Improvements in the radiochemical method for separating 226Ra in solid samples through coprecipitation with BaSO4.

The aim of this work was to improve the commonly used method for 226Ra determination in water and to establish its application in solid samples. This method is based on the coprecipitation of Ra with BaSO4 and gross alpha counting of the precipitate. An exhaustive study of the coprecipitation behaviour of the most abundant cations present in solid samples was performed to avoid incorrect radiochemical yields. As a result, it was considered necessary to introduce two new purification steps into the conventional method. Likewise, two nuclides, 241Am and 226Ra, were compared to obtain the mass efficiency curve given their different behaviour in the coprecipitation process. While Ra behaves similarly to Ba, Am coprecipitates, forming mixed crystals that may behave differently in the self-absorption process. The influence of the cations on the chemical yield with no precipitate purification was: Sr2+≫Fe3+>Mg2+≈Ca2+>K+≈Na+. The method was successfully applied to soil, sediment, and plant ash samples.

Standardization of 226Ra solutions with descendants by 4παß LSC counting.

In this work, a method to standardize 226Ra solutions with descendants by 4παß liquid scintillation counting (LSC) has been used. The standardization can be carried out provided that the equilibrium state of 226Ra solutions, the counting efficiency of short-lived 214Po and/or the counter dead time are known. Procedures to obtain these requirements have been set up.

Inactivation of Aspergillus species in real water matrices using medium pressure mercury lamps.

The aim of this work is to understand the inactivation efficiency of medium pressure mercury lamps, measured in terms of growth inhibition as well as cell death, damage and response, using three strains from three different Aspergillus species (A. fumigatus, A. niger and, A. terreus) spiked in filtered surface water. A complete characterization of the effect of the treatment on each strain of the fungal species was assessed considering spores' morphology, cell wall integrity and enzymatic activity, the formation of pyrimidine dimers in the DNA and proteome analysis. Results showed that, when subjected to medium pressure mercury lamps, A. niger is the most resistant to inactivation, that both A. fumigatus and A. niger suffer more morphological changes and present a higher number of damaged spores and A. terreus presented more dead spores. DNA damages detected in A. niger were able to be repaired to some extent, under both light and dark conditions. Finally, proteome analysis showed that the UV radiation treatment triggered different types of stress response, including cell wall reorganization and DNA repair in A. fumigatus and A. terreus, and oxidative stress responses like the increase in production of citric acid and itaconic acid in A. niger and A. terreus, respectively.

Standardization of non-equilibrium 210Pb solutions by LSC and 2πα counting.

A procedure for the standardization of 210Pb solutions in radioactive disequilibrium, or incompletely purified from its descendants, has been set up and successfully validated. The method, based on joint measurements of 210Po by alpha-particle spectrometry (2πα counting) with grid ionization chamber and liquid scintillation counting for overall activity estimation, is presented as an alternative to 210Pb measurement by LSC with α/ß discrimination.

Small but powerful: Light-emitting diodes for inactivation of Aspergillus species in real water matrices.

This study addressed the effectiveness of light emitting diodes to achieve inactivation of three different Aspergillus species (Aspergillus fumigatus, Aspergillus niger and Aspergillus terreus) in a real water matrix. Three single small ultraviolet-C diodes emitting light at two different wavelengths were tested: 255 nm that is similar to the wavelength emitted by low pressure mercury lamps and 265 nm that is closer to the maximum absorbance wavelength of DNA. The ultraviolet-C diodes emitting light at 265 nm were found to be more effective than the 255 nm, achieving 3-log, 1-log and 5-log inactivations of Aspergillus fumigatus, Aspergillus niger and Aspergillus terreus using less than 20 mJ/cm2 (13,97 mJ/cm2; 7,28 mJ/cm2; 19,74 mJ/cm2). The diodes have also affected the morphology of the fungal spores and increased the percentage of damaged and dead spores.

The link between the microbial ecology, gene expression, and biokinetics of denitrifying polyphosphate-accumulating systems under different electron acceptor combinations.

