Indirect determination of mercury(II) by using magnetic nanoparticles, CdS quantum dots and mercury(II)-binding aptamers, and quantitation of released CdS by graphite furnace AAS.

This work describes an aptamer based method for highly sensitive determination of Hg(II). A Hg(II)-binding ssDNA aptamer was linked to silica-coated magnetic nanoparticles (magNPs). Then, a conjugate composed of graphene and CdS quantum dots (Gr-CdS) was linked to the complementary ssDNA. On mixing the two components, a duplex of type magNP-dsNNA-Gr/CdS is generated. If Hg(II) is added, it wills capturing the aptamer, and this leads to the release of Gr/CdS because of the formation of a stable thymine-Hg2+-thymine link. External magnetic force is used to remove the remaining complex. The released graphene-CdS is decomposed by HNO3 and injected into a graphite furnace AAS. The detectable amount of Cd is proportional to the concentration of Hg(II) in the sample. Under the optimal conditions, the method has a linear response in the 2.50 aM to 0.25 nM Hg(II) concentration range, and the detection limit is as low as 7.6 aM (at S/N = 3). It has high selectivity for Hg(II) over other metal ions. Graphical abstract.

Short-term assessment of cadmium toxicity and uptake from different types of Cd-based Quantum Dots in the model plant Allium cepa L.

We report on the toxicity and bioaccumulation of three different types of Cd-based quantum dots (QDs), dispersed in aqueous medium, for a model plant Allium cepa L. It is believed that encapsulation of nanoparticles should reduce their toxicity and increase their stability in different environments; in this work we studied how QD encapsulation affects their phytotoxicity. Core, core/shell, and core/shell/shell QDs (CdTe, CdTe/ZnS, and CdTe/CdS/ZnS QDs capped by 2-mercaptopropionic acid) were tested and CdCl2 was used as a positive control. After 24-h and 72-h exposure, total Cd content (MCd) and bioaccumulation factors (BAFs) were determined in all parts of A. cepa plants (roots, bulb, shoot), and the total length of the root system was monitored as a toxicity end-point. Measurements of total Cd content versus free Cd2+ content (with Differential Pulse Voltammetry, DPV) in exposure media showed differences in chemical stability of the three QD types. Correspondingly, selected QDs showed different toxicity for A. cepa and different Cd bioaccumulation patterns. CdTe QDs were the most toxic; their effect was similar to CdCl2 due to the release of free Cd2+, which was confirmed by the DPV measurements. Plants exposed to CdTe QDs also bioaccumulated the most Cd among all QD exposure groups. CdTe/ZnS QDs showed no toxicity and very low bioaccumulation of Cd in A. cepa; the main source of measured Cd in the plants were QDs adsorbed on their roots, which was confirmed by fluorescence microscopy. On the contrary, CdTe/CdS/ZnS QD toxicity and bioaccumulation patterns were similar to those of CdTe QDs and pointed to unstable CdS/ZnS shells.

Effects of Cd(II) on wastewater biological nitrogen and phosphorus removal.

Short-term and long-term effects of Cd(II) on wastewater biological nitrogen and phosphorus removal were investigated with respect to microorganism abundances, enzyme activities, and polyhydroxyalkanoates (PHAs) and glycogen transformations. Though no obvious effects on wastewater biological nutrient removal were observed after short-term exposure, the long-term exposure of 10 mg L(-)(1) Cd(II) inhibited nitrification and phosphorus uptake. Compared with the absence of Cd(II), the presence of 10 mg L(-1) of Cd(II) decreased total nitrogen and phosphorus removal efficiencies from 97% and 98% to 88% and 18%, respectively. Mechanism studies revealed that Cd(II) affected the transformations of intracellular PHAs and glycogen, and the activities of oxidoreductase and polyphosphate kinase, resulted in the decrease of nitrite oxidizing bacteria and polyphosphate accumulating organisms abundance, which might be the major reason for the negative effects of long-term exposure to 10 mg L(-1) Cd(II) on biological nitrogen and phosphorus removal.

