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The applicability of a direct injection UHPLC-MS/MS method for the analysis of several perfluoroalkyl acids (PFAAs) in a wide range of water matrices was investigated. The method is based on the direct injection of 100µL of centrifuged water sample, without any other sample treatment. Very good method detection limits (0.014-0.44ngL -1 ) and excellent intra and inter-day precision (RSD% values in the range 1.8-4.4% and 2.7-5.7%, respectively) were achieved, with a total analysis time of 20min per sample. A high number of samples - i.e. 8 drinking waters (DW), 12 ground waters (GW), 13 surface waters (SW), 8 influents and 11 effluents of wastewater treatment plants (WWTP IN and WWTP OUT ) were processed and the extent of matrix effect (ME) was calculated, highlighting the strong prevalence of |ME| < 20%. The occurrence of |ME| > 50% was occasionally observed only for perfluorooctanesulphonic and perfluorodecanoic acids. Linear discriminant analysis highlighted the great contribution of the sample origin (i.e. DW, GW, SW, WWTP IN and WWTP OUT ) to the ME. Partial least square regression (PLS) and leave-one-out cross-validation were performed in order to interpret and predict the signal suppression or enhancement phenomena as a function of physicochemical parameters of water samples (i.e. conductivity, hardness and chemical oxygen demand) and background chromatographic area. The PLS approach resulted only in an approximate screening, due to the low prediction power of the PLS models. However, for most analytes in most samples, the fitted and cross-validated values were such as to correctly distinguish between | ME | higher than 20% or below this limit. PFAAs in the aforementioned water samples were quantified by means of the standard addition method, highlighting their occurrence mainly in WWTP influents and effluents, at concentrations as high as one hundred of µgL -1 ., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A comprehensive investigation on the CE separation mechanisms and on the inclusion complexation with CyDs of the chiral drug S-ambrisentan (S-AMB), its R-enantiomer and other impurities was performed by different techniques. A CE method was previously set up allowing the simultaneous determination of the enantiomeric purity and of impurities of S-AMB, based on the addition of SDS micelles and γ-cyclodextrin (γCyD) to borate buffer. In this study, the electrophoretic behavior of the analytes in terms of selectivity and mobility with respect to the addition of different CyDs was first investigated, evidencing the presence of interactions for all the CyDs, but the unique ability of γCyD for obtaining the separation of all the compounds. By molecular modeling, aggregates between SDS micelles and analytes, and inclusion complexes between CyDs, SDS and/or analytes of different stoichiometries were simulated. The potential and the gain energy of complexes were calculated on the minimized conformations, showing the great tendency of γCyD of forming mixed complexes with one or two SDS molecules and with the analyte, even if with different affinities among the analytes. For 1:1:1 mixed complexes with different CyDs, the highest difference of potential energy between the enantiomers' complexes was observed for γCyD. Two-dimensional NOE spectroscopy experiments were performed for S-AMB and I 1 and pointed out the interactions of the aromatic moiety of the analytes and of SDS aliphatic chain with γCyD protons, confirming the existence of γCyD mixed complexes. The high affinity of SDS for the γCyD cavity was suggested to justify the fundamental role of SDS in modulating and achieving the CE separation, due to its influence both on the stability and on the type of complexes between γCyD and the analytes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Ultra-high-performance liquid chromatography coupled with high-resolution quadrupole-time of flight mass spectrometry with both negative and positive ionization was used for comprehensively investigating the phenolic and polyphenolic compounds in berries from three spontaneous or cultivated Vaccinium species (i.e., Vaccinium myrtillus, Vaccinium uliginosum subsp. gaultherioides, and Vaccinium corymbosum). More than 200 analytes, among phenolic and polyphenolic compounds belonging to the classes of anthocyanins, monomeric and oligomeric flavonols, flavanols, dihydrochalcones, phenolic acids, together with other polyphenolic compounds of mixed structural characteristics, were identified. Some of the polyphenols herein investigated, such as anthocyanidin glucuronides and malvidin-feruloyl-hexosides in V. myrtillus, or anthocyanindin aldopentosides and coumaroyl-hexosides in V. uliginosum subsp. gaultherioides and a large number of proanthocyanidins with high molecular weight in all species, were described for the first time in these berries. Principal component analysis applied on original LC-TOF data, acquired in survey scan mode, successfully discriminated the three Vaccinium berry species investigated, on the basis of their polyphenolic composition, underlying one more time the fundamental role of mass spectrometry for food characterization.

