Low-cost, disposable colourimetric sensors for metal ions detection

Abstract In this work, two colourimetric sensors for metal ions detection are presented. The devices are obtained by fixing two classical dyes, Eriochrome Black T (EBT) and 1-(2-pyridylazo)-2-naphthol (PAN), on the commercial paper sheet "Colour Catcher®" (here named under the acronym CC) generally used in the washing machine to prevent colour run problems. The devices are optical sensors, since the indicator dye, fixed on the solid material, changes its spectral properties (colour and hence UV-vis spectrum) upon contact with the metal ion solution. We used the partial least squares (PLS) regression for obtaining the relationship between the metal ion content and the UV-vis spectrum change of each sensor

Dynamics of trace metal sorption by an ion-exchange chelating resin described by a mixed intraparticle/film diffusion transport model. The Cd/Chelex case

The time-evolution of Cd2+ ion sorption by Chelex 100 resin was studied in batch experiments as a function of time, pH, ionic strength, stirring rate, mass of resin and initial metal ion concentration. In the experimental conditions, the amount of resin sites are in excess with respect to the amount of metal ion, leading to extensive depletion of metal in bulk solution when equilibrium is reached. The data were described using a mixed control mass transport model in finite volume conditions (MCM) that includes explicitly both intraparticle and film diffusion steps. Exact numerical computations and a new approximate analytical expression of this model are reported here. MCM successfully predicts the influence of pH and ionic strength on the experimental Cd(II)/Chelex kinetic profiles (which cannot be justified by a pure film diffusion controlled mechanism) with a minimum number of fitting parameters. The overall diffusion coefficient inside the resin was modelled in terms of the Donnan factor and the resin/cation binding stability constant. The values of the latter coefficient as a function of pH and ionic strength were estimated from the Gibbs-Donnan model. Even though MCM is numerically more involved than models exclusively restricted to film or intraparticle diffusion control, it proves to be accurate in a wider range of values of the mass transfer Biot number and solution/resin metal ratios.The authors gratefully acknowledge support for this research from the Spanish Ministry MINECO (Projects CTM2013-48967 and CTM2016-78798) and by the “Comissionat d'Universitats i Recerca de la Generalitat de Catalunya” (2014SGR1132). FQ acknowledges a grant from AGAUR

Determination of cadmium(II), copper(II), manganese(II) and nickel(II) species in Antarctic seawater with complexing resins

The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log αM(I)=11.6 at pH=7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 1020 M−1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log αM(I)=5.5 and 6.5 at pH=7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite G-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations

speciation of copper ii in natural waters in the presence of ligands of high and intermediate strength

AbstractA new procedure is presented for the determination of the ligands of copper(II) in natural waters, based on titration with the metal ion, monitored by measuring the concentration of copper(II) sorbed on the carboxylic resin Amberlite CG 50. The data are treated by the Ruzic linearization method to obtain the concentration of the ligands and the conditional stability constant of the complexes. Ligands with reaction coefficient αM higher than 0.1 K*w/V are detected, where K* is the ratio of the concentration of sorbed metal to the concentration of free metal in solution, which can be evaluated from the sorption equilibria of copper(II) on Amberlite CG 50, w is the amount of water in the resin phase, and V the volume of the solution phase. Some natural waters at high and low salinity were examined. The ligand concentration determined in these samples ranged from around 50 to 2000 nM, while the original copper concentrations from 11 to 130 nM. The ligand concentration was always much higher than that ..

Naked-Eye Food Freshness Detection: Innovative Polymeric Optode for High-Protein Food Spoilage Monitoring

An innovative smart label for naked-eye protein food freshness evaluation, based on polymeric sensing films, is presented. The proposed device consists of six miniaturized sensors, obtained by cova..

Application of the new electroanalytical technique AGNES for the determination of free Zn concentration in river water

Absence of gradients and Nernstian equilibrium stripping (AGNES) is a recently developed electroanalytical technique specifically designed for the direct determination of free concentrations of metal ions. AGNES is applied here to the determination of free Zn concentration in a river water sample. The method has been validated with synthetic solutions of low ionic strengths containing Zn and 2,6-pyridinedicarboxylic acid and then applied to synthetic river waters and to a natural sample collected from Besòs River in Montcada i Reixac (Catalonia, North-Eastern Spain). In the river sample, an average free Zn concentration of 12.8(4) nM was obtained, while the total dissolved Zn concentration was 0.51(8) μM. To control and maintain pH and pCO2 constant during AGNES measurements, a novel device for N2/CO2 mixed purging has been developed

Novel DFO-functionalized mesoporous silica for iron sensing. Part 2. Experimental detection of free iron concentration (pFe) in urine samples.

