System Of Units Traceability Research Articles

Magnification calibration of X-ray 3D microscopy using micro-line structures.

X-ray microscopy using computed tomography (CT) is an excellent three-dimensional imaging instrument. Three-dimensional X-ray microscopy (3DXRM) is a nondestructive imaging technique used to inspect internal and external structures in units of submicrometers or less. The 3DXRM, although attractive, is mostly used as an observation instrument and is limited as a measurement system in quantitative evaluation and quality control. Calibration is required for use in measurement systems such as coordinate measurement systems, and specific standard samples and evaluation procedures are needed. The certified values of the standard samples must ideally be traceable to the International System of Units (SI). In the 3DXRM measurement system, line structures (LSs) are fabricated as prototype standard samples to conduct magnification calibration. In this study, we evaluated the LS intervals using calibrated cross-sectional scanning electron microscopy (SEM). A comparison of the evaluation results between SEM and 3DXRM for the LS intervals provided the magnification calibration factor for 3DXRM and validated the LSs, whereby the interval methods and feasibility of constructing an SI traceability system were evaluated using the calibrated SEM. Consequently, a magnification calibration factor of 1.01 was obtained for 3DXRM based on the intervals of the LSs evaluated by SEM. A possible route for realizing SI-traceable magnification calibration of 3DXRM has been presented.

Development of a Primary Iridium Solution Standard Traceable to the International System of Units.

The purpose of this work was to develop a primary solution standard for iridium (Ir) that is directly traceable to the International System of Units (SI). The candidate starting material was ammonium hexachloroiridate hydrate, ((NH4)3IrCl6·3H2O), the Ir salt. The SI traceability of the Ir salt was established by the gravimetric reduction (GR) of the salt to the metal under H2. GR traces the results of the analysis directly to the SI base unit of mass, the kg. The GR was also performed on high-purity Ir metal powder, an independent source of Ir, used as a comparison material for the salt. A method for dissolving the Ir metal was developed by modifying information found in the literature. Trace metallic impurities (TMI) analysis was performed on the Ir salt using ICP-OES and ICP-MS. Inert gas fusion (IGF) analysis provided data for the O, N, and H content of the gravimetrically reduced and unreduced Ir metals. The combined results of the TMI and IGF analyses provided the purity data, a required component for the claim to SI traceability. Solution standards were gravimetrically prepared from the candidate SI traceable Ir salt. Solution standards for comparison were prepared from the dissolved, unreduced high-purity Ir metal powder. These solutions were compared by a high-precision ICP-OES method. Agreement in the results between these Ir solutions, with uncertainty estimates calculated by error budget analysis, confirmed the accuracy of the Ir assay in the candidate SI traceable Ir salt, (NH4)3IrCl6·3H2O, thus confirming the concentrations and uncertainties for the primary SI traceable Ir solution standards made from the (NH4)3IrCl6·3H2O.

On the way to SI traceable primary transfer standards for amount of substance measurements in inorganic chemical analysis

During its 25 years of existence, the Inorganic Analysis Working Group of the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM IAWG) has achieved much in establishing comparability of measurement results. Impressive work has been done on comparison exercises related to real-world problems in fields such as ecology, food, or health. In more recent attempts, measurements and comparisons were focused on calibration solutions which are the basis of most inorganic chemical measurements. This contribution deals with the question of how to achieve full and transparent SI traceability for the values carried by such solutions. Within this framework, the use of classical primary methods (CPMs) is compared to the use of a primary difference method (PDM). PDM is a method with a dual character, namely a metrological method with a primary character, based on the bundling of many measurement methods for individual impurities, which lead to materials with certified content of the main component. As in classical methods, where small corrections for interferences are accepted, in PDM, many small corrections are bundled. In contrast to classical methods, the PDM is universally applicable to all elements in principle. Both approaches can be used to certify the purity (expressed as mass fraction of the main element) of a high-purity material. This is where the metrological need of National Metrology Institutes (NMIs) for analytical methods meet the challenges of analytical methods. In terms of methods, glow discharge mass spectrometry (GMDS) with sufficient uncertainties for sufficiently small impurity contents is particularly noteworthy for the certification of primary transfer standards (PTS), and isotope dilution mass spectrometry (IDMS), which particularly benefits from PTS (back-spikes) with small uncertainties, is particularly noteworthy for the application. The corresponding relative uncertainty which can be achieved using the PDM is very low (< 10−4). Acting as PTS, they represent the link between the material aspect of the primary calibration solutions and the immaterial world of the International System of Units (SI). The underlying concepts are discussed, the current status of implementation is summarised, and a roadmap of the necessary future activities in inorganic analytical chemistry is sketched. It has to be noted that smaller measurement uncertainties of the purity of high-purity materials not only have a positive effect on chemical measurements, but also trigger new developments and findings in other disciplines such as thermometry or materials science.Graphical Primary Transfer Standards (PTSs) are the link between the immaterial world of the International System of Units (SI) and the material aspects of the primary calibration solutions.

