Tailoring ionic liquid catalysts: structure, acidity and catalytic activity of protonic ionic liquids based on anionic clusters, [(HSO4)(H2SO4)x]− (x = 0, 1, or 2)

Aiming at inexpensive Brønsted-acidic ionic liquids, suitable for industrial-scale catalysis, a family of protonic ionic liquids based on nitrogen bases and sulfuric acid has been developed. Variation of the molar ratio of sulfuric acid, χH2SO4, was used to tune acidity. The liquid structure was studied using 1H NMR and IR spectroscopies, revealing the existence of hydrogen-bonded clusters, [(HSO4)(H2SO4)]−, for χH2SO4 > 0.50. Acidity, quantified by Gutmann Acceptor Number (AN), was found to be closely related to the liquid structure. The ionic liquids were employed as acid catalysts in a model reaction; Fischer esterification of acetic acid with 1-butanol. The reaction rate depended on two factors; for χH2SO4 > 0.50, the key parameter was acidity (expressed as AN value), while for χH2SO4 > 0.50 it was the mass transport (solubility of starting materials in the ionic liquid phase). Building on this insight, the ionic liquid catalyst and reaction conditions have been chosen. Conversion values of over 95% were achieved under exceptionally mild conditions, and using an inexpensive ionic liquid, which could be recycled up to eight times without diminution in conversion or selectivity. It has been demonstrated how structural studies can underpin rational design and development of an ionic liquid catalyst, and in turn lead to a both greener and economically viable process.

Seasonal differences in the effects of oscillatory and uni-directional flow on the growth and nitrate-uptake rates of juvenile Laminaria digitata (Phaeophyceae)

The influence of oscillatory versus unidirectional flow on the growth and nitrate-uptake rates of juvenile kelp, Laminaria digitata, was determined seasonally in experimental treatments that simulated as closely as possible natural environmental conditions. In winter, regardless of flow condition (oscillatory and unidirectional) or water velocity, no influence of water motion was observed on the growth rate of L. digitata. In summer, when ambient nitrate concentrations were low, increased water motion enhanced macroalgal growth, which is assumed to be related to an increase in the rate of supply of nutrients to the blade surface. Nitrate-uptake rates were significantly influenced by water motion and season. Lowest nitrate-uptake rates were observed for velocities <5 cm · s−1 and nitrate-uptake rates increased by 20%–50% under oscillatory motion compared to unidirectional flow at the same average speed. These data further suggested that the diffusion boundary layer played a significant role in influencing nitrate-uptake rates. However, while increased nitrate-uptake in oscillatory flow was clear, this was not reflected in growth rates and further work is required to understand the disconnection of nitrate-uptake and growth by L. digitata in oscillatory flow. The data obtained support those from related field-based studies, which suggest that in summer, when insufficient nitrogen is available in the water to saturate metabolic demand, the growth rate of kelps will be influenced by water motion restricting mass transfer of nitrogen.

Analytical strategies for the early quality and safety assurance in the global feed chain. Approaches for nitrogen adulterants in soybean meal and mineral and transformer oils in vegetable oils.

In the past decade, several major food safety crises originated from problems with feed. Consequently, there is an urgent need for early detection of fraudulent adulteration and contamination in the feed chain. Strategies are presented for two specific cases, viz. adulterations of (i) soybean meal with melamine and other types of adulterants/contaminants and (ii) vegetable oils with mineral oil, transformer oil or other oils. These strategies comprise screening at the feed mill or port of entry with non-destructive spectroscopic methods (NIRS and Raman), followed by post-screening and confirmation in the laboratory with MS-based methods. The spectroscopic techniques are suitable for on-site and on-line applications. Currently they are suited to detect fraudulent adulteration at relatively high levels but not to detect low level contamination. The potential use of the strategies for non-targeted analysis is demonstrated.

Improved preparations of ionic liquids using microwave irradiation

Controlled, multimode microwave irradiation has been employed in a generic solvent-free process to prepare a wide range of ionic liquids based on nitrogen-containing heterocycles. The developed method offers a flexible, small to large-scale approach to prepare ionic liquids, in either sealed or open vessels, in a faster and greener process than any previously described.