A fast and selective capillary electrophoresis method has been developed for the simultaneous determination of the antihypertensive drugs captopril and hydrochlorothiazide and their related impurities in a combined dosage form. Method development was carried out implementing each step of Quality by Design workflow, the new paradigm of quality outlined in International Conference on Harmonisation Guidelines. Captopril is characterized by the lack of a strong chromophore and contains a proline-similar moiety, which gives rise to the presence of interconverting cis-trans isomers and leads to the possible interference between electrophoretic migration and reaction of isomerization. The scouting phase was dedicated to the investigation of several operative modes in order to overcome detection and isomerization issues. The best performances were obtained with sodium cholate-based micellar electrokinetic chromatography with the addition of n-butanol and γ-cyclodextrin. Critical quality attributes were represented by the critical resolution values and by analysis time. Critical process parameters were defined as temperature, voltage, concentration and pH of borate buffer, concentration of sodium cholate, n-butanol and γ-cyclodextrin. Screening experimental design was applied for investigating knowledge space. Response surface methodology pointed out several significant interaction effects, and with Monte-Carlo simulations led to map out the design space at a selected probability level. Robustness testing was carried out and a control strategy based on system suitability tests was defined. The selected working conditions gave a complete separation of the analytes in less than three minutes. The method was validated and applied to the analysis of a real sample of coformulation tablets., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Glyphosate is a worldwide-used herbicide occurring in many monitoring campaigns. Efficient technologies are currently unavailable for glyphosate removal from waters. In this work, a SBA-15 mesoporous silica-based material (Fe-NH 2 -SBA-15) was synthesized and studied for the adsorption of glyphosate from waters. In order to promote specific interactions between the sorbent and glyphosate via phosphoric group, iron oxide nanoparticles were encapsulated and a surface functionalization with (3-aminopropyl)triethoxysilane was accomplished. The adsorption of glyphosate on Fe-NH 2 -SBA-15 was investigated as a function of (i) pH, (ii) ionic strength (I), and (iii) adsorbate to adsorbent ratio (C), using a two-level, three-factor experimental design. The experimental design allowed for understanding the effect of the abovementioned variables and for proposing experimental conditions for quantitative removal (pH = 2.1, I = 1⋅10 -2  M and C = 0.35) under both batch and dynamic conditions. Interaction mechanism between glyphosate and Fe-NH 2 -SBA-15 sorbent was elucidated by studying the adsorption behavior of sorbents derived from the intermediate stages of synthesis and by desorption tests. Fe-NH 2 -SBA-15 sorbent can be quantitatively regenerated by 12.5 mM NaOH, and can be reused at least for five adsorption/desorption cycles. Quantitative removal of glyphosate from inlet and effluent wastewaters from a wastewater treatment plant is shown.

