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Chromatographic separations of complex phenol mixtures are accomplished using different elution conditions on three diverse stationary phases. The best resolution is obtained on a C 18 stationary phase; 28 phenolic compounds are separated in a single run. An optimized cleanup and preconcentration procedure based on liquid-liquid extraction with methylene chloride is set up. Identification of the individual substances is made highly reliable by using multidimensional chromatography

The occurrence of some cases of positive results in anti-doping analysis of octopamine requires clarification as to whether its methylated derivative synephrine could be a metabolic precursor of octopamine itself. Synephrine is a natural phenylethylamine derivative present in some food supplements containing Citrus aurantium, permitted in sport regulations. A simulative laboratory study had been done using a photocatalytic process, to identify all possible main and secondary transformation products, in a clean matrix; these were then sought in biological samples obtained from three human volunteers and four rats treated with synephrine; the parent compound and its new potential metabolic products were investigated in human urine and rat plasma samples. The transformation of synephrine and octopamine and the formation of intermediate products were evaluated, adopting titanium dioxide as photocatalyst. Several products were formed and characterized using the HPLC-HRMS(n) technique. The main intermediates identified in these experimental conditions were compared with the major synephrine metabolites found in in vivo studies on rats and humans. Some more oxidized species, already formed in the photocatalytic process, were also found in urine and plasma samples of treated animals. These new findings could be of interest in further metabolism studies. The main photocatalytic pathway involving synephrine appears to be N-demethylation to give octopamine. On the contrary, we demonstrate the inconsistency of this reaction in both rat and human in vivo determinations, resulting in forensic importance.

Reversed-phase high performance liquid chromatography with diode array detection was used to analyze phenolic compounds contained in bark extracts of two different poplar clones known to have different resistance toDiscosporium populeum infection. Statistical treatments both monovariate and multivariate were applied to the results in order to identify regularities useful to discriminate the polar resistance and to check the importance of seasonal and cultivation site related factors. For the two clones examined phenolic compounds showed great discrimination ability not influenced by either sample collection period or cultivation site.

Two horses were treated with sildenafil, and its metabolic products were sought in both urine and plasma samples. Prior to this, a simulative laboratory study had been done using a photocatalytic process, to identify all possible main and secondary transformation products, in a clean matrix; these were then sought in the biological samples. The transformation of sildenafil and the formation of intermediate products were evaluated adopting titanium dioxide as photocatalyst. Several products were formed and characterized using the HPLC/HRMS(n) technique. The main intermediates identified in these experimental conditions were the same as the major sildenafil metabolites found in in vivo studies on rats and horses. Concerning horse metabolism, sildenafil and the demethylated product (UK 103,320) were quantified in blood samples. Sildenafil propyloxide, de-ethyl, and demethyl sildenafil, were the main metabolites quantified in urine. Some more oxidized species, already formed in the photocatalytic process, were also found in urine and plasma samples of treated animals. Their formation involved hydroxylation on the aromatic ring, combined oxidation and dihydroxylation, N-demethylation on the pyrazole ring, and hydroxylation. These new findings could be of interest in further metabolism studies.

N.l.- L'etude du mouvement des liquides a travers des materiaux poreux conduit en general a des “problemes a frontiere libre”, Un cas typique peut etre schematise sous la forme suivante: sur une base impermeable deux bassins d'eau, de niveaux differents, sont en communication a travers une digue en materieau poreux. L'eau filtre du niveau le plus eleve au niveau le moins e1eve et on veut determiner la “partie mouillee” de la digue, ainsi que les grandeurs physiques (telles que la pression, la vitesse, le debit…) associees au mouvement.

Capillary SFC with supercritical CO2 as mobile phase and flame ionization detection was adopted to separate and determine triacylglycerols in vegetable and fish oils. The effect on separation of many experimental variables has been checked along with the selectivity of several stationary phases of different polarity. A standard mixture of 13 triacylglycerols was used to optimize the procedure and their retention times were used as reference to identify peaks in real samples. In spite of the fact that many peaks remained unidentified, the chromatograms obtained were useful as fingerprint analyses of the real samples examined.

