Application of ICP-QMS for the determination of plutonium in environmental samples for safeguards purposes

Aiming to determine the plutonium amount as well as its isotopic composition, in particular, in swipe samples for safeguards purposes, an analytical method was developed with a plutonium separation step based on extraction chromatography using 2 cm TEVA columns and detection with quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with membrane desolvation system. The method was successfully applied to New Brunswick plutonium certified reference materials as well as to Lawrence Livermore National Laboratory round robin samples, based on the round robin samples provided by the Institute for Reference Materials and Measurements (Belgium), as part of the Regular European Interlaboratory Measurement Evaluation Programme (REIMEP), campaign 16 (isotopic abundances of plutonium in plutonium nitrate samples), with a total plutonium amount between 1 and 0.25 ng per sample. After the introduction of an additional separation step, it was also possible to carry out precise and accurate total plutonium, (240)Pu/(239)Pu, (241)Pu/(239)Pu and (242)Pu/(239)Pu atom ratios determination in sediment sample showing its applicability to environmental samples in general, reaching a detection limit equivalent to 5 mBq(239)Pu kg(-1).     

Females’ sampling strategy to comparatively evaluate prospective mates in the peacock blenny <Emphasis Type="Italic">Salaria pavo</Emphasis>

Emerging evidence suggests the occurrence of comparative decision-making processes in mate choice, questioning the traditional idea of female choice based on rules of absolute preference. In such a scenario, females are expected to use a typical best-of-n sampling strategy, being able to recall previous sampled males based on memory of their quality and location. Accordingly, the quality of preferred mate is expected to be unrelated to both the number and the sequence of female visits. We found support for these predictions in the peacock blenny, Salaria pavo, a fish where females have the opportunity to evaluate the attractiveness of many males in a short time period and in a restricted spatial range. Indeed, even considering the variability in preference among females, most of them returned to previous sampled males for further evaluations; thus, the preferred male did not represent the last one in the sequence of visited males. Moreover, there was no relationship between the attractiveness of the preferred male and the number of further visits assigned to the other males. Our results suggest the occurrence of a best-of-n mate sampling strategy in the peacock blenny.     

Microbial degradation of the benzonitrile herbicides dichlobenil, bromoxynil and ioxynil in soil and subsurface environments--insights into degradation pathways, persistent metabolites and involved degrader organisms

The benzonitriles dichlobenil, bromoxynil and ioxynil are important broad-spectrum or selective herbicides used in agriculture, orchards and public areas worldwide. The dichlobenil metabolite 2,6-dichlorobenzamide is the most frequently encountered groundwater contaminant in Denmark, which suggests that the environmental fate of these three structurally related benzonitrile herbicides should be addressed in detail. This review summarises the current knowledge on microbial degradation of dichlobenil, bromoxynil and ioxynil with particular focus on common features of degradation rates and pathways, accumulation of persistent metabolites and diversity of the involved degrader organisms.     

Taboos and forest governance: informal protection of hot spot dry forest in southern Madagascar

In the dry forest of southern Madagascar, a region of global conservation priority, formally protected areas are nearly totally absent. We illustrate how the continued existence of unique forest habitats in the Androy region is directly dependent on informal institutions, taboos, regulating human behavior. Qualitative interviews to map and analyze the social mechanisms underlying forest protection have been combined with vegetation analyses of species diversity and composition. Of 188 forest patches, 93% were classified as protected, and in Southern Androy all remaining forest patches larger than 5 ha were protected. Eight different types of forests, with a gradient of social fencing from open access to almost complete entry prohibitions, were identified. Transgressions were well enforced with strong sanctions of significant economic as well as religious importance. Analyses of species diversity between protected and unprotected forests were complicated because of size differences and access restrictions. However, since, for example, in southern Androy >90% of the total remaining forest cover is protected through taboos, these informal institutions represent an important, and presently the only, mechanism for conservation of the highly endemic forest species. We conclude that social aspects, such as local beliefs and legitimate sanctioning systems, need to be analyzed and incorporated along with biodiversity studies for successful conservation.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Revisiting the plant hyperaccumulation criteria to rare plants and earth abundant elements

The several established criteria to define a hyperaccumulator plant were applied to a rare and endangered species, Plantago almogravensis, and to the 3rd most abundant element in the earth crust, Al. Using the most common criteria, P. almogravensis undoubtedly is an Al hyperaccumulator plant. If the recent proposed requirements were considered, most of them matching those for a plant to be used in phytoextraction, it can only be considered an unusual accumulator of Al. A discussion is made concerning the several criteria of a hyperaccumulator plant in order to include rare and endemic ones and abundant elements. In ecological terms, the enrichment in Al and Fe observed may account for the differences in the vegetation pattern. Due to the rarity and endangered nature of this plant, the contribution of this work is also relevant for the ecological understanding and the development of conservation options of this endemic species.     

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.