Internal Calibration Procedure Research Articles

Linking Seismic Measurements to the International System of Units

AbstractThe current state of the art in the calibration of seismometers is given by internal calibration procedures which give only incomplete information about a seismometer’s response and are based on transfer functions supplied by manufacturers. Calibrations traceable to the International System of Units (SI) provide an independent and comprehensible characterization of seismometers. These calibrations take part in a laboratory using an electrodynamic shaker or shake table. To overcome the issue that seismometers placed in seismic stations are not supposed to be moved to a calibration laboratory, novel on-site calibration methods incorporating a reference seismometer were developed. Such a reference is placed near the sensor to be calibrated, and the transfer function of the seismometer under test can be derived based on the output of both sensors.

One-Step Precise Characterization of Drug Delivery Systems by PULCON Magnetic Resonance Spectroscopy.

Polymers are extensively used for the realization of drug delivery systems across multiple scales, from nanomedicines to microparticles and macroscopic implantable devices, for their favorable biodegradation profiles and tunable physicochemical features. The accurate quantification of the polymer content is key to finely controlling drug loading and release and ensuring reproducibility, yet it continues to be a major challenge in the design and development of delivery systems. In this study, we introduce a novel protocol based on the PULCON technique to quantify, with a routine NMR spectroscopy analysis, the precise concentration of polymers in various delivery systems. Specifically, the PULCON protocol is applied to characterize the physicochemical and pharmaceutical properties of nanoparticles, microparticles, and implantable devices realized by combining three extensively used polymers, namely, poly(lactic-co-glycolic acid) (PLGA), poly(vinyl alcohol) (PVA), and poly(ethylene glycol) (PEG). Without using internal calibration procedures, in a single step, the PULCON protocol precisely quantifies the concentration of each polymer and the drug content. This approach can be readily implemented on standard NMR spectrometers, enabling accurate characterization of drug delivery systems and facilitating their effective development.

Determination of 145 pharmaceuticals and personal care products in eleven categories in water by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry

Pharmaceuticals and personal care products (PPCPs) are emerging contaminants frequently detected in aquatic environments at trace levels. These chemicals have diverse structures and physicochemical properties and includes pharmaceuticals like antibiotics, antihypertensive drugs, antiviral drugs, and psychotropic drugs that are widely used in large quantities worldwide. Considering the large number of pharmaceuticals currently in usage, it is crucial to establish a priority list of PPCPs that should be monitored and/or treated first. An accurate understanding of the occurrence and levels of PPCPs in aquatic environments is essential for providing objective materials for monitoring these emerging contaminants. Therefore, accurate, efficient, sensitive, and high-throughput screening techniques need to be established for determining and quantifying PPCPs. This study developed a method for the determination of 145 PPCPs (grouped into eleven categories: antibiotics, antihypertensive drugs, antidiabetic drugs, antiviral drugs, β-receptor agonists, nitroimidazoles, H2 receptor antagonists, psychotropic drugs, hypolipidemic drugs, non-steroidal anti-inflammatory drugs, and others) in water. The method was based on large volume direct injection without sample enrichment and cleanup and used ultra-high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS). Water samples were collected and filtered through a 0.22-μm regenerated cellulose (RC) filter membrane. Subsequently, Na2EDTA was added to the samples to adjust their pH to 6.0-8.0. Internal standards were mixed with the solutions, and because of the addition of Na2EDTA, the interference of metal ions could be eliminated in the determination of compounds, especially for tetracycline and quinolone antibiotics. Among the six filter membranes tested in this study (PES, PFTE-Q, PFTE, MCE, GHP, and RC), RC filter membranes were screened for water sample filtration. The UHPLC-MS/MS parameters were optimized by comparing the results of various mobile phases, as well as by establishing the best instrumental conditions. The 145 PPCPs were separated using an Phenomenex Kinetex C18 column (50 mm×3 mm, 2.6 μm) via gradient elution. The mobile phases were 0.1% (v/v) formic acid aqueous solution containing 5 mmol/L ammonium formate and acetonitrile for positive ion modes, 5 mmol/L aqueous solutions of ammonium formate and acetonitrile for negative ion modes. The samples were quantified using the scheduled multiple reaction monitoring (scheduled-MRM) mode with electrospray ionization in positive and negative ion modes. A standard internal calibration procedure was used to calculate contents of sample. The established method was systematically verified, and it demonstrated a good linear relationship. The average recoveries of the 145 PPCPs at the three spiked levels were in the range of 80.4%-128% with relative standard deviations (RSDs, n=6) of 0.6%-15.6%. The method detection limits (MDLs) ranged from 0.015 to 5.515 ng/L. Finally, the optimization method was applied to analyze the 145 PPCPs in 11 surface water samples and 6 drinking water samples. Overall, 93 (64%) out of the 145 analytes were detected. The total contents of the PPCPs in surface water samples ranged from 276.9 to 2705.7 ng/L. The detection frequencies of antidiabetic, antiviral, and psychotropic drugs were 100%. The total contents of the PPCPs in drinking water samples ranged from 140.5 to 211.5 ng/L, and antibiotics, antidiabetic drugs, and antiviral drugs comprised the largest proportion of analytes (by mass concentration) in drinking water samples. Our method exhibited high analytical speed and high sensitivity. It is thus suitable for the trace analysis and determination of the 145 PPCPs in environmental water and showed improved detection efficiency for PPCPs in water, indicating that it has a high potential for practical applications. This study can extend technical support for further pollution-level analysis of PPCPs in water and provide an objective basis for environmental management.

