Particle size distribution of major inorganic species in atmospheric aerosols from Majorca (Spain)

Atmospheric aerosols collected by means of a cascade impaction system at the campus of the University of the Balearic Islands (Majorca, Spain) from November 1993 to February 1994 were analysed for chloride, nitrate, sulphate, ammonium, calcium, magnesium, sodium and potassium. Based on particle size distribution, the species studied were classified into three groups: (a) concentration decrease with particle size (sulphate and ammonium), (b) concentration increase with particle size (chloride, calcium, magnesium and sodium), and (c) independent of particle size (nitrate and potassium). A principal component analysis (PCA) revealed a clear relationship between particle size and analyte origin. Also, the origin of sulphate and potassium fine and coarse particles was found to be different.     

Ultraviolet-induced responses in two species of climax tropical marine macrophytes.

In tropical regions nominal reductions in stratospheric ozone could be detrimental to marine organisms that live near their upper tolerance levels of ultraviolet (UV) radiation and temperature. Well-known plant responses to UV include inhibition of photosynthesis, reductions in chlorophyll content, morphological changes and production of UV absorbing compounds such as flavonoids. An assessment of the effects and responses of two tropical marine macrophytes to full solar radiation and solar radiation depleted of UV were conducted in southwestern Puerto Rico. Changes in concentration of photosynthetic and photoprotective pigments, and in leaf optical properties of the red mangrove Rhizophora mangle and the seagrass Thalassia testudinum, were evaluated in field exclusion experiments. Rhizophora mangle exposed to full solar radiation showed lower leaf reflectance and a shift of 5 nm in the inflection point of the red edge. Thalassia testudinum samples excluded from UV had significant increases in total chlorophyll and carotenoid concentrations. These marine macrophytes showed increments in their concentration of UV-B absorbing compounds with exposure to UV radiation. Results indicate that even minor increases in UV radiation at low latitudes could have significant effects on the pigment composition of these climax species.     

Effects of water stress and high temperature on photosynthetic rates of two species of Prosopis

The main aim of this research was to compare the photosynthetic responses of two species of Prosopis, Prosopis chilensis (algarrobo) and Prosopis tamarugo (tamarugo) subjected to heat and water stress, to determine how heat shock or water deficit, either individually or combined, affect the photosynthesis of these two species. The photosynthetic rates expressed as a function of photon flow density (PFD) were determined by the O(2) liberated, in seedlings of tamarugo and algarrobo subjected to two water potentials: -0.3MPa and -2.5MPa and to three temperatures: 25 degrees C, 35 degrees C and 40 degrees C. Light response curves were constructed to obtain light compensation and light saturation points, maximum photosynthetic rates, quantum yields and dark respiration rates. The photochemical efficiency as the F(v)/F(m) ratio and the amount of RUBISCO were also determined under heat shock, water deficit, and under the combined action of both stress. Photosynthetic rates at a light intensity higher than 500mumole photons m(-2)s(-1) were not significantly different (P>0.05) between species when measured at 25 degrees C under the same water potential. The maximum photosynthetic rates decreased with temperature in both species and with water deficit in algarrobo. At 40 degrees C and -2.5MPa, the photosynthetic rate of algarrobo fell to 72% of that of tamarugo. The quantum yield decreased in algarrobo with temperature and water deficit and it was reduced by 50% when the conditions were 40 degrees C and -2.5MPa. Dark respiration increased by 62% respect to the control at 40 degrees C in tamarugo while remained unchanged in algarrobo. The photochemical efficiency decreased with both, high temperature and water deficit, without differences between species. RUBISCO content increased in algarrobo 35 degrees C. Water deficit reduced the amount of RUBISCO in both species. The results of this work support the conclusion that in both Prosopis species, the interaction between high temperature and water deficit affects photosynthesis responses greater than each individual stress, and that the interactive effect is more pronounce in algarrobo than in tamarugo.     