Total soluble polyphenols (TSP), total monomeric anthocyanins (TMA), radical scavenging activity (RSA), ferric reducing antioxidant power (FRAP), and a number of anthocyanins, phenolic acids, coumarins, flavanols, dihydrochalcones and flavonols were investigated in Tuscan bilberry (i.e. Vaccinium myrtillus) and "false bilberry" (i.e. Vaccinium uliginosum subsp. gaultherioides Bigelow). V. myrtillus berries showed much higher TSP, TMA, RSA and FRAP values than V. uliginosum subsp. gaultherioides fruits. Moreover, very different profiles of individual phenolics were observed in the two species, being V. myrtillus mainly characterised by delphinidin and cyanidin glycosides, together with chlorogenic acid, and V. uliginosum subsp. gaultherioides dominated by malvidin derivatives and flavonols. Strong differences between the two species regarded also metabolites investigated herein for the first time, such as scopoletin, which was approximately two magnitude orders higher in V. uliginosum subsp. gaultherioides than in V. myrtillus berries. Very different abundances were also highlighted for cryptochlorogenic acid and quercetin-3-rhamnoside that were about ten-fold higher in bilberry than in "false bilberry". When the anthocyanin composition pattern of Tuscan "false bilberry" was compared to those elsewhere reported for V. uliginosum fruits harvested in different world areas, some important differences were observed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Three different sorbents (i.e. endcapped octadecylsilane, octasilane and styrene-N-vinylpiperidinone co-polymer) were investigated in order to develop an on-line solid phase extraction-liquid chromatographic tandem mass spectrometric method (on-line SPE-LC-MS/MS) for the simultaneous analysis of alkylphenols polyethoxylate (AP(n)EOs, n = 1-8) and corresponding monocarboxylate (AP1ECs) and phenolic (APs) metabolites. The endcapped octadecylsilane was selected due to its full compatibility with a chromatographic approach, which allowed the elution of positively and negatively ionisable compounds in two distinct retention time windows, using a water-acetonitrile-tetrahydrofuran ternary gradient and a pellicular pentafluorophenyl column. On this SPE sorbent, the composition of the loading/clean-up solution was then optimized in order to achieve the best recoveries of target analytes. Under the best experimental conditions, the total analysis time per sample was 25 min and method detection limits (MDLs) were in the sub-nanograms per litre to nanograms per litre range (0.0081-1.0 ng L(-1)) for AP(n)EOs with n = 2-8, AP1ECs and APs, whereas for AP1EOs, an MDL of about 50 ng L(-1) was found. Using the mass-labelled compound spiking technique, the method performance was tested on inlet and outlet wastewater samples from three activated sludge treatment plants managing domestic and industrial sewages of the urban areas and the textile district of Prato and Bisenzio valley (Tuscany, Italy); in most cases, apparent recovery percentages approximately in the ranges of 50-110% and 80-120% were found for inlet and outlet samples, respectively. The on-line SPE-LC-MS/MS analysis of wastewater samples highlighted the presence of target analytes at concentrations ranging from few nanograms per litre to thousands nanograms per litre, depending on the compound and matrix analysed. AP2ECs were also tentatively identified in outlet samples.

In this study wild type Nicotiana langsdorffii plants were genetically transformed by the insertion of the rat gene (gr) encoding the glucocorticoid receptor or the rolC gene and exposed to water and heat stress. Water stress was induced for 15 days by adding 20% PEG 6000 in the growth medium, whereas the heat treatment was performed at 50 °C for 2 h, after that a re-growing capability study was carried out. The plant response to stress was investigated by determining electrolyte leakage, dry weight biomass production and water content. These data were evaluated in relation to antiradical activity and concentrations of total polyphenols, selected phenolic compounds and some soluble sugars, as biochemical indicators of metabolic changes due to gene insertion and/or stress treatments. As regards the water stress, the measured physiological parameters evidenced an increasing stress level in the order rolC < gr < WT plants (e.g. about 100% and 50% electrolyte leakage increase in WT and gr samples, respectively) and complied with the biochemical pattern, which consisted in a general decrease of antiradical activity and phenolics, together with an increase in sugars. As regard heat stress, electrolyte leakage data were only in partial agreement with the re-growing capability study. In fact, according to this latter evaluation, gr was the genotype less affected by the heat shock. In this regard, sugars and especially phenolic compounds are informative of the long-term effects due to heat shock treatment., (Copyright © 2015 Elsevier Masson SAS. All rights reserved.)

