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A novel lead-free 2D perovskite, namely PEA2SnBr4, shows impressive water-resistance by retaining its original crystal structure and optical properties when placed in contact with water. Such key properties have been advantageously used for the fabrication of a novel co-catalytic system by coupling PEA2SnBr4 with graphitic carbon nitride. PEA2SnBr4/g-C3N4 composites at different metal halide perovskite loadings (5 and 15 wt%) have been prepared and tested in hydrogen photogeneration in an aqueous environment and organic dye degradation (methylene blue). The results show an impressive enhancement of H2 production of the composite with respect to the two separate components with hydrogen evolution rates up to 1600 μmol g−1 h−1 and analogous improvements in the efficiency of methylene blue degradation. The present results, providing a novel water-resistant perovskite and co-catalytic system, pave the way towards the safe, efficient and real use of metal halide perovskites in catalysis.

The application of hybrid photocatalysts made of carbon nitride and lead-free perovskites, namely DMASnBr3/g-C3N4 and PEA2SnBr4/g-C3N4, for the H2 evolution from saccharides aqueous solution is described. The novel composites were tested and compared in terms of hydrogen evolution rate (HER) under simulated solar light, using Pt as a reference co-catalyst, and glucose as a representative sacrificial biomass. The conditions were optimized to maximize H2 generation by a design of experiments involving catalyst amount, glucose concentration and Pt loading. For both materials, such parameters affected significantly H2 photogeneration, with the best performance observed using 0.5 g L&minus, 1 catalyst, 0.2 M glucose and 0.5 wt% Pt. Under optimized conditions, DMASnBr3/g-C3N4 showed a 5-fold higher HER compared to PEA2SnBr4/g-C3N4, i.e., 925 &micro, moles g&minus, 1 h&minus, 1 and 190 &micro, 1, respectively (RSD &le, 11%, n = 4). The former composite, which affords an HER 15-fold higher in aqueous glucose than in neat water, provided H2 also with no metal co-catalyst (around 140 &micro, 1), and it was reusable for at least three photoreactions. Encouraging results were also collected by explorative tests on raw starch solution (around 150 &micro, 1).

In this study, we aimed to investigate in vitro whether the synthetized indium maltolate (InMal) and gallium maltolate (GaMal) could exert either a toxic effect toward breast cancer cell line MDA-MB-231 or an agonistic activity with mitoxantrone (MTX) in comparison to fibroblast cell line NIH-3T3. Both GaMal and InMal reduced viability of MDA-MB-231, and at a lesser extent of NIH3-T3, in a dose- and time-dependent mode, the outcome was more effective in comparison to MTX sole exposure. Both GaMal and InMal toxicity was reverted by iron citrate addition on NIH3-T3, not on MDA-MB-231, showing indirectly that gallium and indium's mechanisms of action may include iron targeting. The agonistic activity against MDA-MB-231 survival was shown pretreating with 100 μM InMal for 24 h followed by medium exchange with MTX at 10 ng mL-1 or vice-versa but not with co-incubation of both compounds. In particular, InMal pretreating resulted more protective to MTX subsequent exposure.

The search for new environment-friendly visible-light absorbing catalysts is an urgent task. g-C3N4 has excellent photocatalytic properties and the possibility of developing cost-effective routes to make this material a viable alternative to the currently used catalysts is required. In this work, we show that a simple chemical oxidation process of g-C3N4 with nitric acid allowed significantly enhancing the hydrogen photogeneration from aqueous triethanolamine, under simulated solar light. An 8-fold improvement of the H2 production, with respect to the pristine sample, was achieved by properly controlling the physical-chemical parameters of the oxidation process, reaching a value of about 4000 μmol g-1 h-1, which is one of the highest hydrogen production rates for bulk g-C3N4. Such high levels of photocatalytic activity result from the combination of improved surface area and changes in the electronic structure induced by the oxidation process.

The treatment of corpses with extremely acid or basic liquids is sometimes performed in criminal contexts. A thorough characterization by chemical analysis may provide further help to macroscopic and microscopic analysis; 63 porcine bone samples were treated with solutions at different pH (1–14) for immersion periods up to 70 days, as well as in extremely acidic sulfuric acid solutions (9 M/18 M) and extremely basic sodium hydroxide. Inductively coupled optical emission spectrometry (ICP-OES)/plasma mass spectrometry (ICP-MS), Fourier transform infrared spectroscopy (FT-IR), energy dispersive X-ray analysis (EDX), X-ray powder diffraction (XRPD), and scanning electron microscopy (SEM) showed that only the sulfuric acid solution 18 M was able to completely dissolve the sample. In addition, chemical analysis allowed to recognize the contact between bone and substances. Hydrated calcium sulfate arose from extreme pH. The possibility of detecting the presence of human material within the residual solution was demonstrated, especially with FT-IR, ICP-OES, and EDX.

