Simultaneous determination of methyl tert.-butyl ether and its degradation products,other gasoline oxygenates and benzene,toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography-mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-microg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 microg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20-40 microg/l) and a maximum concentration of 670 microg/l (doubling the Danish suggested toxicity level of 350 microg/l). Samples with high levels of MTBE contained 0.1-60 microg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.     

AFM characterization of bovine enamel and dentine after acid-etching

Teeth are constituted mainly of hydroxyapatite molecules (Ca₁₀(PO₄)₆(OH)₂), grouped in different microstructural arrangements, depending on the dental layer considered (enamel or dentine). In the present work, these dental microstructural arrangements were characterized by atomic force microscopy. Enamel and dentine samples were cut from freshly extracted bovine incisor teeth. After metallographic polishing, the dental surfaces were etched with lactic acid (113.8 mmol/L, pH 3.3). Three etching times were tested: 1, 3 and 5 min. Atomic force micrographs showed that 1 min of etching time was effective to remove the smear layer, polishing debris and scratches, and display the characteristics of interest for both enamel and dentine. Although the bovine dental enamel rod cross-section presented keyhole-like shape, its measured dimensions (8.8 μm of major axis and 3.7 μm of minor axis) exhibited an insignificant discrepancy from human prisms diameters. Bovine dentinal tubules displayed larger mean diameters (4.0 μm) and a lower density (～17,100 tubules/mm²) than human dentine, suggesting that the use of bovine dentine as a substitute for human dentine in resin adhesion investigations should be reconsidered. Apatite nanoparticles presented a mean radius (22–23 nm) considerably smaller than that of human teeth.     

Excitability mediated by localized structures in a dissipative nonlinear optical cavity

We find and characterize an excitability regime mediated by localized structures in a dissipative nonlinear optical cavity. The scenario is that stable localized structures exhibit a Hopf bifurcation to self-pulsating behavior, that is followed by the destruction of the oscillation in a saddle-loop bifurcation. Beyond this point there is a regime of excitable localized structures under the application of suitable perturbations. Excitability emerges from the spatial dependence since the system does not exhibit any excitable behavior locally. We show that the whole scenario is organized by a Takens-Bogdanov codimension-2 bifurcation point.     

Neutrino cosmology

We present a class of non-stationary cosmological solutions of coupled Einstein-Dirac equations which correspond to an Universe filled solely with neutrinos of right and/or left helicity.     

Cooperation within triplets in the rock-paper-scissors game

We study a population involved in a cyclic game of three strategies – the rock-paper-scissors game – whose agents interact through groups of three individuals (triplets), considering the possibility that two weak agents cooperate and beat a strong one. In a wide range of parameters the system presents a stable heteroclinic cycle, which implies that in a finite population some of the strategies become extinct and others survive. We find that the cooperation within triplets only benefits the survival of the strategy if the cooperation probability is above a certain threshold. We study the survival probabilities of the different strategies as a function of the cooperation parameters through a analytic approximation and compare with simulations, obtaining a good agreement. Results are generalizable to other systems with heteroclinic cycles.     

Strongly Mixing Convolution Operators on Fréchet Spaces of Holomorphic Functions

A theorem of Godefroy and Shapiro states that non-trivial convolution operators on the space of entire functions on \({\mathbb{C}^n}\) are hypercyclic. Moreover, it was shown by Bonilla and Grosse-Erdmann that they have frequently hypercyclic functions of exponential growth. On the other hand, in the infinite dimensional setting, the Godefroy–Shapiro theorem has been extended to several spaces of entire functions defined on Banach spaces. We prove that on all these spaces, non-trivial convolution operators are strongly mixing with respect to a gaussian probability measure of full support. For the proof we combine the results previously mentioned and we use techniques recently developed by Bayart and Matheron. We also obtain the existence of frequently hypercyclic entire functions of exponential growth.     

The Effects of Antioxidants on the Changes in Volatile Compounds in Heated Welsh Onions (Allium fistulosum L.) during Storage