Successful in vivo chelation treatment of iron(III) overload pathologies requires that a significant fraction of the administered drug actually chelates the toxic metal. Increased mobilization of the iron(III) in experiments on animals or humans, most often evaluated from urinary output, is usually used as an assessment tool for chelation therapy. Alternatively, the efficiency of a drug is estimated by calculating the complexing ability of a chelating agent towards Fe(III). The latter is calculated by the pFe value, defined as the negative logarithm of the concentration of the free metal ion in a solution containing 10 μM total ligand and 1 μM total metal at a physiological pH of 7.4. In theory, pFe has to be calculated taking into account all the complexation equilibria involving the metal and the possible ligands. Nevertheless, complexation reactions in complex systems such as serum and urine may hardly be accurately modelled by computer software. The experimental determination of the bioavailable fraction of iron(III) in biological fluids would therefore be of the utmost relevance in the clinical practice. The efficiency of the therapy could be more easily estimated as well as the course of overload pathologies. In this context, the aim of the present work was the development of a sensor to assess the free iron directly in biological fluids (urine) of patients under treatment with chelating agents. In the proposed device (DFO-MS), the strong iron chelator deferoxamine (DFO) is immobilized on the MCM-41 mesoporous silica. The characterization of the iron(III) sorption on DFO-MS was undertaken, firstly in 0.1 M KNO3, then directly in urine samples, in order to identify the sorption mechanism. The stoichiometry of the reaction in the solid phase was found to be: with an exchange constant (average value) of log βex = 40(1). The application of DFO-MS to assess pFe in SPU (Simulating Pathology Urine) samples was also considered. The results obtained were very promising for a future validation and subsequent application of the sensor in samples of patients undergoing chelation therapy

DFO@EVOH and 3,4-HP@EVOH: Towards New Polymeric Sorbents for Iron(III)

The paper presents the synthesis and preliminary characterization of two novel solid-phase sorbents for iron(III), resulting from the functionalization of ethylene-vinyl alcohol copolymer (EVOH) with deferoxamine, DFO (DFO@EVOH), and a novel tripodal 3-hydroxy-4-pyridinone, named 3,4-HP (3,4-HP@EVOH). DFO and 3,4-HP have been covalently bonded to EVOH, using carbonyldiimidazole as a coupling agent. Before their use as Fe(III) sorbents, they were warm-pressed to obtain a thin film. Polymers have been characterized by conventional physico-chemical techniques; furthermore, the sorption properties towards Fe(III) were investigated. The physico-chemical characterization of the new solid-state devices demonstrates the effective linkage of the two receptors on the polymeric support. Despite a relatively low sorption capacity for both materials, the stoichiometry and the complexation constants of Fe(III)/DFO@EVOH and Fe(III)/3,4-HP@EVOH are in pretty good agreement with those obtained for the same ligands in aqueous solutions

Chelating Agents in Soil Remediation: A New Method for a Pragmatic Choice of the Right Chelator

Soil pollution by metal ions constitutes one of the most significant environmental problems in the world, being the ecosystems of extended areas wholly compromised. The remediation of soils is an impelling necessity, and different methodologies are used and studied for reaching this goal. Among them, the application of chelating agents is one of the most promising since it could allow the removal of metal ions while preserving the most meaningful properties of the original soils. The research in this field requires the joined contribute of different expertise spanning from biology to chemistry. In this work, we propose a parsimonious and pragmatic approach for screening among a range of potential chelating agents. This methodology, the Nurchi's method, is based on an extension of the Reilley procedure for EDTA titrations. This allows forecasting the binding ability of chelating agents toward the target polluting metal ions and those typically found in soils, based on the knowledge of the related protonation and complex formation constants. The method is thoroughly developed, and then tested by application to some representative cases. Its use and relevance in biomedical and industrial applications is also discussed

A Speciation study on the perturbing effects of iron chelators on the homeostasis of essential metal ions

A number of reports have appeared in literature calling attention to the depletion of essential metal ions during chelation therapy on β-thalassaemia patients. We present a speciation study to determine how the iron chelators used in therapy interfere with the homeostatic equilibria of essential metal ions. This work includes a thorough analysis of the pharmacokinetic properties of the chelating agents currently in clinical use, of the amounts of iron, copper and zinc available in plasma for chelation, and of all the implied complex formation constants. The results of the study show that a significant amount of essential metal ions is complexed whenever the chelating agent concentration exceeds the amount necessary to coordinate all disposable iron —a frequently occurring situation during chelation therapy. On the contrary, copper and zinc do not interfere with iron chelation, except for a possible influence of copper on iron speciation during deferiprone treatment