Two sensors for the detection of the metal ion Cu(II), based on the same sensing layer, are compared. They rely on different transduction methods, i.e., electrochemistry and surface plasmon resonance (SPR). D,L-penicillamine was used as the specific receptor since it is a strong ligand for copper(II). Moreover it is easily immobilized on a gold layer by a self assembling procedure by contacting the gold layer overnight with water/EtOH (80/20) containing D,L-penicillamine, taking advantage of the spontaneous interaction of thiols with gold surfaces. Both the electrochemical and SPR platforms were derivatized in the same way. In the first case a gold disc was used as working electrode, and in the second one a thin gold layer (60 nm thick) was deposited by sputtering over the exposed core of a plastic optical fiber (POF), after removing the cladding along half circumference.

Nanosized titanium dioxide immobilized on silica gel was synthesized and used as fixed-bed phase for V(V) pre-concentration, followed by inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. Three different sorbents were prepared by sol–gel method starting from a mixture of titanium isopropoxide, 2-propanol and water, and characterized by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and BET analysis. V(V), the most stable and toxic oxidation state of the element, present in water and beverages samples, was selectively sorbed, pre-concentrated, quantitatively eluted by 0.1 M HCl and analyzed by ICP-OES. The effectiveness of the procedure was first assessed on tap water enriched with 1 μg L−1 of V(V) obtaining recoveries up to 92% (n = 4). The pre-concentration step was then optimized for complex matrices such as tea infusions and red and white wines. The reliability of the procedure was assessed on the same beverages samples spiked with 20–250 μg L−1. Quantitative recoveries (82–95%, n = 4) were assured avoiding any sample pre-treatment, generally essential in such complex matrices, obtaining good precision (RSD

Highly sensitive plasmonic optical fiber platforms combined with receptors have been recently used to obtain selective sensors. A low-cost configuration can be obtained exploiting a D-shaped plastic optical fiber covered with a multilayer sensing surface. The multilayer consists of a gold film, functionalized with a specific receptor, where the surface plasmon resonance (SPR) occurs. The signal is produced by the refractive index variation occurring as a consequence of the receptor-to analyte binding. In this work, a selective sensor for copper(II) detection in drinking water, exploiting a self-assembled monolayer (SAM) of d,l-penicillamine as the sensing layer, has been developed and tested. Different concentrations of copper(II) in NaCl 0.1 M solutions at different pH values and in a real matrix (drinking water) have been considered. The results show that the sensor is able to sense copper(II) at concentrations ranging from 4 &times, 10-6 M to 2 &times, 10-4 M. The use of this optical chemical sensor is a very attractive perspective for fast, in situ and low-cost detection of Cu(II) in drinking water for human health concerns. Furthermore, the possibility of remote control is feasible as well, because optical fibers are employed.

Two different zinc-based metal-organic frameworks (MOFs) were investigated to remove one of the most used fluoroquinolone antibiotic, Ofloxacin (OFL), from polluted water. The most common zeolitic imidazolate framework-8 (ZIF-8) and the green Zn(II) and benzene-1,3,5-tri-carboxylate (Zn3(BTC)2) were prepared through a facile synthetic route and characterized by means of Fourier-Transform Infrared (FT-IR) Spectroscopy, X-Ray Powder Diffraction (XRPD), and Scanning Electron Microscopy (SEM) analyses. The two MOFs were compared in terms of both adsorption and kinetic aspects under real conditions (tap water, natural pH). Results showed that OFL was adsorbed in remarkable amounts, 95 ± 10 and 25.3 ± 0.8 mg g−1 on ZIF-8 and Zn3(BTC)2, respectively, following different mechanisms. Specifically, a Langmuir model well described the ZIF-8 profile, while for Zn3(BTC)2, cooperative adsorption occurred. Moreover the kinetic results were quite different, pseudo-second-order and sigmoidal, respectively. The suitability of ZIF-8 and Zn3(BTC)2 as adsorbent phases for water depollution was tested on tap water samples spiked with OFL 10 µg L−1. The obtained removal efficiencies, of 88% for ZIF-8 and 72% for Zn3(BTC)2, make these materials promising candidates for removing fluoroquinolone antibiotics (FQs) from polluted waters, notwithstanding their limited reusability in tap water, as demonstrated by in-depth characterization of the two MOFs after usage.

