The equivalence of diffusive samplers to reference methods for monitoring O3, benzene and NO2 in ambient air

A study of the equivalence to the reference methods of the Radiello samplers for ozone (O(3)) and benzene as well as the membrane-closed Palmes tube (MCPT) for nitrogen dioxide (NO(2)) is presented. These samplers benefit from new model equations capable of estimating their uptake rate. For O(3), the aim here was to demonstrate the equivalence for the reference period of 8 h and 120 microg m(-3), the target value of the 3rd European Daughter Directive. For benzene, the demonstration of equivalence to the annual limit value of 5 microg m(-3) of the 2nd European Daughter Directive was examined. In the case of NO(2), the equivalence to the annual limit value of the 1st European Daughter Directive (40 microg m(-3)) was considered. Results show that the radial sampler for O(3) fails to meet the Data Quality Objective (DQO) for continuous monitoring. However, with an expanded uncertainty of less than 30%, the O(3) diffusive sampler fulfils the DQO for indicative measurements. For benzene, the Radiello sampler exposed for 7 days gave satisfying results showing the ability of the sampler to meet the DQO of the reference method. Nevertheless, the field tests should be complemented by measurements for a wider range of benzene concentrations. In the case of NO(2), all the results of the laboratory and field experiments respected the requirements necessary for the demonstration of equivalence. Overall, these findings thus show that the Radiello sampler and the MCPT are equivalent to the reference methods only for assessment of benzene and NO(2), respectively.     

Spectroscopic and conformational properties of size-fractions separated from a lignite humic acid

A lignite humic acid (HA) was fractionated by preparative high performance size-exclusion chromatography (HPSEC) in seven different size-fractions. The size-fractions were characterized by cross polarization (CP) magic angle spinning (MAS) (13)C NMR spectroscopy and a further analytical HPSEC elution under UV and fluorescence detection. The alkyl hydrophobic components mainly distributed in the largest molecular-size-fraction, whereas the amount of oxidized carbons increased with decreasing size of fractions. Cross polarization time (T(CH)) and proton spin-lattice relaxation time in the rotating frame (T(1rho)(H)) were measured from variable contact time (VCT) experiments. The bulk HA was characterized by the shortest T(CH) values and the longest T(1rho)(H) values which suggested, respectively, one. an aggregation of components in a large conformation that favored a fast H-C cross polarization, and, two. consequent steric hindrances that prevented fast local molecular motions and decreased proton relaxation rates. Conversely, the separated size-fractions showed longer T(CH) values and shorter T(1rho)(H) values than the bulk HA, thereby indicating that they were constituted by a larger number of mobile molecular conformations. The UV and fluorescence absorptions were both low in the large size-fractions that mainly contained alkyl carbons, whereas they increased in the olephinic- and aromatic-rich fractions with intermediate molecular-size, and decreased again in the smaller fractions which were predominantly composed by oxidized carbons. These results support the supramolecular structure of humic substances and indicate that the observed variation in conformational distribution in humic association may be used to explain environmental processes with additional precision.     

Assessment of global bioenergy potentials

So far, various studies assessed global biomass potentials and came up with widely varying results. Existing potential estimates range from 0 EJ/a up to more than 1,550 EJ/a which corresponds to about three times the current global primary energy consumption. This paper provides an overview of the available research on bioenergy potentials and reviews the different assessments qualitative way with the objective to interpret previous research in an integrated way. In the context of this paper we understand bioenergy as energy from biomass sources including energy crops, residues, byproducts and wastes from agriculture, forestry, food production and waste management. In this review special attention was paid to the difference between residue and energy potentials, land availability estimates, and the geographical resolution of existing potential estimates. The majority of studies concentrate on energy crop potentials retrieved from surplus agricultural land and only few publications assess global potentials separated by different world regions. It results that land allocated to the exclusive production of energy crops varies from 0 to 7,000 ha, depending on land category and scenario assumptions. Only a small number of available potential assessments consider residue potentials as well as energy crop potentials from degraded land. Future energy crop potentials are assumed to vary in the mean from 200 to 600 EJ/yr. In contrast residue potentials are expected to contribute between 62 and 325 EJ/yr. The highest potentials are assigned to Asia, Africa and South America while Europe, North America and the Pacific region contribute minor parts to the global potential.     

Reference values for acetyl and butyrylcholinesterases in cattle under actual management conditions,hepatic and renal function by application of chlorpyrifos

Chlorpyrifos is an anticholinesterase organophosphate insecticide widely used in Argentina in the production of food derived from animal, fruit and horticultural origin and is reported as a residue within these products. Local reference values for acetyl and butyrylcholinesterase were determined in Aberdeen Angus bovine and cross bred cattle (n = 25), a requirement to be able to evaluate toxicity of commercial organophosphate and carbamate formulations. The activity of cholinesterase enzymes presented an overall mean of 2,183.00 ± 485.6 IU L^?1 for erythrocyte acetylcholinesterase and 203.1 ± 42.06 IU L^?1 for plasma butyrylcholinesterase, which are used as reference values for meat steers within a system of intensive production in a semi-arid region. The toxic potential of chlorpyrifos in steers of the same breeds (n = 12) was assessed applying chlorpyrifos 15.00% Tipertox® in a single therapeutic dose of 7.50 mg kg^?1 by topical route. Prior to application and then on day 1 and day 21 post-application, both blood cholinesterases, serum chlorpyrifos concentration by ultra-high resolution liquid chromatography with mass detector, analysis of blood counts, total proteins, liver enzymes, urea and creatinine were evaluated. The mean plasma concentration of chlorpyrifos was 27.90 ug L^?1 at 24 h. The findings indicate that the therapeutic treatment of castrated male bovines treated with chlorpyrifos, applied by pour-on according to the manufacturer's instructions, does not cause changes in the variables evaluated.     