A fast and selective CE method for the determination of zolmitriptan (ZOL) and its five potential impurities has been developed applying the analytical Quality by Design principles. Voltage, temperature, buffer concentration, and pH were investigated as critical process parameters that can influence the critical quality attributes, represented by critical resolution values between peak pairs, analysis time, and peak efficiency of ZOL-dimer. A symmetric screening matrix was employed for investigating the knowledge space, and a Box-Behnken design was used to evaluate the main, interaction, and quadratic effects of the critical process parameters on the critical quality attributes. Contour plots were drawn highlighting important interactions between buffer concentration and pH, and the gained information was merged into the sweet spot plots. Design space (DS) was established by the combined use of response surface methodology and Monte Carlo simulations, introducing a probability concept and thus allowing the quality of the analytical performances to be assured in a defined domain. The working conditions (with the interval defining the DS) were as follows: BGE, 138 mM (115-150 mM) phosphate buffer pH 2.74 (2.54-2.94); temperature, 25°C (24-25°C); voltage, 30 kV. A control strategy was planned based on method robustness and system suitability criteria. The main advantages of applying the Quality by Design concept consisted of a great increase of knowledge of the analytical system, obtained throughout multivariate techniques, and of the achievement of analytical assurance of quality, derived by probability-based definition of DS. The developed method was finally validated and applied to the analysis of ZOL tablets., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Quality by Design (QbD) approach was followed having as analytical target profile the determination of different antimigraine drugs (seven triptans, TRP) available on the market. Multivariate strategies were used for defining the design space and solvent-modified MEKC was the selected analytical method. The versatility of electrophoretic technique, allowing a fine modulation of experimental parameters, made it possible to define the design space (DS). The DS limited a suitable range of experimental parameters in which all possible combinations of variables led to an electrokinetic method able to determine all the considered analytes with a predefined quality. Design of experiments and risk analysis fully assisted the method development from the initial investigation of MEKC knowledge space to the DS definition and finally to the control strategy. Applying the working operative conditions, the baseline separation of TRP was obtained in less than 9 min. The method was finally used for the quantification of three TRP in different pharmaceutical products., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Seven quick, easy, cheap, effective, rugged and safe (QuEChERS)-based procedures, differing in both the extraction and clean-up steps, were investigated for the recovery of bentazone (BTZ), atrazine (ATZ), carbamazepine (CBZ), phenytoin (PNT) and its metabolite 5-(p-hydroxyphenyl-),5-phenylhydantoin (HPPH) from soil. Target analytes were chosen for their extensive use and/or occurrence in soil, as well as for their medium-high polarity characteristics (log K OW values in the range 0.88-2.80), which have been reported as a critical parameter for the recovery from soil with QuEChERS approaches. Liquid chromatography coupled with UV and pulsed amperometric (PA) detection at a glassy carbon electrode was used as instrumental technique. The recovery data obtained within each tested procedure were discussed for each compound investigated, highlighting different behaviour depending on the specific physicochemical characteristics of the analytes. The optimized QuEChERS conditions consisted of the extraction of analytes with CH3CN:H2O 70:30, 5 % CH3COOH, followed by a dispersive solid-phase extraction (d-SPE) clean-up step with C18 sorbent. This method, in which water is directly added to the soil together with acetonitrile and salts, allowed the rehydration step to be avoided, which can be as long as 30 min. Matrix effects were evaluated for both the detection techniques at different concentration levels, and they were below 24 % for both the detection technique used. The recoveries were evaluated at three concentration levels by a matrix-matched calibration and were in the ranges of 83-113 % (relative standard deviations (RSD) ≤ 14 %) and 88-109 % (RSD ≤ 11 %) for UV and PA detection, respectively, highlighting very good performances of the method, even for the more polar analytes. Method detection limits ranged from 4 μg/kg (BTZ) to 493 μg/kg (PNT) and from 4 μg/kg (HPPH) to 11 μg/kg (BTZ) for UV and PA detection, respectively. The method was finally compared with a microwave-assisted extraction procedure which provided less satisfactory extraction performances than the optimized QuEChERS procedure.