WASP-31b: a low-density planet transiting a metal-poor, late-F-type dwarf star

We report the discovery of the low-density, transiting giant planet WASP-31b. The planet is 0.48 Jupiter masses and 1.55 Jupiter radii. It is in a 3.4-day orbit around a metal-poor, late-F-type, V = 11.7 dwarf star, which is a member of a common proper motion pair. In terms of its low density, WASP-31b is second only to WASP-17b, which is a more highly irradiated planet of similar mass. Based in part on observations made with the HARPS spectrograph on the 3.6-m ESO telescope (proposal 085.C-0393) and with the CORALIE spectrograph and the Euler camera on the 1.2-m Euler Swiss telescope, both at the ESO La Silla Observatory, Chile.The photometric time-series and radial-velocity data used in this work are available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/531/A60

Vehicle-barrier tracking of a scaled crash test for roadside barrier design

In this paper the tracking system used to perform a scaled vehicle-barrier crash test is reported. The scaled crash test was performed as part of a wider project aimed at designing a new safety barrier making use of natural building materials. The scaled crash test was designed and performed as a proof of concept of the new mass-based safety barriers and the study was composed of two parts: the scaling technique and of a series of performed scaled crash tests. The scaling method was used for 1) setting the scaled test impact velocity so that energy dissipation and momentum transferring, from the car to the barrier, can be reproduced and 2) predicting the acceleration, velocity and displacement values occurring in the full-scale impact from the results obtained in a scaled test. To achieve this goal the vehicle and barrier displacements were to be recorded together with the vehicle accelerations and angular velocities. These quantities were measured during the tests using acceleration sensors and a tracking system. The tracking system was composed of a high speed camera and a set of targets to measure the vehicle linear and angular velocities. A code was developed to extract the target velocities from the videos and the velocities obtained were then compared with those obtained integrating the accelerations provided by the sensors to check the reliability of the method.

Mass spectrometry-based metabolomics applied to the chemical safety of food

Mass spectrometry (MS)-based metabolomics is emerging as an important field of research in many scientific areas, including chemical safety of food. A particular strength of this approach is its potential to reveal some physiological effects induced by complex mixtures of chemicals present at trace concentrations. The limitations of other analytical approaches currently employed to detect low-dose and mixture effects of chemicals make detection very problematic. Besides this basic technical challenge, numerous analytical choices have to be made at each step of a metabolomics study, and each step can have a direct impact on the final results obtained and their interpretation (i.e. sample preparation, sample introduction, ionization, signal acquisition, data processing, and data analysis). As the application of metabolomics to chemical analysis of food is still in its infancy, no consensus has yet been reached on defining many of these important parameters. In this context, the aim of the present study is to review all these aspects of MS-based approaches to metabolomics, and to give a comprehensive, critical overview of the current state of the art, possible pitfalls, and future challenges and trends linked to this emerging field. (C) 2010 Elsevier Ltd. All rights reserved.

Trends in adult body-mass index in 200 countries from 1975 to 2014: a pooled analysis of 1698 population-based measurement studies with 19·2 million participants

Background: Underweight and severe and morbid obesity are associated with highly elevated risks of adverse health outcomes. We estimated trends in mean body-mass index (BMI), which characterises its population distribution, and in the prevalences of a complete set of BMI categories for adults in all countries.