Pneumatically assisted electrospray was demonstrated to be a powerful ionization source for the analysis of oligosaccharides. A mass spectrometer was interfaced to an HPLC system, using this interface, to determine oligosaccharides from the enzymatic digestion of heparin separated on a reversed-phase column. To set up the technique, and particularly to clarify the ionization process, purified disaccharides, from enzymatic digestion of chondroitin sulphates, were measured. The use of a suitable counter ion in the mobile phase, tetrapropylammonium (TPA to optimize the HPLC separation, gave, with sulphated di- and oligosaccharides, adducts [M + nTPA - (n + m)H]m-, which were unexpectedly stable to fragmentation; molecular ions [M - (n + 1)H]n−, in the presence of the counter ion, were observed only with desulphated or monosulphated disaccharides. The stability of the adducts and the use of a deuterated ion-pair reagent permitted an exact evaluation of the molecular masses of disaccharides and oligosaccharides of unknown structure. Spectra obtained in the absence of the counter ion contained singly or multiply charged molecular ions and fragmentation ions mainly from loss of the sulphate groups; under these ionization conditions the exact mass determination and interpretation of the spectra were difficult. After removal of the counter ion, tandem mass spectra could be obtained with some interesting data for the characterization of these molecules. Complete spectral analyses were performed with amounts of samples of 50 μg but, using microbore columns, one twentieth of this amount may give good spectra.

The phenolic content in the bark of poplar trees was analysed by RP-HPLC with the aim of finding some evidence of a relationship between the presence of phenols (either the total amount or the amount of an individual specific compound) and the differential resistance to the fungus Dothichiza populea that is found in different clones of these trees. Direct comparison of chromatographic results did not allow any useful information to be gleaned on this subject. On the other hand, the application of principal component analysis and linear discriminant analysis methods to the quantitative chromatographic data gave very promising results, allowing discrimination between resistant and susceptible poplars and the identification of phenolic compounds that are important for such discrimination.

The equivalence between stabilized finite element methods (or Galerkin-least-squares tyoe methods, Ga.l.s.) and the standard Galerkin method with bubble functions is established in an abstract framework. The results are applicable to various finite element spaces, including high order elements, and applications to the advective diffusive model and to the Stokes problem are presented, illustrating the potential of the abstract theory introduced here.

An efficient RP-HPLC separation technique was used in combination with mass spectrometric detection with an ionspray ionization source to analyse complexes between nucleosides and cis -dichlorodiamineplatinum(II). Conventional detection techniques (UV and atomic absorption spectrometry) were also used as starting points for the setting-up of this HPLC-MS approach. The method was developed using complexes obtained either by reaction of free deoxynucleosides with cis -dichlorodiamineplatinum or by reaction in vitro of DNA samples with the same drug. DNA samples before HPLC-MS were completely depolymerized by digestion with nuclease P1 and alkaline phosphatase, in order easily to separate and determine the complexes formed. The sensitivity obtained makes this technique very suitable for future application in biological studies. The detection level, defined as the detector response with a signal-to-noise ratio of 2, corresponds to 2 pmol injected. In DNA samples treated with cis -dichlorodiamineplatinum, a series of cis -dichlorodiamineplatinum—deoxynucleoside complexes not previously described were also detected.