This work was planned for providing useful information about the use of excluder metallophytes for phytostabilization of soils contaminated also with elements scarcely represented in the metalliferous environment of origin. To this aim, we investigated tolerance and accumulation of several different elements in a metallicolous and a nonmetallicolous population of Silene paradoxa through a hydroponic experiment. S. paradoxa metallicolous population showed increased tolerance not only to all the metals highly represented in the environment of origin but also to some of those scarcely present. Therefore, our results deposed in favor of the occurrence of the co-tolerance phenomenon in S. paradoxa for some elements. Metal accumulation was higher in the roots than in the shoots and lower in the metallicolous population than in the nonmetallicolous one, thus showing tolerance mechanisms to be based largely on metal exclusion. Anyway, the relative contribution of avoidance and of internal tolerance to metal tolerance was shown to be element-dependent. Present data revealed that metallicolous plants can effectively posses metal co-tolerances, which deserve to be investigated; as such, plants can actually represent a precious and exploitable tool also for the phytostabilization of soils contaminated with elements underrepresented in the environment of their origin.

Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) is an extraction and clean-up technique originally developed for recovering pesticide residues from fruits and vegetables. Since its introduction, and until December 2013, about 700 papers have been published using the QuEChERS technique, according to a literature overview carried out using SciFinder, Elsevier SciVerse, and Google search engines. Most of these papers were dedicated to pesticide multiresidue analysis in food matrices, and this topic has been thoroughly reviewed over recent years. The QuEChERS approach is now rapidly developing beyond its original field of application to analytes other than pesticides, and matrices other than food, such as biological fluids and non-edible plants, including Chinese medicinal plants. Recently, the QuEChERS concept has spread to environmental applications by analyzing not only pesticides but also other compounds of environmental concern in soil, sediments, and water. To the best of our knowledge, QuEChERS environmental applications have not been reviewed so far; therefore, in this contribution, after a general discussion on the evolution and changes of the original QuEChERS method, a critical survey of the literature regarding environmental applications of conventional and modified QuEChERS methodology is provided. The overall recoveries obtained with QuEChERS and other extraction approaches (e.g., accelerated solvent extraction, ultrasonic solvent extraction, liquid/solid extraction, and soxhlet extraction) were compared, providing evidence for QuEChERS higher recoveries for various classes of compounds, such as biopesticides, chloroalkanes, phenols, and perfluoroalkyl substances. The role of physicochemical properties of soil (i.e., clay and organic carbon content, as well as cation exchange capacity) and target analytes (i.e., log KOW, water solubility, and vapor pressure) were also evaluated in order to interpret recovery and matrix effect data.

Chromium accumulation, dry weight (DW) biomass yield, water content and concentrations of some selected phenolic compounds and carbohydrates were determined in root and shoot of Nicotiana langsdorffii, either wild type (WT) or genetically modified by the insertion of GR and rolC genes, in response to the presence of Cr(VI) in the growth medium. A biomass decrease was observed for WT plants, but not for GR and rolC transformations, in response to Cr(VI) in the growth medium, highlighting a stress situation only in WT line. Shoot chromium concentrations were in all cases about 300 mg kg(-1) DW. In root higher concentrations were found in rolC than in GR and WT (3843, 2600 and 2751 mg kg(-1) DW, respectively). Based on the DW biomass, GR and WT accumulated higher chromium quantities than rolC, both in root (330 and 424 versus 85 μg Cr per plant) and shoot (282 and 275 versus 121 μg Cr per plant). Therefore, GR should be preferred to WT as a promising candidate for chromium phytoremediation. Metabolic shifts of sugars and phenolics were generally observed in response to either gene insertions or exposure to Cr(VI), being the latter more related to the resistance to Cr(VI) than the former., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Recently our findings have shown that the integration of the gene coding for the rat gluco-corticoid receptor (GR receptor) in Nicotiana langsdorffii plants induced morphophysiological effects in transgenic plants through the modification of their hormonal pattern. Phytohormones play a key role in plant responses to many different biotic and abiotic stresses since a modified hormonal profile up-regulates the activation of secondary metabolites involved in the response to stress. In this work transgenic GR plants and isogenic wild type genotypes were exposed to metal stress by treating them with 30ppm cadmium(II) or 50ppm chromium(VI). Hormonal patterns along with changes in key response related metabolites were then monitored and compared. Heavy metal up-take was found to be lower in the GR plants. The transgenic plants exhibited higher values of S-abscisic acid (S-ABA) and 3-indole acetic acid (IAA), salicylic acid and total polyphenols, chlorogenic acid and antiradical activity, compared to the untransformed wild type plants. Both Cd and Cr treatments led to an increase in hormone concentrations and secondary metabolites only in wild type plants. Analysis of the results suggests that the stress responses due to changes in the plant's hormonal system may derive from the interaction between the GR receptor and phytosteroids, which are known to play a key role in plant physiology and development., (Copyright © 2013 Elsevier GmbH. All rights reserved.)

