Sewage treatment plant (STP) effluents with primarily domestic inputs are strongly suspected to be an important source of natural and synthetic estrogens contaminating the aquatic environment. Even a few ng/L of some of these substances can provoke reproductive disturbances in riverine fish. The main purpose of this investigation has been that of ascertaining whether activated sludge STPs (ASSTPs) are able to produce significant amounts of free estrogens. For this purpose, we have monitored monthly estriol (E 3 ), estradiol (E 2 ), estrone (E 1 ) and ethinylestradiol (EE 2 ) in influents and effluents of six Roman ASSTPs for five months. To do this, we have developed an original analytical method involving analyte extraction with a Carbograph 4 cartridge and LC coupled with negative turbo ion spray tandem mass spectrometry in the selected reaction monitoring mode. Analyte recovery ranged between 86 and 91%, and limits of quantification were below 1 ng/ L. Over five months, inlet concentrations of E 3 , E 2 , E 1 and EE 2 at the six plants averaged respectively 80, 12, 52 and 3.0 ng/L. On the basis of the daily human excretion of conjugated estrogens, the above values suggest that deconjugation occurs preferentially in sewers. The activated sludge treatment efficiently removed E 3 (95%), E 2 (87%), EE 2 (85%), but not E 1 (61%). In four events out of thirty, E 1 outlet levels were even larger than inlet levels. Median concentrations of the two most potent estrogens, that is E 2 and EE 2 leaving the six ASSTPs were respectively 1 and 0.45 ng/L. Analysis of a river (Tiber) water sampled downstream of small towns whose sewages are treated by percolating filter STPs or directly discharged into the river revealed the presence of all four estrogens at levels between 0.04 (EE 2 ) and 1.5 ng/L (E 1 ).

The physical and chemical properties of a new class of lithium conducting polymer electrolytes formed by dispersing ceramic powders at the nanoscale particle size into a poly(ethylenoxide) (PEO)-lithium salt, LiX complexes, are reported and discussed. These true solid-state PEO-LiX nanocomposite polymer electrolytes have in the 30-80 °C range an excellent mechanical stability (due to the network of the ceramic fillers into the polymer bulk) and high ionic conductivity (promoted by the high surface area of the dispersed fillers). These important and unique properties are accompanied by a wide electrochemical stability and by a good compatibility with the lithium electrode (assured by the absence of any liquids and by the interfacial stabilizing action of the dispersed filler), all this making these nanocomposite electrolytes of definite interest for the development of advanced rechargeable lithium batteries.

Summary'Free' steroidal estrogens have been identified as compounds possibly responsible for endocrine-disruption of aquatic fauna populating rivers in which municipal sewage-treatment plants (STP) discharge their effluents. Natural ancl synthetic estrogens are excreted, as glucuronicles ancl sulfates, by man, in the urine but these are bioconvertecl back to the unconjugatecl forms in wastewater clischarges. For this reason we have developed a sensitive analytical procedure, without clerivatization, for identification ancl quantitation of conjugated ancl free estrogens in surface ancl waste waters. The hormones were extracted ancl fractionatecl, by use of Carbograph cartridges, into neutral ancl acicl fractions which were then analyzed by liquid chromatography-tandem mass spectrometry. Recoveries were be~een 66 ancl 100% ancl limits of detection (LOD) be~een 15.0 ancl 0.003 ng L 1, depending on the compound ancl the water matrix. When this methodology was applied to real sewage ancl river water we could measure the main free estrogens at ng L 1 levels.Among the conjugateswe always observed the presence of estrone 3-sulfate (at levels be~een 8.0 ancl 0.5 ng L 1).

This paper describes a novel and efficient analytical method to define the profile of fat-soluble micronutrients in milk from different animal species. Overnight cold saponification was optimized as a simultaneous extraction procedure. Analytes were separated by nonaqueous reversed-phase (NARP) chromatography: carotenoids on a C(30) column and fat-soluble vitamins on a tandem C(18) column system. Besides 12 target analytes for which standards are available (all-trans-lutein, all-trans-zeaxanthin, all-trans-β-cryptoxanthin, all-trans-β-carotene, all-trans-retinol, α-tocopherol, γ-tocopherol, δ-tocopherol, ergocalciferol, cholecalciferol, phylloquinone, and menaquinone-4), the DAD-MS combined detection allowed the provisional identification of other carotenoids on the basis of the expected retention times, the absorbance spectra, and the mass spectrometric data. Retinol and α-tocopherol were the most abundant fat-soluble micronutrients and the only ones found in donkey's milk along with γ-tocopherol. Ewe's milk also proved to be a good source of vitamin K vitamers. Bovine milk showed a large variety of carotenoids that were absent in milk samples from other species with the only exception of all-trans-lutein and all-trans-zeaxanthin.