Tracing an Osmium Solution Standard to the International System of Units (SI).

The purpose of this work was to develop an accurate osmium (Os) solution standard that is traceable to the International System of Units, the SI. A gravimetric reduction (GR) method was developed to accurately assay the Os in ammonium hexachloroosmate salt, (NH4)2OsCl6, the chosen starting material for the Os solution standard. This GR method was also applied to -200 mesh high-purity Os metal powder, which served as an independent source of Os for comparison. An alkali fusion method was developed to create water-soluble salts from the Os metal GR products of both the (NH4)2OsCl6 and -200 mesh high-purity Os metal powder. Quantitatively prepared Os solutions from each of these water-soluble salts were compared by inductively coupled plasma spectrometry, ICP-OES. The purities of the Os starting materials were determined by quantitatively performed trace metallic impurities analysis, by ICP-OES and ICP-MS; the O, N, and H impurities were determined by inert gas fusion analysis. The percent purities of the starting materials were applied as corrections to the Os assay results obtained by GR. The agreement between these Os solutions, corrected for random and systematic errors by error budget analysis, confirmed the accuracy of the Os assay in the (NH4)2OsCl6. The SI traceability of the Os assay in the (NH4)2OsCl6 salt was established through the GR procedure and the purity analysis of this material. An SI traceable Os solution standard was gravimetrically prepared from this batch of (NH4)2OsCl6, based on the accurate Os assay and the percent purity of the starting material.

Traceable Radiometry Underpinning Terrestrial- and Helio-Studies (TRUTHS): An Element of a Space-Based Climate and Calibration Observatory

The Earth’s climate is undoubtedly changing; however, the time scale, consequences, and causal attribution remain the subject of significant debate and uncertainty. Detection of subtle indicators from a background of natural variability requires measurements over a time-base of decades. This places severe demands on the instrumentation used, requiring measurements of sufficient accuracy and sensitivity that can allow reliable judgements to be made decades apart. The International System of Units (SI) was developed to address such requirements, providing a reference framework tied to invariant constants of nature. However, ensuring and maintaining SI traceability of sufficient accuracy in instruments orbiting the Earth presents a significant new challenge to the Earth Observation and metrology communities. This paper describes a new satellite mission, called Traceable Radiometry Underpinning Terrestrial- and Helio- Studies (TRUTHS), which enables, for the first time, high-accuracy SI traceability to be established in orbit. The direct use of a ‘primary standard’ and replication of the terrestrial traceability chain extends the SI into space, in effect realizing a ‘metrology laboratory in space’ providing and enabling SI-traceable measurements of unequivocal accuracy in the solar reflective domain—an enabling element of an international space-based climate observing system. TRUTHS will not only provide a benchmark of the radiation state of the planet (incoming and outgoing) from which to compare change in the shortest time possible, but also facilitate an upgrade in performance of the Earth Observing system as a whole, through ‘in-orbit’ reference calibration.

Calibration of a torque measuring device using an electromagnetic force torque standard machine

To realize a microtorque standard, we have been investigating the principle of torque generation with an electromagnetic force by referring to the Kibble balance method used for the redefinition of the kilogram in the International System of Units (SI). In a previous study, we developed an electromagnetic force torque standard machine (EMTSM) to create precise torque using the Kibble balance method and realize an SI-traceable, non-gravity-based torque standard. To assure the SI traceability of torque standards used in Japanese industry, it is necessary to apply the calibration procedure for torque measuring devices (TMDs) described in the Japan Measuring Instruments Federation guideline JMIF-015 when calibrating TMDs with torque standard machines (TSMs). In this study, we developed a calibration procedure for TMDs using the EMTSM with calibration procedures based on JMIF-015. In addition, we introduced a highly accurate programmable voltage/current source to expand the calibration range of the EMTSM to 0.27 μN∙m to 100 mN∙m. The relative expanded uncertainty Wtsm_e of the torque realized by the EMTSM was evaluated to be 1.7 × 10−3, with a coverage factor k of 2 over this torque range. The calibration results for a low-capacity TMD using the EMTSM with calibration procedures based on JMIF-015 were equivalent to those of a typical strain gauge torque transducer calibrated using a deadweight torque standard machine.

