In situ and ex situ study of the enhanced modification with iron of clinoptilolite-rich zeolitic tuff for arsenic sorption from aqueous solutions.

Adsorption methods have been developed for the removal of arsenic from solution motivated by the adverse health effects of this naturally occurring element. Iron exchanged natural zeolites are promising materials for this application. In this study we introduced iron species into a clinoptilolite-rich zeolitic tuff by the liquid exchange method using different organic and inorganic iron salts after pretreatment with NaCl and quantified the iron content in all trials by XRF spectroscopy. The materials were characterized by XRD, FTIR, FTIR-DR, UV-vis, cyclic voltammetry, ESR and Mössbauer spectroscopies before and after adsorption of arsenite and arsenate. The reached iron load in the sample T+Fe was %Fe(2)O(3)-2.462, n(Fe)/n(Al)=0.19, n(Si)/n(Fe)=30.9 using FeCl(3), whereby the iron leachability was 0.1-0.2%. The introduced iron corresponded to four coordinated species with tetrahedral geometry, primarily low spin ferric iron adsorbing almost 12 mug g(-1) arsenite (99% removal) from a 360 mug(As(III)) L(-1) and 6 mug g(-1) arsenate from a 230 mug(As(V)) L(-1). Adsorption of arsenite and arsenate reached practically a plateau at n(Fe)/n(Si)=0.1 in the series of exchanged tuffs. The oxidation of arsenite to arsenate in the solution in contact with iron modified tuff during adsorption was observed by speciation. The reduction of ferric iron to ferrous iron could be detected in the electrochemical system comprising an iron-clinoptilolite impregnated electrode and was not observed in the dried tuff after adsorption.

Chromatographic and electrochemical determination of quercetin and kaempferol in phytopharmaceuticals.

An NP-HPLC method both with diode-array (DAD) and electrochemical detection (ED) was developed and validated for the determination of quercetin and kaempferol, the principal active constituents in phytopharmaceuticals of Ginkgo Biloba. Calculated retention of the two flavonoids was contrasted with experimental values in five different reversed phase columns for methanol-water, acetonitrile-water, THF-water and dioxane-hexane binary mixtures as mobile phases. The capacity factor k, selectivity alpha and asymmetry factor F were evaluated and compared in DAD-RP-HPLC, DAD-NP-HPLC, ED-RP-HPLC and ED-NP-HPLC. The methods were used for the quantitative analysis of acid hydrolyzed extracts of tablet phytopharmaceuticals. Calibration curves were linear within the range 10 and 40 microg ml(-1) for the DAD and 10-270 microg ml(-1) for the ED, whereby limits of detection ranged from 0.5 microg ml(-1) (quercetin) to 0.1 microg ml(-1) (kaempferol). The electrochemical method based on differential pulse voltammetry (DPV) with a C-PVC electrode resolved the quercetin and kaempferol peaks and exhibited a two orders higher sensitivity in comparison with a carbon fiber electrode. DPV calibration curves were linear within the range 96-300 microg ml(-1) for quercetin and 68-960 microg ml(-1) for kaempferol. The respective oxidation peaks appeared at 462 and 518+/-2 mV and were used in the direct determination of quercetin in extracts of commercial phytopharmaceuticals.

Degradation of the textile dyes Basic yellow 28 and Reactive black 5 using diamond and metal alloys electrodes.

Basic yellow 28 (SLY) and Reactive black 5 (CBWB), which are respectively methine and sulfoazo textile dyes were individually exposed to electrochemical treatment using diamond-, aluminium-, copper- and iron-zinc alloy electrodes. The generated current was registered with time during electrolysis of the dye solutions and the color variation and the formation of degradation products were followed using HPLC with diode array detection. Four different electrodic materials were tested by applying different potentials in the range -1.0 to -2.5 V and presented 95% color removal and COD removal of up to 65-67% in the case of CBWB dye solution treated with the copper and iron electrodes. Efficiency was enhanced with stirring and flow in relation to the stationary regime. The kinetic parameter reaction rate was used to establish the effect of flow, potential, electrode nature and pH. The formation and characterization of the precipitate formed under certain conditions is reported and discussed.

Removal of metal ions from aqueous solution by adsorption on the natural adsorbent CACMM2.

The adsorption of Cd2+, Cr3+, Cu2+, Fe3+, Ni2+, Pb2+ and Zn2+ from aqueous solution was used to study the sorption properties of the adsorbent CACMM2 extracted from a cactus. Quantitation of the cation concentrations was performed by HPLC with diode array detection using on-column complex formation with 8-hydroxyquinoline. Removal degree from 100 mg M(n+) l(-1) solutions followed the series: Cu>Cd>Fe>Ni>Cr>Zn. Henry and Freundlich constants were determined since adsorption did not reach saturation plateaux in the studied concentration interval. Sorption of chromium by CACMM2 was stronger than the sorption onto lignin, calcium oxalate and cellulose up to 1,000 mg Cr3+ l(-1). Copper and iron were desorbed to a greater extent, while lead adsorption was practically irreversible. CACMM2 was able to remove more than 83% of chromate in a freshly prepared and exhausted chromate commercial solution.

Electrochemical treatment of textile dyes and their analysis by high-performance liquid chromatography with diode array detection.

Several textile dyes were individually exposed to electrochemical treatment. Chromaticity variation and the formation of degradation products were followed using a UV spectrophotometer and HPLC with diode array detection. Dyes studied belong to the azo (color index, C.I. 15,510), methine (C.I. 48,013), indigo (C.I. 73,040), natural (C.I. 75,760) and arylmethane (C.I. 42,000) classes. Aliquots of the solutions treated at constant potential were analyzed and compared with control dye solutions. The final electrolysis solutions obtained by using different electrode materials: Pt, Ti and diamond presented different chromatograms. It was found that the novel (in this application) diamond electrode is efficient in studying the degradation of various dyes. Possible fragmentation and molecule moiety rearrangement are proposed as a result of the electrochemical treatment.