Dechlorane Plus in eggs of two gull species (Larus michahellis and Larus audouinii) from the southwestern Mediterranean Sea

Dechlorane Plus (DP) and some of its possible degradation products were measured in eggs from the yellow-legged gull (Larus michahellis) and Audouin's gull (Larus audouinii) from a protected area in the southwestern Mediterranean Sea. Statistically significant differences were found between both gull species, with yellow-legged gull eggs showing the highest average total DP concentration (209?pg/g wet weight). According to stable nitrogen and carbon isotope values, variations in DP concentrations in the gull species studied are explained by foraging behavior and diet rather than by the trophic position. Both DP stereoisomers were quantified in all the samples studied, and a slight enrichment of the anti-DP could have occurred in both species. The quantification of anti-[DP-1Cl] only in ～58?% of yellow-legged gulls support the hypothesis of a species-dependent factor influencing the bioaccumulation and/or biotransformation of Dechlorane-related compounds. This study reports on the first measurements of Dechlorane-related compounds in biota from the North African continent, contributing to the knowledge about DP environmental fate and distribution. In the light of our results, more research on differences in species-dependent bioaccumulation and biotransformation capabilities as well as ecological effects is encouraged in future Dechlorane-related compound studies.     

Luminescence and upconversion from thulium(iii) species in solution

Thulium salts and complexes are shown to be emissive from three states in the excited state manifold of Tm(3+). Formation of the (1)D(2) state can result in luminescence, or in energy transfer to the lower energy (1)G(4) and (3)H(4) emissive states. Where chromophores are present in the ligand structure, emission is restricted to thulium centred emissive states that are lower in energy than the chromophore centred donor state. We have also observed direct multi-photon excitation of the thulium excited state manifold. Furthermore, additional transitions are observed in the multi-photon excitation spectra that are consistent with upconversion as a consequence of sequential single photon absorption and relaxation processes within the thulium excited state manifold.     

Cu(I)-catalyzed diamination of conjugated dienes. Complementary regioselectivity from two distinct mechanistic pathways involving Cu(II) and Cu(III) species

Conjugated dienes can be diaminated at the internal and/or terminal double bonds using Cu(I) as catalyst and N,N-di-t-butyldiaziridinone (1) as nitrogen source. The regioselectivity is highly dependent upon the choice of Cu(I) catalyst and the substituents on diene substrates. The diamination likely proceeds via two mechanistically distinct pathways. The N-N bond of N,N-di-t-butyldiaziridinone (1) is first homolytically cleaved by the Cu(I) catalyst to form four-membered Cu(III) species A and Cu(II) radical species B, which are in rapid equilibrium. The internal diamination likely proceeds in a concerted manner via Cu(III) species A, and the terminal diamination likely involves Cu(II) radical species B. Kinetic studies have shown that the diamination is first-order in N,N-di-t-butyldiaziridinone (1), zero-order in olefin, and first-order in total Cu(I) catalyst, and the cleavage of the N-N bond of 1 by the Cu(I) catalyst is the rate-determining step. The internal diamination is favored by use of CuBr without ligand and electron-rich dienes. The terminal diamination is favored when using CuCl-L and dienes with radical-stabilizing groups.     

Glucosinolates in wild and cultivated Brassica montana Pourret (Brassicaceae) from southern France

Abstract

The glucosinolate (GL) profiles of wild and cultivated Brassica montana Pourret (seed, stem, leaf, root) from southern France were established using LC-MS analysis. In this investigation we have confirmed the presence of 9 known GLs: but-3-enyl- (1), prop-2-enyl- (2), pent-4-enyl- (3), (2R)-2-hydroxybut-3-enyl- (4), 4-hydroxyindol-3-ylmethyl- (5), 4-(methylsulfinyl)butyl- (6), 4-(methylsulfanyl)butyl- (7), 1-methoxyindol-3-ylmethyl- (8), and indol-3-ylmethyl (9) GL. In addition, we tentatively identified for the first time the presence in the plant of 1-methylpropyl GL (10) in all plant parts. In addition, we have pointed out differences in GL profiles between plant organs and between wild and cultivated B. montana.     

Experimental and modeling study of 241Am uptake by suspended matter in freshwater environment from southern Spain

Radiotracer experiments are presented on ²⁴¹Am uptake in natural aqueous suspensions from a reservoir and a river in SW Spain. The uptake was followed by measuring the ²⁴¹Am activity in water using a liquid scintillation technique. Experimental results revealed a three-step kinetics in the uptake, which could be satisfactorily described by a model of two parallel and reversible reactions followed by a consecutive weakly-reversible reaction. This paper also studies the effects of the concentration of suspended matter and the specific surface area on the kinetic transfer coefficients. This revised version was published online in July 2006 with corrections to the Cover Date.     