Methods: We analysed, with use of a consistent protocol, population-based studies that had measured height and weight in adults aged 18 years and older. We applied a Bayesian hierarchical model to these data to estimate trends from 1975 to 2014 in mean BMI and in the prevalences of BMI categories (<18·5 kg/m2 [underweight], 18·5 kg/m2 to <20 kg/m2, 20 kg/m2 to <25 kg/m2, 25 kg/m2 to <30 kg/m2, 30 kg/m2 to <35 kg/m2, 35 kg/m2 to <40 kg/m2, ≥40 kg/m2 [morbid obesity]), by sex in 200 countries and territories, organised in 21 regions. We calculated the posterior probability of meeting the target of halting by 2025 the rise in obesity at its 2010 levels, if post-2000 trends continue.
Findings: We used 1698 population-based data sources, with more than 19·2 million adult participants (9·9 million men and 9·3 million women) in 186 of 200 countries for which estimates were made. Global age-standardised mean BMI increased from 21·7 kg/m2 (95% credible interval 21·3–22·1) in 1975 to 24·2 kg/m2 (24·0–24·4) in 2014 in men, and from 22·1 kg/m2 (21·7–22·5) in 1975 to 24·4 kg/m2 (24·2–24·6) in 2014 in women. Regional mean BMIs in 2014 for men ranged from 21·4 kg/m2 in central Africa and south Asia to 29·2 kg/m2 (28·6–29·8) in Polynesia and Micronesia; for women the range was from 21·8 kg/m2 (21·4–22·3) in south Asia to 32·2 kg/m2 (31·5–32·8) in Polynesia and Micronesia. Over these four decades, age-standardised global prevalence of underweight decreased from 13·8% (10·5–17·4) to 8·8% (7·4–10·3) in men and from 14·6% (11·6–17·9) to 9·7% (8·3–11·1) in women. South Asia had the highest prevalence of underweight in 2014, 23·4% (17·8–29·2) in men and 24·0% (18·9–29·3) in women. Age-standardised prevalence of obesity increased from 3·2% (2·4–4·1) in 1975 to 10·8% (9·7–12·0) in 2014 in men, and from 6·4% (5·1–7·8) to 14·9% (13·6–16·1) in women. 2·3% (2·0–2·7) of the world's men and 5·0% (4·4–5·6) of women were severely obese (ie, have BMI ≥35 kg/m2). Globally, prevalence of morbid obesity was 0·64% (0·46–0·86) in men and 1·6% (1·3–1·9) in women.

Interpretation: If post-2000 trends continue, the probability of meeting the global obesity target is virtually zero. Rather, if these trends continue, by 2025, global obesity prevalence will reach 18% in men and surpass 21% in women; severe obesity will surpass 6% in men and 9% in women. Nonetheless, underweight remains prevalent in the world's poorest regions, especially in south Asia.

Determination of multi-mycotoxin occurrence in maize based porridges from selected regions of Tanzania by liquid chromatography tandem mass spectrometry (LC-MS/MS), a longitudinal study

Residents of certain areas of Tanzania are exposed to mycotoxins through the consumption of contaminated maize based foods. In this study, 101 maize based porridge samples were collected from villages of Nyabula, Kikelelwa and Kigwa located in different agro-ecological zones of Tanzania. The samples were collected at three time points (time point 1, during maize harvest; time point 2, 6 months after harvest; time point 3, 12 months after harvest) over a 1-year period. Ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) was used to detect and quantify 9 mycotoxins: aflatoxin B1 (AFB1), aflatoxin B2 (AFB2), aflatoxin G1 (AFG1), aflatoxin G2 (AFG2), fumonisin B1 (FB1), fumonisin B2 (FB2), deoxynivalenol (DON), ochratoxin A (OTA) and zearaleneone (ZEN) in the samples following a QuEChERS extraction method. Eighty two percent of samples were co-contaminated with more than one group of mycotoxins. Fumonisins (FB1 + FB2) had the highest percentage occurrence in all 101 samples (100%) whereas OTA had the lowest (5%). For all three villages the mean concentration of FB1 was lowest in samples taken from time point 2. Conversely, In Kigwa village there was a distinct trend that AFB1 mean concentration was highest in samples taken from time point 2. DON concentration did not differ greatly between time points but the percentage occurrence varied between villages, most notably in Kigwa where 0% of samples tested positive. ZEN occurrence and mean concentration was highest in Kikelelwa. The results suggest that mycotoxin contamination in maize can vary based on season and agro-ecological zones. The high occurrence of multiple mycotoxins found in maize porridge, a common weaning food in Tanzania, presents a potential increase in the risk of exposure and significant health implications in children.

Is perception of upper body orientation based on the inertia tensor? Normogravity versus microgravity conditions