Novel Robust Internal Calibration Procedure for Precise FT-IR Measurements of Nitrogen Impurities in Diamonds

FT-IR spectroscopy is the basic finger-print method for qualitative and quantitative analysis of nitrogen, boron, and hydrogen impurities in natural and synthetic diamonds. In quantitative measurements of impurity concentrations, external standard samples are required for the calibration procedure during the analysis. In this study, the double-phonon mid-IR absorption coefficient of optical phonons of the diamond host matrix, the robust internal mid-IR absorption standard, was accurately measured for tens of diverse diamond samples, thus enabling precise calibrated measurements of ultra-low detectable impurity concentrations.

Recommendations and Protocols for the Use of the Isotope Ratio Infrared Spectrometer (Delta Ray) to Measure Stable Isotopes from CO2: An Application to Volcanic Emissions at Mount Etna and Stromboli (Sicily, Italy)

Among major volatiles released from the Earth’s interior, CO2 is an important target for the international community. The interest is keenly motivated by the contribution of CO2 in the Earth’s carbon budget and its role on past, current, and future climate dynamics. In particular, the isotopic signature of CO2 is fundamental to characterize the source of this gas and its evolution up to the atmosphere. The recent development of new laser-based techniques has marked an important milestone for the scientific community by favoring both high-frequency and in situ stable isotope measurements. Among them, the Delta Ray IRIS (Thermo Scientific Inc., Waltham, USA) is one of the most promising instruments thanks to its high precision, its limited interferences with other gaseous species (such as H2S and/or SO2), and its internal calibration procedure. These characteristics and the relative easiness to transport the Delta Ray IRIS have encouraged its use on the field to analyze volcanic CO2 emissions in recent years but often with distinct customized protocols of measurements. In this study, various tests in the laboratory and on the field have been performed to study the dependence of CO2 isotope measurements on analytical, instrumental, and environmental conditions. We emphasize the exceptional ability of the Delta Ray IRIS to perform isotope measurements for a large range of CO2 concentration (200 ppm–100%) thanks to a dilution system and to get a reliable estimation of the real CO2 content from the diluted one. These tests lead to point out major recommendations on the use of Delta Ray IRIS and allow the development of adapted protocols to analyze CO2 emissions like in volcanic environments.

