Application of cavity ring-down spectroscopy and a novel near surface Gaussian plume estimation approach to inverse model landfill methane emissions.

Fugitive methane emissions from municipal solid waste landfills impact global climate change and reliable emissions quantification is of increasing importance. Ground-based cavity ring-down spectrometer (CRDS) measurements were used to determine methane concentrations and isotopic compositions of carbon in CH4. Then, CH4 oxidation through various cover materials was assessed using the Keeling plot method. A novel inverse modeling approach using Gaussian dispersion analysis, termed near-surface Gaussian plume estimation (NSGPE), was developed to predict whole-site landfill methane emissions. The concentration data obtained around the landfill perimeter with the mobile ground-based CRDS were used. Methane concentration data were integrated to parameterize discretized point source emissions from a Gaussian dispersion model. Post-processing algorithms were applied to refine modeling predictions to account for the influence of topographical and meteorological conditions on methane transport. Results indicate spatially resolved and consistent emissions estimates among multiple optimization simulations, with refinements increasing the resolution and spatial trends of emissions. Post-processing algorithms resolve consistent overestimation of emissions commonly observed using conventional Gaussian dispersion models.•Ground-based CRDS used to obtain methane concentration and oxidation data.•Novel inverse Gaussian dispersion modeling approach developed to predict methane emissions from landfills accounting for site-specific topography and meteorology.•Post-processing algorithms refine emissions estimates.

Thermogravimetric pyrolysis of onion skins: Determination of kinetic and thermodynamic parameters for devolatilization stages using the combinations of isoconversional and master plot methods.

Thermogravimetric pyrolysis of onions skins was studied thoroughly for the first time. Kinetic calculations of devolatilization stages were performed applying direct Arrhenius plot (DAP) method and combinations of isoconversional and Criado's Z(α) master plot (CZMP) methods. The kinetic parameters calculated using combined methods were utilized successfully to reproduce the experimental kinetic curves whereas those calculated using DAP method failed in this sense. The average Ea values of isoconversional methods were between 164.0 and 172.0 kJ/mol. The CZMP method yielded multiple F-type reaction mechanisms. The simplified kinetic models of combined methods were also developed by using single reaction mechanisms deduced from multiple reaction mechanisms. The Friedman-CZMP combination was the best option for developing simplified/unsimplified kinetic models. Determination of reaction mechanism using DAP method by searching for the highest R2 value of regression equation among several candidates was found unreliable. ΔH, ΔG and ΔS values were calculated for 10 °C/min heating rate.

Application of the Southwell Plot method to determine equilibrium time in phosphate adsorption.

Among the different factors that influence the liquid-solid adsorption technique, equilibrium time is one of the most relevant and requires a large number of experiments over a long period of time for its determination. This work evaluates the Southwell Plot as a further tool that can contribute to determining the equilibrium time in adsorption processes. It can also optimize the operating conditions in a batch system for the removal of phosphate in adsorbents produced from domestic sewage sludge and clam shell residue. Sewage sludge and clam shell residues were ground, sieved and sintered at 700 °C for 1 h. The material was characterized by thermal analyses (TG/DTG), chemical analysis (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and adsorption studies. The kinetic studies were investigated by varying the initial concentration of the phosphate solution and mass of the adsorbent. The equilibrium time was determined by applying the Southwell Plot method to the kinetic data and the results showed some fluctuations as a function of the adsorbent mass. At 0.30 g of the adsorbent in 30 mL of the phosphate solution, regardless of the initial phosphate concentration, the equilibrium time determined by the Southwell Plot was 4 h. The maximum phosphate adsorption capacity in this condition, determined by the Langmuir equation, was 49.45 mg g-1.

Feasibility of Using Boltzmann Plots to Evaluate the Stark Broadening Parameters of Cu(I) Lines.

