Enantioseparations by thin-layer chromatography.

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-ß-cyclodextrin as mobile phase additive and the separation of the enantiomers of warfarin and p-chlorowarfarin using bovine serum albumin as mobile phase additive.

Thin-layer chromatography enantioseparations on chiral stationary phases: a review.

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.

The use of levoglucosan for tracing biomass burning in PM2.5 samples in Tuscany (Italy).

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.

One year intensive PM2.5 bound polycyclic aromatic hydrocarbons monitoring in the area of Tuscany, Italy. Concentrations, source understanding and implications.

Polycyclic aromatic hydrocarbons (PAHs) associated to PM(2.5) particles were monitored at three sites in the region of Tuscany, Italy, during the period March 2009-March 2010. PAH concentrations ranged between 0.92 ng m(-3) and 13 ng m(-3). The spatial and seasonal differences observed at the three sites are discussed and attributed to specific PAH sources. Benzo[a]Pyrene average annual values were below the EU limit value of 1.0 ng m(-3). The results of this study suggest that emissions from commuting and work related traffic play an important role for the city of Florence, whereas for the city of Livorno, the harbor activities seem to impact the PAH burden substantially, as well. The PAH cancer risk (expressed as the "BaPE index") has shown a 6-fold decline compared to early 1990's concentrations and 2- to 3-fold decline compared to the late 1990's.

Distribution and mass balance of hexavalent and trivalent chromium in a subsurface, horizontal flow (SF-h) constructed wetland operating as post-treatment of textile wastewater for water reuse.

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.

Organochlorine pesticide air-water exchange and bioconcentration in krill in the Ross Sea.

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.

Seawater Ca2+ concentration influences solar orientation in Talitrus saltator (Crustacea, Amphipoda).

The role of salinity in the ecophysiology of many intertidal invertebrates has been extensively investigated. Calcium (Ca(2+)), magnesium (Mg(2+)), potassium (K(+)) and sodium (Na(+)) are the major constituents of seawater and it has been demonstrated that sandhoppers tested under the sun in diluted seawater (3.5 per thousand) head seaward, instead of going landward as expected. Therefore, the variation in seawater salinity (from 35 per thousand to 3.5 per thousand) influences their directional choice. This paper investigates the contribution of different cations to the sea-land directional choice of Talitrus saltator (Crustacea, Amphipoda) by the sun compass orientation mechanism. Results of releases carried out in basic seawater selectively deprived of Ca(2+), Mg(2+) or K(+) and containing the same concentration of Na(+) indicate that only the reduction in Ca(2+) concentration affects the capacity of solar orientation. The pH does not influence the directional choice of sandhoppers and nor do small variations in salinity in the range 32-39 per thousand. Moreover, the clear photopositive tendency registered in experiments of phototaxis in Ca(2+)-deprived seawater indicates that the absence of Ca(2+) does not affect the normal functioning of the visual cells. Therefore, our results show that Ca(2+) seawater concentration is important for the correct functioning of one of the principal mechanisms of orientation in supralittoral amphipods and it could affect their survival in the field.

Polyphenol levels and free radical scavenging activities of four apple cultivars from integrated and organic farming in different italian areas.

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.

Gas-particle concentration and distribution of n-alkanes and polycyclic aromatic hydrocarbons in the atmosphere of Prato (Italy).

Air samples were collected in an urban and industrialised area of Prato (Italy) during 2002, as part of a study to identify and measure aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs). Total concentrations of aliphatic hydrocarbons ranged between 170 and 282ngm(-3) in the gas phase and from 48.9 to 276ngm(-3) in the particulate phase. The average total PAH concentrations (gas+particulate) were 59.4+/-26.5ngm(-3), and both gas and particulate phase PAH concentrations decreased with increasing temperature. Source identification using diagnostic ratios and principal component analysis identified automobile traffic, in particular, the strong influence of diesel fuel burning, as the major PAH source. Gas-particle partition coefficients (K(p)'s) of n-alkane and PAHs were well correlated with the sub-cooled liquid vapour pressure (P(L)(0)) and indicate stronger sorption of PAHs to aerosol particles compared with n-alkanes.

Alkylphenol polyethoxylate removal in a pilot-scale reed bed and phenotypic characterization of the aerobic heterotrophic community.

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.

Determination of polycyclic aromatic hydrocarbons (PAHs) and total fats in human milk.

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.

Enrichment of organic pollutants in the sea surface microlayer (SML) at Terra Nova Bay, Antarctica: influence of SML on superficial snow composition.

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.

Characterization of n-alkanes and PAHs in PM10 samples in Prato (Italy).

This study reports the characterization of n-alkanes and PAHs in 13 PM10 samples collected in the South area of Prato (Italy) during the period April-July 2002. n-Alkanes concentrations ranged between 9.45 and 182.64 ng/mc while PAHs concentrations ranged from 3.058 to 22.048 ng/mc. No correlation was evidenced between benzo(a)pirene and PM10 concentrations. Total carbonaceous aerosol was also measured and it meanly accounted for 21.5% of the PM10 mass ranging from 12.4% to 27.1%.

Olive mill wastewater treatment by a pilot-scale subsurface horizontal flow (SSF-h) constructed wetland.

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.