CALIPSO IIR Version 2 Level 1b calibrated radiances: analysis and reduction of residual biases in the Northern Hemisphere.

Version 2 of the Level 1b calibrated radiances of the Imaging Infrared Radiometer (IIR) on board the Cloud-Aerosol Lidar and Infrared Satellite Observation (CALIPSO) satellite has been released recently. This new version incorporates corrections of small but systematic seasonal calibration biases previously revealed in Version 1 data products mostly north of 30° N. These biases of different amplitudes in the three IIR channels 8.65 µm (IIR1), 10.6 µm (IIR2), and 12.05 µm (IIR3) were made apparent by a striping effect in images of IIR inter-channel brightness temperature differences (BTDs) and through seasonal warm biases of nighttime IIR brightness temperatures in the 30–60° N latitude range. The latter were highlighted through observed and simulated comparisons with similar channels of the Moderate Resolution Imaging Spectroradiometer (MODIS) on board the Aqua spacecraft. To characterize the calibration biases affecting Version 1 data, a semi-empirical approach is developed, which is based on the in-depth analysis of the IIR internal calibration procedure in conjunction with observations such as statistical comparisons with similar MODIS/Aqua channels. Two types of calibration biases are revealed: an equalization bias affecting part of the individual IIR images and a global bias affecting the radiometric level of each image. These biases are observed only when the temperature of the instrument increases, and they are found to be functions of elapsed time since night-to-day transition, regardless of the season. Correction coefficients of Version 1 radiances could thus be defined and implemented in the Version 2 code. As a result, the striping effect seen in Version 1 is significantly attenuated in Version 2. Systematic discrepancies between nighttime and daytime IIR–MODIS BTDs in the 30–60° N latitude range in summer are reduced from 0.2 K in Version 1 to 0.1 K in Version 2 for IIR1–MODIS29. For IIR2–MODIS31 and IIR3–MODIS32, they are reduced from 0.4 K to close to zero, except for IIR3–MODIS32 in June, where the night-minus-day difference is around −0.1 K.

A new instrument for stable isotope measurements of <sup>13</sup>C and <sup>18</sup>O in CO<sub>2</sub> – instrument performance and ecological application of the Delta Ray IRIS analyzer

Abstract. We used the recently developed commercially available Delta Ray isotope ratio infrared spectrometer (IRIS) to continuously measure the CO2 concentration c and its isotopic composition δ13C and δ18O in a managed beech forest in central Germany. Our objectives are (a) to characterize the Delta Ray IRIS and evaluate its internal calibration procedure and (b) to quantify the seasonal variability of c, δ13C, δ18O and the isotopic composition of nighttime net ecosystem CO2 exchange (respiration) Reco13C and Reco18O derived from Keeling plot intercepts. The analyzer's minimal Allan deviation (as a measure of precision) was below 0.01 ppm for the CO2 concentration and below 0.03 ‰ for both δ values. The potential accuracy (defined as the 1σ deviation from the respective linear regression that was used for calibration) was approximately 0.45 ppm for c, 0.24 ‰ for 13C and 0.3 ‰ for 18O. For repeated measurements of a target gas in the field, the long-term standard deviation from the mean was 0.3 ppm for c and below 0.3 ‰ for both δ values. We used measurements of nine different inlet heights to evaluate the isotopic compositions of nighttime net ecosystem CO2 exchange Reco13C and Reco18O in a 3-month measurement campaign in a beech forest in autumn 2015. During this period, an early snow and frost event occurred, coinciding with a change in the observed characteristics of both Reco13C and Reco18O. Before the first snow, Reco13C correlated significantly (p < 10−4) with time-lagged net radiation Rn, a driver of photosynthesis and photosynthetic discrimination against 13C. This correlation became insignificant (p > 0.1) for the period after the first snow, indicating a decoupling of δ13C of respiration from recent assimilates. For 18O, we measured a decrease of 30 ‰ within 10 days in Reco18O after the snow event, potentially reflecting the influence of 18O depleted snow on soil moisture. This decrease was 10 times larger than the corresponding decrease in δ18O in ambient CO2 (below 3 ‰) and took 3 times longer to recover (3 weeks vs. 1 week). In summary, we conclude that (1) the new Delta Ray IRIS with its internal calibration procedure provides an opportunity to precisely and accurately measure c, δ13C and δ18O at field sites and (2) even short snow or frost events might have strong effects on the isotopic composition (in particular 18O) of CO2 exchange on an ecosystem scale.