To promote bio-based products for the industry, six bio-organic substances (cHALi) isolated from yard trimmings (green) and food (humid) urban residues aged under aerobic digestion for 0–60 days were investigated for their potential to perform as sensitizers for azo-dyes photodegradation. Ethylorange (EO) was used as probe molecule at 5 mg L −1 starting concentration and irradiated in a closed Pyrex ® cell with a Xenon (1500 W) lamp and a cut-off filter for wavelengths below 340 nm or in a cylindrical photochemical reactor equipped with a 125 W medium pressure Hg lamp. The cHALi/EO ratio in the starting EO solution varied in the 0–200 (w/w) range. The % dye abatement was found a function of the irradiation time, of the type of cHALi substance and of the cHALi/EO ratio. The best results were achieved with cHALi isolated after 7 days biomass aerobic digestion. Total dye abatement was achieved within relatively short few hours. A progressive dye mineralization was observed under the same experimental conditions. On the contrary no significant degradation was evident for the cHALi substances within the same irradiation time. Several hydroxylated azo compounds were identified as likely responsible of residual color after total EO abatement. The results, coupled to the previously reported good performance of the same cHALi substances as auxiliaries for textile dyeing, augur well for the development of both efficient and environmentally friendly textile dyeing processes.

An ealier mathematical model for the prediction of retention times, under gradient elution conditions, on the basis of experimental isocratic data was validated by examining different classes of chemical compounds (amines, aldehydes and hydroxy-, amino- and methylquinolines) with various stationary and mobile phases. Here, the range of validity of the model is extended by using several polynuclear aromatic hydrocarbons, which exhibit apolar properties and chemical geometries very different from those of the compounds previously envisaged. The present data and the earlier data are used to provide a definite relationship between the error of prediction and the retention times.

Glycosaminoglycan contents were evaluated in plasma and urine samples from volunteers treated intravenously with a mixture of dermatan sulphate and heparin, combining a novel liquid chromatographic-mass spectrometric technique for the determination of oligosaccharides from glycosaminoglycans with a classical technique for the extraction of glycosaminoglycans from biological samples (precipitation with cetylpyridinium chloride). In plasma samples dermatan sulphate and heparin can be measured for 2 h after treatment; urine excretion was detectable for 24 h. These results suggest that this novel approach is promising for future studies on the pharmacokinetics of glycosaminoglycans, although some technical aspects need further improvement, mainly regarding the procedures for sample clean-up; cetylpiridinium precipitation is a complex procedure and the recovery is limited.

A method to determine polyunsaturated fatty acids (linoleic and α-linolenic acids and its long chain metabolite, DHA) in milk samples, avoiding the fat separation step, was developed and validated. The transesterification reaction was carried out directly on freeze-dried milk samples to produce fatty acid methyl esters. Separation, identification and quantification of analytes were performed by GC-MS. In these experimental conditions the matrix effect was negligible. Values for repeatability and intermediate precision demonstrate excellent method precision. To test the method applicability, goat's, cow's and human's milk with different fat contents and essential fatty acids concentrations were examined.

Pattern recognition techniques were applied to the classification of essential mint oils using their gas chromatographic data. A study has been completed on 59 samples of three different geographic origins: U.S.A., France and Italy. Principal component analysis provided new variables for an effective classification of the samples according to the different areas of origin. The pattern of the result was further analysed by means of a fuzzy clustering algorithm which permitted the quantification of the differences between the three classes. The chemical information contained in the gas chromatographic data was sufficient to characterize the geographic origin of the samples.

High-performance liquid chromatography coupled to ultraviolet diode array detection and electrospray ionization mass spectrometry was applied to monitor the photocatalytic degradation mediated by TiO2 of three sulfonated monoazo dyes (Orange I, Orange II, and Ethylorange) present in aqueous solution. Photobleaching, organic carbon, nitrogen and sulfur evolution were also followed during the process. Delayed carbon mineralization was observed with respect to both dyes disappearance and photobleaching, due to the formation of transient intermediate compounds which were in turn completely degraded. Among the intermediates produced during the initial degradation steps the formation of several hydroxylated derivatives, mostly coloured, was evidenced. The MS(2) spectra allowed one to formulate hypothesis about the OH attack positions; a peculiar reactivity of the azo moiety was shown by Orange I and Orange II.

