Method Validation and Characterization of the Associated Uncertainty for Malondialdehyde Quantification in Exhaled Breath Condensate

There are several methods for quantifying malondialdehyde (MDA), an oxidative stress biomarker, in exhaled breath condensate (EBC). However, due to the very diluted nature of this biological matrix, a high variability is observed at low concentrations. We aimed to optimize a 2,4-dinitrophenylhydrazine-based method using liquid chromatography coupled to tandem mass spectrometry and characterize the uncertainty associated with this method. We investigated the following parameters for the method validation: calibration linearity, limit of detection (LOD), precision, recovery, and matrix effect. The results were used to identify the main sources of uncertainty and calculating the combined uncertainty. The applicability of this method was evaluated in an ongoing epidemiological study by analyzing 164 EBC samples collected from different professional groups in subway environments. The optimized method was sensitive (LOD: 70 pg/mL), precise (inter-day variation < 19%) and accurate (recovery range: 92–106.5%). The calculated analytical uncertainty was the highest at the LOQ level and reached 23%. Although the analytical uncertainty was high at low MDA concentrations, it was significantly lower than that the observed inter-individual variability. Hence, this method performs sufficiently well and can be recommended for future use in epidemiological researches relying on between-subject differences.

MUF Calculation of Indonesian 10-MWt RDE Experimental HTGR Using Combined Uncertainty Approach

A safeguards assessment for the 10-MWt RDE Experimental HTGR needs to be established in order to fulfill the requirements needed to construct it. Methods and instruments used for the RDE’s nuclear material accounting and safeguards system are reviewed in this paper. Material unaccounted for (MUF) is calculated using the uncertainty of each method and instrument. The effectiveness of the safeguards system is examined by comparing the resulting MUF with the number of SQ ( = significant quantity, i.e. the approximate amount of nuclear material for which the possibility of manufacturing of a nuclear explosive device cannot be excluded). The total uncertainty from each KMP showed a number less than 10%. The number of MUF in each KMP according to total uncertainty showed a number below 1 kg of U-235 in one inventory period (~12 months). According to the number of MUF counted, it is impossible to reach 1 SQ if the diversion done is only by taking the advantage of MUF in the measurement. The result of total uncertainty and MUF calculation showed that the safeguards system and the material measurement designed for RDE is amendable. The sets of instruments and measurements designed will give a comprehensive data of each nuclear material in the RDE. The low number of MUF in comparison with the SQ showed that the RDE has a high proliferation resistance.

Density Measurements of an Air-Like Binary Mixture over the Temperature Range from 100 K to 298.15 K at Pressures up to 8.0 MPa

Densities of an air-like binary mixture (0.2094 oxygen + 0.7906 nitrogen, mole fractions) were measured along six isotherms over the temperature range from 100 K to 298.15 K at pressures up to 8.0 MPa, using a low-temperature single-sinker magnetic suspension densimeter. The measurements were carried out at T = (100, 115, and 130) K in the homogeneous gas and liquid region, and at T = (145, 220, and 298.15) K in the supercritical region (critical temperature TC = 132.35 K); in total, we present results for 52 (T, p) state points. The relative expanded combined uncertainty (k = 2) of the experimental densities was estimated to be between 0.03 % and 0.13 %, except for four values near the critical point. The largest error is caused by the magnetic suspension coupling in combination with the mixture component oxygen, which is strongly paramagnetic; the resulting force transmission error is up to 1.1 %. However, this error can be corrected with a proven correction model to an uncertainty contribution in density of less than 0.044 %. Due to a supercritical liquefaction procedure and the integration of a special VLE-cell, it was possible to measure densities in the homogeneous liquid phase without changing the composition of the liquefied mixture. Moreover, saturated liquid and saturated vapor densities were determined at T = (100, 115, and 130) K by extrapolation of the experimental single-phase densities to the saturation pressure. The new experimental results were compared with the mixture model of Lemmon et al. for the system (nitrogen + argon + oxygen) and the GERG-2008 equation of state.