This paper provides a review of the latest applications of carbon-based materials for magnetic solid-phase extraction (MSPE), an advantageous sample pre-treatment increasingly adopted in analytical chemistry. In particular, this review focuses on the pre-concentration procedures developed for the determination of various classes of pollutants in environmental matrices. Beside the recent advances in the application of carbon nanotubes (CNTs), the newest carbonaceous materials have been considered, namely differently arranged nanocarbons (NCs), graphene (GN) and graphitic carbon nitride (g-C3N4). The analytical performance of the magnetic composites was critically discussed in relation to the physical–chemical properties resultant from the synthetic routes. The new sorbents generally afforded high extraction efficiency, good selectivity in complex matrices and durability for tens adsorption/desorption cycles, mainly due to high surface area, chemical stability, dispersibility in aqueous solution and, importantly, multi-type interaction. In particular, this was greatly enhanced by combining magnetic GN with other substrates or using derivatized GN, obtaining mixed-mode sorbents. The ease of preparation, durability and high enrichment factor make this new generation of MSPE carbon-based sorbents a valid alternative to the commercial solid phases.

The aim of this work is the systematic study of the photocatalytic activity of bulk graphitic carbon nitride (g-C3N4) in relation with the physical-chemical, structural and optical properties of the semiconductor. Fourteen g-C3N4 samples have been prepared by thermal condensation starting from three different precursor (melamine, dicyandiamide and urea) and exploring various temperatures (in the range 500-700 °C). The materials obtained have been deeply characterized by high resolution scanning electron microscopy, thermogravimetric analysis, X-ray diffraction, nitrogen adsorption measurements (BET method), X-ray photoelectron spectroscopy and diffuse reflectance spectroscopy. Each semiconductor, coupled with Pt co-catalyst, was tested for hydrogen gas production from aqueous triethanolamine as model sacrificial agent, under simulated solar light. The hydrogen evolution profiles turned out to be strictly dependent on precursor type and synthesis temperature, with the highest evolution rate observed for the samples series produced from urea (up to ca. 4400 μmol g−1 h−1). The results, corroborated by the excellent inter-day precision of irradiation tests (RSD < 5%, n = 3) together with the good batch-to-batch reproducibility (RSD < 11%, n = 3), were critically discussed. Apart from the appealing production values obtained using the as-prepared materials, it was importantly pointed out that, besides crystallinity and visible light absorption, the photocatalytic behavior is definitely correlated to the surface area, which is dependent on the synthesis conditions, that is polymerization temperature and nature of g-C3N4 precursor. Overall, this systematic investigation demonstrated that, contrary to the polymerization degree (sp2/sp3 carbon ratio), surface area is the real determinant parameter for g-C3N4 hydrogen evolution activity. © The Royal Society of Chemistry.

This work presents the results obtained in using olive mill wastewater (OMW) as sacrificial agent for the photocatalytic H 2 evolution from water, at ambient temperature and pressure. The effects of irradiation time, catalyst amount, pH, and OMW concentration have been investigated. Under the best experimental conditions (4 h UV-A irradiation, 2 g L −1 Pt/TiO 2 , OMW 3.3% v/v, COD 944 mg L −1 , pH 3) up to 44 μmol H 2 were generated from aqueous samples. Consecutive irradiation cycles (4 × 4 h) on the same sample provided ca. 280 μmol H 2 , corresponding to 82% of the yield observed, under the same conditions and COD value, by using glucose as test sacrificial agent. H 2 evolution was strongly improved (+81%) by pre-treating OMW with magnesium silicate (125 g L −1 , 6 h contact), achieving a production of ca. 80 μmol H 2 by 4 h UV-A irradiation. The possibility to exploit sunlight in the photocatalytic process was gained by using Eosin Y/Pt/TiO 2 . Under solar light the H 2 yield resulted to be 66% with respect to that obtained by UV-A radiation. Beside some general mechanistic aspects of the photocatalytic process, benefits and drawbacks in recycling OMW for photocatalytic H 2 evolution from water have been highlighted.