We have studied the photocatalytic transformation of atenolol, 4-[2-hydroxy-3-[(1-methyl)amino]propoxyl]benzeneacetamide, a cardioselective β-blocking agent used to treat cardiac arrhythmias and hypertension, under simulated solar irradiation using titanium dioxide as photocatalyst. The investigation involved monitoring drug decomposition, identifying intermediate compounds, assessing mineralization, and evaluating toxicity. High-performance liquid chromatography (HPLC) coupled to high-resolution mass spectrometry (HRMS) via an electrospray ionization (ESI) interface was a powerful tool for the identification and measurement of the degradation products; 23 main species were identified. Intermediates were characterized through their chromatographic behavior and evolution kinetics, coupled with accurate mass information. Through the full analysis of MS and MSn spectra and a comparison with parent drug fragmentation pathways, the diverse isomers were characterized. Neither atenolol nor the intermediates formed exhibit acute toxicity. All intermediates are easily degraded and no compound identified could withstand 2 h irradiation. Photomineralization of the substrate in terms of carbon mineralization and nitrogen release was rapid and, within 4 h of irradiation, organic nitrogen and carbon were completely mineralized. Copyright © 2008 John Wiley & Sons, Ltd.

The RP-HPLC technique has been applied to the analysis of the flavonoid content of leaf extracts from various genotypes ofPopulus nigra andPopulus deltoides and from several of their hybrids. Two elution procedures different either as regards gradient program or the type of organic modifier used were checked to optimize the reliability of the results obtained. Before making any identification, the chromatographic profiles proved so typical of each species as to allow of their use as fingerprints in this type of taxonomic problem. Individual identifications were carried out by spiking real samples with known amounts of standard substances. The presence of flavonoid compounds previously identified was confirmed and a few new identifications were proposed.

We present an abstract stabilization method which covers previous concrete applications to advection-diffusion equations and to the Stokes equations for incompressible fluids. We then apply the method to stabilize domain decomposition formulations for elliptic problems. We obtain a method that allows the treatment of internal variables, interface variables and Lagrange multipliers (normal derivatives) by piecewise polynomials of arbitrary order.

The analysis of diuretic compounds has become of great concern because of their extensive use both in therapy and in illicit treatments (such as masking agents in sport doping and drug abuse). The variety of chemical structures of this class of drugs encouraged the development of new methods and techniques of analysis, especially as regards to acidic compounds. LC/MS has so grown to be the reference technique for this kind of analysis in forensic and anti-doping confirmation purposes. Multiple stage MS permits identification of single drugs with high selectivity, but some unexpected pathways could weaken the entire process. In this work we aim to explain some unusual fragmentation steps using high-resolution MSn. For example, in the case of amiloride an intense product ion in MS3 analysis generates an apparent loss of 10Da. Water adduct formation and successive carbon monoxide elimination can explain this uncommon behavior, which was studied using different ion traps. Bendroflumethiazide MSn spectra show instead three successive HF losses, in spite of the presence of a radical site in the parent structure. Homolytic cleavages with radical ion production occur also in the case of protonated positive ion of ethacrynic acid (loss of chlorine radical) showing that such fragmentation behavior is not so rare as generally reported. Different ionization modes were studied and a tentative correlation with acidic-base properties was done. Multiple stage high-resolution mass spectra of positive and negative ions were discussed.

Thiourea methyl-derivatives photocatalytic degradation has been studied by adopting titanium dioxide as a photocatalyst. A combined study has been performed and had involved: (1) the study of (methyl)thioureas degradation rate; (2) the identification of intermediate compounds, obtained by HPLC tandem mass spectrometry and (3) the assessment of the mineralization process. Thiourea is mainly transformed into cyanamide and urea and then (very slowly) mineralized (up to 24 h of irradiation are required). For its methyl derivatives, the formation of the corresponding methylureas is realized; in addition, several dimeric compounds have been identified. Methyl thiourea gives the formation of CH3NHC(NH)CH2NHCONHCH3 and methylcyanamide dimeric form, while dimethylthiourea forms NCNHCH(OH)CH2NHCONHCH3, but no cyano derivatives are observed. The rate of mineralization gets higher at the increasing of the number of the methyl groups. Sulphur is easily released as sulphate ions in all cases. The nitrogen is preferentially released as ammonium ions, with a ratio ammonium versus nitrate ions of 2:1, observed in all cases but with dimethylthiourea, where instead an initial major formation of ammonium ions, at the increasing of the irradiation time a slight inversion between nitrate and ammonium formation is seen.