Analysis of UV filters in tap water and other clean waters in Spain

The present paper describes the development of a method for the simultaneous determination of five hormonally active UV filters namely benzophenone-3 (BP3), 3-(4-methylbenzylidene) camphor (4MBC), 2-ethylhexyl 4-(dimethylamino) benzoate (OD-PABA), 2-ethylhexyl 4-methoxycinnamate (EHMC) and octocrylene (OC) by means of solid-phase extraction and gas chromatography–electron impact ionization–mass spectrometry. Under optimized conditions, this methodology achieved low method limits of detection (needed for clean waters, especially drinking water analysis), between 0.02 and 8.42 ng/L, and quantitative recovery rates higher than 73% in all cases. Inter- and intraday precision for all compounds were lower than 7% and 11%, respectively. The optimized methodology was applied to perform the first survey of UV absorbing compounds in tap water from the metropolitan area and the city of Barcelona (Catalonia, Spain). In addition, other types of clean water matrices (mineral bottled water, well water and tap water treated with an ion-exchange resin) were investigated as well. Results evidenced that all the UV filters investigated were detected in the water samples analyzed. The compounds most frequently found were EHMC and OC. Maximum concentrations reached in tap water were 290 (BP3), 35 (4MBC), 110 (OD-PABA), 260 (EHMC), and 170 ng/L (OC). This study constitutes the first evidence of the presence of UV filter residues in tap water in Europe.     

Novel bioactive diterpenoid metabolites from tropical marine algae of the genus halimeda (Chlorophyta)

Four new diterpenoid metabolites, halimedarial (1), 3, 4 and 5, have been isolated from several species of the tropical green algae Halimeda (Udoteaceae). These new compounds show potent antimicrobial and cytotoxic properties in laboratory bioassays.     

UV photoelectron spectroscopy of transient species: germanium dhodide (GeI2)

Valence ionization energies of the transient species GeI₂, obtained with He(I) photoelectron (PE) spectroscopy, are presented. The interpretation of the results is aided by Hartree-Fock-Slater calculations in which relativistic effects have been taken into account through perturbation theory. A comparison with PE data of the other germanium dihalides is made.     

UV photoelectron spectroscopy of transient species: germanium difluoride (GeF2)

The He(1) photoelectron spectrum of germanium difluoride (GeF₂) is reported. Results are analyzed on the basis of Hartree-Fock-Slater quantum-chemical calculations. A comparison is made with previous data for GeCl₂, GeBr₂, CF₂ and SiF₂.     

Concentration of ochratoxin A in wines from supermarkets and stores of Valencian Community (Spain)

Ochratoxin A (OTA) is a mycotoxin produced by fungi species belonging to the genera Aspergillus and Penicillium being isolated in alcoholic beverages. The aim of this work is developed and applied a procedure for the analysis of OTA in wines. An analytical method based on immunoaffinity column (IAC) for clean-up, liquid chromatography with fluorescence detection (LC-FD), and LC-FD after of OTA methylation was used to determine the occurrence of OTA in wines. Recoveries of this mycotoxin spiked to red wines at 0.5 ng/ml level were >90% with an average of relative standards deviations of 4%. Furthermore, 116 wine samples from designation of origin (DO) and three samples from food stores of Valencian Community (Spain) were examined for the occurrence of OTA being the levels of this mycotoxin ranged from <0.01 to 0.76 ng/ml. Finally, the estimated daily intake of OTA in this study was 0.15 ng/kg bw per day.     

