Rapid confirmatory method for the determination of sixteen synthetic growth promoters and bisphenol A in bovine milk using dispersive solid-phase extraction and liquid chromatography-tandem mass spectrometry

A rapid liquid chromatographic-tandem mass spectrometric (LC-MS/MS) multi-residue method for the simultaneous quantitation and identification of sixteen synthetic growth promoters and bisphenol A in bovine milk has been developed and validated. Sample preparation was straightforward, efficient and economically advantageous. Milk was extracted with acetonitrile followed by phase separation with NaCl. After centrifugation, the extract was purified by dispersive solid-phase extraction with C18 sorbent material. The compounds were analysed by reversed-phase LC-MS/MS using both positive and negative ionization and operated in multiple reaction monitoring (MRM) mode, acquiring two diagnostic product ions from each of the chosen precursor ions for unambiguous confirmation. Total chromatographic run time was less than 10 min for each sample. The method was validated at a level of 1 mu g L-1. A wide variety of deuterated internal standards were used to improve method performance. The accuracy and precision of the method were satisfactory for all analytes. The confirmative quantitative liquid chromatographic tandem mass spectrometric (LC-MS/MS) method was validated according to Commission Decision 2002/657/EC. The decision limit (CC alpha) and the detection capability (CC beta) were found to be below the chosen validation level of 1 mu g L-1 for all compounds. (C) 2010 Elsevier B.V. All rights reserved.

How long is a piece of Strix? Methods in measuring and measuring the measurers

An experiment to quantify intra- and interobserver error in anatomical measurements found that interobserver measurements can vary by over 14% of mean specimen length; disparity in measurement increases logarithmically with the number of contributors; instructions did not reduce variation or measurement disparity; scale of the specimen influenced the precision of measurement (relative error increasing with specimen size); different methods of taking a measurement yielded different results, although they did not differ in terms of precision, and topographical complexity of the elements being considered may potentially influence error (error increasing with complexity). These results highlight concerns about introduction of noise and potential bias that should be taken into account when compiling composite datasets and meta-analyses.

The Secret Life of Oilbirds: New Insights into the Movement Ecology of a Unique Avian Frugivore

Background: Steatornis caripensis (the oilbird) is a very unusual bird. It supposedly never sees daylight, roosting in huge aggregations in caves during the day and bringing back fruit to the cave at night. As a consequence a large number of the seeds from the fruit they feed upon germinate in the cave and spoil.

SuperWASP observations of pulsating Am stars

We have studied over 1600 Am stars at a photometric precision of 1 mmag with SuperWASP photometric data. Contrary to previous belief, we find that around 200 Am stars are pulsating d Sct and ? Dor stars, with low amplitudes that have been missed in previous, less extensive studies. While the amplitudes are generally low, the presence of pulsation in Am stars places a strong constraint on atmospheric convection, and may require the pulsation to be laminar. While some pulsating Am stars have been previously found to be d Sct stars, the vast majority of Am stars known to pulsate are presented in this paper. They will form the basis of future statistical studies of pulsation in the presence of atomic diffusion. An extended version of Table 1 containing all the detected frequencies and amplitudes is only 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/535/A3

Development and validation of rapid disequilibrium enzyme-linked immunosorbent assays for the detection of Methyl Yellow and Rhodamine B dyes in foods

Sensitive and specific enzyme-linked immunosorbent assays (ELISAs) were developed for the detection of two illegal synthetic dyes: Methyl Yellow (MY) and Rhodamine B (RB) in food. Polyclonal antibodies were raised against synthesised immunogens and employed in unique direct disequilibrium ELISAs. The time of the assays was only twenty minutes (five minutes for each incubation step with sample and enzyme conjugate and ten minutes with enzyme substrate). The IC50 for MY was in the range 1.4-4.2 ng mL(-1) and for RB 0.1-0.5 ng mL(-1). A simple sample preparation method was developed for the analysis of a range of sauces. In the case of spices a dispersive solid phase extraction was applied to purify the extracts. The testing of twenty samples took approximately one and a half hours (including sample preparation and analysis). Both assays were validated according to the Commission Decision 2002/657/EC criteria for use in sauces and spices. The detection capability for MY in sauces and spices was determined to be less than 15 ng g(-1) and 50 ng g(-1), respectively and for RB, 10 ng g(-1) for both types of food samples. The precision of the developed assays was determined in a repeatability study. The intra-and inter-assay coefficients of variation were less than 25% for both tests and matrix types. The simplicity and performance of both assays indicate that they will be very reliable screening methods for the detection of the illegal dyes MY and RB in a range of food products.