Quantum dots exhibit less bioaccumulation than free cadmium and selenium in the earthworm Eisenia andrei.

The present study addresses the bioaccumulation behavior of cadmium selenide quantum dots by Eisenia andrei earthworms in a terrestrial environment. Earthworms were exposed to quantum dot-treated soil for up to 4 wk and analyzed for cadmium and selenium concentration using inductively coupled plasma mass spectrometry. Results were compared with those from earthworms exposed to cadmium nitrate and selenious acid, as positive controls, and those exposed in untreated soil (negative control). Earthworms exposed to quantum dots showed significant bioaccumulation of cadmium and selenium (5.3- and 1.5-fold higher concentration over negative controls, respectively) after 4 wk. Over the same 4 wk, positive control earthworms accumulated 9.2- and 2.2-fold higher cadmium and selenium, respectively, than negative controls for a much more substantial final body burden of the 2 elements. The concentrations also increased with exposure time; cadmium concentrations increased from 3600 ± 310 ng/g to 8080 ± 660 ng/g, from 1 to 4 wk, suggesting that further bioaccumulation may take place with even longer exposure time. The molar ratio of cadmium to selenium in the quantum dot-exposed worms (6.2) is closer to the ratios seen in positive control worms (7.2) than to the pure quantum dots (1.8), which implies that quantum dots are taken up predominantly in the degraded form. The results suggest that chemical modification of quantum dots to protect them from environmental degradation could potentially reduce bioaccumulation of the nanoparticles by earthworms.

Chelation of cadmium by combining deferasirox and deferiprone in rats.

The present research aimed to characterize the potential efficiency of two chelators after cadmium administration for 60 days following two dose levels of 20 and 40 mg/kg body weight daily to male rats. However, the hypothesis that the two chelators might be more efficient as combined therapy than as single therapy in removing cadmium from the body was considered. In this way, two known chelators deferasirox and deferiprone (L(1)) were chosen and tested in the acute rat model. Two chelators were given orally as a single or combined therapy for the period of a week. Cadmium and iron concentrations in various tissues were determined by graphite furnace and flame atomic absorption spectrometry methods, respectively. The combined chelation therapy results show that Deferasirox and L(1) are able to remove cadmium ions from the body while iron concentration returned to the normal level and symptoms are also decreased.

The cumulative effect of three decades of phosphogypsum amendments in reclaimed marsh soils from SW Spain: (226)Ra, (238)U and Cd contents in soils and tomato fruit.

Phosphogypsum (PG), a by-product of the phosphate fertiliser industries, has been applied as soil amendment to reduce Na saturation in soils, as in the reclaimed marsh area from SW Spain, where available PG has a typical fingerprint of 710+/-40 Bq kg(-1) of (226)Ra, 165+/-15 Bq kg(-1) of (238)U and 2.8+/-0.4 mg kg(-1) of Cd. This work was focussed on the cumulative effects of PG amendments on the enrichment of these pollutants in cultivated soils and plants (Lycopersicum esculentum Mill L.) from the area studied, where PG has been applied since 1978 at recommended rates of 20-25 Mg ha(-1) every 2-3 years. A field experiment was conducted over three years to compare activity concentrations of (226)Ra ((214)Pb) and (238)U ((234)Th) in non-reclaimed soils, reclaimed soils with no additional PG application, and reclaimed soils with two additional PG applications. A non-significant effect of two PG amendments (in three years) was observed when compared with non-amended reclaimed plots. Nevertheless, a significant (p<0.05) enrichment of (226)Ra was observed in the surface horizon (0-30 cm) of reclaimed plots relative to deeper horizons and also when compared with the surface horizon of non-reclaimed soil (p<0.05), thereby revealing the cumulative effect of three decades of PG applications. Furthermore, the effect of a continuous application of PG was studied by analysing soils and tomato fruits from six commercial farms with different cumulative rates of PG applied. Cadmium concentrations in tomatoes, which were one order of magnitude higher than those found in tomatoes from other areas in South Spain, were positively correlated (r = 0.917) with (226)Ra-concentration in soils, which can be considered an accurate index of the cumulative PG rate of each farm.