A method is presented for the detection of six toxins of fungal origin in various foods: peanuts, a sample of maize feed and whole milk. Extraction and HPLC-APCI-MS detection were discussed. The performances of MS/MS, MS3 and SRM detection modes were checked and best conditions of sensitivity were obtained in MS/MS mode.

Diclofenac (2-[2,6'-(dichlorophenyl)amino]phenylacetic acid) is a non-steroidal anti-inflammatory drug used to treat inflammatory and painful diseases of rheumatic and non-rheumatic origin. The present work deals with the photocatalytic transformation of diclofenac, under simulated solar irradiation using titania suspensions as catalyst, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The variation of TiO2 amount and initial diclofenac concentration on the reaction rate, were systematically investigated. The use of the response surface methodology allowed to fit the optimal values of the parameters leading to the degradation of the pollutant. Also, a single polynomial expression modeling the reaction was obtained. Photomineralization of the substrate in terms of chlorine ions release was rather a quick process (within 1 h), while the amino moiety is mainly transformed into NH4+ and in a lesser extend into NO3- ions. Evolution of CO2 (loss of TOC) was found to occur within 2 h of irradiation. LC/MS was brought to bear in assessing the temporal course of the photocatalyzed process. Based on our findings a tentative degradation pathway is proposed for the photocatalytic degradation of diclofenac based on the formation of hydroxy-derivatives before the complete mineralization of the starting molecule. In addition Microtox bioassay (Vibrio fischeri) was employed in evaluating the ecotoxicity of solutions treated by photocatalysis. Results clearly demonstrate the efficiency of the photocatalytic process in the detoxification of the irradiated solution. (c) 2006 Elsevier B.V. All rights reserved. Applied Catalysis B-Environmental

Azoxystrobin, carbendazim, and mepanipyrim, widely used heterocyclic fungicides, have been photocatalytically degraded in aqueous solution on TiO2. Several concomitant pathways occur, concerning re...

The light-induced degradation of alkylurea derivatives under simulated solar irradiation has been investigated in aqueous solutions containing TiO(2) as a photocatalyst. Herein, we will focus on how the presence of one or more methyl (or ethyl) groups on urea modifies the kinetics of disappearance and influences both the ratio and the extent of the inorganic nitrogen formation caused by different degradation pathways. In the present work, we have elucidated a mechanism for the formation of transformation products of the alkyl derivatives by combining several analytical and spectroscopic procedures and the theoretical simulation of ab initio calculations. In all cases, N-demethylation represents only a secondary pathway, while the main transformation proceeds through an unexpected cyclization, involving (m)ethyl- and di(m)ethylureas with the formation of (methyl)amino-2,3-dihydro-1,2,4-oxadiazol-3-one as the principal intermediate of the reaction (with a yield of 60 %). This behaviour is rather unexpected and in contrast with the typical photocatalyzed transformation pathways, which proceed through the formation of more simple structures.

Salvinorin A is the most potent naturally occurring hallucinogen known and rivals synthetic LSD in potency. Structurally it belongs to the neoclerodane diterpenoids, and it is the only known non-nitrogenous kappa-opioid-selective agonist. Salvia divinorum (Diviner's sage) is a member of the mint family that was used in ancient Mexican traditional practices. Today it is widely cultivated in Europe as a recreational marijuana substitute; it is illegal to buy, sell or possess the plant or the active principle in some countries. Six different salvinorins and three divinatorins have been isolated from Salvia divinorum leaves. The ion fragmentation, separation and quantitation of these diterpenes by liquid chromatography/electrospray ionization multistage mass spectrometry (LC/ESI-MSn) are described. The importance of LC in herbal extract determination and the chemical diagnostic power of MSn in the analysis of classes of natural organic products are discussed. Copyright © 2005 John Wiley & Sons, Ltd.