Progress in Traceable Nanoscale Capacitance Measurements Using Scanning Microwave Microscopy

Reference samples are commonly used for the calibration and quantification of nanoscale electrical measurements of capacitances and dielectric constants in scanning microwave microscopy (SMM) and similar techniques. However, the traceability of these calibration samples is not established. In this work, we present a detailed investigation of most possible error sources that affect the uncertainty of capacitance measurements on the reference calibration samples. We establish a comprehensive uncertainty budget leading to a combined uncertainty of 3% in relative value (uncertainty given at one standard deviation) for capacitances ranging from 0.2 fF to 10 fF. This uncertainty level can be achieved even with the use of unshielded probes. We show that the weights of uncertainty sources vary with the values and dimensions of measured capacitances. Our work offers improvements on the classical calibration methods known in SMM and suggests possible new designs of reference standards for capacitance and dielectric traceable measurements. Experimental measurements are supported by numerical calculations of capacitances to reveal further paths for even higher improvements.

Speeds of Sound in Methanol at Temperatures from 233.33 to 353.21 K at Pressures up to 20 MPa

We report experimental speeds of sound in methanol. Measurements were conducted at temperatures from 233 to 353 K with pressures up to 20 MPa using the double-path length pulse-echo technique. The relative expanded combined uncertainty (k = 2) in measurement was estimated to vary from 0.012 to 0.014%, considering contributions from temperature, pressure, path length calibration, pulse timing, and purity of the sample. Experimental speeds of sound gained in the scope of this work were compared with the equation of state by de Reuck and Craven, as well as with further data from literature.

Density Measurements of Two Liquefied Biomethane-Like Mixtures over the Temperature Range from (100 to 180) K at Pressures up to 9.0 MPa

Densities of two synthetic biomethane-like mixtures were measured in the homogeneous liquid phase and the supercritical region using a low-temperature single-sinker magnetic-suspension densimeter. Both mixtures consist of methane, nitrogen, hydrogen and oxygen, whereas the second mixture additionally contains carbon dioxide. For the first mixture, four isotherms from (100 to 160) K were studied over the pressure range from (1.5 to 6.6) MPa. The second mixture was investigated along three isotherms from (140 to 180) K at pressures of (2.6 to 9.0) MPa, where only the densities at 180 K are usable due to solidification of the carbon dioxide at the lower temperatures. The relative expanded combined uncertainty (k = 2) of the experimental densities was estimated to be in the range of (0.022 to 0.027) % for the first mixture and (0.046 to 0.054) % for the second mixture, respectively. Due to a supercritical liquefaction procedure and the integration of a special VLE-cell, densities in the homogeneous liquid phase could be measured without changing the composition of the liquefied mixture. Moreover, saturated-liquid densities were determined by extrapolation of the experimental single-phase liquid densities to the vapor pressure, which was determined experimentally for the mixture without carbon dioxide and calculated with an equation of state (EOS) for the mixture containing carbon dioxide. The relative expanded combined uncertainty (k = 2) of the saturated-liquid densities is less than 0.08 % in most cases. The new experimental results were compared with the GERG-2008 equation of state; the deviations are less than 0.17 %.

Characterization of NIS neutron irradiation facility for calibration and metrological application

In this study, the Neutron Irradiation Facility (NIF) of the National Institute of Standards (NIS) was characterized for metrological applications to improve the accuracy of the calibration process. The NIS neutron irradiation facility consists of a 5 Ci Am-Be and 0.1 μg Cf-252 sources. The flux and dose rate of the Am-Be source was calculated by using MCNP5 code simulation at different distances from the source. The dose rate delivered by the source was determined using NM2-neutron monitor at different source-to-detector distances. A comparison between the measured and the calculated dose rate was performed and the deviation between them was explained in the skeletal arrangement of room scattering contribution. A shadow cone was designed and constructed to determine the scattering contribution at different source-to-detector distances. The optimum source-distance used for calibration was specified. It was found that the Am-Be calculated flux vary with distances from about 107–104 (n/cm2.S−1). The measured and the calculated dose rates were in agreement up to 150 cm distance from the source center after which the measured dose was greater than that calculated. The determined neutron scattering calculated from the measured-to-calculate dose ratio increased from 7% to 25% with increased distances from 150 to 300 cm. Moreover, the standard dose used in the calibration should be measured by a standard neutron monitor at each distance due to the higher value of the room scattering contribution where the optimum distance for calibration was 150 cm. The combined uncertainty of the measured neutron dose was 4.04%.