This is the first-time reporting on the photocatalytic production of hydrogen gas (H2) via water splitting in the presence of swine sewage (SS) as sacrificial agent. H2 was evolved upon both UV-A and solar light irradiation in presence of platinised titania as the catalyst. The influences of irradiation time, catalyst amount, pH and SS concentration on the reaction yield were investigated. Under the best conditions, up to 50 μmol of H2 were produced from aqueous SS (1.7% v/v, COD 82 mg L−1), with good within-laboratory reproducibility (RSD

Borosilicate materials are of interest for many technological applications. Whereas sol-gel techniques are well suited for the preparation of these materials, the nominal concentration of boron is often not maintained, and a considerable amount of boron is lost during the preparation procedure. In this work we deal with the synthesis of borosilicate systems in order to analyse the problem of the boron loss. Different sol-gel precursors of B2O3 were explored and organically modified silicon alcoxide were tested, in addition P2O5 co-doping was proposed. IR spectroscopy, differential Scanning Calorimetry, Thermogravimetry and ICP-OES analyses were performed. Sol-gel synthesis of SiO2-B2O3 xerogels with a high boron content (>18 wt.%) was successfully obtained by employing trimethoxyboroxine and 3-aminopropyltriethoxysilane. (C) 2012 Elsevier B.V. All rights reserved.

A gold electrode modified by chemisorption of Coenzyme A (CoA-CME) has been prepared. Exploiting its complexation properties towards heavy metal ions usually present in natural waters, it was shown that CoA has a stronger interaction with Cu than with the Pb and Cd; the complexation constants of bounded CoA with these ions were calculated by a novel approach. The metal ions can be determined in natural waters at the CoA-CME by open circuit preconcentration followed by medium exchange in citrate buffer before the anodic stripping voltammetry. The presence in solution of competing ligands and important aspects regarding the complexation were investigated.

The photochemical fate of Marbofloxacin (MAR) and Enrofloxacin (ENR), two Fluoroquinolones (FQs) largely used as veterinary bactericides known to be present in surface waters, was investigated in aqueous solution. The degradation of these pollutants (5-50 microg L(-1) starting concentration) was complete in about 1 h by exposure to solar light (summer) and obeyed a first-order kinetics. The structure of the primary photoproducts was determined. Those from ENR arose through three paths, namely, oxidative degradation of the piperazine side-chain, reductive defluorination, and fluorine solvolysis. More heavily degraded products that had been previously reported were rationalized as secondary photoproducts from the present ones. As for MAR, this underwent homolytic cleavage of the tetrahydrooxadiazine moiety to give two quinolinols. All of the primary products were themselves degraded in about 1 h. The photoreactions rates were scarcely affected by Ca(2+) (200 mg L(-1)), Mg(2+) (30 mg L(-1)), Cl(-) (30 mg L(-1)), and humic acid (1 mg L(-1)), but increased in the presence of phosphate (20 mg L(-1)). The fastest degradation of ENR occurred at pH about 8 where the zwitterionic form was present, while in the case of MAR the cationic form was the most reactive.

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) microM. To control and maintain pH and pCO(2) constant during AGNES measurements, a novel device for N(2)/CO(2) mixed purging has been developed.

A chemically modified electrode (CME) on a gold surface assembled with a ω-phosphonic acid terminated thiol was investigated for its capability to complex uranyl ions. The electrode, characterized by electrochemical techniques, demonstrated to be effective for the determination of uranyl at sub-μgL(-1) level by differential pulse adsorptive stripping voltammetry (DPAdSV) in environmental waters, also in presence of humic matter and other potential chelating agents. The accuracy of the measurements was investigated employing as model probes ligands of different complexing capability (humic acids and EDTA).

The aim of this paper was to evaluate silicon (Si) concentration in human whole ventricular blood as a further potential chemical marker in the diagnosis of drowning. We employed an acidic digestion for the extraction of soluble Si, and an alkaline digestion for the determination of total Si, including particulate matter, both arising from drowning medium. 29 suspected drowning situations, 24 in fresh water (Fw) and 5 in seawater (Sw), were examined. The difference in Si concentration between the left and right ventricular blood (Si ΔL-R) was measured and alkaline Si ΔL-R seems, indeed, a potentially significant complementary tool in the diagnosis of Fw drowning, because insoluble silicon fraction does not undergo hemo-dilution or hemo-concentration, and the ΔL-R is not affected by exogenous factors. In spite of the limited number of cases investigated, a good correlation was observed between the analytical results and the macro-microscopic autoptic findings.

d , l -Penicillamine and thiodimethylglyoxime (TDMG) self-assembled monolayers (SAMs) on gold electrode were prepared and characterized by electrochemical measurements. The two sensors exhibit sensitive and selective response to Cu(II), both forming 2:1 complexes, the first one in acetic buffer and the second one in ammonia buffer. Copper determination at trace level (LOQ 0.2 and 0.3 μg/L for d , l -penicillamine and TDMG, respectively) is possible with both the electrodes as verified in tap, spring and sea water. The influence on copper determination of most common ions present in natural waters and of organic matter has been investigated. Accuracy was checked by recovery test on spiked samples.