Nitrogen content of amidosulfuric acid assayed by coulometric titration with electrogenerated hypobromite ions: establishment of SI traceability of nitrogen involving amidosulfuric acid, ammonium chloride and sodium chloride

The nitrogen content of amidosulfuric acid was first measured directly by coulometric titration. Ammonium ions generated by decomposition of amidosulfuric acid were oxidized with electrogenerated hypobromite ions to nitrogen gas, and the amount of which was linked to the International System of Units (SI) based on Faraday’s laws of electrolysis. Conditions of the decomposition in an acidic medium were examined under different periods of heating. The comprehensive evaluation of the measurement uncertainties for amidosulfuric acid as an acid and as nitrogen was carried out, resulting in the establishment of a certified reference material (CRM) for both measurands with SI traceability. A novel measurement method for nitrogen content of amidosulfuric acid was ascertained. The relationship of three materials, amidosulfuric acid, ammonium chloride and sodium chloride, was also presented. The traceability among three materials was clarified through three different reactions, neutralization, oxidation-reduction and precipitation reactions. The assays of these materials were all consistent; consequently, the accuracy of measurement methods used was ascertained. Providing the CRM with the SI traceable nitrogen content enables one to obtain reliable analytical data in several applications such as the Kjeldahl method.

Accurate determination of formaldehyde amount fraction in cylinders using mixtures of primary standards of formaldehyde in nitrogen prepared by a gravimetric permeation method

A reliable method for the quantification of formaldehyde (HCHO) amount fractions is required, because the results of comparisons between individual techniques used for the quantification of HCHO amount fractions often disagree owing to unknown causes. One reliable method comprises the quantification of HCHO using working gas standards in which the HCHO amount fraction is linked to the International System of Units (SI). In this work, the SI traceability of HCHO amount fractions in mixtures of commercial HCHO in nitrogen in cylinders used as working gas standards was established by calibrating them against primary gas standard mixtures (mixtures of HCHO in N2), which were prepared by a permeation method and were traceable to SI. The expanded relative uncertainties (k = 2) of the amount fractions in the primary gas standard mixtures were less than 0.6 %. The quantitative values of the amount fractions in the working gas standards had relative expanded uncertainties (k = 2) of 0.7 %–0.9 %.

Establishment of an analytical method for accurate purity evaluations of acylcarnitines by using quantitative 1H NMR spectroscopy

Recently, it has become possible to examine metabolism abnormalities by detecting increases in specific acylcarnitines in blood tests of newborn babies using tandem mass spectrometer. However, acylcarnitine standard solutions with metrological traceability to the International System of Units (SI) for accurate calibration of tandem mass spectrometer are not yet available worldwide. In this study, we examined a quantitative 1H NMR procedure for obtaining accurate and SI-traceable purity evaluations of acylcarnitines having different numbers of carbon atoms as each raw material for their standard solutions. In particular, the solvent composition and measurement temperature were optimized to reduce the influence of water signal overlapping on analyte signals. It was found that, when the signal of that 1H which directly bound to the asymmetric carbon of the acylcarnitine is the target signal, it was possible to reduce overlapping of the water signal on the target signal by using deuterium oxide as a solvent. On the other hand, in the case of an acylcarnitine that was poorly soluble in deuterium oxide, it was possible to reduce overlapping of the water signal on the target signal by adding an appropriate amount of deuterium oxide to methanol-d 4 in which the acylcarnitine had high solubility. At this time, the optimum mixing volume ratio of methanol-d 4/deuterium would be 80:20. The overlapping of the water signal could be also reduced when the measurement temperature was 15 °C to 40 °C. When the measurement temperature was an around room temperature (in this study, 25 °C), fine shimming could be performed easily. Therefore, the optimum temperature would be 25 °C, because fine shimming was essential to quantify any signal area accurately. Finally, this study confirmed that accurate values with SI traceability could be obtained at about 1 % or less expanded uncertainty for five kinds of acylcarnitines.

