Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.     

Dealing with urban noise: vermilion flycatchers sing longer songs in noisier territories

In noisy conditions, several avian species modulate their songs in amplitude and in the temporal or frequency domains, presumably to improve communication. Most studies on how passerine birds perform such adjustments have been carried out in oscines, a group well known for the importance of learning in the development of their songs. On the other hand, suboscines, in which learning appears to have little influence on the development of their songs, have been largely neglected. We evaluated song adjustment to noise in the vermilion flycatcher (Pyrocephalus rubinus), a suboscine bird. We conducted song recordings and noise measurements at several territories within Mexico City during the length of the dawn chorus. Males living in noisier places sang long songs, while those males inhabiting quieter places sang both short and long songs. We also found evidence of individual song plasticity, as males sang less versatile songs (i.e., songs with more introductory elements) later in the morning when noise levels were higher. This individual shift in song seems to be more associated to time of the day rather than to the observed rise in noise. However, we cannot discard an effect of noise, which should be evaluated with an experiment. We discuss our results in the context of other studies with oscine passerines and other taxa and consider implications for signaling in intra- and intersexual contexts.     

Technological applications of organo-montmorillonites in the removal of pyrimethanil from water: adsorption/desorption and flocculation studies

Environmental Science and Pollution Research - Pyrimethanil (2-aniline-4, 6-dimethylpyrimidine, PRM) is used in fruit packing plants to control fungal infections and diseases. The effluents greatly...     

Sources and spatial distribution of polycyclic aromatic hydrocarbons in coastal sediments of the Basque Country (Bay of Biscay)

This contribution characterises the sources and distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Basque coast (Bay of Biscay). Different source characterisation approaches (i.e. GIS assisted-chemometrics, PAH diagnostic ratios and analyses of composition profiles) were used in combination to successfully identify the factors determining the origin and distribution of PAHs. Urban/industrial combustion processes were identified as the main PAH source. However, the analysis of PAH composition patterns and diagnostic ratios identified secondary natural and petrogenic PAH sources on small spatial scales. The median ∑18PAH concentration ranged from 66 μg kg^?1 (d.w.) to 7021 μg kg^?1 (d.w.). The Ibaizabal estuary, which supports most of the anthropogenic pressure in the region (i.e. urban development, industrialisation, commercial and recreational harbours), also showed the highest PAH concentrations. On the shelf, human activities, hydrodynamic conditions and geomorphological features led to spatial differences in the PAH concentrations among sectors: the offshore and west sectors were characterised by higher concentrations, while the lowest values were found in the mid and east sectors. The results enhance the knowledge on PAH-related contamination processes and could be used to support the environmental assessment process required under current European marine legislation.     

Decontamination of polycyclic aromatic hydrocarbons and nonylphenol from sewage sludge using hydroxypropyl-β-cyclodextrin and evaluation of the toxicity of leachates

A decontamination technique based in cyclodextrin extraction has been developed to eliminate nonylphenol (NP) and 16 polycyclic aromatic hydrocarbons (PAHs; the US Environmental Protection Agency priority pollutants list) from sewage sludge. In a first step, PAHs and NP were characterised in six sludges to determine contamination levels according to limit values proposed by the European Union Sludge Directive draft. There were few variations in the total PAHs content with levels of 1.88 to 3.05 mg kg^?1. Three-ring PAHs predominated, but fluoranthene and pyrene were also present. None of the sludge exceeded the PAHs limit proposed by the European Union’s draft Directive. On the contrary, NP content in four of the six sludges was over the recommended limits of 50 mg kg^-1 for NP ethoxylates. With the aim of obtaining NP values below the concentration limits proposed to use the sewage sludge as agricultural amendments, a preliminary study using hydroxypropyl-β-cyclodextrin (HPBCD) extractions as a decontamination technique was carried out. About 90 % of NP content was removed with only one extraction with HPBCD, whereas after three sequential extractions using an aqueous solution without HPBCD, the NP extraction percentage was less than 1 %. Simultaneously, PAHs extraction percentages obtained with HPBCD were also much higher than when aqueous solution was used, especially in the case of two- and three-ring PAHs. Finally, the potential environmental hazard of HPBCD leachates to aquatic organisms (Daphnia magna) was tested. These results indicate that the treatment of sewage sludge with cyclodextrin could allow their safe use as fertiliser in agriculture.     