A comparison of two micro-beam X-ray emission techniques for actinide elemental distribution in microscopic particles originating from the hydrogen bombs involved in the Palomares (Spain) and Thule (Greenland) accidents

In order to validate and to gain confidence in two micro-beam techniques: particle induced X-ray emission with nuclear microprobe technique (μ-PIXE) and synchrotron radiation induced X-ray fluorescence in a confocal alignment (confocal SR μ-XRF) for characterization of microscopic particles containing actinide elements (mixed plutonium and uranium) a comparative study has been performed. Inter-comparison of the two techniques is essential as the X-ray production cross-sections for U and Pu are different for protons and photons and not well defined in the open literature, especially for Pu.The particles studied consisted of nuclear weapons material, and originate either in the so called Palomares accident in Spain, 1966 or in the Thule accident in Greenland, 1968. In the determination of the average Pu/U mass ratios (not corrected by self-absorption) in the analysed microscopic particles the results from both techniques show a very good agreement. In addition, the suitability of both techniques for the analysis with good resolution (down to a few μm) of the Pu/U distribution within the particles has been proved. The set of results obtained through both techniques has allowed gaining important information concerning the characterization of the remaining fissile material in the areas affected by the aircraft accidents. This type of information is essential for long-term impact assessments of contaminated sites.     

Speciation analysis of antimony in marine biota by HPLC-(UV)-HG-AFS: Extraction procedures and stability of antimony species

Speciation analysis of antimony in marine biota is not well documented, and no specific extraction procedure of antimony species from algae and mollusk samples can be found in the literature. This work presents a suitable methodology for the speciation of antimony in marine biota (algae and mollusk samples). The extraction efficiency of total antimony and the stability of Sb(III), Sb(V) and trimethylantimony(V) in different extraction media (water at 25 and 90 °C, methanol, EDTA and citric acid) were evaluated by analyzing the algae Macrosystis integrifolia (0.55 ± 0.04 μg Sb g⁻¹) and the mollusk Mytilus edulis (0.23 ± 0.01 μg Sb g⁻¹). The speciation analysis was performed by anion exchange liquid chromatography (post-column photo-oxidation) and hydride generation atomic fluorescence spectrometry as detection system (HPLC-(UV)-HG-AFS). Results demonstrated that, based on the extraction yield and the stability, EDTA proved to be the best extracting solution for the speciation analysis of antimony in these matrices. The selected procedure was applied to antimony speciation in different algae samples collected from the Chilean coast. Only the inorganic Sb(V) and Sb(III) species were detected in the extracts. In all analyzed algae the sum of total antimony extracted (determined in the extracts after digestion) and the antimony present in the residue was in good agreement with the total antimony concentration determined by HG-AFS. However, in some extracts the sum of antimony species detected was lower than the total extracted, revealing the presence of unknown antimony species, possibly retained on the column or not detected by HPLC-(UV)-HG-AFS. Further work must be carried out to elucidate the identity of these unknown species of antimony.     

Photoinhibition of photosynthesis in Macrocystis pyrifera (Phaeophyceae), Chondrus crispus (Rhodophyceae) and Ulva lactuca (Chlorophyceae) in outdoor culture systems

The effect of solar radiation on photosynthesis and chlorophyll fluorescence associated to photosystem II (PS II) was determined in the Phaeophyta Macrocystis pyrifera, the Rhodophyta Chondrus crispus and the Chlorophyta Ulva lactuca by oxygen evolution and pulse-amplitude-modulated (PAM) fluorescence. The algae were maintained in 1.2 m3 outdoor tanks with constant aeration and at 8, 26 and 100% incident irradiance (E(o)). All three species showed a decrease in deltaF/F'm values during solar noon compared to values in the morning and afternoon, suggesting a photoinhibition of photosynthesis. In general, photoinhibition was negatively correlated to increasing daily irradiance in all three species. Photoinhibition in C. crispus occurred in tissue incubated at 8, 26 and 100% E(o), while in M. pyrifera and U. lactuca a decrease in deltaF/F'm values was only observed in tissue incubated at 100% E(o). This suggests that species that naturally grow at greater depths might be more susceptible to excessive light when cultured in shallow waters compared to species that naturally inhabit shallower depths. In M. pyrifera, deltaF/F'm values were lower in the afternoon than those in the morning, suggesting slower repair mechanisms of the photosystem II compared to the other species. The results suggest that photoinhibition could be reduced by reducing incident irradiance to culture systems or increasing of biomass to promote self-shading. Gross oxygenic photosynthesis increased linearly at low electron transport rates after which it saturated in all three species. This suggests that chlorophyll fluorescence could be used as an indicator of the physiological status of macroalgae maintained in dense aquaculture systems.