Cinosulfuron is a sulfonylurea herbicide largely used in the extensive cultures of flooded rice in North Italy. The degradation of cinosulfuron has been investigated in sterile aqueous solutions at 30 degrees C at different pH values. It was rapidly degraded at acidic pH (half-lives 3, 9 and 43 days at pH 4, 5 and 6, respectively) while the half-life was1 year at pH 7 and 9. Two degradation products formed by cleavage of the sulfonylurea bridge were identified by LC-MS. Degradation by selected mixed microbial cultures tested in aerobic and anaerobic conditions was very slow and attributable to chemical hydrolysis due to the acidic pH of the cultural broths. Degradation took place in freshly collected rice field water treated for two years with cinosulfuron but, in this case also, chemical hydrolysis prevailed over microbial degradation. In contrast, in flooded sediment simulating the paddy field environment, the dissipation rate of cinosulfuron was higher than expected from chemical hydrolysis according to the pH of the system, indicating the involvement of soil microflora. Although the herbicide exhibited a reduced affinity for the sediment surfaces demonstrated by the low value of the K(f) Freundlich coefficient (0.87 on a micromolar basis), the rapid dissipation observed in the simulated paddy field should prevent its leaching to ground water.

This study deals with the biodegradation of the polycyclic aromatic hydrocarbons (PAH)s present in a soil contaminated by soot waste, characterised by a total PAHs content in the 200 mg kg(-1) range. A challenging characteristic of the waste soil treated was its high alkalinity, with a pH of about 12.8. The waste came from a soot-contaminated area located in the industrial zone of Porto Marghera, Venice (Italy). The biodegradation process employed was the composting of the waste with sewage sludge and yard waste. The process was carried out on a pilot scale using a closed tank with forced aeration for a period of 60 days, followed by 70 days with natural aeration. The time evolution of the process was monitored by following the time change in the concentration of the 16 US-EPA PAHs, as well as temperature, pH, electrical conductivity, C and N contents. Also phytotoxicity parameters, such as the growth and respiration indexes, were monitored. An induction time of about 30 days was observed, which corresponded to the time required before observing a significant self-drop in the waste pH and an increase in mass temperature. Afterward, a progressive drop in the PAHs concentration was observed, up to reaching after 130 days an overall degradation percentage in the order of 68%. The degradation was more effective on rather low molecular weight PAHs (2-4 rings).

Benzene (B) is a typical micro-pollutant present in air, especially urban air. In this study a possible correlation between personal benzene exposure and S-phenylmercapturic acid (S-PMA) as a biomarker of internal dose was evaluated in a cohort of traffic policemen. The results confirm that S-PMA is significantly correlated to benzene measured in personal air. B and S-PMA were analyzed considering seasonality, work quarters, time spent indoors, outdoors, and directing traffic, but no significant differences were recorded.

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the MicrotoxTM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs). Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water. Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.

The degradation of Methyl Orange (C(14)H(14)N(3)SO(3)Na), chosen as a model sulfonated azo dye, was investigated in aqueous solutions containing suspended polycrystalline TiO(2) particles under irradiation with simulated sunlight. The dye disappearance and the formation of the mineralization end products were monitored; the formation of the main transient intermediates was also examined in detail. Particular attention was devoted to the identification and to the evolution of fragments retaining the chromophoric group. The comparison of data coming from various analytical techniques led to a possible reaction mechanism for the degradation process, giving insight into an aspect of the treatment which has not been considered in previous studies.