Speeds of Sound in n-Hexane and n-Heptane at Temperatures from (233.33 to 353.21) K and Pressures up to 20 MPa

The speed of sound in high-purity n-hexane and n-heptane was experimentally studied utilizing the double-path length pulse-echo technique. Measurements with each alkane were carried out at temperatures from (233 to 353) K with pressures up to 20 MPa. Considering the uncertainty contributions from temperature, pressure, path-length calibration, pulse timing and sample purity, the relative expanded combined uncertainty (k = 2) in the speed of sound in n-hexane ranges from (0.012 to 0.042) % over the investigated ranges of pressure and temperature; for n-heptane, the uncertainty varies from (0.014 to 0.018) %. The sound speed data measured in n-hexane were among the data used for the development of a new fundamental equation of state, which is, however, not described in this work. The experimental data of n-heptane can be considered appropriate for modeling purposes and validation of existing equations of state.

Absorbed dose to water standard for 192Ir HDR sources using Fricke Dosimetry

The Fricke solution is a chemical dosimeter that is based on the oxidation of ferrous ions to ferric ions in the solution after interaction with ionizing radiation. It is composed of 96% water (by weight), and its density is thus remarkably similar to that of water. In addition, studies show that the Fricke dosimeter can be used as a primary dosimeter in the determination of the absorbed dose to water for high dose rate (HDR) 192Ir brachytherapy. The Radiological Sciences Laboratory of the University of Rio de Janeiro State (LCR/UERJ) has been investigating the use of the Fricke dosimeter in various applications for more than ten years, particularly in the area of radiotherapy. This review paper presents important improvements in recent years by the LCR/UERJ in the determination of the absorbed dose to water for 192Ir sources. This includes a newly designed irradiation vessel, a new reading device, a description of the need for careful temperature control during irradiation and reading, a more accurate calculation of the correction factors and the results of an intercomparison with the National Calibration Laboratory of Canada. Careful preparation of the Fricke solution is one of the most critical steps in the process. Over the years, the LCR/UERJ has tested different methods of preparing the solution and the final procedure is presented. Regarding the irradiation vessel, a molded double-walled, spherical flask for the Fricke solution was first constructed and used to measure the absorbed dose to water. However, as it was difficult to manipulate the spherical flask, a second design also made with PMMA was molded as a cylinder, with a central tube where the source was centrally positioned. Different methodologies have been reported in the determination of the G-value, a key parameter in Fricke dosimetry, and herein, two different methodologies used by the LCR are reviewed. For the absorbed-dose-to-water determination for 192Ir sources, the overall combined uncertainty associated with the measurements is estimated to be less than 1% for k = 1. Thus, the obtained uncertainties for the determination of the absorbed dose to water using Fricke dosimetry are lower than those obtained using the standard protocols. With respect to clinical practice, this could improve the accuracy in the calculation of the dose delivered to the patients. Overall, the results show that Fricke dosimetry is a reliable system to measure absorbed dose to water as a standard for HDR 192Ir.

Research on Absolute Calibration of GNSS Receiver Delay through Clock-Steering Characterization

The receiver delay has a significant impact on global navigation satellite system (GNSS) time measurement. This article comprehensively analyzes the difficulty, composition, principle, and calculation of GNSS receiver delay. A universal method, based on clock-steering characterization, is proposed to absolutely calibrate all types of receivers. We use a hardware simulator to design several experiments to test the performance of GNSS receiver delay for different receiver types, radio frequency (RF) signals, operation status and time-to-phase (TtP). At first, through the receivers of Novatel and Septentrio, the channel delay of Septentrio is 2 ns far lower than 65 ns for Novatel, and for the inter-frequency bias of GLONASS L1, Septentrio tends to increase within 10 ns compared with decreasing of Novatel within 5 ns. Secondly, a representative receiver of UniNav-BDS (BeiDou) is chosen to test the influence of Ttp which may be ignored by users. Under continuous operation, the receiver delay shows a monotone reduction of 10 ns as TtP increased by 10 ns. However, under on-off operation, the receiver delay represents periodic variation. Through a zero-baseline comparison, we verifies the relation between receiver delay and TtP. At last, the article analyzes instrument errors and measurement errors in the experiment, and the combined uncertainty of absolute calibration is calculated with 1.36 ns.