During lateral leg raising, a synergistic inclination of the supporting leg and trunk in the opposite direction to the leg movement is performed in order to preserve equilibrium. As first hypothesized by Pagano and Turvey (J Exp Psychol Hum Percept Perform, 1995, 21:1070-1087), the perception of limb orientation could be based on the orientation of the limb's inertia tensor. The purpose of this study was thus to explore whether the final upper body orientation (trunk inclination relative to vertical) depends on changes in the trunk inertia tensor. We imposed a loading condition, with total mass of 4 kg added to the subject's trunk in either a symmetrical or asymmetrical configuration. This changed the orientation of the trunk inertia tensor while keeping the total trunk mass constant. In order to separate any effects of the inertia tensor from the effects of gravitational torque, the experiment was carried out in normo- and microgravity. The results indicated that in normogravity the same final upper body orientation was maintained irrespective of the loading condition. In microgravity, regardless of loading conditions the same (but different from the normogravity) orientation of the upper body was achieved through different joint organizations: two joints (the hip and ankle joints of the supporting leg) in the asymmetrical loading condition, and one (hip) in the symmetrical loading condition. In order to determine whether the different orientations of the inertia tensor were perceived during the movement, the interjoint coordination was quantified by performing a principal components analysis (PCA) on the supporting and moving hips and on the supporting ankle joints. It was expected that different loading conditions would modify the principal component of the PCA. In normogravity, asymmetrical loading decreased the coupling between joints, while in microgravity a strong coupling was preserved whatever the loading condition. It was concluded that the trunk inertia tensor did not play a role during the lateral leg raising task because in spite of the absence of gravitational torque the final upper body orientation and the interjoint coupling were not influenced.

The VLT-FLAMES survey of massive stars: mass loss and rotation of early-type stars in the SMC

We have studied the optical spectra of a sample of 31 O- and early B-type stars in the Small Magellanic Cloud, 21 of which are associated with the young massive cluster NGC 346. Stellar parameters are determined using an automated fitting method (Mokiem et al. 2005, A&A, 441, 711), which combines the stellar atmosphere code FASTWIND (Puls et al. 2005, A&A, 435, 669) with the genetic algorithm based optimisation routine PIKAIA (Charbonneau 1995, ApJS, 101, 309). Comparison with predictions of stellar evolution that account for stellar rotation does not result in a unique age, though most stars are best represented by an age of 1-3 Myr. The automated method allows for a detailed determination of the projected rotational velocities. The present day v(r) sin i distribution of the 21 dwarf stars in our sample is consistent with an underlying rotational velocity (v(r)) distribution that can be characterised by a mean velocity of about 160-190 km s(-1) and an effective half width of 100-150 km s(-1). The vr distribution must include a small percentage of slowly rotating stars. If predictions of the time evolution of the equatorial velocity for massive stars within the environment of the SMC are correct (Maeder & Meynet 2001, A&A, 373, 555), the young age of the cluster implies that this underlying distribution is representative for the initial rotational velocity distribution. The location in the Hertzsprung-Russell diagram of the stars showing helium enrichment is in qualitative agreement with evolutionary tracks accounting for rotation, but not for those ignoring vr. The mass loss rates of the SMC objects having luminosities of log L-star/L-circle dot greater than or similar to 5.4 are in excellent agreement with predictions by Vink et al. (2001, A&A, 369, 574). However, for lower luminosity stars the winds are too weak to determine. M accurately from the optical spectrum. Three targets were classified as Vz stars, two of which are located close to the theoretical zero-age main sequence. Three lower luminosity targets that were not classified as Vz stars are also found to lie near the ZAMS. We argue that this is related to a temperature effect inhibiting cooler from displaying the spectral features required for the Vz luminosity class.

Isotopic composition of tropospheric and soil N2O from successive depths of agricultural plots with contrasting crops and nitrogen amendments

Agricultural soils are the dominant contributor to increases in atmospheric nitrous oxide (N2O). Few studies have investigated the natural N and O isotopic composition of soil N2O. We collected soil gas samples using horizontal sampling tubes installed at successive depths under five contrasting agricultural crops (e.g., unamended alfalfa, fertilized cereal), and tropospheric air samples. Mean d 15N and d 18O values of soil N2O ranged from -28.0 to +8.9‰, and from +29.0 to +53.6‰. The mean d 15N and d 18O values of tropospheric N2O were +4.6 ± 0.7‰ and +48.3 ± 0.2‰, respectively. In general, d values were lowest at depth, they were negatively correlated to soil [N2O], and d 15N was positively correlated to d 18O for every treatment on all sampling dates. N2O from the different agricultural treatments had distinct d 15N and d 18O values that varied among sampling dates. Fertilized treatments had soil N2O with low d values, but the unamended alfalfa yielded N2O with the lowest d values. Diffusion was not the predominant process controlling N2O concentration profiles. Based on isotopic and concentration data, it appears that soil N2O was consumed, as it moved from deeper to shallower soil layers. To better assess the main process(es) controlling N2O within a soil profile, we propose a conceptual model that integrates data on net N2O production or consumption and isotopic data. The direct local impact of agricultural N2O on the isotopic composition of tropospheric N2O was recorded by a shift toward lower d values of locally measured tropospheric N2O on a day with very high soil N2O emissions.