The emission of the greenhouse gas nitrous oxide (N2O) can occur during biological nutrient removal. Denitrifying enhanced biological phosphorus removal (d-EBPR) systems are an efficient means of removing phosphate and nitrogen, performed by denitrifying polyphosphate-accumulating organisms (d-PAOs). The aim of this work was to study the effect of various combinations of electron acceptors, nitrate (NO3-), nitrite (NO2-), and N2O, on the denitrification pathway of a d-EBPR system. Batch tests were performed with different electron acceptor combinations, to explore the denitrification pathway. Reverse transcriptase-qPCR (RT-qPCR) and high-throughput sequencing, combined with chemical analysis, were used to study gene expression, microbial diversity, and denitrification kinetics. The potential for N2O production was greater than the potential for its reduction in most tests. A strong correlation was observed between the N2O reduction rate and the relative gene expression of nitrous oxide reductase per nitrite reductase (nosZ/(nirS + nirK)), suggesting that the expression of denitrifying marker genes is a strong predictor of the N2O reduction rate. The d-EBPR community maintained a core population with low variations throughout the study. Furthermore, phylogenetic analyses of the studied marker genes revealed that the organisms actively involved in denitrification were closely related to Thauera sp., Candidatus Accumulibacter phosphatis, and Candidatus Competibacter denitrificans. Moreover, Competibacter-related OTUs seem to be important contributors to the N2O reduction capacity of the system, likely scavenging the N2O produced by other organisms. Overall, this study contributes to a better understanding of the microbial biochemistry and the genetics involving biological denitrification removal, important to minimize N2O emissions in wastewater treatment plants.

Reference materials produced for a European metrological research project focussing on measurements of NORM.

Reliable measurement of Naturally Occurring Radioactive Materials is of significance in order to comply with environmental regulations and for radiological protection purposes. This paper discusses the standardisation of three reference materials, namely sand, tuff and TiO2 to serve as quality control materials for traceability, method validation and instrument calibration. The sample preparation, material characterization via γ, α and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the assignment of values for both the 4n (Thorium) and 4n+2 (Uranium) decay series are described.

Biogenic platinum and palladium nanoparticles as new catalysts for the removal of pharmaceutical compounds.

Pharmaceutical products (PhP) are one of the most alarming emergent pollutants in the environment. Therefore, it is of extreme importance to investigate efficient PhP removal processes. Biologic synthesis of platinum nanoparticles (Bio-Pt) has been reported, but their catalytic activity was never investigated. In this work, we explored the potential of cell-supported platinum (Bio-Pt) and palladium (Bio-Pd) nanoparticles synthesized with Desulfovibrio vulgaris as biocatalysts for removal of four PhP: ciprofloxacin, sulfamethoxazole, ibuprofen and 17ß-estradiol. The catalytic activity of the biological nanoparticles was compared with the PhP removal efficiency of D. vulgaris whole-cells. In contrast with Bio-Pd, Bio-Pt has a high catalytic activity in PhP removal, with 94, 85 and 70% removal of 17ß-estradiol, sulfamethoxazole and ciprofloxacin, respectively. In addition, the estrogenic activity of 17ß-estradiol was strongly reduced after the reaction with Bio-Pt, showing that this biocatalyst produces less toxic effluents. Bio-Pt or Bio-Pd did not act on ibuprofen, but this could be completely removed by D. vulgaris whole-cells, demonstrating that sulfate-reducing bacteria are among the microorganisms capable of biotransformation of ibuprofen in anaerobic environments. This study demonstrates for the first time that Bio-Pt has a high catalytic activity, and is a promising catalyst to be used in water treatment processes for the removal of antibiotics and endocrine disrupting compounds, the most problematic PhP.

The response of a fast scintillator screen (YAP:Ce) to low energy ions (0-40 keV) and its use to detect fast-ion-loss in stellarator TJ-II.

A systematic study of scintillation materials was undertaken to improve the time resolution of the fast ion diagnostic currently installed at TJ-II stellarator. It was found that YAP:Ce (formula YAlO3:Ce, Yttrium Aluminum Perovskite doped with Cerium) ionoluminescence offers better sensitivity and time response compared to the standard detector material, SrGa2S4:Eu (TG-Green), currently used in TJ-II. A comparison between both materials was carried out by irradiating them with H+ ions of up to 40 keV using a dedicated laboratory setup. It is found that for the low energy ions of interest at TJ-II, YAP:Ce offers 20 times higher sensitivity than TG-Green and much faster decay time, 27 ns versus 540 ns. It is expected that the use of YAP:Ce in combination with a faster data acquisition and an ion counting software as part of the TJ-II ion luminescent probe will provide 20 times faster data on ion loss.

Plant growth-promoting Burkholderia species isolated from annual ryegrass in Portuguese soils.