Trace element (TE) characterization and analysis in epiphytic lichens collected in different areas of the Himalayas (Nepal) and of the Alps (Italy) is presented. The results give information for the assessment of TE distribution present in the two different areas. The evaluation of the enrichment factors may provide information for many elements about their association to long-distance atmospheric transport phenomena. To this purpose, samples of superficial soils, collected in the same areas of those of the lichens, have also been analyzed. Most of the trace elements were determined by instrumental neutron activation analysis (INAA), while lead and cadmium measurements were carried out with electrothermal atomic absorption spectroscopy (ET-AAS).

A 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) sorb...

A speciation method of inorganic nickel compounds in airborne particulate, based on selective sequential extractions, is described. It allows the separation and the determination of Ni(0), Ni(II) soluble salts such as sulphate and chloride, Ni insoluble compounds such as nickel oxide and sulphide, to which a different toxicity and therefore a different risk are related. The nickel concentration in each fraction was determined by Flame or Furnace Atomic Absorption Spectroscopy. The proposed procedure has been tested first, on synthetic samples prepared with the different nickel compounds, in the presence of atmospherical particulate matter not containing nickel, in order to take into account the possible matrix influence. The speciation was then repeated on four different samples (fly ash deriving from a solid waste incinerator and three RSMS from NIST: Coal Fly ash SRM 1633b, Urban Particulate 1648, Washington Dust 1649), followed by an evaluation of matrix spiking and recovery analyses. Performing multiple analyses of the spiked samples assessed the repeatability of the procedure.

A thermal treatment at 900°C (under nitrogen) of a milled mixture MnO-Fe2O3 yields MnFe2O4 mainly as the product of the reaction between Mn3O4 (produced by ball milling) and Fe2O3. Under the same experimental conditions but starting from an unmilled MnO- Fe2O3 mixture, the formation of MnFe2O4 is only partial and occurs through Mn3O4 (formed by oxidation of MnO). The same thermal treatment (900°C under nitrogen) of a milled Mn3O4-Fe2O3 mixture yields MnFe2O4 mainly as the product of the reaction between Mn3O4 and Mn2O3/MnO2 (the higher Mn oxides being produced by ball milling) and Fe2O3. The effect of high energy milling is more pronounced in the case of the Mn3O4-Fe2O3 system since no MnFe2O4 formation is observed when starting from a physical mixture.

This work presents a systematic study of cellulose (CLS) as a sacrificial biomass for photocatalytic H2 evolution from water. The idea is indeed to couple a largely available and not expensive biomass, and water, with a renewable energy like solar radiation. An aqueous CLS suspension irradiated either at 366 nm (UV-A) or under sunlight in the presence of Pt/TiO2 behaves as a H2 evolving system. The effects of irradiation time, catalyst and CLS concentrations, pH and water salinity are studied. Addition of CLS to the sample significantly improved H2 evolution from water splitting, with yields up to ten fold higher than those observed in neat water. The mechanism of the photocatalytic process relies on the TiO2-mediated CLS hydrolysis, under irradiation. The polysaccharide depolymerisation generates water-soluble species and intermediates, among them 5-hydroxymethylfurfural (HMF) was identified. These intermediates are readily oxidized following the glucose photoreforming, thus enhancing water hydrogen ion reduction to give gas-phase H2. The formation of “colored” by-products from HMF self-polymerization involves a sort of “in situ dye sensitization” that allows an effective photoreaction even under solar light. The procedure is evaluated and successfully extended on cellulosic biomasses, i.e. rice husk and alfalfa (Medicago sativa) stems, not previously investigated for this application.

This article presents the first results demonstrating that total silicon trace concentration in human ventricular whole blood may be used as a further marker in the diagnosis of drowning. The difference in silicon content between the left and right ventricles was significantly higher for drowning cases than that from individuals who had not drowned. These findings were in full agreement with autoptic responses, supporting silicon as a marker of freshwater drowning. The procedure entails an alkaline microwave-assisted digestion using tetramethylammonium hydroxide (TMAH) in the presence of H(2)O(2) followed by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) detection, whose accuracy was obtained for Seronorm whole blood reference material. Satisfactory recoveries (91-98%) were gained on whole ventricular blood, with a silicon content lower than the method detection limit (MDL), spiked at 5 to 7μgg(-1) with materials consistent with drowning media constituents, that is, freshwater plankton (CRM [certified reference material] 414), silicon dioxide, diatomaceous earth powder, and a silicon standard solution. Good within-lab reproducibility (4-10%) and sensitivity (MDL=0.46μgg(-1)) were achieved as well. The procedure was applied to blood samples from 18 different real cases of death.