Experimental bond dissociation energies of benzylpyridinium thermometer ions determined by threshold-CID and RRKM modeling

Benzylpyridinium salts (BPs) have often been used as thermometer ions to obtain an energy calibration of mass spectrometric experiments (in particular to determine internal energy distributions of ions after the ionization process). Fragmentation of BP+ molecular ions is characterized by specific Bond Dissociation Energies (BDE) which depend on the substituent group and its location on the benzyl ring. Although those BDE values are regularly re-evaluated by quantum chemical calculations, their experimental determination is still missing from the literature. In this paper, a modified Quadrupole-hexapole-Quadrupole (QhQ) mass spectrometer is used to obtain such values on 4 BP+ molecular ions (characterized by a wide range of CN bond strengths) using Threshold Collision-Induced Dissociations (TCID) and Rice–Ramsperger–Kassel–Marcus (RRKM) kinetic modeling. It is found that experimental values are systematically 0.5eV lower than their most recent theoretical evaluations. Despite this shift, the absolute critical energy values are maintained in the same order (pOMe<pMe<pCl<pCN), and the relative energy differences are in very good agreement. We argue that the observed 0.5eV shift relates to the energy dependence of the Transition State’s number of states that is typical for barrier-less fragmentation processes and, relates to a kinetic rather than an energetic bottleneck. Notably, by taking into account the bond elongations characterizing the transition states and their corresponding calculated critical energies (E0), close agreement is found with experimentally obtained E0 values. We thus conclude that much care should be taken when describing the transition state during an internal energy calibration procedure where the involved energy is lower than 3–4eV.

Blending process modeling and control by multivariate curve resolution

The application of the Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) method to model and control blend processes of pharmaceutical formulations is assessed. Within the MCR-ALS framework, different data analysis approaches have been tested depending on the objective of the study, i.e., knowing the effect of different factors in the evolution of the blending process (modeling) or detecting the blend end-point and monitoring the concentration of the different species during and at the end of the process (control). Data analysis has been carried out studying multiple blending runs simultaneously taking advantage of the multiset mode of the MCR-ALS method. During the ALS optimization, natural constraints, such as non-negativity (spectral and concentration directions) have been applied for blend modeling. When blending control is the main purpose, a variant of the MCR-ALS algorithm with correlation constraint in the concentration direction has been additionally used. This constraint incorporates an internal calibration procedure, which relates resolved concentration values (in arbitrary units) with the real reference concentration values in the calibration samples (known references) providing values in real concentration scale in the final MCR-ALS results. Two systems consisting of pharmaceutical mixtures of an active principle (acetaminophen) with two or four excipients have been investigated. In the first case, MCR results allowed the description of the evolution of the individual compounds and the assessment of some physical effects in the blending process. In the second case, MCR analysis allowed the detection of the end-point of the process and the assessment of the effects linked to variations in the concentration level of the compounds.