An up-to-date overview of thin-layer chromatography (TLC) techniques for chiral separations of various significant and/or recent examples of enantioresolutions is reported. Furthermore, examples for chiral separations obtained on achiral commercially available C18 TLC plates are described in detail. These include the enantioseparation of methylthiohydantoin-phenylalanine and methylthiohydantoin-tyrosine using hydroxyethyl-β-cyclodextrin as mobile phase additive and the separation of the enantiomers of warfarin and p-chlorowarfarin using bovine serum albumin as mobile phase additive.

The current state of chiral separations by thin-layer chromatography using chiral stationary phases is reviewed. Both stationary phases essentially constituted by the chiral selector and those obtained by the impregnation of achiral plates with appropriate chiral selectors are described. Particular attention is paid to commercial and non-commercial cellulose and cellulose-derivative plates, as well as commercially available Chiralplate™, which are currently the most widely used. Some of the most important results obtained to date are reported and discussed; the examples provided illustrate the very wide range of structurally different solutes that can be readily resolved into their enantiomers by planar chromatographic methods. Special attention is paid to the discussion of the retention and resolution factors that influence chiral discrimination. The quantitative analysis of enantiomers is also discussed, especially from the point of view of determination of enantiomeric purity.

High-performance liquid chromatography coupled with ion spray mass spectrometry in the tandem mode with both negative and positive ionization was used for investigating a variety of polyphenolic compounds in four genotypes of Fragaria vesca berries. About 60 phenolic compounds belonging to the compound classes of phenolic acids, ellagitannins, ellagic acid derivatives, flavonols, monomeric and oligomeric flavanols, dihydrochalcones and anthocyanins were reported, providing for the first time a quite complete picture of polyphenolic composition of F. vesca berries. Some of the polyphenols herein investigated, such as a tris-galloyl-hexahydroxydiphenoyl-hexose, two castalagin/vescalagin-like isomers and peonidin-malonylglucoside, were described for the first time. Principal component analysis applied on original HPLC-MS/MS data, acquired in multiple reaction monitoring mode, successfully discriminated the four investigated cultivars on the basis of their polyphenolic composition, highlighting the fundamental role of mass spectrometry for food characterization., (Copyright © 2012 John Wiley & Sons, Ltd.)