A linear Boltzmann plot was constructed using Cu(I) lines of well-known atomic parameters. Aligning other spectral lines to the plot was adopted as a viable way to estimate the most probable values of Stark broadening parameters of Cu(I) lines at 330.79, 359.91, and 360.2 nm. Plasma was generated by focusing neodymium-doped yttrium aluminum garnet (Nd:YAG) laser radiation at wavelength 532 nm on a pure copper target in open air. Plasma emission was recorded at delay times of 3, 4, 5, 7, and 10 µs. The in situ optically thin Hα line was used to determine the plasma reference electron density over the entire experiment. Following this method, the missing values of the Stark broadening parameters of the three Cu(I) lines turn out to be about 0.15 ± 0.05 Å (for 330.79 nm transition) and 0.17 ± 0.05 Å (for 359.91 360.20 nm transition) at reference electron density of (1 ± 0.09) × 1017 cm-3 and temperature of 10 800 ± 630 K. The apparent variation in plasma parameters at different delay times was found to scale with electron density and temperature as ∼ne.Te0.166.

Methods to determine the kinetic performance limit of contemporary chromatographic techniques.

By combining separation efficiency data as a function of flow rate with the column permeability, the kinetic plot method allows to determine the limits of separation power (time vs. efficiency) of different chromatographic techniques and methods. The technique can be applied for all different types of chromatography (liquid, gas, or supercritical fluid), for different types of column morphologies (packed beds, monoliths, open tubular, micromachined columns), for pressure and electro-driven separations and in both isocratic and gradient elution mode. The present contribution gives an overview of the methods and calculations required to correctly determine these kinetic performance limits and their underlying limitations.

Evaluation of [18F]pitavastatin as a positron emission tomography tracer for in vivo organic transporter polypeptide function.

INTRODUCTION: To understand the pathways involved in drug clearance from the body, quantitative evaluations of the hepatobiliary transport of drugs are important. The organic anion transporting polypeptide (OATP) family transporter, particularly OATP1B1 and 1B3, are considered to play an important role in hepatic uptake of organic anion compounds. Pitavastatin is a substrate of OATP, and it includes a fluorine group. Therefore, it represents an acceptable positron-emission tomography (PET) tracer using fluorine-18 to image in vivo hepatic transporter functions. METHOD: [18F]Pitavastatin was synthesized using the method we previously reported. To evaluate the potential of [18F]pitavastatin in PET imaging of in vivo OATP functions, we investigated the hepatic uptake with/without rifampicin as an OATP inhibitor after administration in normal SD rats. [18F]Pitavastatin metabolite was evaluated using reverse-phase thin-layer chromatography (TLC) autoradiography. We subsequently analyzed the PET image results and demonstrated that [18F]pitavastatin selectively accumulated in the liver post-administration. Result and discussion In metabolite analysis using reverse-phase TLC, we found that the radioactivity detected in the plasma, liver (>90% intact), and bile mostly originated from the parent pitavastatin of the PET study (~40 min). [18F]pitavastatin's hepatic uptake decreased (approximately 76%) with rifampicin co-administration in PET analysis. Because [18F]pitavastatin has lower clearance in rats than other previously reported OATP1B PET s, it holds the potential of an imaging tracer that has a higher sensitivity in monitoring hepatic OATP1B function's changes. CONCLUSION: Compared with the previously reported OATP imaging tracers, [18F]pitavastatin is more suitable for the sensitive detection of functional changes in OATP transporters. We believe that [18F]pitavastatin enables quantitative analysis of the hepatobiliary transport system for organic anion compounds.

MR-based wall shear stress measurements in fully developed turbulent flow using the Clauser plot method.