Silica-quaternary ammonium “Fixed-Quat” nanofilm coated fiberglass mesh for water disinfection and harmful algal blooms control

Intensification of pollution loading worldwide has promoted an escalation of different types of disease-causing microorganisms, such as harmful algal blooms(HABs), instigating detrimental impacts on the quality of receiving surface waters. Formation of unwanted disinfection by-products(DBPs) resulting from conventional disinfection technologies reveals the need for the development of new sustainable alternatives. Quaternary Ammonium Compounds(QACs) are cationic surfactants widely known for their effective biocidal properties at the ppm level. In this study, a novel silica-based antimicrobial nanofilm was developed using a composite of silica-modified QAC(Fixed-Quat) and applied to a fiberglass mesh as an active surface via sol–gel technique. The synthesized Fixed-Quat nanocoating was found to be effective against E. coli with an inactivation rate of 1.3 × 10~(-3) log reduction/cm min. The Fixed-Quat coated fiberglass mesh also demonstrated successful control of Microcystis aeruginosa with more than 99% inactivation after 10 hr of exposure.The developed antimicrobial mesh was also evaluated with wild-type microalgal species collected in a water body experiencing HABs, obtaining a 97% removal efficiency. Overall,the silica-functionalized Fixed-Quat nanocoating showed promising antimicrobial properties for water disinfection and HABs control, while decreasing concerns related to DBPs formation and the possible release of toxic nanomaterials into the environment.     

Sex pheromone component ratios and mating isolation among three Lygus plant bug species of North America

The plant bugs Lygus hesperus, Lygus lineolaris, and Lygus elisus (Hemiptera: Miridae) are major pests of many agricultural crops in North America. Previous studies suggested that females release a sex pheromone attractive to males. Other studies showed that males and females contain microgram amounts of (E)-4-oxo-2-hexenal, hexyl butyrate, and (E)-2-hexenyl butyrate that are emitted as a defense against predators. Using gas chromatography–mass spectrometry, we found that female L. lineolaris and L. elisus have a 4:10 ratio of hexyl butyrate to (E)-2-hexenyl butyrate that is reversed from the 10:1 ratio in female L. hesperus (males of the three species have ~10:1 ratio). These reversed ratios among females of the species suggest a behavioral role. Because both sexes have nearly equal amounts of the major volatiles, females should release more to attract males. This expectation was supported because L. hesperus females released more hexyl butyrate (mean of 86 ng/h) during the night (1800–0700 hours) than did males (<1 ng/h). We used slow-rotating pairs of traps to test the attraction of species to blends of the volatiles with a subtractive method to detect synergism. Each species’ major butyrate ester was released at 3 μg/h, the minor butyrate according to its ratio, and (E)-4-oxo-2-hexenal at 2 μg/h. The resulting catches of only Lygus males suggest that (E)-4-oxo-2-hexenal is an essential sex pheromone component for all three species, (E)-2-hexenyl butyrate is essential for L. elisus and L. lineolaris, and hexyl butyrate is essential for L. hesperus. However, all three components are recognized by each species since ratios of the butyrate esters are critical for conspecific attraction and heterospecific avoidance by males and thus play a role in reproductive isolation among the three species. Because L. hesperus males and females are known to emit these major volatiles for repelling ant predators, our study links defensive allomones in Lygus bugs with an additional use as sex pheromones.     

Are there any job resources capable of moderating the effect of physical demands on work ability? A study among kindergarten teachers

Background. It is recognized that teaching in a preschool context is physically demanding. Despite this, the consequences of physical demands on psychophysical health (including work ability) are significantly understudied among kindergarten teachers. Objectives. The aim of the present study is to examine (a) the association between physical demands and work ability and (b) whether psychosocial job resources buffer the negative impact of physical demands among kindergarten teachers. Method. A total of 426 kindergarten teachers employed in the municipal educational services of a city in northwest Italy filled out a self-reported questionnaire. Results. High association was found between physical demand and work ability. Moderated hierarchical regressions showed that decision authority, skill discretion, reward and meaning of work buffer the hampering effect of physical demands and work ability. No buffering effects were observed for support from superiors and colleagues. Conclusion. The present study has relevant, practical implications, highlighting the importance of investing in interventions encompassing a holistic perspective (e.g., psychosocial and ergonomic) in order to effectively combat the hampering effect of physical demands on work ability.     

Hydrolytic degradation of azimsulfuron, a sulfonylurea herbicide

The chemical degradation of the herbicide azimsulfuron was investigated in aqueous solutions at different pH values. The hydrolysis rate, determined by HPLC analyses, was pH dependent and was much faster in acidic than in neutral or weakly basic conditions. The metabolites formed at different pH values were compared with standards when possible or isolated and identified using ESI-LC-MS/MS, (1)H NMR and (13)C NMR. The two main products of hydrolysis in mild acidic solution were identified as 2-amino-4,6-dimethoxy-pyrimidine and 2-methyl-4-(2-methyl-2H-tetrazol-5-yl)-2H-pyrazole-3-sulfonamide, both produced as a result of the sulfonylurea bridge cleavage. Under basic conditions, a new product, a substituted 2-pyrimidinamine, deriving from the contraction of the sulfonylurea bridge, was isolated and completely characterized for the first time.