Levoglucosan was present in all samples and its concentrations showed a pronounced annual cycle with maximum levels in the cold season. The annual percentage of ratios of levoglucosan to OC ranged from 0.04 to 9.75% evidencing a major contribution of biomass burning to the aerosol OC during the winter. In the urban-background site, OC was strongly correlated with EC in winter, suggesting that the major fraction of OC was generated as primary particles along with EC. A background levoglucosan component showed that biomass burning was continuously taking place in all the investigated sites. The biomass burning contribution to the Tuscany aerosol was made up of a background component and an additional component during winter probably due to wood burning for domestic heating., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In this study, during a two-year period, we investigated the fate of hexavalent and trivalent chromium in a full-scale subsurface horizontal flow constructed wetland planted with Phragmites australis. The reed bed operated as post-treatment of the effluent wastewater from an activated sludge plant serving the textile industrial district and the city of Prato (Italy). Chromium speciation was performed in influent and effluent wastewater and in water-suspended solids, at different depths and distances from the inlet; plants were also analyzed for total chromium along the same longitudinal profile. Removals of hexavalent and trivalent chromium equal to 72% and 26%, respectively were achieved. The mean hexavalent chromium outlet concentration was 1.6 ± 0.9 μg l(-1) and complied with the Italian legal limits for water reuse. Chromium in water-suspended solids was in the trivalent form, thus indicating that its removal from wastewater was obtained by the reduction of hexavalent chromium to the trivalent form, followed by accumulation of the latter inside the reed bed. Chromium in water-suspended solids was significantly affected by the distance from the inlet. Chromium concentrations in the different plant organs followed the same trend of suspended solids along the longitudinal profile and were much lower than those found in the solid material, evidencing a low metal accumulation in P. australis., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Mean hexachlorobenzene (HCB) and hexachlorocyclohexane (HCH) concentrations, measured in seawater and air samples, confirmed the decline in levels of these compounds in Antarctic air and water. However, low alpha/gamma-HCH ratios in air at the beginning of the sampling period suggest a predominance of fresh lindane entering the Antarctic atmosphere during the Austral spring probably due to current use in the Southern Hemisphere. Water-air fugacity ratios demonstrate the potential for HCH gas deposition to coastal Antarctic seas, while the water-air fugacity ratios for HCB imply that volatilization does not account for the observed decrease of HCB in surface seawater. HCH concentrations found in krill samples were correlated with seawater concentrations indicative of bioconcentration of HCHs from seawater.

This paper investigates the influence of cultivar (Annurca, Golden Delicious, Red Chief, and Stayman Neepling), rural practice (integrated and organic), and growing region (different Italian regions) on polyphenol composition and antiradical activity of the pulp and skin of apples, as presented to the consumer at the market. Antiradical activity of fruit was strongly related with the total polyphenolic content, determined both by the spectrophotometric Folin-Ciocalteu method ( R (2) = 0.90; P < 0.01) and by HPLC ( R (2) = 0.85; P < 0.01). Considering the edible portion of the fruit, polyphenolics contribute toward explaining approximately 90% of the overall antiradical activity, thus highlighting their important role in human health protection. Therefore, the data indirectly indicated that ascorbic acid and other antiradical molecules differing from polyphenols play a much less important role in explaining the health-protecting properties of apples. Cultivar effect was by far the most important, and Annurca and Golden Delicious were respectively the best and the worst apples from the point of view of the health-protecting attributes.

The removal of the non-ionic surfactant Triton X-100, dosed at 30 and 300 mg/L in a pilot-scale subsurface horizontal flow reed bed, and the aerobic heterotrophic cultivable community associated with the roots and with the substrate gravel in both absence and presence of Triton X-100 were investigated. t-Octylphenol (OP) and its mono-, di- and tri-ethoxyl derivatives, among others, were found in the outlet. A mass balance allowed us to calculate that approximately 40% of the Triton X-100 metabolites OP and octylphenol polyethoxylate derivatives flowed out of the reed bed during the dosage and postdosage experiments. More aerobic heterotrophic microorganisms adhered to the roots than to the gravel. The appearance of new strains (Aeromonas, Flavobacterium, and Aquaspirillum) and the increased presence of others (Pseudomonas) during the dosage of Triton may be linked to the capacity of these bacteria to adapt to the presence of the surfactant or to use it as a nourishment.

Concentrations of dissolved and particle-associated n-alkanes, phthalates and polycyclic aromatic hydrocarbons (PAHs) were measured in sea surface microlayer (SML) and sub-surface water (SSL) samples collected in the coastal area of Terra Nova Bay, Antarctica, during the Austral spring 1998/1999. SML concentrations of the selected organic compounds were higher than SSL values and the enrichment factors were greater in the particulate phase than in the dissolved phase. During the same campaign, "fresh" snow samples, collected at different altitudes (from sea level up to 2670 m) near the coast on Mt Melbourne, immediately after a snowy event, were analysed in order to provide more information on air/sea exchange processes. The same classes of organic compounds found in sea water were also present in "fresh" snow samples. The surfactant fluorescent organic matter (SFOM), adsorbed on the microdrop aerosol surface, could be considered the main constituent of the enrichment and the carrier at higher altitudes of organic compounds. In fact, hydrocarbons (n-alkanes and PAHs), which are not surfactants like phthalates, could interact with SFOM and follow the same fate.

