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In this work, the inner filter effect (IFE) of caffeine (CF) over the fluorescence signal of glibenclamide (GLB) was used for the determination of CF in beverage samples. The system worked in a turn-off mode since the absorption spectrum of CF overlaps the excitation band of GLB resulting in a decline in its fluorescence signal (λexc = 234 nm, λem = 350 nm). No changes in the fluorescence lifetime of GLB (0.29 ns) were observed in the presence of CF up to 127.6 mg L-1 concentration. The parameters that affect the fluorescence intensity were investigated, such as fluorophore concentration (16 mg L-1), pH (3.2) and temperature (25 °C). Under optimized conditions, the IFE-based approach can determine CF in a range between 1.00 and 100.0 mg L-1, with a detection limit (LOD) of 0.10 mg L-1. The relative standard deviation (% RSD) values for the intra-day and inter-day precision were 0.75 and 1.24, respectively. The new method was successfully tested in the determination of the target analyte in beverage samples without previous treatment. The results were compared with those obtained by a reference method, leading to the conclusion that there were no significant differences at the studied confidence level (α = 0.05).

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A new green method was developed for the quantification of paraquat (PQ) in water samples based on the fluorescence emission enhancement of the herbicide signal after adsorption on sodium montmorillonite clay (MMT). Radiant emission processes are favored by increasing the molecular rigidity of the PQ since it adopts a planar position between the nano-sheets of the MMT. The advantages of the use of this clay are nontoxic, low cost and found in abundance in natural reserves. The proposed method was successfully used in determining PQ in natural water samples with recoveries of 73% to 95%. The fluorescence emission showed a good linear relationship with PQ concentrations from 2.0 to 8.0 µmol L-1 with a detection limit of 0.37 µmol L-1. The method is simple, inexpensive and does not require the use of reagents or organic solvents; which makes it very promising to achieve the goals of green chemistry. The proposed methodology could be the beginning of the development of future green sensors.

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Phosphate adsorption at the metal oxide-water interface has been intensely studied, and the system phosphate-goethite in aqueous media is normally used as a model system with abundant information regarding adsorption-desorption under very different conditions. In spite of this, there is still discussion on whether the main inner-sphere surface complexes that phosphate forms on goethite are monodentate or bidentate. A new spectroscopic technique, InfraRed Surface Titration (IRST), is presented here and used to systematically explore the surface speciation of phosphate on goethite in the pH range 4.5-9.5 at different surface coverages. IRST enabled to construct distribution curves of surface species and distribution curves of dissolved phosphate species. In combination with the CD-MUSIC surface complexation model it was possible to conclude that surface complexes are monodentate. Very accurate distribution curves were obtained, showing a crossing point at pH5.5 at a surface coverage of 2.0µmolm-2, with a mononuclear monoprotonated species predominating at pH>5.5 and a mononuclear diprotonated species prevailing at pH<5.5. On the contrary, at the low surface coverage of 0.7µmolm-2 there is no crossing point, with the mononuclear monoprotonated species prevailing at all pH. IRST can become a powerful technique to investigate structure, properties and reactions of any IR-active surface complex at the solid-water interface.

RESUMO

The effects of humic acid (HA) on the adsorption/desorption of glyphosate (Gly) on goethite were investigated under pseudo equilibrium conditions by adsorption isotherms and under kinetic conditions by ATR-FTIR spectroscopy. Isotherms reveal that the attachment of Gly is almost completely inhibited by HA molecules. The opposite effect is not observed: HA adsorption is not affected by the presence of Gly. ATR-FTIR allowed the simultaneous detection of adsorbed HA and Gly during kinetic runs, revealing that HA at the surface decreases markedly the adsorption rate of Gly likely as a result of a decreased availability of sites for Gly adsorption and because of electrostatic repulsion. In addition, HA in solution increases the desorption rate of Gly. The rate law for Gly desorption could be determined giving important insights on the desorption mechanism. The herbicide is desorbed by two parallel processes: i) a direct detachment from the surface, which is first order in adsorbed Gly; and ii) a ligand exchange with HA molecules, which is first order in adsorbed Gly and first order in dissolved HA. Rate constants for both processes were quantified, leading to half-lives of 3.7 h for the first process, and 1.4 h for the second process in a 400 mg L(-1) HA solution. These data are important for modeling the dynamics of glyphosate in environmentally relevant systems, such as soils and surface waters.

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The desorption of glyphosate from goethite as induced by the adsorption of phosphate was investigated by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy in combination with adsorption isotherms. Desorption of glyphosate was very low in the absence of phosphate. Addition of phosphate promoted glyphosate desorption. At low initial surface coverages, added phosphate adsorbed on free surface sites, mainly, displacing a small amount of glyphosate. At high initial surface coverages, on the contrary, phosphate adsorption resulted in a significant glyphosate desorption. In the latter conditions, the ratio desorbed glyphosate to adsorbed phosphate was 0.60. The desorption process can be explained by assuming that phosphate adsorbs first forming a monodentate mononuclear complex, which rapidly evolves into a bidentate binuclear complex that displaces glyphosate.

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The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4-10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acid

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The binding between an oxazine dye and a humic acid was studied in aqueous solutions in the pH range 4-10 and in the supporting electrolyte (KCl) range 0.001-0.1M. A rather simple spectrophotometric method was developed to construct binding isotherms under conditions were traditional centrifugation or filtration methods fail. The use of this method is possible because humic acid molecules have the ability of changing the spectrum of dye molecules, and this ability is used to quantify the isotherms. All binding isotherms have a Langmuirian shape. The amount of bound dye is strongly dependent on the ionic strength and less dependent on the pH of the solution. The binding is rather strong and mainly driven by non-electrostatic forces. Whereas the Langmuir binding constant is independent of the pH and electrolyte concentration, the number of assessable sites in humic acid for binding oxazine increases by increasing pH and decreasing electrolyte concentration. These results can be directly related to the flexibility of humic acid molecules, which can swell at high pH and low ionic strength, increasing consequently the availability of binding sites. The results also indicate that humic substances may strongly affect the mobility and fate of dyes and related pollutants in the environment.

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