In arterial blood flow wall shear stress (WSS) quantifies the frictional force that flowing blood exerts on a vessel wall. WSS can be directly estimated from phase-contrast (PC) MR velocity measurements and has been suggested as a biomarker in cardio-vascular diseases. We present and investigate the application of the Clauser plot method for estimating WSS in fully developed turbulent stationary flow using PC velocity measurements. The Clauser plot method estimates WSS from the logarithmic region of boundary layer in fully developed turbulent stationary flow. The Clauser plot method was evaluated using 2D PC-MR phantom measurements at 3 T for different in-plane resolutions at various Reynolds numbers. WSS values derived from the Clauser plot were compared to results from Laser Doppler Velocimetry (LDV) measurements and theoretical results calculated using the friction factor formula for smooth pipe flow. For all Reynolds numbers, WSS values derived from the Clauser plot were in good agreement with results from LDV measurements and values using the friction factor formula (relative deviations ∼5%). Furthermore, Clauser plot derived results were almost independent of spatial resolution, in contrast to WSS results obtained with our in-house software tool for MR-based WSS quantification showing relative deviations of more than 100%. In fully developed turbulent flow, the Clauser plot method provides highly consistent WSS independent of the underlying spatial resolution. Therefore, it renders a valuable approach for MR-based WSS estimates in controllable flow settings. Although its direct in vivo applicability is severely limited because of the different flow character, it may serve as helpful approach for validation of MR-based WSS quantification algorithms prior to their clinical application.

Underestimation of myocardial blood flow by dynamic perfusion CT: Explanations by two-compartment model analysis and limited temporal sampling of dynamic CT.

PURPOSE: Previous studies using dynamic perfusion CT and volume perfusion CT (VPCT) software consistently underestimated the stress myocardial blood flow (MBF) in normal myocardium to be 1.1-1.4 ml/min/g, whilst the O 15-water PET studies demonstrated the normal stress MBF of 3-5 ml/min/g. We hypothesized that the MBF determined by VPCT (MBF-VPCT) is actually presenting the blood-to-myocardium transfer constant, K1. In this study, we determined K1 using Patlak plot (K1-Patlak) and compared the results with MBF-VPCT. MATERIAL AND METHODS: 17 patients (66 ± 9 years, 7 males) with suspected coronary artery disease (CAD) underwent stress dynamic perfusion CT, followed by rest coronary CT angiography (CTA). Arterial input and myocardial output curves were analyzed with Patlak plot to quantify myocardial K1. Significant CAD was defined as >50% stenosis on CTA. A simulation study was also performed to investigate the influence of limited temporal sampling in dynamic CT acquisition on K1 using the undersampling data generated from MRI. RESULTS: There were 3 patients with normal CTA, 7 patients with non-significant CAD, and 7 patients with significant CAD. K1-patlak was 0.98 ± 0.35 (range 0.22-1.67) ml/min/g, whereas MBF-VPCT was 0.83 ± 0.23 (range 0.34-1.40) ml/min/g. There was a linear relationship between them: (MBF-VPCT) = 0.58 x (K1-patlak) + 0.27 (r(2) = 0.65, p < 0.001). The simulation study done on MRI data demonstrated that Patlak plot substantially underestimated true K1 by 41% when true K1 was 2.0 ml/min/g with the temporal sampling of 2RR for arterial input and 4RR for myocardial output functions. CONCLUSIONS: The results of our study are generating hypothesis that MBF-VPCT is likely to be calculating K1-patlak equivalent, not MBF. In addition, these values may be substantially underestimated because of limited temporal sampling rate.

Reproducibility Between Brain Uptake Ratio Using Anatomic Standardization and Patlak-Plot Methods.

UNLABELLED: The Patlak-plot and conventional methods of determining brain uptake ratio (BUR) have some problems with reproducibility. We formulated a method of determining BUR using anatomic standardization (BUR-AS) in a statistical parametric mapping algorithm to improve reproducibility. The objective of this study was to demonstrate the inter- and intraoperator reproducibility of mean cerebral blood flow as determined using BUR-AS in comparison to the conventional-BUR (BUR-C) and Patlak-plot methods. METHODS: The images of 30 patients who underwent brain perfusion SPECT were retrospectively used in this study. The images were reconstructed using ordered-subset expectation maximization and processed using an automatic quantitative analysis for cerebral blood flow of ECD tool. The mean SPECT count was calculated from axial basal ganglia slices of the normal side (slices 31-40) drawn using a 3-dimensional stereotactic region-of-interest template after anatomic standardization. The mean cerebral blood flow was calculated from the mean SPECT count. Reproducibility was evaluated using coefficient of variation and Bland-Altman plotting. RESULTS: For both inter- and intraoperator reproducibility, the BUR-AS method had the lowest coefficient of variation and smallest error range about the Bland-Altman plot. Mean CBF obtained using the BUR-AS method had the highest reproducibility. CONCLUSION: Compared with the Patlak-plot and BUR-C methods, the BUR-AS method provides greater inter- and intraoperator reproducibility of cerebral blood flow measurement.