Role of free cadmium and selenium ions in the potential mechanism for the enhancement of photoluminescence of CdSe quantum dots under ultraviolet irradiation.

The present study describes an enhancement of the photoluminescence of CdSe quantum dots under long-term ultraviolet irradiation in organic solvents. The photoenhancement effect followed multiexponential kinetics and was found to depend on several factors: intensity of ultraviolet light, polarity of the solvent, presence of capping agents on the nanocrystal surface, and presence of free Cd and Se ions in the solution. High intensity ultraviolet irradiation provoked a rapid enhancement of the photoluminescence of CdSe nanocrystals, reaching the maximum with subsequent photoluminescence decay. Low-intensity ultraviolet irradiation provoked a comparatively slow enhancement of the photoluminescence of CdSe nanocrystals, reaching saturation after 5-6 hours of irradiation in organic solvents (butanol and chloroform). The photoenhancement effect was reversible or irreversible depending on the additional ingredients. The role of free Cd and Se in these processes was clarified. The results are discussed in the context of ultraviolet induced liberation of free Cd and Se ions from the nanocrystal surface and their hypothetical reversible deposition with trapping of the surface holes and influencing the efficiency of radiative versus nonradiative exciton decay during the enhancement of photoluminescence.

Photoluminescence and raman study of CdS-Al2O3 nanocomposite films prepared by sol-gel techniques.

The optical and microstructural properties of CdS-Al2O3 nanocomposite (CdS-Al2O3 = 20:80 to 50:50) thin films synthesized by sol-gel techniques were studied. Optical transmission spectra indicated a marked blue shift of the absorption edge due to quantum confinement. Band gaps of CdS-Al2O3 nanocomposites were found to vary in the range 3.69-2.61 eV. The sizes of the nanocrystals, estimated from the blue shift (0.2-1.2 eV) of the absorption edges and transmission electron microscopy, were found to vary in the range 2.8-7.0 nm. X-ray diffraction studies showed reflections from (111), (200), (220), and (311) planes of CdS in the cubic phase. Microstructural characterization by high-resolution transmission electron microscope (HRTEM) indicated well crystallinity of the nanoparticles and lattice fringes supported the cubic phase of CdS. Raman spectroscopy was carried out for CdS-Al2O3 nanocomposites, which indicated a prominent peak at approximately 299 cm(-1). Significant changes in the peak position and intensity of the Raman peak were observed with varying the annealing temperature (373-573 K). Photoluminescence measurements indicated a prominent broad peak at approximately 1.81 eV due to the surface defects in the CdS nanocrystallites. The present study revealed Al2O3 to be a good capping material for CdS nanoparticles.

Monodispersed spherical colloids of Se@CdSe: synthesis and use as building blocks in fabricating photonic crystals.

Monodispersed spherical core-shell colloids of Se@Ag(2)Se have been exploited as a chemical template to synthesize Se@CdSe core-shell particles using a cation-exchange reaction. A small amount of tributylphosphine could facilitate the replacement of Ag(+) by Cd(2+) in methanol at 50 degrees C to complete the conversion within 150 min. The orthorhombic structure of beta-Ag(2)Se changed to a well-defined wurtzite lattice for CdSe. The CdSe shells could be converted back to beta-Ag(2)Se by reacting with AgNO(3) in methanol at room temperature. Because of the uniformity in size and high refractive index associated with the Se@CdSe core-shell colloids, they could serve as a new class of building blocks to fabricate photonic crystals with wide and strong stop bands.