Nitrogen-15 and Oxygen-18 Natural Abundance of Potassium Chloride Extractable Soil Nitrate Using the Denitrifier Method

In agroecosystems, most isotopic investigations of NO3- involve the use of tracers that are artificially enriched in 15N. Although the dual isotope composition of NO3-— d15N and d18O is especially beneficial for understanding the origin and fate of NO3-, its use for KCl-extractable soil NO3- has been hampered by the lack of a suitable analytical technique. Our objective was to test whether the denitrifier method, whereby NO3- is reduced to N2O before mass spectrometric analysis, can be used to determine the N and O isotopic composition of NO3- from 2 M KCl soil extracts. Several internationally accepted NO3- standards were dissolved in 2 M KCl, the conventional extractant for soil inorganic N, and inoculated with the bacterial strain Pseudomonas aureofaciens (ATCC no. 13985). The standard deviation of the NO3- standards analyzed did not exceed 0.2‰ for d15N and 0.3‰ for d18O values. After appropriate corrections, differences between our measured and consensus d15N and d18O values of standard NO3- generally were within the standard deviations given for the consensus values. Both d15N and d18O values were reproducible among separate analytical runs. The method was also tested on genuine 2 M KCl extracts from unfertilized and fertilized soils. Depending on N fertilization, the soils had distinct d15N and d18O values, which were attributed to amendment with NH4NO3 fertilizer. Hence, our data indicate that the denitrifier method provides a fast, reliable, precise, and accurate way of simultaneously analyzing the natural abundances of 15N and 18O in KCl-extractable soil NO3-.

Nitrogen budget for the Oldman River Basin, southern Alberta, Canada

The Oldman River Basin (OMRB), located in southern Alberta (Canada), with an area of 28,200 km2, is mainly forested in its western part and is used for intensive agriculture in its eastern part. The objective of this paper is to estimate the nitrogen (N) budget for the Oldman River Basin as a whole and its sub-basins, and to discuss differences in the N budget between various sub-basins. Better knowledge of the N budget in this watershed may be also utilized for understanding N dynamics in similar watersheds within semi-arid climatic regions. The model used is a mass balance spreadsheet model that takes into account N inputs and N export through surface water. During the last 120 years, anthropogenic N inputs to the OMRB have increased circa 40 fold. By the end of the 20th century, the OMRB received an annualN input of about 5174 kg N km-2 yr-1, whereas only about 25 kg N km-2 yr-1 were exported via riverine flow. For the sub-basins, annual N inputs ranged from 2516 to 19011 kg N km-2 yr-1, and annual N export via riverine flows varied between 6 and 277 kg N km-2 yr-1. Over 85% of total N inputs to the OMRB are due to anthropogenic activities, including manure (55%), synthetic fertilizer (27%), and N fixation on agricultural lands (4%). Sewage accounted for less than 1%, and N inputs from atmospheric deposition and fixation in forests represented 6 and 8% respectively. Despite increasing anthropogenic N inputs, N export with riverine flow currently accounts for only 1% of the inputs, indicating thatmost of theNinputs are currently retained in the OMRB or are re-emitted into the atmosphere.

Knowledge-based risk assessment under uncertainty in engineering projects

In this paper we describe how an evidential-reasoner can be used as a component of risk assessment of engineering projects using a direct way of reasoning. Guan & Bell (1991) introduced this method by using the mass functions to express rule strengths. Mass functions are also used to express data strengths. The data and rule strengths are combined to get a mass distribution for each rule; i.e., the first half of our reasoning process. Then we combine the prior mass and the evidence from the different rules; i.e., the second half of the reasoning process. Finally, belief intervals are calculated to help in identifying the risks. We apply our evidential-reasoner on an engineering project and the results demonstrate the feasibility and applicability of this system in this environment.