The photocatalytic transformation of buspirone, an analgesic anxiolytic drug, and the formation of intermediates products have been evaluated by adopting titanium dioxide as a photocatalyst. Several molecules resulting from buspirone degradation have been identified and characterized by using HPLC/MS/MS technique. The main intermediates formed in these experimental conditions agree with the major buspirone metabolites found “in vivo” on rats and horses: hydroxy and dihydroxy-buspirone, despyrimidinyl buspirone and 1-pyrimidinyl piperazine. This shows that the photocatalytic system could provide in the present case a useful simulation of the metabolic transformation of dopant substances. Moreover, some more oxidized species have been recognized with the photocatalytic process, and this could offer a suggestion for yet to come metabolism studies.

The photocatalytic oxidation of methyl-orange (C14H14N3SO3Na) dye was carried out in aqueous suspensions of polycrystalline TiO2 irradiated with artificial light until its complete mineralization was achieved. The performances of two widely used semiconductor powders were studied for comparison purposes. The dependence of dye photo-oxidation rate on various experimental parameters, including substrate concentration, semiconductor amount, and pH was investigated by using both catalysts. The observed dye degradation rates followed pseudo-first order kinetics with respect to the substrate concentration under the experimental conditions used. The two investigated TiO2 powders (Degussa P25 and Merck) showed different photoactivities. TOC analyses confirmed the complete mineralization achievable using both photocatalysts. Three main transient products still maintaining the chromophoric azo group were identified prior to their transformation into other degradation products which are non-absorbing in the visible region.

The purpose of this study is to artificially produce degradation intermediates of thiabendazole, which could be reasonably similar to those really present in the environment. The formation of by-products from thiabendazole transformation has been evaluated by adopting irradiated titanium dioxide as a photocatalyst. Several species more hydrophilic than the thiabendazole have been identified and characterized by HPLC-multiple MS. A pattern of reactions accounting for the observed intermediates is proposed. Two different parallel pathways are operating (and through these pathways the transformation of the molecule proceeds) leading to several intermediate compounds. The main steps involved are: (1) the hydroxylation of the molecule on the aromatic ring with the formation of a species having [M+H]+ 218; a further oxidation leads to the ring-opening and to the formation of aldehydic and alcoholic structures ([M+H]+ 270, 268 and 152); and (2) the cleavage of a C-C bond and the formation of a species having [M+H]+ 119.

The photocatalytic transformation of dexamethasone and the formation of its intermediate compounds have been studied using titanium dioxide as a photocatalyst. The degradation of dexamethasone occurs easily through the formation of several hydroxy derivatives whose characterization has been made by HPLC/MS/MS. Even if both oxidative and reductive processes can be operating, only oxidative products have been identified in air saturated aqueous suspensions. A pattern of reaction pathways accounting for the observed intermediates is proposed. The obtained experimental evidence may be rationalized postulating the existence of a double initial mechanism. A single oxidation step resulting from the attack by one ·OH radical leading to the formation of five hydroxy-derivatives and a concomitant attack involving two ·OH radicals leading to the hydroxylation of the quinoid moiety of the molecule.

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almeria” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H2O2, S2O82−) and some ions (Cl−, SO42−) on the process was also studied.

The photocatalytic degradation of the anthraquinonic dye Acid Blue 80 in aqueous solutions containing TiO2 dispersions has been investigated. The process has been monitored by following either the disappearance of the dye (via HPLC) and the formation of its end-products (via IC, GC, and TOC analysis). Although a relatively fast decolorization of the solutions has been observed, the mineralization is slower, and the presence of residual organic compounds was evidenced even after long term irradiation, confirming the relevant stability of anthraquinone derivatives. The identification of various unstable intermedi ates formed after low irradiation times was performed by HPLC-MS, allowing us to give insight into the early steps of the degradation process which mainly involve C−N bonds breaking and substrate hydroxylation. Complete and relatively fast mineralization of the substrate was achieved by irradiating the semiconductor dispersions in the presence of added K2S2O8.