A gravimetric approach to providing SI traceability for concentration measurement results of mercury vapor at ambient air levels

Current measurement and calibration capabilities for mercury vapor in air are maintained at levels of 0.2–40 μg Hg m−3. In this work, a mercury vapor generator has been developed to establish metrological traceability to the international system of units (SI) for mercury vapor measurement results ≤15 ng Hg m−3, i.e. closer to realistic ambient air concentrations (1–2 ng Hg m−3) [].Innovations developed included a modified type of diffusion cell, a new measurement method to weigh the loss in (mercury) mass of these diffusion cells during use (ca. 6–8 μg mass difference between successive weighings), and a new housing for the diffusion cells to maximize flow characteristics and to minimize temperature variations and adsorption effects.The newly developed mercury vapor generator system was tested by using diffusion cells generating 0.8 and 16 ng Hg min−1. The results also show that the filter system, to produce mercury free air, is working properly. Furthermore, and most importantly, the system is producing a flow with a stable mercury vapor content.Some additional improvements are still required to allow the developed mercury vapor generator to produce SI traceable mercury vapor concentrations, based upon gravimetry, at much lower concentration levels and reduced measurement uncertainties than have been achieved previously. The challenges to be met are especially related to developing more robust diffusion cells and better mass measurement conditions.The developed mercury vapor generator will contribute to more reliable measurement results of mercury vapor at ambient and background air levels, and also to better safety standards and cost reductions in industrial processes, such as the liquefied natural gas field, where aluminum main cryogenic heat exchangers are used which are particularly prone to corrosion caused by mercury.

ACRIM3 and the Total Solar Irradiance database

The effects of scattering and diffraction on the observations of the ACRIMSAT/ACRIM3 satellite TSI monitoring mission have been characterized by the preflight calibration approach for satellite total solar irradiance (TSI) sensors implemented at the LASP/TRF (Laboratory for Atmospheric and Space Physics/Total Solar Irradiance Radiometer Facility). The TRF also calibrates the SI (International System of units) traceability to the NIST (National Institute of Standards and Technology) cryo-radiometric scale. ACRIM3’s self-calibration agrees with NIST to within the uncertainty of the test procedure (∼500 ppm). A correction of ∼5000 ppm was found for scattering and diffraction that has significantly reduced the scale difference between the results of the ACRIMSAT/ACRIM3 and SORCE/TIM satellite experiments. Algorithm updates reflecting more than 10 years of mission experience have been made that further improve the ACRIM3 results by eliminating some thermally driven signal and increasing the signal to noise ratio. The result of these changes is a more precise and detailed picture of TSI variability. Comparison of the results from the ACRIM3, SORCE/TIM and SOHO/VIRGO satellite experiments demonstrate the near identical detection of TSI variability on all sub-annual temporal and amplitude scales during the TIM mission. The largest occurs at the rotational period of the primary solar activity longitudes. On the decadal timescale, while ACRIM3 and VIRGO results exhibit close agreement throughout, TIM exhibits a consistent 500 ppm upward trend relative to ACRIM3 and VIRGO. A solar magnetic activity area proxy for TSI has been used to demonstrate that the ACRIM TSI composite and its +0.037 %/decade TSI trend during solar cycles 21–23 is the most likely correct representation of the extant satellite TSI database. The occurrence of this trend during the last decades of the 20th century supports a more robust contribution of TSI variation to detected global temperature increase during this period than predicted by current climate models.

A Second-Generation Blackbody System for the Calibration and Verification of Seagoing Infrared Radiometers

AbstractQuasi-operational shipborne radiometers provide a fiducial reference measurement (FRM) for satellite validation of satellite sea surface skin temperature (SSTskin) retrievals. External reference blackbodies are required to verify the performance and to quantify the accuracy of the radiometer calibration system. They provide a link in an unbroken chain of comparisons between the shipborne radiometer and a traceable reference standard. A second-generation water bath blackbody reference radiance source has been developed for this purpose. The second generation Concerted Action for the Study of the Ocean Thermal Skin (CASOTS-II) blackbody has a 110-mm-diameter aperture cylinder-cone geometry coated with NEXTEL suede 3103 paint. Interchangeable aperture stops reduce the cavity aperture diameter and minimize stray radiation. Monte Carlo modeling techniques show the effective emissivity of the cavity to be &gt;0.9999 (aperture &lt; 30 mm). The cavity is immersed in a water bath that is vigorously stirred using a pump that slowly heats the water bath at a mean rate of ~0.6 K h−1. The temperature of the water bath is measured using a thermometer traceable to the International System of Units (SI) standards. The worst-case radiance temperature of the CASOTS-II blackbody system is traceable to the SI with an uncertainty of 58 mK (millikelvin). When operating under typical laboratory conditions using an aperture of 40 mm, the uncertainty is 16 mK. An intercomparison with the U.K. National Physical Laboratory Absolute Measurements of Blackbody Emitted Radiance (AMBER) reference radiometer found no significant differences within 75 mK (110-mm aperture) or 50 mK (40-mm aperture), which is the combined uncertainty of the comparison and the reference standard for SI traceability of ISAR radiometer SSTskin records used for satellite SST validation. Applications of the CASOTS-II blackbody to monitor the calibration of shipborne radiometers are described and measurement protocols are proposed.