We report a facile strategy to obtain multiwalled carbon nanotubes (MWCNTs) functionalized with covalently bonded lysozyme. The functionalization procedure has been investigated by means of several techniques, including thermogravimetry, Raman spectroscopy, transmission electron microscopy, and cyclic voltammetry. A functionalization of about 1 lysozyme molecule every 4000 carbon atoms is obtained. The modified lysozyme-CNTs nanocomposite shows a significant increase of the antibacterial activity towards the Gram-positive S. aureus if compared with lysozyme in solution.

The periodic analytical control of waste landfill leachate is of fundamental importance not only to check the presence of possible toxic substances, but also to assess changes in concentration levels and behaviour with time. This work identifies some of the difficulties which arise during the analysis of some heavy metals and trace elements in leachate samples from a controlled industrial wastes landfill located in north Italy. The analytical problems encountered using both electro-thermal atomic absorption spectroscopy (ETAAS) and neutron activation analysis (NAA) for the determination of a series of elements, Cu, Cd, Pb, Ni, Mn, V, As, Se, Sb, Th, Sn, Cs, W, Cr, with concentration often at nanogram levels, are presented and evaluated. To solve these problems two selective chemical procedures have been developed to separate and to eliminate the matrix interfering compounds or elements (i.e., organic matter, complexing agents, Cl − , Br − , S 2− , Na + ) which reduce and in some cases impair the sensitivity of the technique. For the analyses by ETAAS a preliminary preconcentration and separation procedure, based on the ion exchange resin Chelex-100 has been developed to determine Pb, Cd, Co, Cu, Ni and Sn. In the case of NAA a specific radiochemical separation had to be studied for the analysis of Sn, V, W, Mn, Cr, As, Sb, Se, Th in presence of high bromine and sodium concentrations. Procedures blanks and yields have been controlled and evaluated and quality assurance measurements have been carried out analyzing, with the proposed methods, standard reference materials from BCR and NIST. Furthermore, different mineralization procedures using both microwave and Teflon bomb have been compared and evaluated.

A method based on selective sequential dissolutions is proposed to determine total vanadium(V) in particulate matter of emissions and working areas at concentrations 1,000 times lower than the threshold limit of 0.05 mg m(-3). Separation and preconcentration of vanadium(V) has been achieved by solid-phase extraction on Chelex 100 resin. Possible influence of the matrix has been investigated for two standard reference materials (SRMs), NIST SRM 1648 and BCR-038, before and after spiking, with vanadium(V) recovery in the range 97-103%.

In this paper we provide a detailed biochemical and structural characterization of the active site of recombinant human prolidase, a dimeric metalloenzyme, whose misfunctioning causes a recessive connective tissue disorder (prolidase deficiency) characterized by severe skin lesions, mental retardation and respiratory tract infections. It is known that the protein can host two metal ions in the active site of each constituent monomer. We prove that two different kinds of metals (Mn and Zn) can be simultaneously present in the protein active sites with the protein partially maintaining its enzymatic activity. Structural information extracted from X-ray absorption spectroscopy measurements have been used to yield a full reconstruction of the atomic environment around each one of the two monomeric active sites. In particular, as for the metal ion occupation configuration of the recombinant human prolidase, we have found that one of the two active sites is occupied by two Zn ions and the second one by one Zn and one Mn ion. In both dinuclear units a histidine residue is bound to a Zn ion.

A speciation method was developed for the determination of inorganic indium compounds in the particulate matter of emissions and from the workplace, based on selective sequential extractions. The main inorganic indium compounds that are expected to be present in the atmospheric particulate matter involving the industrial production of indium and in the manufacture of indium compounds were separated and determined. The procedure has been tested on standard reference materials. The indium recovery was in the range 93 - 105%.

The aluminium species in different tea infusions were investigated, by determining their stability constants and concentration. This was done for some particular samples using a simple experimental method based on the sorption of aluminium on the strongly sorbing resin Chelex 100, by a batch procedure. From the thermodynamic information obtained it is possible to calculate the concentration of the different species, and in particular that of the free metal ion, which is very important for evaluating the adsorption of aluminium on biological membranes. It was found that aluminium in the tea infusions here considered is present at high total concentration, approximately 0.1 mM, but mainly linked to strong complexes, for instance with side reaction coefficient higher than 10(5.11) at pH 3.95 in one case (tea 1). This could be the reason for the low toxicity of aluminium in tea. These strong complexes were not dissociated even in the presence of Chelex 100. In this case only a limiting value of the reaction coefficient could be evaluated. The presence of the very strong complexes was found in all the tea sample here considered. In two of the considered samples (one black and one green tea) a part of Al(III) was linked to less strong complexes, for example with a reaction coefficient 10(4.14) (tea 2, pH 4.20). The presence in the considered tea infusions of other substances able to complex aluminium was also detected, by the well known ligand titration procedure, at concentration ranging from 0.65 to 3.37 mM in three tea infusions, and at somewhat higher concentration in the case of the ready drink, which was also considered for comparison.