Structure of arboreal and herbaceous strata in a neotropical seasonally flooded monodominant savanna of Tabebuia aurea / Estrutura do estrato arbóreo e herbáceo em uma savana neotropical monodominante sazonalmente inundada de Tabebuia aurea

Large areas in the Pantanal wetland are covered by monodominant formations, e.g. typical landscapes with local names such as “paratudal”, dominated by T. aurea. Studies on structure of these formations generally include only woody strata, consequently the species richness registered is usually low due to the absence of the ‘ground layer’ of herbaceous and others low species. We recorded 13 species, 12 genera and 11 families for the arboreal stratum. Considering arboreal flora without the dominant (T. aurea) individuals showed great establishment in relation to the flood level between 35 – 45 cm while the individuals of the dominant species of 30 – 45 cm. The diameter distribution revealed that the population of T. aurea did not show the reverse J curve, the usual pattern for species in constant regeneration, also evidenced in inconstant Licourt quotient, indicating an episodic recruitment that could lead to future changes in structure. In the herbaceous strata we recorded 78 species, included in 62 genera and 27 families. Using plots method we sampled 46 species, 40 genera and 22 families, while in line interception we found 65 species distributed in 57 genera and 26 families. The floristic similarity of Sørensen between both methods was 59.4%, with 33 species in common, and the method of line interception was more efficient in detecting richness, with 35% more species found in the same time. According to the methods of plots and line interception applied on the woody stratum, our results gave similar detailed information on the structure of this type of savanna, and in spite of being monodominant it shows high species richness when the herbaceous stratum is taken into account. Plots and line interception methods showed similar results for the woody stratum and high species richness of the herbaceous stratum.

Amplas áreas no Pantanal são cobertas por formações monodominantes, tipicamente com nomes locais como “paratudal” dominado por Tabebuia aurea. Estudos na estrutura dessas formações geralmente incluem somente estrato arbóreo, consequentemente, a riqueza de espécies detectada geralmente é baixa devido à ausência do “estrato terrestre” das herbáceas e outras poucas espécies. Nós registramos 13 espécies, 12 gêneros e 11 famílias para o estrato arbóreo. Considerando a flora arbórea sem a espécie dominante (T. aurea) apresentaram um ótimo de estabelecimento em relação ao nível de inundação entre 35 – 45cm, enquanto os indíviduos da espécie dominante de 30 – 45cm. A distribuição diamétrica revelou que a população de T. aurea não apresentou o J reverso, o modelo usual para espécies em constante regeneração, também evidenciado pela não constante no quoeficiente de Licourt. Indicando episódio de recrutamento que poderia levar a futuras mudanças na estrutura. Para o estrato herbáceo geral registramos 78 espécies, incluindo 68 gêneros e 27 famílias. Usando o método de parcelas amostramos 46 espécies, 40 gêneros e 22 famílias, enquanto na interseção na linha nós encontramos 65 espécies distribuídas em 57 gêneros e 26 famílias. A similaridade florísitca de Sørensen entre ambos métodos foi de 59,4%, com 33 espécies em comum, e o método de interseção na linha foi mais eficiente na detecção da riqueza, 35% das espécies foram encontradas no mesmo tempo. De acordo com os métodos de parcelas e interseção na linha aplicado no estrato arbóreo, os nossos resultados deram uma semelhante informação detalhada na estrutura deste tipo de savana, e que apesar de ser monodominante mostrou alta riqueza de espécies quando o estrato herbáceo é levado em conta. Os métodos de parcelas e interseção na linha mostraram resultados similares para o estrato arbóreo e alta riqueza de espécies do estrato herbáceo.