The presence of sulphonated derivatives of naphthalene was investigated in river, tap and bottled water samples, by means of HPLC with fluorescence detection and GC-MS, after SPE pre-concentration and, in the case of GC-MS analysis, derivatization. These methods showed detection limits in the low ng/L range, and were capable of providing spectroscopic information on the unknown substances, which were of help for assessing the presence of target analytes in the examined samples. In particular, concentrations ranging from 8.9 to 220 ng/L of 2-naphthalenesulphonate were found in samples of the Italian rivers Po and Sangone, and concentrations of this same substance ranging from 6 to 21 ng/L of were found also in the tap water of the city of Torino, part of which is collected from the river Po. The presence of 2-naphthalenesulphonate at concentrations close to the detection limits of both analytical techniques was also suspected in some samples of bottled water.

Principal component analysis and classification techniques were used to investigate the effect on the properties of wine of different fungicide treatments performed on the grapes. 55 variables were determined, 17 on the grape just-collected and the others on the wines. 27 samples of grape and wine were considered, produced in 1992, 1993" acceptdate="and 1994. The wines were classified as a function of the production year but no important correlation was found between fungicide treatment and the wine features. The classification was performed by a SIMCA method. Clustering analysis, on the other hand, allowed a separation of the wine samples in three clusters, relative to three main kinds of grape treatments, i.e. based on i) copper sulfate, ii) copper hydroxide and iii) Mancozeb (the only one that does not contain Cu). The treatments based on copper oxychloride and the blank, that are the less active or characterized treatments, gave mixed results within the three clusters.

Etude de l'Ag(II) en solutions aqueuses. Oxydation de H 2 O, des ions metalliques, des composes organiques

The kinetics and mechanism of oxidation of a series of alcohols, namely cyclohexanol, cyclopentanol, pentan-2-ol and benzyl alcohol, by silver(II) perchlorate in perchloric acid solution. have been investigated by the stopped-flow technique. These oxidations proceed through two parallel pathways involving Ag2+ and AgOH+ species. In the case of benzyl alcohol, the hydroxo species, which has been found to be almost universally reactive toward different organic substrates, is inactive; this behaviour has been interpreted in terms of interaction of the oxidant with the aromatic moiety in the alcohol. The reactivities are discussed in terms of substrate reaction sites with reference to electronic availability and reaction products.

We prove an algebraic result which gives a new characterization of the A-stability property for linear multistep methods. This enables us to obtain a new simple proof of the equivalence between A-stability and G-stability for one-leg methods. Using the algebraic result, we also give an alternative proof of the second Dahlquist barrier.

The kinetics and mechanisms of the oxidation of 4,4′-biphenyldiol ([1,1′-biphenyl]-4,4′-diol, I) to 4,4-biphenoquinone ([bi-2,5-cycloexadiene-(1,1′-cycloexadiene-(1,1′-ylidene)]-4,4′-dione, II) as well as the oxidative decomposition of II by means of some metal ions (MnIII, CeIV and AgII) have been investigated in aqueous perchlorate media at different temperatures and acidities. The oxidation of I follows the empirical rate law: − d[I ] d t = k[ I][M ]f([ H + ]) , where M represents the oxidizing metal ion, and the decomposition of II: − d[II] d t = k′[ II ][ M ] a f′([ H + ]) , where a = 1 for AgII and a = 0 for CeIV and MnIII. The reaction mechanisms are proposed.

A new method of studying unconfined flow through porous media has been illustrated. This method is based on the use of variational inequalities which allows us to obtain uniqueness and existence theormes.

Un problema di frontiera libera (moto di un fluido attraverso una diga in terra non omogenea) e ricondotto allo studio di una disequazione variazionale. Si danno condizioni sul coefficiente di permeabilita sufficienti ad assicurare che la parte bagnata della diga e un sottografico.

Gradient elution RP-HPLC has been applied to the separation of the constituents of synthetic tanning agents. Information obtained from the chromatographic results was used to assess the possibility of optimizing the conditions of synthesis, to find out the number of species formed and to make a start at correlating the composition of the tanning agents and their properties.