Decay of 185Tl, 185m+gHg, 189m+gPb and energy location of the 13/2+ isomeric states in 185Hg, 189Pb, 193Po and 197Rn

The $ \beta^{{+}}_{}$ /EC decay of 185Tl was studied at the ISOLDE facility, the $ \gamma$ -rays belonging to 185Hg have been identified and a partial low-spin level scheme of 185Hg has been built. The decay of 185m+gHg was studied at the ISOCELE facility. Conversion electron lines of very low-energy transitions were observed for the first time. Electron data have been obtained for four transitions in 185Au and two transitions in 185Hg . From the analysis performed using an internal energy calibration procedure the energy location of the 185mHg has been determined to be $ E_{IS}= 103.7(4)$ keV. This $ E_{IS}$ value is consistent with that determined independently, $ E_{IS}=94(13)$ keV, using 185m+gHg $ \alpha$ -decay data from literature. New $ \alpha$ particles emitted from 189m+gPb have been detected and their origins determined by in-source laser spectroscopy at the ISOLDE facility. $ \alpha$ - $ \gamma$ coincidence results have served to locate the $ 13/2^{+}$ isomeric state of 189Pb at $ E_{IS}=40(4)$ keV. This latter $ E_{IS}$ value added to $ \alpha$ -decay data from literature have allowed the energy location of the $ 13/2^{+}$ isomeric states of 193Po and 197Rn at 95(7)keV and 194(12)keV, respectively. The nuclear structure of the isomeric and ground states in the nuclei of the three $ \alpha$ -emitter chains starting with 195m+g, 197m+g, 199m+gRn are discussed.

Applications of a remote sensing-based two-source energy balance algorithm for mapping surface fluxes without in situ air temperature observations

The two-source energy balance (TSEB) model uses remotely sensed maps of land–surface temperature (LST) along with local air temperature estimates at a nominal blending height to model heat and water fluxes across a landscape, partitioned between dual sources of canopy and soil. For operational implementation of TSEB, however, it is often difficult to obtain representative air temperature data that are compatible with the LST retrievals, which may themselves have residual errors due to atmospheric and emissivity corrections. To address this issue, two different strategies in applying the TSEB model without requiring local air temperature data were tested over a typical Mediterranean agricultural area using a set of high-resolution multispectral airborne remote sensing images. Alleviating the need for accurate local air temperature data as input, these two approaches estimate the surface-to-air temperature gradient that drives the sensible heat flux by directly exploiting the information available in the image. The two approaches include: 1) a scene-based internal calibration (TSEB-IC) procedure that estimates air temperature over a well-watered and fully vegetated pixel in the LST image, and 2) a disaggregation scheme (DisALEXI) that uses air temperature estimates from a time-differential coupled TSEB-atmospheric boundary layer model of atmosphere–land exchange (ALEXI). A comparison of the air temperatures modeled by TSEB-IC and DisALEXI with in situ weather station observations shows good agreement, with average differences on the order of 1K, comparable with the uncertainties in the remotely sensed surface temperature maps. Surface fluxes estimated by each method agree well with micro-meteorological measurements acquired over an olive orchard within the aircraft imaging domain. In comparison with fluxes generated with TSEB using local measurements of air temperature, instantaneous fluxes from these alternative methods show good spatial agreement, with differences of less than 10Wm−2 across the domain. Finally, a sensitivity analysis of the three models, performed by introducing artificial errors into the model inputs, demonstrates that the DisALEXI and TSEB-IC approaches are relatively insensitive to errors in absolute surface temperature calibration, while turbulent fluxes from TSEB applications using local air temperature measurements show sensitivity of approximately 30Wm−2 per degree temperature perturbation. This highlights the value of both internal calibration and time-differential estimation of the surface-to-air temperature gradient within a surface energy balance framework.