AIMS: To search for culturable Burkholderia species associated with annual ryegrass in soils from natural pastures in Portugal, with plant growth-promoting effects. METHODS AND RESULTS: Annual ryegrass seedlings were used to trap Burkholderia from two different soils in laboratory conditions. A combined approach using genomic fingerprinting and sequencing of 16S rRNA and recA genes resulted in the identification of Burkholderia strains belonging to the species Burkholderia graminis, Burkholderia fungorum and the Burkholderia cepacia complex. Most strains were able to solubilize mineral phosphate and to synthesize indole acetic acid; some of them could produce siderophores and antagonize the phytopathogenic oomycete, Phytophthora cinnamomi. A strain (G2Bd5) of B. graminis was selected for gnotobiotic plant inoculation experiments. The main effects were the stimulation of root growth and enhancement of leaf lipid synthesis and turnover. Fluorescence in situ hybridization and confocal laser microscopy evidenced that strain G2Bd5 is a rhizospheric and endophytic colonizer of annual ryegrass. CONCLUSIONS: This work revealed that annual ryegrass can naturally associate with members of the genus Burkholderia. A novel plant growth promoting strain of B. graminis was obtained. SIGNIFICANCE AND IMPACT OF THE STUDY: The novel strain belongs to the plant-associated Burkholderia cluster and is a promising candidate for exploitation as plant inoculant in field conditions.

Biodegradation of pesticides using fungi species found in the aquatic environment.

Relatively limited attention has been given to the presence of fungi in the aquatic environment compared to their occurrence in other matrices. Taking advantage and recognizing the biodegradable capabilities of fungi is important, since these organisms may produce many potent enzymes capable of degrading toxic pollutants. Therefore, the aim of this study was to evaluate the potential ability of some species of filamentous fungi that occur in the aquatic environment to degrade pesticides in untreated surface water. Several laboratory-scale experiments were performed using the natural microbial population present in the aquatic environment as well as spiked fungi isolates that were found to occur in different water matrices, to test the ability of fungi to degrade several pesticides of current concern (atrazine, diuron, isoproturon and chlorfenvinphos). The results obtained in this study showed that, when spiked in sterile natural water, fungi were able to degrade chlorfenvinphos to levels below detection and unable to degrade atrazine, diuron and isoproturon. Penicillium citrinum, Aspergillus fumigatus, Aspergillus terreus and Trichoderma harzianum were found to be able to resist and degrade chlorfenvinphos. These fungi are therefore expected to play an important role in the degradation of this and other pollutants present in the aquatic environment.

Bottled water: analysis of mycotoxins by LC-MS/MS.

The presence of mycotoxins in food samples has been widely studied as well as its impact in human health, however, information about its distribution in the environment is scarce. An analytical method comprising a solid phase extraction procedure followed by liquid chromatography tandem mass spectrometry analysis was implemented and validated for the trace analysis of mycotoxins in drinking bottled waters. Limits of quantification achieved for the method were between 0.2ngL(-1) for aflatoxins and ochratoxin, and 2.0ngL(-1) for fumonisins and neosolaniol. The method was applied to real samples. Aflatoxin B2 was the most frequently detected mycotoxin in water samples, with a maximum concentration of 0.48±0.05ngL(-1) followed by aflatoxin B1, aflatoxin G1 and ochratoxin A. The genera Cladosporium, Fusarium and Penicillium were the fungi more frequently detected. These results show that the consumption of these waters does not represent a toxicological risk for an adult.

Preparation and characterisation of a (226)Ra spiked slag as reference material for radioactive control of steelworks.

One of the issues of the European Research Project MetroMetal is to develop reference materials in order to provide SI-traceable radioactivity monitoring in foundries. For this purpose, a protocol for preparing a set of identical standard slag samples, containing known activity concentrations of (226)Ra, has been developed. This paper describes the preparation of the raw material, the characterisation in terms of its mineralogical, chemical and radiological features, the spiking procedure and the homogeneity testing of the spiked samples.

High-resolution alpha-particle spectrometry of ²³8U.

The alpha-particle emission probabilities associated with the three main alpha transitions of (238)U were measured by high-resolution alpha-particle spectrometry. Highly enriched (238)U material was used and its isotopic composition characterised by mass spectrometry. Source production through electrodeposition was optimised to reconcile conflicting demands for good spectral resolution and statistical precision. Measurements were performed at IRMM and CIEMAT for 1-2 years in three different set-ups. A new magnet system was put into use to largely eliminate true coincidence effects with low-energy conversion electrons. Finally the accuracy and precision of the relative emission probabilities for the three transitions - 77.01 (10)%, 22.92 (10)% and 0.068 (10)%, respectively - have been improved significantly.

New insights concerning the occurrence of fungi in water sources and their potential pathogenicity.

Fungi are known to occur ubiquitously in the environment. In the past years, the occurrence of filamentous fungi in the aquatic environment has been a subject of growing interest. This study describes the occurrence of various fungal genera in different drinking water sources being Penicillium and Trichoderma the most representative ones (30% and 17%, respectively). Also, 24 fungal species that have not been previously described in the aquatic environment are reported in this study, being once again the major species from the Penicillium genera. This study therefore contributes to the knowledge on the richness of fungi diversity in water. 68% of the described species were found to be able to grow at 30 °C but only Aspergillus fumigatus, Aspergillus viridinutans and Cunninghamella bertholletiae were able to grow at the higher temperature tested (42 °C). 66% of the species that were able to grow at 30 °C have spore sizes below 5 µm which enables them to cause breathing infections. These were therefore identified as potential pathogenic species.

