamar and Mero estuaries and agreed with reported values for other estuaries. These high K(d) values indicate the particle reactive nature of silver with oxic sediments. In contrast, low K(d) values (1.4-2.7) were observed in the Fal system, which may have been due to enhanced benthic inputs of dissolved silver coupled to limited scavenging of silver on to sediments rich in Fe oxide.

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.

Adsorptive behaviour of mercury on algal biomass: competition with divalent cations and organic compounds.

Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed.

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.

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.

Automation of a flow injection system for the determination of dissolved silver at picomolar concentrations in seawater with inductively coupled plasma mass spectrometry

An automated flow injection system for the determination of dissolved silver at ultratrace concentrations in seawater, and controlled under LabVIEW™, is described. The flow injection system allows online processing of seawater samples before their analysis using a magnetic sector inductively coupled plasma mass spectrometry (MS-ICP-MS) instrument. Samples were analysed with a minimum amount of manipulation, thereby reducing the risk of contamination. In addition, the flow injection approach with incorporation of an anion exchange minicolumn allowed ready removal of analytical interferences caused by the saline matrix. The software allowed full control of all flow injection components (valves and pumps) and removed manual time control and, therefore, operator errors. The optimized system was capable of five sample injections per h, including preconcentration and wash steps. The limit of detection was 0.5 pM for a 240-s sample load time, which allowed the determination of dissolved silver in open ocean waters, where picomolar concentration levels are typically encountered.

The salting coefficient and size of alkylamines in saline media at different temperatures: estimation from Pitzer equations and the mean spherical approximation

Abstract The renewed theoretical interest in the proton transfer associated to the amino group together with the scarcity of acid-base studies of amines in moderate to concentrated saline media focussed our attention on the study of the basicities of some alkylamines, namely monomethyl, dimethyl and trimethylamine, in aqueous saline solutions of KCl at various temperatures. A non-conventional analysis of stoichiometric equilibrium constants versus ionic strength data is carried out. On one hand, Pitzer’s model is easily applied to calculate the salting coefficient and the thermodynamic equilibrium constant of the alkylamines. On the other hand, the mean spherical approximation has the advantage over the Debye–Huckel based theories that it can account for effects produced by species of different sizes. Here, it is applied to predict the dependence of the salting behavior on the size of the alkylamines.

A physicochemical study of Al(+3) interactions with edible seaweed biomass in acidic waters.

UNLABELLED In this article, a study of the Al(+3) interactions in acidic waters with biomass of different edible seaweeds: brown (Fucus vesiculosus, Saccorhiza polyschides), red (Mastocarpus stellatus, Gelidium sesquipedale, Chondrus crispus), and green (Ulva rigida, Codium tomentosum), has been performed. The influence of both, the initial concentration of metal and the solution pH, on the Al-uptake capacity of the biomass has been analyzed. From preliminary tests, species Fucus vesiculosus and Gelidium sesquipedale have been selected for a more exhaustive analysis. Sorption kinetic studies demonstrated that 60 min are enough to reach equilibrium. The intraparticle diffusion model has been used to describe kinetic data. Equilibrium studies have been carried out at pH values of 1, 2.5, and 4. Langmuir isotherms showed that the best uptake values, obtained at pH 4, were 33 mg/g for F. vesiculosus and 9.2 mg/g for G. sesquipedale. These edible seaweeds have been found particularly effective in binding aluminum metal ions for most of the conditions tested. Physicochemical data reported at these low pH values could be of interest, not only in modeling aluminum-containing antacids-food pharmacokinetic processes produced in the stomach (pH values 1 to 3) but in remediation studies in acidic waters. PRACTICAL APPLICATION Aluminum is thought to be linked to neurological disruptions such as Alzheimers disease. In this article, the adsorption ability of different types of edible seaweeds toward aluminum has been studied. The choice of low pH values is due to the fact that stomach region is acidic with a pH value between 1 and 3 as a consequence of hydrochloric secretion; so physicochemical data reported in this study could be of interest in modeling drug-food interactions, in particular those referring to aluminum-containing antacids-food pharmacokinetic processes produced in the gastrointestinal tract.

Trend and energetics of pK* vs. ionic strength for o-chlorobenzoic, m-nitrobenzoic and benzoic acids in aqueous KNO3 solutions at 298 K

Ionization constants for benzoic, m-nitrobenzoic and o-chlorobenzoic acids are experimentally determined in aqueous KNO3 solutions and ionic strength dependence of data are analysed by using Guggenheims model for activity coefficients. Moreover, for benzoic acid, energetic contributions ΔGex in the minimum of the pK–ionic strength curve are calculated. It is found that ca. 20% of the total excess energy is due to the non-Debye–Huckel term. A discussion of pK*(I) in terms of solvation energy is also given.

The mean spherical approximation and the prediction of the size of the species involved in an ionization equilibrium in saline media

The unrestricted version of the mean spherical approximation is applied to describe the ionization equilibrium of benzoic acid, as a typical simple system for carboxylic acids, in the presence of an excess of background electrolyte and variable ionic strength. When the activity coefficients are theoretically determined by use of the mean spherical approximation (MSA), the thermodynamic properties of the ionization equilibrium in 1:1 electrolytes for ionic strengths up to 2.5 M can be accurately described, provided different sizes are assumed for each species in solution. The results of this study show that the application of MSA allows one to estimate the size of the species involved in an ionization process from experimental data of stoichiometric equilibrium constants, an alternative normally not explored. However, results suggest that it is necessary to include more sophisticated models of MSA in order to develop this approach with more confidence.