Temporal variability of airborne bacterial community structure in an urban area

Temporal airborne bacterial genetic community structure and meteorological factors were analysed above an urban area in the northwest of France from December 2003 to April 2004 with a sampling strategy considering different time intervals (from an hour to a month). Principal component analysis (PCA) of B-ARISA (Bacterial-Automated Ribosomal Intergenic Spacer Analysis) profiles revealed a hierarchy in the temporal variability of bacterial community: daily<weekly<seasonal. Co-inertia analysis between B-ARISA data and meteorological factors demonstrated the correlation between the seasonal variability in the bacterial community and climatic conditions such as temperature and relative humidity, whereas daily and weekly variability seemed likely to be managed by other factors such as anthropogenic activities.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Microbial secondary metabolites in school buildings inspected for moisture damage in Finland, The Netherlands and Spain

Secondary metabolites produced by fungi and bacteria are among the potential agents that contribute to adverse health effects observed in occupants of buildings affected by moisture damage, dampness and associated microbial growth. However, few attempts have been made to assess the occurrence of these compounds in relation to moisture damage and dampness in buildings. This study conducted in the context of the HITEA project (Health Effects of Indoor Pollutants: Integrating microbial, toxicological and epidemiological approaches) aimed at providing systematic information on the prevalence of microbial secondary metabolites in a large number of school buildings in three European countries, considering both buildings with and without moisture damage and/or dampness observations. In order to address the multitude and diversity of secondary metabolites a large number of more than 180 analytes was targeted in settled dust and surface swab samples using liquid chromatography/mass spectrometry (LC/MS) based methodology. While 42%, 58% and 44% of all samples collected in Spanish, Dutch and Finnish schools, respectively, were positive for at least one of the metabolites analyzed, frequency of detection for the individual microbial secondary metabolites - with the exceptions of emodin, certain enniatins and physcion - was low, typically in the range of and below 10% of positive samples. In total, 30 different fungal and bacterial secondary metabolites were found in the samples. Some differences in the metabolite profiles were observed between countries and between index and reference school buildings. A major finding in this study was that settled dust derived from moisture damaged, damp schools contained larger numbers of microbial secondary metabolites at higher levels compared to respective dust samples from schools not affected by moisture damage and dampness. This observation was true for schools in each of the three countries, but became statistically significant only when combining schools from all countries and thus increasing the sample number in the statistical analyses.     

Kinship recognition and grouping in hatchling green iguanas

Summary The research addressed two questions: (1) doIguana iguana hatchlings recognize their kin, and (2) what are the recognition mechanisms? Eggs were collected from wild and captive-raised females and hatched in semi-natural incubators. In the first experiment we used eggs from two females. One of the clutches was subdivided to be placed in different incubators. Immediately after emergence one of these hatchling groups was introduced into a 10 m x 10 m enclosure. At the same time we introduced hatchlings from another female. The remaining hatchling group was kept separate for 3 weeks and was then introduced into the same cage. Unrelated hatchlings separated from each other. Related but separated hatchlings grouped according to introduction date. In the second experiment we maintained eight kin groups in individual cages and two hatchlings per kin group in an additonal cage. Hatchlings from the mixed group showed no preference for their kin before physical contact with pure kin groups had occurred. After physical contact hatchling recognized their kin by feces smell. Body odor is likely to be also involved.     

Do newborn domestic rabbits Oryctolagus cuniculus compete for thermally advantageous positions in the litter huddle?

Competition among mammalian siblings for scarce resources can be severe. Whereas research to date has focused on competition for the mother’s milk, the young of many (particularly altricial) species might also be expected to compete for thermally favorable positions within the nest, den, or litter huddle. We investigated this in newborn pups of the European rabbit Oryctolagus cuniculus, a species in which the altricial young are not brooded by the mother, and in which competition for milk is severe. In eight unculled litters (N = 86 pups) of a domestic chinchilla strain, we calculated huddling indexes for individual pups on postnatal days 2–5 as a measure of the degree of insulation they received from littermates. Pups maintained almost constant physical contact with the litter huddle. They performed brief but frequent rooting and climbing behaviors, which usually improved their huddling index, interspersed with longer periods of quiescence during which their huddling index declined. As expected, we found a significant positive relation between pups’ mean huddling index and body temperature. Unexpectedly, however, we did not find a relation between huddling index and pups’ birth weight, survival, milk intake, or efficiency of converting milk to body mass. We conclude that rather than competing for thermally advantageous positions within the huddle newborn rabbits share out thermally advantageous positions as they move in a continual dynamic flow through it. Thus, in newborn rabbits, competition for the mother’s milk exists alongside mutual “cooperative” benefits of littermate presence. This contribution is part of the special issue “Sibling competition and cooperation in mammals” (guest editors: Robyn Hudson and Fritz Trillmich).