Population pharmacokinetic model of canrenone after intravenous administration of potassium canrenoate to paediatric patients

Objectives: To characterize the population pharmacokinetics of canrenone following administration of potassium canrenoate in paediatric patients. Patients and Methods: Data were collected prospectively from 23 paediatric patients (2 days to 10 years of age; median weight 4 kg, range 2.16-28.0 kg) who received intravenous potassium canrenoate (K-canrenoate) as part of their intensive care therapy for removal of retained fluids e.g. in pulmonary oedema due to chronic lung disease and for the management of congestive heart failure. Plasma samples were analysed by HPLC for determination of canrenone (the major metabolite and pharmacologically active moiety) and the data subjected to pharmacokinetic analysis using NONMEM. Results: A one-compartment model best described the data. The only significant covariate was weight (WT). The final population models for canrenone clearance (CL/F) and volume of distribution (V/F) were CL/F (L/hr) = 11.4 × (WT /70.0)(0.75) and V/F (L) = 374.2 × (WT/70) where WT is in kg. The values of CL/F and V/F in a 4 kg child would be 1.33 L/hr and 21.4 L, respectively, resulting in an elimination half-life of 11.2 hr. Conclusions: The range of estimated CL/F in the study population was 0.67-7.38 L/hr. The data suggest that adjustment of K-canrenoate dosage according to body weight is appropriate in paediatric patients

Confirmatory method for the determination of various acetylgestagens in animal kidney fat using liquid chromatography-tandem mass spectrometry

A confirmatory method has been developed and validated that allows for the simultaneous detection of medroxyprogesterone acetate (MPA), megestrol acetate (MGA), melengestrol acetate (MLA), chlormadinone acetate (CMA) and delmadinone acetate (DMA) in animal kidney fat using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The compounds were extracted from kidney fat using acetonitrile, defatted using a hexane wash and subsequent saponification. Extracts were then purified on Isolute CN solid-phase extraction cartridges and analysed by LC-MS/MS. The method was validated in animal kidney fat in accordance with the criteria defined in Commission Decision 2002/657/EC. The decision limit (CC) was calculated to be 0.12, 0.48, 0.40, 0.63 and 0.54 g kg-1, respectively, for MPA, MGA, MLA, DMA and CMA, with respective detection capability (CC) values of 0.20, 0.81, 0.68, 1.07 and 0.92 g kg-1. The measurement uncertainty of the method was estimated at 16, 16, 19, 27 and 26% for MPA, MGA, MLA, DMA and CMA, respectively. Fortifying kidney fat samples (n = 18) in three separate assays showed the accuracy of the method to be between 98 and 100%. The precision of the method, expressed as % RSD, for within-laboratory reproducibility at three levels of fortification (1, 1.5 and 2 g kg-1 for MPA, 5, 7.5 and 10 g kg-1 for MGA, MLA, DMA and CMA) was less than 5% for all analytes.

PREDICTION OF NETILMICIN DISPOSITION IN NEONATES

Multiple regression analyses of data from 33 neonates who received netilmicin therapy showed that concurrent treatment with other drugs (Drg), creatinine clearance (CL(cr)), gestational age (GA), and an apgar score of less than 6 at 1 min (Agl') were significant determinants of netilmicin clearance. Apparent volume of distribution was significantly affected by postnatal age (PNA), gender, the presence of ascites and/or oedema (A/O), and whether or not the neonate was small for gestational age (SGA). The following formulae were obtained: CL (ml min-1 kg-1) = -0.108 - 0.210 (Drg) + 0.152(CL(cr)) + 0.019(GA) -0.128(Agl') (multiple R = 0.725, p

Modeling of subsurface pulsed radar for nondestructive testing of structures

The use of pulsed radar for investigating the integrity of structural elements is gaining popularity and becoming firmly established as a nondestructive test method in civil engineering. Difficulties can often arise in the interpretation of results obtained, particularly where internal details are relatively complex. One approach that can be used to understand and evaluate radar results is through numerical modeling of signal propagation and reflection. By comparing the results of a numerical modeling with those from field measurements, engineers can gain valuable insight into the probable features embedded beneath the surface of a structural element. This paper discusses a series of numerical techniques for modeling subsurface radar and compares the precision of the results with those taken from real field data. It is found that more complex problems require more sophisticated analysis techniques to obtain realistic results, with a consequential increase in the computational resources to carry out the modeling.

Low-pressure solubilities and thermodynamics of solvation of eight gases in 1-butyl-3-methylimidazolium hexafluorophosphate

Experimental values for the solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon and carbon monoxide in 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6] - a room temperature ionic liquid - are reported as a function of temperature between 283 and 343 K and at pressures close to atmospheric. Carbon dioxide is the most soluble and hydrogen is the least soluble of the gases studied with mole fraction solubilities of the order of 10-2 and 10-4, respectively. All the mole fraction solubilities decrease with temperature except for hydrogen for which a maximum is observed at temperatures close to 310 K. From the variation of solubility, expressed as Henry's law constants, with temperature, the partial molar thermodynamic functions of solvation such as the standard Gibbs energy, the enthalpy, and the entropy are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is better than ±1%. © 2005 Elsevier B.V. All rights reserved.

Solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon, and carbon monoxide in 1-butyl-3-methylimidazolium tetrafluoroborate between temperatures 283 K and 343 K and at pressures close to atmospheric

Experimental values for the solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon and carbon monoxide in 1-butyl-3- methylimidazolium tetrafluoroborate, [bmim][BF4] - a room temperature ionic liquid - are reported as a function of temperature between 283 K and 343 K and at pressures close to atmospheric. Carbon dioxide is the most soluble gas with mole fraction solubilities of the order of 10-2. Ethane and methane are one order of magnitude more soluble than the other five gases that have mole fraction solubilities of the order of 10-4. Hydrogen is the less soluble of the gaseous solutes studied. From the variation of solubility, expressed as Henry's law constants, with temperature, the partial molar thermodynamic functions of solvation such as the standard Gibbs energy, the enthalpy, and the entropy are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations is of 1%. © 2005 Elsevier Ltd. All rights reserved.

Influence of the cation on the solubility of CO2 and H 2 in ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion

Experimental values for the solubility of carbon dioxide and hydrogen in three room temperature ionic liquids based on the same anion- (bistrifluoromethylsulfonyl)imide [Ntf2]-and three different cations-1-butyl-3-methylimidazolium, [C4mim], 1-ethyl-3- methylimidazolium, [C2mim] and trimethyl-butylammonium, [N 4111]-are reported between 283 and 343 K and close to atmospheric pressure. Carbon dioxide, with a mole-fraction solubility of the order of 10-2, is two orders of magnitude more soluble than hydrogen. The solubility of CO2 is very similar in the three ionic liquids although slightly lower in the presence of the [C2mim] cation. In the case of H2, noticeable differences were observed with larger mole fraction solubilities in the presence of [N4111] followed by [C 4mim]. All of the mole-fraction solubilities decrease with increasing temperature. From the variation of Henry's law constants with temperature, the thermodynamic functions of solvation were calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is always better than ±1%. © Springer Science+Business Media, LLC 2007.

Thermophysical properties, low pressure solubilities and thermodynamics of solvation of carbon dioxide and hydrogen in two ionic liquids based on the alkylsulfate anion

Densities and viscosities of the ionic liquid 1-butyl-3-methylimidazolium octylsulfate, [C4C1Im][C8SO4] were measured as a function of temperature between 313 K and 395 K. Solubilities of hydrogen and carbon dioxide were determined, between 283 K and 343 K, and at pressures close to atmospheric in [C4C1Im][C 8SO4] and in another ionic liquid based on the alkylsulfate anion-1-ethyl-3-methylimidazolium ethylsulfate, [C 2C1Im][C2SO4]. Density and viscosity were measured using a vibrating tube densimeter from Anton Paar and a rheometer from Rheometrics Scientific with accuracies of 10-3 g cm -3 and 1%, respectively. Solubilities were obtained using an isochoric saturation technique and, from the variation of solubility with temperature, the partial molar thermodynamic functions of solvation, such as the standard Gibbs energy, the enthalpy, and the entropy, are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is better than ±1%. © The Royal Society of Chemistry.

Carbon-14 wiggle-match dating of peat deposits: advantages and limitations

Carbon-14 wiggle-match dating (WMD) of peat deposits uses the non-linear relationship between 14C age and calendar age to match the shape of a series of closely spaced peat 14C dates with the 14C calibration curve. The method of WMD is discussed, and its advantages and limitations are compared with calibration of individual dates. A numerical approach to WMD is introduced that makes it possible to assess the precision of WMD chronologies. During several intervals of the Holocene, the 14C calibration curve shows less pronounced fluctuations. We assess whether wiggle-matching is also a feasible strategy for these parts of the 14C calibration curve. High-precision chronologies, such as obtainable with WMD, are needed for studies of rapid climate changes and their possible causes during the Holocene.

Interaction of combined chloride and sulfate ingression in concrete

Chloride is the most severe form of deterioration experienced by concrete and one of the principal sources of chlorides is sea water. However, the presence of sulfates in seawater will influence the movement of chloride ions and vice versa. This interaction is not well understood and current codes of practice provide no guidelines for such dual exposure.
An investigation to monitor combined effect of the ingress of chlorides and sulfates during a realistic 12 month wetting and drying exposure regime to simulate conditions in which multiple mode transport mechanisms are active was conducted on a variety of binders (PC, PFA and GGBS). Penetration was evaluated using water and acid soluble chloride profiles and sulfate profiles.
It was found that the nature of the exposure provided multiple modes of transport within the concrete, thus creating a complex pattern of distribution of ions. The presence of sulfates decreased the penetration of chlorides in the PC system at all ages relative to a chloride only control. The matrices containing PFA and GGBS also showed an initial decrease in chloride penetration. However, after six months the presence of sulfates then increased chloride penetration.