Stability of core/shell quantum dots-role of pH and small organic ligands

The improvement of knowledge about the toxicity and even processability, and stability of quantum dots (QD) requires the understanding of the relationship between the QD binding head group, surface structure, and interligand interaction. The scanned stripping chronopotentiometry and absence of gradients and Nernstian equilibrium stripping techniques were used to determine the concentration of Cd dissolved from a polyacrylate-stabilized CdTe/CdS QD. The effects of various concentrations of small organic ligands such as citric acid, glycine, and histidine and the roles of pH (4.5–8.5) and exposure time (0–48 h) were evaluated. The highest QD dissolution was obtained at the more acidic pH in absence of the ligands (52 %) a result of the CdS shell solubility. At pH 8.5 the largest PAA ability to complex the dissolved Cd leads to a further QD solubility until the equilibrium is reached (24 % of dissolved Cd vs.4 % at pH 6.0). The citric acid presence resulted in greater QD dissolution, whereas glycine, an amino acid, acts against QD dissolution. Surprisingly, the presence of histidine, an amino acid with an imidazole functional group, leads to the formation of much strong Cd complexes over time, which may be non-labile, inducing variations in the local environment of the QD surface

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives. (C) 2016 Elsevier Ltd. All rights reserved

Aggregation of Titanium Dioxide Nanoparticles: Role of a Fulvic Acid

The increasing use of nanomaterials in consumer products has led to increased concerns about their potential environmental and health impacts. To better understand the transport, fate, and behavior of nanoparticles in aquatic systems, it is essential to understand their interactions with different components of natural waters including natural organic matter over a broad range of physicochemical conditions. Fluorescence correlation spectroscopy was used to determine the diffusion coefficients of TiO2 nanoparticles having a nominal size of 5 nm. The effects of a various concentrations of the Suwannee River Fulvic Acid (SRFA) and the roles of pH and ionic strength were evaluated. Aggregation of the bare TiO2 nanoparticles increased for pH values near the zero point of charge. At any given pH, an increase in ionic strength generally resulted in increased aggregation. Furthermore, conditions which favored adsorption of the SRFA resulted in less aggregation of the TiO2 nanoparticles, presumably due to increased steric repulsion. Under the conditions studied here, nanoparticle dispersions were often stable for environmentally relevant conditions of SRFA, pH, and ionic strength, suggesting that in the natural environment, TiO2 dispersion might occur to a greater extent than expected

Deposition of TiO2 Nanoparticles onto Silica Measured Using a Quartz Crystal Microbalance with Dissipation Monitoring

Titanium dioxide (TiO2) nanoparticles introduced into subsurface environments may lead to contamination of drinking water supplies and can act as colloidal carriers for sorbed contaminants. A model laboratory system was used to examine the influence of water chemistry on the physicochemical properties of TiO2 nanoparticles and their deposition. Deposition rates of TiO2 particles onto a silica surface were measured over a broad range of solution conditions (pH and ionic strength) using a quartz crystal microbalance with energy dissipation monitoring (QCM-D). Higher particle deposition rates were observed under favorable interaction conditions (i.e., in the presence of attractive electrostatic interactions) in comparison to unfavorable deposition conditions where electrostatic repulsion dominates particle−surface interactions. Nanoparticle sizes were characterized by fluorescence correlation spectroscopy (FCS), dynamic light scattering (DLS), and atomic force microscopy (AFM). These analyses confirmed the nanoscale of the system under study as well as the presence of TiO2 aggregates in some cases. TiO2 deposition behavior onto silica measured using QCM-D was generally found to be in qualitative agreement with the Derjaguin−Landau−Verwey−Overbeek (DLVO) theory of colloidal stability

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives. (C) 2016 Elsevier Ltd. All rights reserved.COST - European Cooperation in Science and TechnologyEuropean Cooperation in Science and Technology (COST)The authors thank COST - European Cooperation in Science and Technology - and the COST Action ES1205 members for the kind support, exchange of ideas and discussions

AGNES at vibrated gold microwire electrode for the direct quantification of free copper concentrations

The free metal ion concentration and the dynamic features of the metal species are recognized as key to predict metal bioavailability and toxicity to aquatic organisms. Quantification of the former is, however, still challenging. In this paper, it is shown for the first time that the concentration of free copper (Cu2+) can be quantified by applying AGNES (Absence of Gradients and Nernstian equilibrium stripping) at a solid gold electrode. It was found that: i) the amount of deposited Cu follows a Nernstian relationship with the applied deposition potential, and ii) the stripping signal is linearly related with the free metal ion concentration. The performance of AGNES at the vibrating gold microwire electrode (VGME) was assessed for two labile systems: Cu-malonic acid and Cu-iminodiacetic acid at ionic strength 0.01 M and a range of pH values from 4.0 to 6.0. The free Cu concentrations and conditional stability constants obtained by AGNES were in good agreement with stripping scanned voltammetry and thermodynamic theoretical predictions obtained by Visual MinteQ. This work highlights the suitability of gold electrodes for the quantification of free metal ion concentrations by AGNES. It also strongly suggests that other solid electrodes may be well appropriate for such task. This new application of AGNES is a first step towards a range of applications for a number of metals in speciation, toxicological and environmental studies for the direct determination of the key parameter that is the free metal ion concentration

Isolation and purification treatments change the metal-binding properties of humic acids: effect of HF/HCl treatment

International audienceWe studied the changes in metal binding characteristics of extracted humic acids induced by HF/HCl treatment followed by dialysis, i.e. the last step of the International Humic Substances Society (IHSS) extraction protocol. We performed metal binding experiments with both the alkaline-extracted material (AE) and the fully purified (FP) humic acid using the electrochemical stripping technique (AGNES) and modelled the results using the NICA-Donnan model. The results showed an increase of free Zn, Cd and Pb concentrations of ~1 order of magnitude for the AE compared with the FP. These differences may be mostly explained by the different carbon content (51.3 % FP and 36.5 % AE) associated with an AE/FP carboxyl ratio of 0.5. Simulations using the NICA-Donnan model showed that halving the amount of carboxylic groups (Qmax,1) for the FP reduced this difference to 0.25 log units for Cd and Zn and to 0.15 log unit for Pb. There is a clear need for further research on the differences between purified v. less-disturbed natural organic material, which will contribute to improved modelling of metal binding to organic matter in soils, hence providing a basis for a more realistic risk assessment

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives