Methylmercury and inorganic mercury determination in blood by using liquid chromatography with inductively coupled plasma mass spectrometry and a fast sample preparation procedure

Despite the necessity to differentiate chemical species of mercury in clinical specimens, there area limited number of methods for this purpose. Then, this paper describes a simple method for the determination of methylmercury and inorganic mercury in blood by using liquid chromatography with inductively coupled mass spectrometry (LC-ICP-MS) and a fast sample preparation procedure. Prior to analysis, blood (250 mu L) is accurately weighed into 15-mL conical tubes. Then, an extractant solution containing mercaptoethanol, L-cysteine and HCI was added to the samples following sonication for 15 min. Quantitative mercury extraction was achieved with the proposed procedure. Separation of mercury species was accomplished in less than 5 min on a C18 reverse-phase column with a mobile phase containing 0.05% (v/v) mercaptoethanol, 0.4% (m/v) L-cysteine, 0.06 mol L(-1) ammonium acetate and 5% (v/v) methanol. The method detection limits were found to be 0.25 mu g L(-1) and 0.1 mu Lg L(-1) for inorganic mercury and methylmercury, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). The proposed method was also applied to the speciation of mercury in blood samples collected from fish-eating communities and from rats exposed to thimerosal. With the proposed method there is a considerable reduction of the time of sample preparation prior to speciation of Hg by LC-ICP-MS. Finally, after the application of the proposed method, we demonstrated an interesting in vivo ethylmercury conversion to inorganic mercury. (C) 2009 Elsevier B.V. All rights reserved.

Determination of total and inorganic mercury in whole blood by cold vapor inductively coupled plasma mass spectrometry (CV ICP-MS) with alkaline sample preparation

A simple method with a fast sample preparation procedure for total and inorganic mercury determinations in blood samples is proposed based on flow injection cold vapor inductively coupled plasma mass spectrometry (FI-CVICP-MS). Aliquots of whole blood (500 mL) are diluted 1 + 1 v/v with 10.0% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 3 h at room temperature and then further diluted 1 + 4 v/v with 2.0% v/v HCl. The inorganic Hg was released by online addition of L-cysteine and then reduced to elemental Hg by SnCl(2). On the other hand, total mercury was determined by on-line addition of KMnO(4) and then reduced to elemental Hg by NaBH(4). Samples were calibrated against matrix-matching. The method detection limit was found to be 0.80 mu g L(-1) and 0.08 mu g L(-1) for inorganic and total mercury, respectively. Sample throughput is 20 samples h(-1). The method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). For additional validation purposes, human whole blood samples were analyzed by the proposed method and by an established CV AAS method, with no statistical difference between the two techniques at 95% confidence level on applying the t-test.

Simultaneous Analysis of Tramadol, O-Desmethyltramadol, and N-Desmethyltramadol Enantiomers in Rat Plasma by High-Performance Liquid Chromatography-Tandem Mass Spectrometry: Application to Pharmacokinetics

Tramadol (T) is available as a racemic mixture of (+)-trans-T and (-)-trans-T. The main metabolic pathways are O-demethylation and N-demethylation, producing trans-O-desmethyltramadol (M1) and trans-N-desmethyltramadol (M2) enantiomers, respectively. The analgesic effect of T is related to the opioid activity of (+)-trans-T and (+)-M1 and to the monoaminergic action of (+/-)-trans-T. This is the first study using tandem mass spectrometry as a detection system for the simultaneous analysis of trans-T, M1, and M2 enantiomers. The analytes were resolved on a Chiralpak (R) AD column using hexane: ethanol (95.5:4.5, v/v) plus 0.1% diethylamine as the mobile phase. The quantitation limits were 0.5 ng/ml for trans-T and M1 and 0.1 ng/ml for M2. The method developed and validated here was applied to a pharmacokinetic study in rats. Male Wistar rats (n = 6 at each time point) received a single oral dose of 20 mg/kg racemic trans-T. Blood samples were collected up to 12 h after drug administration. The kinetic disposition of trans-T and M2 was enantioselective (AUC((+)/(-)) ratio = 4.16 and 6.36, respectively). The direction and extent of enantioselectivity in the pharmacokinetics of trans-T and M2 in rats were comparable to data previously reported for healthy volunteers, suggesting that rats are a suitable model for enantioselective studies of trans-T pharmacokinetics. Chirality 23: 287-293, 2011. (C) 2010 Wiley-Liss, Inc.

Aerodynamic Drag Reduction for Satellites in Low Earth Orbit

Stalker (AIAA Paper 87-0403) has suggested that, by ejecting molecules directly upstream from the entire face of a satellite, it is possible to reduce the drag on a satellite in low-Earth orbit and hence maintain orbit with a total fuel mass (for forward ejection and conventional reaction rockets) less than the typical mass requirements of conventional rockets. An analytical analysis is presented here, as well as Monte Carlo simulations. These indicate that to reduce the overall drag on the satellite significantly, collisions between the freestream and ejected molecules must occur at least two satellite diameters upstream. This can be achieved if the molecules are ejected far upstream from the satellite’s surface through a sting that projects forward from the satellite. Using some estimates of what would be feasible sting arrangements, we find that the drag on the satellite can be reduced to such an extent that the satellite’s orbit can be maintained with a total fuel mass of less than 60% of that required for reaction rockets alone. Upstream ejection is effective in reducing the drag for freestream Knudsen numbers less than approximately 250, but not otherwise.

Undergraduate student experiences and perceptions of group projects

This paper reports the experiences and perceptions of student group projects of three cohorts of undergraduates: a 3rd year capstone course in professional communication (N = 54), a 3rd year elective in chemical engineering (N = 29), and a core 2nd-year course in chemical engineering (N = 74).

Undergraduate teaching of ideal and real fluid flows: The value of real-world experimental projects

This study describes the pedagogical impact of real-world experimental projects undertaken as part of an advanced undergraduate Fluid Mechanics subject at an Australian university. The projects have been organised to complement traditional lectures and introduce students to the challenges of professional design, physical modelling, data collection and analysis. The physical model studies combine experimental, analytical and numerical work in order to develop students’ abilities to tackle real-world problems. A first study illustrates the differences between ideal and real fluid flow force predictions based upon model tests of buildings in a large size wind tunnel used for research and professional testing. A second study introduces the complexity arising from unsteady non-uniform wave loading on a sheltered pile. The teaching initiative is supported by feedback from undergraduate students. The pedagogy of the course and projects is discussed with reference to experiential, project-based and collaborative learning. The practical work complements traditional lectures and tutorials, and provides opportunities which cannot be learnt in the classroom, real or virtual. Student feedback demonstrates a strong interest for the project phases of the course. This was associated with greater motivation for the course, leading in turn to lower failure rates. In terms of learning outcomes, the primary aim is to enable students to deliver a professional report as the final product, where physical model data are compared to ideal-fluid flow calculations and real-fluid flow analyses. Thus the students are exposed to a professional design approach involving a high level of expertise in fluid mechanics, with sufficient academic guidance to achieve carefully defined learning goals, while retaining sufficient flexibility for students to construct there own learning goals. The overall pedagogy is a blend of problem-based and project-based learning, which reflects academic research and professional practice. The assessment is a mix of peer-assessed oral presentations and written reports that aims to maximise student reflection and development. Student feedback indicated a strong motivation for courses that include a well-designed project component.

Evaluation of multifrequency bioelectrical impedance data for predicting lean tissue mass in beef cattle

Multifrequency bioimpedance analysis has the potential to provide a non-invasive technique for determining body composition in live cattle. A bioimpedance meter developed for use in clinical medicine was adapted and evaluated in 2 experiments using a total of 31 cattle. Prediction equations were obtained for total body water, extracellular body water, intracellular body water, carcass water and carcass protein. There were strong correlations between the results obtained through chemical markers and bioimpedance analysis when determined in cattle that had a wide range of liveweights and conditions. The r(2) values obtained were 0.87 and 0.91 for total body water and extracellular body water respectively. Bioimpedance also correlated with carcass water, measured by chemical analysis (r(2) = 0.72), but less well with carcass protein (r(2) = 0.46). These correlations were improved by inclusion of liveweight and sex as variables in multiple regression analysis. However, the resultant equations were poor predictors of protein and water content in the carcasses of a group of small underfed beef cattle, that had a narrow range of liveweights. In this case, although there was no statistical difference between the predicted and measured values overall, bioimpedance analysis did not detect the differences in carcass protein between the 2 groups that were apparent following chemical analysis. Further work is required to determine the sensitivity of the technique in small underfed cattle, and its potential use in heavier well fed cattle close to slaughter weight.

Effects of geological inhomogeneity on high Rayleigh number steady state heat and mass transfer in fluid-saturated porous media heated from below

A parametric study is carried out to investigate how geological inhomogeneity affects the pore-fluid convective flow field, the temperature distribution, and the mass concentration distribution in a fluid-saturated porous medium. The related numerical results have demonstrated that (1) the effects of both medium permeability inhomogeneity and medium thermal conductivity inhomogeneity are significant on the pore-fluid convective flow and the species concentration distribution in the porous medium; (2) the effect of medium thermal conductivity inhomogeneity is dramatic on the temperature distribution in the porous medium, but the effect of medium permeability inhomogeneity on the temperature distribution may be considerable, depending on the Rayleigh number involved in the analysis; (3) if the coupling effect between pore-fluid flow and mass transport is weak, the effect of the Lewis number is negligible on the pore-fluid convective flow and temperature distribution, hut it is significant on the species concentration distribution in the medium.

Geochemical mass-balance and oxygen-isotope constrains on silcrete formation and its paleoclimatic implications in Southern Australia

Two geographically distinct silcrete associations are present in southern Australia, inland and eastern; these were sampled in central South Australia and central Victoria, respectively, At each site, both silicified and immediately adjacent unsilicified parent material were collected. Analytical data from these pairs were used to construct isocons, assuming Zr immobility, and to calculate the volume change and amount of silica introduced during silicification, These results, together with whole-rock oxygen isotope compositions, were used to determine the delta(18)O of th, introduced silica, The results show that the eastern silcretes in central Victoria are probably linked genetically to the associated basalts, weathering of which supplied the introduced silica, This conclusion is based on the close spatial connection between the two, as well as the substantial amount of introduced silica in the silcretes (greater than in the inland silcretes), resulting in volume increases in some eastern silcretes, Oxygen isotopic calculations for the silcretes indicate that the silica precipitated from groundwaters at temperatures slightly higher than present conditions. Silcrete formation apparently occurred during the Miocene and Pliocene (basalts in Victoria younger than Pliocene lack associated silcrete) and may reflect the much wetter climate in southeastern Australia at that time. The inland silcretes of central South Australia can be divided into pedogenic (the most common) and groundwater varieties. The pedogenic silcretes, which show typical soil features like columnar and nodular textures, contain moderate amounts of introduced silica that precipitated by evaporation from saline groundwaters, For the groundwater silcretes, which have massive textures and formed at or close to the water table, insufficient data are available to determine the mode of formation. The inland pedogenic silcretes have probably been farming from the Eocene-Miocene to the present, implying that conditions of seasonally high evaporation have occurred in central Australia during this time period. Thus silcrete formation depends on a complex interplay between climate and silica supply, and it is impossible to generalize that the presence of silcrete is indicative of a particular climate. Likewise, the elemental composition of silcretes, particularly Ti content, is not necessarily of climatic significance, Nevertheless, detailed geochemical and oxygen isotopic studies of a silcrete and its parent material can elucidate the mechanisms of silcrete formation, and if evaporation is indicated as a major factor in silcrete formation, then the climate at the time was likely to have been at least seasonally arid.

A numerical study of pore-fluid, thermal and mass flow iu fluid-saturated porous rock basins

We present a numerical methodology for the study of convective pore-fluid, thermal and mass flow in fluid-saturated porous rock basins. lit particular, we investigate the occurrence and distribution pattern of temperature gradient driven convective pore-fluid flow and hydrocarbon transport in the Australian North West Shelf basin. The related numerical results have demonstrated that: (1) The finite element method combined with the progressive asymptotic approach procedure is a useful tool for dealing with temperature gradient driven pore-fluid flow and mass transport in fluid-saturated hydrothermal basins; (2) Convective pore-fluid flow generally becomes focused in more permeable layers, especially when the layers are thick enough to accommodate the appropriate convective cells; (3) Large dislocation of strata has a significant influence off the distribution patterns of convective pore;fluid flow, thermal flow and hydrocarbon transport in the North West Shelf basin; (4) As a direct consequence of the formation of convective pore-fluid cells, the hydrocarbon concentration is highly localized in the range bounded by two major faults in the basin.