Theoretical evaluation of the advantages and limitations of constant pressure versus constant flow rate gradient elution separation in supercritical fluid chromatography.

This study reports on the possible advantages of switching from constant flow (cF) based gradient elution separations to constant pressure (cP) based ones in Supercritical fluid chromatography (SFC) by means of mathematical models. All the important parameters (e.g. viscosity) were fitted as a function of pressure and mol% methanol in CO2. It is shown that when switching towards a cP approach in SFC, a time gain of 34% at the end of a 0 to 50% methanol in CO2 gradient is expected. Actual analysis time gains depend on the point at which it is evaluated (e.g. up to 41% after the equilibration step). Due to the dependence of retention on density, cF- and cP-mode do not yield the same selectivity even if the same volumetric-based gradient program is used. Because the components experience a higher average pressure in the cP-mode, the apparent retention factor is slightly lower.

Possibilities and limitations of the kinetic plot method in supercritical fluid chromatography.

Although supercritical fluid chromatography (SFC) is becoming a technique of increasing importance in the field of analytical chromatography, methods to compare the performance of SFC-columns and separations in an unbiased way are not fully developed. The present study uses mathematical models to investigate the possibilities and limitations of the kinetic plot method in SFC as this easily allows to investigate a wide range of operating pressures, retention and mobile phase conditions. The variable column length (L) kinetic plot method was further investigated in this work. Since the pressure history is identical for each measurement, this method gives the true kinetic performance limit in SFC. The deviations of the traditional way of measuring the performance as a function of flow rate (fixed back pressure and column length) and the isopycnic method with respect to this variable column length method were investigated under a wide range of operational conditions. It is found that using the variable L method, extrapolations towards other pressure drops are not valid in SFC (deviation of ∼15% for extrapolation from 50 to 200bar pressure drop). The isopycnic method provides the best prediction but its use is limited when operating closer towards critical point conditions. When an organic modifier is used, the predictions are improved for both methods with respect to the variable L method (e.g. deviations decreases from 20% to 2% when 20mol% of methanol is added).

Effects of Bathing on Cerebral Blood Flow in Healthy Volunteers. Using Patlak plot method with Technetium-99m ethyl cysteinate dimer / 日本温泉気候物理医学会雑誌

We studied the effects of bathing in warm water on cerebral blood flow (CBF). Seven healthy male volunteers were subjected to experiments. The subjects were bathed in warm water at 39°C for 20 minutes in a sitting position immersed up to the neck. Each subject received two CBF examinations: one under normal conditions and the other after taking a bath mentioned above. There was an interval of at least seven days between the two examinations. To measure CBF, we used the Patlak plot method with technetium-99m ethyl cysteinate dimer (99m-Tc ECD). To examine CBF after bathing, 99m-Tc ECD was injected within 10 minutes after bathing. Brain perfusion index (BPI) and regional CBF (rCBF) were used as indexes for evaluating CBF. The body temperature, pulse, blood pressure, arterial oxygen and carbon dioxide pressure, and hematocrit were also measured. Wilcoxon's signed rank test was used for statistical analyses. The following were observed:<br>1) BPI increased significantly after bathing (p<0.05).<br>2) rCBF in the cerebral cortex, particularly in the frontal lobe, tended to increase after bathing (p<0.05). No definite changes were observed in the cerebellar cortex, caudate nucleus, or thalamus.<br>3) The body temperature and pulse increased significantly after bathing. No definite changes were observed in blood pressure, arterial oxygen and carbon dioxide pressure, or hematocrit. From the above, we conclude that bathing in warm water causes the cerebral blood flow to increase in healthy subjects.