Welsh onion (Allium fistulosum L.) is usually used to enhance the flavor characteristics of various foods. Volatile compounds in Welsh onions, including sulfur-containing compounds, may vary during heat process and storage. Accordingly, the changes in the volatile compounds in Welsh onions, subjected to heat and antioxidant (ascorbic acid and glutathione) treatments during storage, are investigated in the present study. The majority of sulfur-containing compounds in Welsh onions showed significant differences between the untreated Welsh onions and heated Welsh onions. During the heating of the Welsh onions, some sulfur-containing compounds, such as 2-methylthiirane, 1-(methyldisulfanyl)prop-1-ene, 1-[[(E)-prop-1-enyl]disulfanyl]propane, 1-(propyltrisulfanyl)propane, 1-[[(E)-prop-1-enyl]trisulfanyl]propane, and (methyltetrasulfanyl)methane, showed significant differences between the untreated and heated Welsh onions (p < 0.05). In addition, partial least square discriminant analysis (PLS-DA) was applied to discriminate the heated Welsh onion samples added with different antioxidants. The heated Welsh onion samples added with ascorbic acid was mainly associated with 2-phenylacetaldehyde, acetic acid, methylsulfanylmethane, prop-2-ene-1-thiol, undecan-2-one, and (2E,4E)-deca-2,4-dienal. Moreover, the key volatile compounds in the heated Welsh onion samples added with glutathione were 3-ethylthiophene, 1-(methyldisulfanyl)-1-methylsulfanylpropane, 1-methylsulfanylpentane, 2-prop-2-enylsulfanylpropane, and 1-propan-2-ylsulfanylbutane.     

Removal of sulfonamide antibiotics upon conventional activated sludge and advanced membrane bioreactor treatment

This work reports the removal efficiencies of nine sulfonamides (SAs) and one of their acetylated metabolites during conventional activated sludge (CAS) and membrane bioreactor (MBR) treatments. Two different types of membranes were studied, hollow-fiber membranes and flat-sheet membranes, in two separate pilot plants operating in parallel to a full-scale CAS treatment. A total of 48 water samples and 16 sewage sludge samples were analyzed by liquid chromatography-tandem mass spectrometry. We obtained 100% elimination in the MBR effluents for three SAs (sulfadiazine, sulfadimethoxine, and sulfamethoxypyridazine) and the metabolite. For the rest of the SAs, the removal efficiencies during CAS and MBR treatments were similar and usually below 55%. Sulfamethizole was the most recalcitrant SA, exhibiting negative removal efficiencies in all the treatments investigated. The concentrations of SAs in the different sewage sludge types were also calculated and ranged from 0.01 to 11 ng g(-1). Furthermore, adsorption and biodegradation of SAs in activated sludge were investigated in two sets of batch reactors, which were spiked at high and low concentration (1,000 and 50 ng mL(-1), respectively). All SAs followed a similar trend and, with the exception of sulfathiazole, were not fully eliminated after 25 days of treatment.     

Study of the performance of three LC-MS/MS platforms for analysis of perfluorinated compounds

The analytical suitabilities of three different liquid chromatography–tandem mass spectrometry (LC-MS/MS) systems, (1) triple quadrupole (QqQ), (2) conventional 3D ion trap (IT), and (3) quadrupole–linear IT (QqLIT), to determine trace levels of perfluorinated compounds (PFCs) in fish and shellfish were compared. Sample preparation was performed using alkaline extraction and solid-phase-extraction cleanup. This evaluation was focused on both quantitative (sensitivity, precision, and accuracy) and qualitative (identification capabilities) aspects. In the three instruments, the former facet was evaluated using selected reaction monitoring (SRM), which is the standard mode for quantitative LC-MS/MS analysis. Accuracy was similar in the three systems, with recoveries always over 70 %. Precision was better for the QqLIT and QqQ systems (7–15%) than for the IT system (10–17%). The QqLIT (working in SRM mode) and QqQ systems offered a linear dynamic range of at least 3 orders of magnitude, whereas that of the IT system was 2 orders of magnitude. The QqLIT system achieved at least 20-fold higher sensitivity than the QqQ system, and this was at least tenfold higher sensitivity than for the IT system. In the IT system, identification was based on sensitive full mass range acquisition and MS ⁿ fragmentation and in the QqLIT system, it was based on the use of an information-dependent-acquisition scan function, which allows the combination of an SRM or MS full scan acting as the survey scan and an enhanced product ion scan followed by MS³ as the dependent scan in the same analysis. Three instruments were applied to monitor the content in fish and shellfish (anchovies, swordfish, tuna, mussels, and oysters) obtained from Valencia and Barcelona markets (Spain). The eight target PFCs were detected at mean concentrations in the range from 10 ng ?kg^-1 (perfluoro-7-methyloctanoic acid and perfluoro-1-decanesulfonate) to 4,200 ng ?kg^-1 (perfluoropentanoic acid). Furthermore, perfluoroheptanoic and perfluoroundecanoic acids (not covered as target analytes) were identified in some samples.

Anisotropic Bianchi VIII/IX cosmological models with matter and electromagnetic fields

We present a class of cosmological solutions of Einstein equations, with matter and electromagnetic field, which are anisotropic and spatially homogeneous of Bianchi types VIII and IX.