A multi‐scale approach to determine accurate elemental and isotopic ratios by nano‐scale secondary ion mass spectrometry imaging

Nano-scale secondary ion mass spectrometry (NanoSIMS) is still hampered by a lack of appropriate calibration method for the quantification of elemental and isotopic ratios in heterogeneous materials such as soil samples. The potential of (13)C-(15)N-labeled density fractions of soil to calibrate the C/N, (13)C/(12)C and (15)N/(14)N ratios provided by NanoSIMS was evaluated. The spatial organization of soil particles found at the macro- and micro-scales were compared. The C/N, (13)C/(12)C and (15)N/(14)N ratios measured at the macroscopic scale from different density fractions using an elemental analyzer coupled to an isotope ratio mass spectrometer (EA/IRMS) were compared with the corresponding micro-scale NanoSIMS measurements. When the macro- and micro-scales patterns were similar, macroscopic scale measurements obtained by EA/IRMS and the corresponding NanoSIMS C/N and (15)N/(14)N ratios averaged per fraction were used to obtain correction equations. The correction method using the internal calibration procedure was compared with the traditional one using a single organic standard. It was demonstrated that the correction method using an internal calibration procedure was applicable for NanoSIMS images acquired on more than 500 µm(2) per fraction and provided more accurate C/N and (15)N/(14)N ratios than the traditional correction method. As long as the NanoSIMS sampling was representative of the macroscopic properties, the correction method using an internal calibration procedure allowed better quantification of the isotope tracers and characterization of the C/N ratios. This method not only produced qualitative images, but also accurate quantitative parameters from which ecological interpretations can be derived.

Comparação entre métodos de quantificação em cromatografia gasosa: um experimento para cursos de química

COMPARISON OF QUANTIFICATION METHODS IN GAS CHROMATOGRAPHY: AN EXPERIMENT FOR CHEMISTRY COURSES. This article describes an experiment designed to teach quantitative determination in gas chromatography (GC) in Organic and Analytical Chemistry practical classes. The experiment consisted of extracting and analyzing eugenol from clove seeds to perform a quantitative approach aimed at comparing results obtained by external and internal calibration procedures. Therefore, this experiment proved to be very effective tool to enhance students awareness on the need to understand different types of calibration in GC and on how to avoid common experimental errors, and to find the best ways to eliminate their interference during the quantitative analysis phase.

Accuracy of allele frequency estimates in pool DNA analyzed by high-density Illumina Human 610-Quad microarray

Purpose: DNA pooling method has been previously proven successful for allele frequency estimation using earlier versions of Illumina Beadchip and Affymetrix GeneChip microarrays. The aim of this study was to evaluate the accuracy of the DNA pooling using the High Density Illumina Infinium microarray system.Patients & methods: The accuracy of three different methods of allele frequency estimation on the High Definition Infinium II Beadchip (Human 610-Quad) was tested using the DNA samples obtained from saliva collected from seven Caucasian subjects who had been individually genotyped. Our first approach was to calculate estimated allelic frequency (expressed as B allele frequency) from pooled DNA sample based on the correlation coefficient obtained for individual SNPs, and to correlate it with the true (real) allele frequency computed using individually genotyped samples. The second approach was to estimate SNP frequency in the pooled DNA sample as calculated automatically by the proprietary Beadstudio software, which is based on the internal calibration and normalization procedures. The third approach was to study the pool allele frequency calculated using the estimation of correlation coefficient from microarray SNP sub-pools.Results and conclusions: All analyzed methods of allelic frequency estimates from pooled DNA produced similar results in respect to the calculated correlation coefficient (R) (R ranging from 0.947 to 0.958 with R>0.99 for correlation between each three of them). All three methods of calculations seem to be sufficient and equally effective for calculation of individual allelic frequency for the given SNPs from the pooled DNA.