Within the framework of the Ev-K2-CNR research program of the Italian National Research Council a specific task project has been initiated for the identification of trace elements in lichens in remote high altitude areas. This is to evaluate the possibility of using lichens as biomonitors of trace elements of atmospheric pollution. In this preliminary study, more than 20 elements havebeen determined in some species of lichens collected at different altitudes (from 1300 to 5000 in) in the region of the Sagarmatha National Park (Nepal). Samples of superficial soils were also collected and analyzed to calculate the trace element enrichment factors (EF) using scandium as a normalizing element. Most of the trace elements were determined by instrumental neutron activation analysis (INAA), while lead and cadmium measurements were carried out with electrothermal atomic absorption spectroscopy (ET-AAS). The EF values as well as the elemental concentrations are reported and discussed.

A sequential extraction procedure for separating and determining Be(0), soluble Be(II) inorganic compounds, BeO and beryllium silicates in samples such as particulate matter of emissions and working areas, has been developed. The proposed procedure has been tested on synthetic samples prepared with the inorganic beryllium compounds, in the presence of atmospherical particulate matter sampled in a laboratory of the Department, previously checked for the absence of beryllium. The speciation was then repeated on a sample of fly ash deriving from a solid waste incinerator and on a reference material (Coal Fly ash SRM 1633a, by NIST), followed by an evaluation of matrix spiking and recovery analyses. Performing multiple analyses of the spiked samples assessed the repeatability of the procedure. Quantitative determinations have been made by inductively coupled plasma optical emission spectrometry (ICP-OES) and electrothermal atomic absorption spectrometry (ETAAS). The possible interferences of the most common ions have been investigated. The selective sequential extractions allow one to separate and to determine different inorganic beryllium species, to which a different toxicity and therefore, a different risk are related: it is the case for example of metallic beryllium and beryllium oxide.

A sequential extraction procedure for separating and concentrating soluble Cd(II) salts, CdO, Cd(0), CdS, CdSe and cadmium-aluminosilicates, has been developed for the cadmium speciation in samples such as particulate matter in emissions and working areas. The proposed procedure has been tested first on synthetic samples prepared in a laboratory with the different cadmium salts, then also in the presence of atmospherical particulate matter sampled in a laboratory of the Department of Analytical Chemistry, previously checked for the absence of cadmium. Finally the speciation was tested on particulate matter collected near the emission of a power plant fed by coal, after emission's treatment by electrostatic precipitator: matrix spiking and recovery analyses have been evaluated and the repeatability of the cadmium speciation was assessed by performing multiple analyses of the spiked samples. Quantitative determinations have been made by FAAS and GFAAS through the standard additions method.

A model which allows the evaluation of the elution volume V(E) and the central point V(C) of the breakthrough curve of a metal ion at trace level on a chromatographic column containing a chelating resin is presented. V(E) and V(C) mainly depend on the complexation properties of the active groups, and on the acidity and composition of the aqueous solution, according to the Gibbs-Donnan model for the resin. The model has been tested in the case of strong base anion exchange resins in chloride form functionalized with two different sulphonated azo ligands (T-azo-C, T-azo-R). The chromatographic behaviour of copper(II) and thorium(IV) is as expected from the formation of a complex with the azo dye in the resin, while that of zinc(II) and cadmium(II) is fully described by also taking into account the formation of anionic chloro complexes inside the resin.

Gallium(III) is sorbed by a strong base anion exchange resin loaded with a sulphonated azo-dye, T-azo-R [1-(tetrazolylazo)-2-hydroxynaphthalene-3,6-disulphonic acid], which is able to complex it in aqueous solution. As sorption takes place at acidities at which the hydrolysis of gallium is not negligible, it must be considered as conconmitant equilibrium. The distribution equilibria depend on the amount of ligand sorbed, and on the volume, acidity and ionic composition of the aqueous solution, according to the Gibbs-Donnan model. The thermodynamic complexation constant in the resin phase can be calculated from the experimental distribution coefficients; the value of log K = −1.24(0.20) is in acceptable agreement with that in aqueous solution [log K = −0.75(0.33)] which was also determined in the present investigation. Two equations deriving from the Gibbs-Donnan model are used for predicting the conditions for sorption and elution of gallium by a batch procedure, and for separating it from aluminium.