A simple and rapid method able to determine residues of 12 sulfonamide (SAs) antibacterials in cattle and trout muscle tissues is presented. This method is based on the matrix solid-phase dispersion technique with hot water as extractant followed by liquid chromatography-mass spectrometry (LC-MS). The LC-MS instrumentation was equipped with an electrospray source and a single quadrupole. After 0.8 g of a flesh sample containing the analytes is deposited on sand (crystobalite), this material is packed into an extraction cell. SAs are extracted by flowing 4 mL of water through the cell heated at 80 degrees C. A 0.5-mL aliquot of the bovine tissue extract is then directly injected into the LC column, while the fish tissue extract is filtered prior to LC-MS analysis. MS data acquisition was performed in the positive-ion mode and monitoring at least three ions for each target compound. Confirmatory ions were produced by the in-source collision-induced dissociation process. At the tolerance levels issued by the EU and U.S. Food and Drug Administration, i.e., 100 ppb, recovery of the analytes in bovine and trout muscle tissues was 75-98% with RSDs ranging between 1 and 8%. Estimated limits of quantification (S/N = 10) were 6-15 ppb for SAs in bovine muscle tissue and 3-13 ppb in trout fillet. When trying to reduce the analysis time by using a short chromatographic run time, severe ion signal suppression was experienced for the early-eluted SAs. This effect was traced to competition effects by polar endogenous coextractives, maybe proteinaceous species, which are eluted in the first part of the chromatographic run. This unwelcome effect was removed by simply adopting more selective chromatographic conditions.

No abstract

Microcystins (MCs) and cylindrospermopsin (CYL) are potent natural toxins produced by cyanobacteria (blue-green algae) that grow worldwide in eutrophic freshwaters and cause animal and human water-based toxicoses. The main purpose of this work has been assessing the contamination levels of some MCs and CYL in eutrophic Italian lake (Albano) water. To do this, we have developed an original analytical method involving MC extraction with a sorbent (Carbograph 4) cartridge. CYL is a highly polar compound that is scarcely retained by any sorbent material. To analyze this toxin, we directly injected 0.5 mL of filtered lake water into the liquid chromatography (LC) column. Analytes were quantified by LC coupled to tandem mass spectrometry in the multireaction monitoring mode. The recovery of five selected MCs added to an analyte free lake water sample at three different concentrations (50, 150, and 500 ng/L) ranged between 93 and 103% with RSD values no larger than 8%. Limits of quantification (LOQ) of the five MCs were within the 2-9 ng/L range, whereas the LOQ of CYL was 300 ng/L. The occurrence and abundance of cyanotoxins in Lake Albano was monitored over four months (Sept-Dec 2004) by analyzing water samples collected monthly at the center of the lake and at different depths (from 0 to -30 m). During survey and with the MS/MS system operating in the parent ion scan mode, we individuated two demethylated forms of MC-RR and one demethylated variety of MC-LR. Demethylated MC-RRs are known to be even more toxic than MC-RR toward zooplanktic grazers. CYL was the most-abundant toxin during the first three monitoring months. To the best of our knowledge, this is the first work reporting concentration levels of CYL in lake water.

An analytical procedure for the simultaneous determination in human plasma and oral fluids of several illicit drugs belonging to different chemical and toxicological classes is presented. Amphetamine, methamphetamine, morphine, 6-monoacetylmorphine, methylenedioxyamphetamine, methylenedioxyethylamphetamine, methylenedioxymethamphetamine, cocaine, benzoylecgonine, tetrahydrocannabinol, carboxytetrahydrocannabinol, ketamine, and phencyclidine have been quantified in real samples using a very rapid sample treatment, basically a protein precipitation. The quantitative analysis was performed by liquid chromatography-tandem mass spectrometry and has been fully validated. All the analytes were detected in positive ionization mode using a TurboIonSpray source, except carboxytetrahydrocannabinol, which was detected in negative ionization mode. The use of a diverter valve between the column and the mass spectrometer allows the preservation of the ion source performances for high-throughput analysis.