A sensitive and reliable analytical method was developed for the simultaneous extraction of PAHs and total fats and their determination in the human milk. The method involved a liquid-liquid extraction of PAHs and fats, followed by the gravimetric determination of the latter. PAHs were separated from lipids by size exclusion chromatography eluting with methylene chloride and analysed by gaschromatography coupled with mass spectrometry (GC/MS). The recovery of analytes was in the range of 42-101% and agreed well with their boiling temperatures (R2=0.779). Precision of the method was found between 7.6 and 19%. Quantification and detection limits for individual PAHs ranged from 0.011 to 0.032 and from 0.006 to 0.022 microg/Kg milk (wet weight), respectively. Quantification limit for the total fat determination was 0.26 g/Kg milk (wet weight). This procedure, applied to milk samples of ten healthy, non-smoking, Italian primiparae, living in rural or low-traffic zones, allowed for the identification and quantitative determination of naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene in the mean concentration range 0.114-6.95 microg/Kg milk (wet weight). The most volatile compounds, which were not investigated elsewhere, were found at much higher concentrations than those observed for the others. No relation was found between PAH and total fat concentrations.

Performances of a pilot-scale reed bed for the olive mill wastewater (OMW) treatment were investigated, by monitoring influent and effluent pH, total suspended solids (TSS), chemical oxygen demand (COD), total Kjeldahl nitrogen (TKN), total phosphorus and polyphenols. In order to reduce the suspended matter concentration and to avoid clogging, OMW was pre-treated by adding lime putty, calcium hydroxide and hydraulic lime. The best results were obtained with 2 g/L of hydraulic lime. Pre-treated OMW was dosed in the reed bed at dilution ratios of 1/3 and 1/10 (v/v), pointing up that the latter only did not give rise to reed suffering and allowed to obtain good and durable removal efficiencies, above all for COD (74.1+/-17.6%) and polyphenols (83.4+/-17.8%). Recycling of the effluent was quite effective for the improvement of the wastewater quality, allowing a further removal of 26-70%, depending on the parameter taken into account. A post-dosage study, carried out by feeding the reed bed with the effluent of an activated sludge plant, pointed up a rapid decreasing of the outlet concentrations of the investigated parameters to values compatible with Italian regulations concerning wastewater discharge in surface water. Polyphenols were the exception, being their outlet concentration at the end of post-dosage study around 2 mg/L.

This work evaluated sub-surface flow (SSF) constructed wetlands and activated sludge plant efficiency in pathogen removal. The two were also compared. The removal of fecal bacteria (total coliforms, fecal coliforms, fecal streptococci) was evaluated. Analysis was carried out during one year by determining the amount of bacteria in the inflow and the outflow of four systems: three SSF systems (two were pilot plants and one a fully operating plant) and an activated sludge plant. MPN techniques were used to determine the quantity-value of the microorganisms. Percentages of fecal bacteria removal in wetlands systems were as good as (and sometimes better than) those recorded in the activated sludge plant. Optimal values of these bacteria were obtained in the outflow of the post-treatment pilot plant: very high bacterial removal percentages (>99%) were recorded. SFS constructed wetlands are a valid solution for the final treatment of the outflow of existing plants.

Pooled human milk was subjected to Holder pasteurization and storage at -20 degrees C up to 90 days and examined for its content of fat and L-lactate and for lipid composition. This treatment reduced fats by 6% and L-lactate by at least 7%. In addition, pasteurization and storage induced triglyceride hydrolysis. The absolute amount of free fatty acids (FFAs) which was 0.5% after collection, doubled after pasteurization and rose even more after storage. Different FFA compositions were found by several authors using the same analytical method even for milk samples subjected to the same treatment. More detailed information on procedures must be given to explain the different results.