Accurate radiometry from space: an essential tool for climate studies

The Earth's climate is undoubtedly changing; however, the time scale, consequences and causal attribution remain the subject of significant debate and uncertainty. Detection of subtle indicators from a background of natural variability requires measurements over a time base of decades. This places severe demands on the instrumentation used, requiring measurements of sufficient accuracy and sensitivity that can allow reliable judgements to be made decades apart. The International System of Units (SI) and the network of National Metrology Institutes were developed to address such requirements. However, ensuring and maintaining SI traceability of sufficient accuracy in instruments orbiting the Earth presents a significant new challenge to the metrology community. This paper highlights some key measurands and applications driving the uncertainty demand of the climate community in the solar reflective domain, e.g. solar irradiances and reflectances/radiances of the Earth. It discusses how meeting these uncertainties facilitate significant improvement in the forecasting abilities of climate models. After discussing the current state of the art, it describes a new satellite mission, called TRUTHS, which enables, for the first time, high-accuracy SI traceability to be established in orbit. The direct use of a 'primary standard' and replication of the terrestrial traceability chain extends the SI into space, in effect realizing a 'metrology laboratory in space'.

A methodology for obtaining on-orbit SI-traceable spectral radiance measurements in the thermal infrared

A methodology to achieve spectral thermal radiance measurements from space with demonstrable on-orbit traceability to the International System of Units (SI) is described. This technique results in measurements of infrared spectral radiance , with spectral index in cm−1, with a relative combined uncertainty of 0.0015 (k = 1) for the average mid-infrared radiance emitted by the Earth. This combined uncertainty, expressed in brightness temperature units, is equivalent to ±0.1 K at 250 K at 750 cm−1. This measurement goal is achieved by utilizing a new method for infrared scale realization combined with an instrument design optimized to minimize component uncertainties and admit tests of radiometric performance. The SI traceability of the instrument scale is established by evaluation against source-based and detector-based infrared scales in defined laboratory protocols before launch. A novel strategy is executed to ensure fidelity of on-orbit calibration to the pre-launch scale. This strategy for on-orbit validation relies on the overdetermination of instrument calibration. The pre-launch calibration against scales derived from physically independent paths to the base SI units provides the foundation for a critical analysis of the overdetermined on-orbit calibration to establish an SI-traceable estimate of the combined measurement uncertainty. Redundant calibration sources and built-in diagnostic tests to assess component measurement uncertainties verify the SI traceability of the instrument calibration over the mission lifetime. This measurement strategy can be realized by a practical instrument, a prototype Fourier-transform spectrometer under development for deployment on a small satellite. The measurement record resulting from the methodology described here meets the observational requirements for climate monitoring and climate model testing and improvement.

Characterization of a New Certified Reference Material for Human Cardiac Troponin I

To address the continuing need for the standardization of clinical human cardiac troponin I (cTnI) assays, NIST, with the assistance of the AACC/IFCC Cardiac Troponin I Standardization Committee, has developed a new certified reference material, Standard Reference Material (SRM) 2921: Human Cardiac Troponin Complex. The concentration of cTnI in SRM 2921 was determined through a combination of reversed-phase liquid chromatography (LC) with ultraviolet detection and amino acid analysis. Characterization of the intact troponin subunits was accomplished through reversed-phase LC coupled with mass spectrometry. Posttranslational modifications to the cTnI in SRM 2921 were investigated by combining proteolytic digestion with matrix-assisted laser desorption/ionization mass spectrometry. Additionally, reference concentration values for cTnT and cTnC were also determined. The concentration of human cTnI in SRM 2921 is 31.2 (1.4) mg/L (where 1.4 mg/L is the uncertainty at a 95% level of confidence), as certified through a method that provides traceability to the International System of Units (SI). Reference concentration values of the cTnT and cTnC subunits were determined to be 36.9 (3.8) mg/L and 24.2 (1.3) mg/L, respectively. This first cTnI reference material should provide SI traceability to clinical cTnI assays once commutability has been validated, and could assist in the international harmonization of cTnI assays as a tool for understanding the underlying causes of interassay variability.