Cyclic voltammetric scans for methylarsonic acid, dimethylarsinic acid and 3-acetamido-4-hydroxyphenylarsonic acid at a mercury electrode in an acidic medium show anodic adsorption waves when the starting potential is sufficiently negative; the related arsines are formed on the electrode. Detection limits are at the micromolar level for the absorption peak found at about −0.1 V vs. SCE for all three compounds. Interferences are discussed.

The protonation coefficients of three poly(amido-amino acid) resins (GLY, ALA, GABA) and of one poly(amido-amine) resin (RN2C4) were determined at 25°C, in sodium chloride and sodium sulphate aqueous solutions. The results can be interpreted on the basis of the existence of a Donnan potential at the interface resin-solution, due to the fact that all the ionic species, excepted those which are permanently linked to the backbone of the resin, are free to diffuse between the two phases. The importance of the activity coefficients inside and outside the resin phase is pointed out. The calculated intrinsic protonation constants are in good agreement with the protonation constants of the proper monomeric models.

Etudes electrochimiques, fonction de la temperature, du comportement du couple redox Ni IV /Ni II , complexe a des macrocycles contenant de l'azote (tetraaza-1,4,8,11 cyclotetradecane, pentaazacyclohexadecane, triazacyclononane, etc.)

Le complexe d'Ag(II) avec l'hexamethyltetraazacyclotetradecane, en solution aqueuse, subit une oxydation reversible a un electron avec formation du complexe d'Ag(III)

Two sulphonated azo-dyes, which bear a nitrogen donor atom in the diazo group and are known to complex many heavy metal ions in aqueous solution, have been found to be sorbed by a strong-base anion-exchange resin (Dowex 1-X8) simply by ion-exchange. The resin containing the dyes behaves like a chelating resin, able to sorb copper(II) and nickel(II) from aqueous solution, if the proper conditions are chosen. The acidity, ionic composition and volume of the aqueous solution, and the amount and nature of the sorbed ligand are the factors which determine the fraction of metal ion sorbed when the batch technique is used. The experimental results are interpreted by using a model of the resin based on the Donnan equilibrium concept, which allows prediction of the sorption conditions on the basis of some independently determined quantities, such as the protonation and complex formation constants in aqueous solution, and the activity of the counter-ion in the resin phase. The exchange of protons between the resin and the aqueous solution can also be explained with this model.

A method for determining iodate and iodine(+1) in aqueous solutions is proposed. The assay is similar to a previously described method for the determination of iodide and iodine(0), which were titrated with standard iodate in hydrochloric acid solution. A sample solution made 0.5–1.5 M in hydrochloric acid is titrated with a standard iodide solution and monitored spectrophotometrically at 230 nm. The species involved have strong absorbances that are well differentiated at this wavelength. By combining the two titrations it is possible to resolve any mixture of species of iodine in different oxidation states. The precision of the method (standard deviation) is the same both when determining a single species (IO–3, I+, I2 or I–) and a mixture, and is equal to 2 × 10–7M. Chloride and bromide, even at very high concentrations, do not interfere.

Concentrated hydrochloric acid is added to samples of natural waters containing 2 × 10–7–5 × 10–5M iodine and the solutions are then oxidised with hydrogen peroxide on a boiling water-bath. They are then reduced with sodium sulphite, which is subsequently removed by bubbling a stream of inert gas through the solution. All of the inorganic iodine, now present in the solution in the –1 oxidation state, can be titrated spectrophotometrically with standard potassium iodate solution, following a method previously described in which interferences from oxidants and reductants are eliminated.

The sulphonated azo dye Chromotrope 2B is sorbed quantitatively by the strong anion exchanger AG 1-X8. A chelating resin is obtained, which is able to sorb aluminium from aqueous solutions selectively. The distribution equilibria were investigated under different conditions and interpreted on the basis of a Donnan equilibrium based model for the resin. A separation and pre-concentration method for aluminium in natural waters is proposed, based on the use of the modified resin in a column at ambient pressure. The selectivity with respect to other metal ions was good; this was to be expected because Chromotrope 2B in solution is also selective for aluminium. Recoveries of 100 ± 1% were obtained, with a pre-concentration factor of 50, at a total aluminium concentration of 2 × 10–6 mol kg–1.