Application of radiofrequency glow discharge-optical emission spectrometry for direct analysis of main components of glass samples

An internal standard calibration methodology for radiofrequency glow discharge optical emission spectrometry (rf-GD-OES) has been evaluated for the quantitative analysis of glass samples. Glasses of very different composition and thickness (from 2.8 to 5.8 mm thick) were used for calibration. The absence of spectral interferences from sputtered oxygen was first investigated. For calibration, Si was selected as the internal standard and, when plotting intensity ratios (Ix/ISi) versus concentration ratios (Cx/CSi), linear graphs over the entire range of tested concentrations were obtained. In all cases, concentrations of the oxides of different elements have been used instead of elemental concentrations as is habitually done for the analysis of conductors. Thus, the proposed methodology allows us to quantify the oxygen indirectly without measuring its emission intensity. In addition, the internal standard calibration procedure was applied for the determination of the glass major components (SiO2, Na2O, CaO, MgO, Al2O3 and K2O) by rf-GD-OES in two glass samples and results showed good agreement with the certified values.

Operational aspects of satellite-based energy balance models for irrigated crops in the semi-arid U.S.

SEBAL and METRIC remote sensing energy-balance based evapotranspiration (ET) models have been applied in the western United States. ET predicted by the models was compared to lysimeter-measured ET in agricultural settings. The ET comparison studies showed that the ET estimated by the remote sensing models corresponded well with lysimeter-measured ET for agricultural crops in the semi-arid climates. Sensitivity analyses on impacts of atmospheric correction for surface temperature and albedo showed that the internal calibration procedures incorporated in the models helped compensate for errors in temperature and albedo estimation. A repeatability test by two totally independent model applications using different images, operators and weather datasets showed that seasonal estimations by the models have high repeatability (i.e. stable results over ranges in satellite image timing, operator preferences and weather datasets). These results imply that the SEBAL/METRIC remote sensing models have a high potential for successful ET estimation in the semi-arid United States.

Femoral Neck Trabecular Microstructure in Ovariectomized Ewes Treated With Calcitonin: MRI Microscopic Evaluation

Ovariectomy induces deterioration of the trabecular structure in the femoral neck of ewes, as depicted by MR microscopic imaging. This structural deterioration is prevented by salmon calcitonin treatment. This study evaluated the trabecular (Tb) microarchitecture of an ovariectomy (OVX)-induced osteoporotic model in ewes and determined the effects of salmon calcitonin (sCT), an osteoclast inhibitor, on the Tb structure. This is the first report of OVX-induced changes in the Tb structure in the femoral neck in the ewes and effect of sCT on the microarchitecture. Ewes (5-8 years old, n = 28) were equally allocated into sham (Sham), OVX injected with vehicle, or OVX injected with sCT at 50 or 100 IU, three injections per week. They were killed 6 months after OVX. The femoral neck was examined with an MR imager at 9.4 T in axial, coronal, and sagittal planes. An internal calibration procedure as a means of standardizing image analysis was used to adjust the segmentation threshold. Data from all three planes were averaged. Compared with Sham, OVX induced significant changes (p < 0.0125) in the MRI-derived femoral neck Tb structure: Tb bone volume fraction (BV/TV), -18%; Tb number, -20%; Tb separation, +23%; number of free ends, +28%; number of nodes, -39%; number of Tb branches, -23%; mean length of Tb branches, -19%. Compared with OVX, treatment of sCT at 100 IU significantly improved all the Tb structural parameters to the Sham level (p < 0.0001 approximately p = 0.0281), whereas 50 IU significantly increased the Tb number and the mean length of the Tb branches. BV/TV explained 74% of the variation of compressive stress of the trabecular cylinder cores of the femoral neck. Combining all structural parameters in a multivariate regression analysis significantly improved the explanation to 84%, and adding BMD further improved the predictive ability of the model to 92%. We conclude that OVX induces deterioration of the MRI-derived Tb microstructure in the femoral neck of ewes. sCT treatment prevents OVX-induced changes. The femoral neck microarchitecture significantly correlates with its biomechanical properties. Combining microstructural parameters with BMD further improves the prediction of bone biomechanical properties. The effects of sCT on OVX ewes may help explain reduced fracture risk in postmenopausal osteoporotic women treated with sCT.

Reverse iontophoresis as a noninvasive tool for lithium monitoring and pharmacokinetic profiling.

Transdermal iontophoresis was investigated as a noninvasive tool for drug monitoring and pharmacokinetic profiling. Lithium, a frequently monitored drug, was used as a model. The objectives were a) to demonstrate the linear dependence of the iontophoretic extraction flux of lithium on the subdermal concentration of the drug, b) to evaluate the capacity of iontophoresis to monitor sudden changes in the subdermal level, c) to investigate the utility of reverse iontophoresis as a tool in pharmacokinetic studies, and d) to examine the validity of an internal standard calibration procedure to render the method completely noninvasive. Transdermal, iontophoretic extraction was performed in vitro using dermatomed pig-ear skin. The subdermal solution consisted of a physiological buffer containing lithium chloride at concentrations in the therapeutic range and two putative internal standards, sodium and potassium, at fixed physiological levels. The subdermal concentration of lithium was changed either in a stepwise fashion or by simulating one of two pharmacokinetic profiles. Lithium was extracted via electromigration to the cathode. A excellent correlation between subdermal lithium concentration and iontophoretic extraction flux was observed. Iontophoresis tracked sudden concentration changes and followed kinetic profiles. In addition, the effective elimination rate constant could be directly, and noninvasively, estimated from the extraction flux data. Reverse iontophoresis is a potentially useful and noninvasive tool for lithium monitoring.

Development of a ground-based radar for scattering measurements

A ground-based C-band scatterometer system has been constructed at the Multimedia University, Malaysia. This is an inexpensive FM-CW radar that was efficiently constructed from a combination of commercially available components and in-house fabricated circuitry. The system has full polarimetric capability for determining the complete backscattering matrix of a natural target. It will be used to conduct in-situ backscatter measurements on Earth terrain, such as vegetation fields, forests, and soil surfaces. This paper presents the system design and the evaluation results of the scatterometer system. The system was tested at a football field. A metal sphere was used as the calibration target. The backscattering matrices of an 8 trihedral corner reflector and of a 4 /spl times/ 8 dihedral corner reflector were measured. The dihedral was rotated at different angles to provide different sets of polarimetric data. The results were compared with the theoretical values to verify the effectiveness of the calibration technique. The external calibration and internal calibration procedures, as well as the approach used in measuring the relative phase response, are discussed.

Development of a gas chromatographic/ion trap mass spectrometric method for the determination of levoglucosan and saccharidic compounds in atmospheric aerosols. Application to urban aerosols.

We developed and validated a gas chromatographic/ion trap mass spectrometric method for the determination of levoglucosan and the related monosaccharide anhydrides, mannosan, galactosan and 1,6-anhydro-beta-D-glucofuranose in urban atmospheric aerosols collected on quartz fiber filters. The method is based on extraction with dichloromethane-methanol (80 : 20, v/v), trimethylsilylation, multiple reaction monitoring in the tandem mass spectrometric mode using the ion at m/z 217, and the use of an internal standard calibration procedure with the structurally related compound methyl beta-L-arabinopyranoside. In addition, the method allows the quantification of other saccharidic compounds, arabitol, mannitol, glucose, fructose, inositol and sucrose, which were found to be important in summer aerosols. The recovery of levoglucosan was estimated by spiking blank filters and was better than 90%. The precision evaluated by analyzing parts of the same filters was about 2% for the monosaccharide anhydrides and 7% for the other saccharidic compounds in the case of a winter aerosol sample, and the corresponding values for a summer aerosol sample were 5% and 8%. The method was applied to urban PM(10) (particulate matter of <10 microm aerodynamic diameter) aerosols collected at Ghent, Belgium, during a 2000-2001 winter and a 2001 summer episode and revealed interesting seasonal variations. While monosaccharide anhydrides were relatively more important during the winter season owing to wood burning, the other saccharidic compounds were more prevalent during the summer season, with some of them, if not all, originating from the vegetation.