Modelling the biodegradation of non-steroidal anti-inflammatory drugs (NSAIDs) by activated sludge and a pure culture.

A model describing ibuprofen and ketoprofen biodegradation by activated sludge from three different wastewater treatment plants (WWTP) was developed in this study. This model successfully described the biodegradation profiles observed at two different initial concentrations of each compound, where a lag-phase was observed prior to the biodegradation of each compound. Twelve ibuprofen and ketoprofen degrading isolates were identified in this study from the WWTP sludge showing the best removal performance. One of these isolates was characterised via another model, where biodegradation was dependent on biomass growth rate as well as the ibuprofen concentration. The fact that different models were needed to describe the biodegradation by activated sludge and a pure culture suggests that the biodegradation of non-steroidal anti-inflammatory drugs (NSAIDs) depends on the microbial community, thus pharmaceutical biodegradation models may require adaptation depending upon the system. This study provides an advance towards modelling pharmaceutical biodegradation in WWTPs.

Free chlorine inactivation of fungi in drinking water sources.

The effectiveness of free chlorine for the inactivation of fungi present in settled surface water was tested. In addition, free chlorine inactivation rate constants of Cladosporium tenuissimum, Cladosporium cladosporioides, Phoma glomerata, Aspergillus terreus, Aspergillus fumigatus, Penicillium griseofulvum, and Penicillium citrinum that were found to occur in different source waters were determined in different water matrices (laboratory grade water and settled water). The effect of using different disinfectant concentrations (1 and 3 mg/l), temperatures (21 and 4 °C), and pH levels (6 and 7) was addressed. The sensitivity degree of different fungi isolates to chlorine disinfection varied among different genera with some species showing a higher resistance to disinfection and others expected to be more prone to protection from inactivation by the water matrix components. When the disinfection efficiency measured in terms of the chlorine concentration and contact time (Ct) values needed to achieve 99% inactivation were compared with the Ct values reported as being able to achieve the same degree of inactivation of other microorganisms, fungi were found to be more resistant to chlorine inactivation than bacteria and viruses and less resistant than Cryptosporidium oocysts.

Occurrence and low pressure ultraviolet inactivation of yeasts in real water sources.

Low pressure ultraviolet photolysis proved to be an efficient treatment to achieve inactivation of different yeast species (Candida sp., Cryptococcus carnescens, Metschnikowia viticola/Candida kofuensis, Rhodosporidium babjevae, Rhodotorula minuta, and Rhodotorula mucilaginosa) isolated from water sources with very different compositions. The sensitivity degree of various yeast isolates to UV treatment varied among different genera. Species isolated from surface water gained additional photoprotective resistance as a defence mechanism to be able to survive under constant sunlight conditions compared to the groundwater isolates. Yeasts were found to be more resistant to UV treatment than E. coli, Cryptosporidium, and Giardia.

Quantitative proteomic analysis of ibuprofen-degrading Patulibacter sp. strain I11.

Ibuprofen is the third most consumed pharmaceutical drug in the world. Several isolates have been shown to degrade ibuprofen, but very little is known about the biochemistry of this process. This study investigates the degradation of ibuprofen by Patulibacter sp. strain I11 by quantitative proteomics using a metabolic labelling strategy. The whole-genome of Patulibacter sp. strain I11 was sequenced to provide a species-specific protein platform for optimal protein identification. The bacterial proteomes of actively ibuprofen-degrading cells and cells grown in the absence of ibuprofen was identified and quantified by gel based shotgun-proteomics. In total 251 unique proteins were quantitated using this approach. Biological process and pathway analysis indicated a number of proteins that were up-regulated in response to active degradation of ibuprofen, some of them are known to be involved in the degradation of aromatic compounds. Data analysis revealed that several of these proteins are likely involved in ibuprofen degradation by Patulibacter sp. strain I11.

Investigating the performance of an ion luminescence probe as a multichannel fast-ion energy spectrometer using pulse height analysis.

We investigate the capability of a fast-ion luminescent probe to operate as a pulse height ion energy analyzer. An existing high sensitivity system has been reconfigured as a single channel ion detector with an amplifier to give a bandwidth comparable to the phosphor response time. A digital pulse processing method has been developed to determine pulse heights from the detector signal so as to obtain time-resolved information on the ion energy distribution of the plasma ions lost to the wall of the TJ-II stellarator. Finally, the potential of this approach for magnetic confined fusion plasmas is evaluated by studying representative TJ-II discharges.