Improving Interoperability by Incorporating UnitsML Into Markup Languages.

Maintaining the integrity of analytical data over time is a challenge. Years ago, data were recorded on paper that was pasted directly into a laboratory notebook. The digital age has made maintaining the integrity of data harder. Nowadays, digitized analytical data are often separated from information about how the sample was collected and prepared for analysis and how the data were acquired. The data are stored on digital media, while the related information about the data may be written in a paper notebook or stored separately in other digital files. Sometimes the connection between this "scientific meta-data" and the analytical data is lost, rendering the spectrum or chromatogram useless. We have been working with ASTM Subcommittee E13.15 on Analytical Data to create the Analytical Information Markup Language or AnIML-a new way to interchange and store spectroscopy and chromatography data based on XML (Extensible Markup Language). XML is a language for describing what data are by enclosing them in computer-useable tags. Recording the units associated with the analytical data and metadata is an essential issue for any data representation scheme that must be addressed by all domain-specific markup languages. As scientific markup languages proliferate, it is very desirable to have a single scheme for handling units to facilitate moving information between different data domains. At NIST, we have been developing a general markup language just for units that we call UnitsML. This presentation will describe how UnitsML is used and how it is being incorporated into AnIML.

Qualification of a fluorescence spectrometer for measuring true fluorescence spectra.

New analytical methods using fluorescence detection are becoming increasingly quantitative and require easy-to-use material standards for fluorometer qualification and method validation. NIST is responding to this need by developing and producing such standards. Reported here is the first step in this process, which is to qualify a research-grade fluorescence spectrometer for measuring true fluorescence spectra of reference material candidates. "True" spectra are defined here as those with fluorescence intensity, either relative or absolute as required, and wavelength both being reported with high accuracy and known precision, after wavelength has been calibrated and corrections for excitation intensity and detection system response have been applied. The uncertainties determined in relative and absolute intensity-corrected fluorescence spectra using both calibrated source (CS)- and calibrated detector (CD)-based methods were compared. The CS-based method gave uncertainties, typically about +/-5% for relative spectral correction, that were about half that of the CD-based method for determining both relative and absolute spectral correction factors. Absolute spectral correction factors can be determined using either method without knowing the optical geometry of the instrument. The absolute spectral correction factors were found to have much larger uncertainties than the corresponding relative correction factors with uncertainties for the CS-based method of +/-10% to +/-15% being typical and +/-20% or more not being uncommon, particularly for excitation and emission wavelengths below 400 nm. Uncertainties arising from detection system nonlinearity and instrument polarization ratios were also explored.

An international evaluation of holmium oxide solution reference materials for wavelength calibration in molecular absorption spectrophotometry.

Commercial spectrophotometers typically use absorption-based wavelength calibration reference materials to provide wavelength accuracy for their applications. Low-mass fractions of holmium oxide (Ho2O3) in dilute acidic aqueous solution and in glass matrixes have been favored for use as wavelength calibration materials on the basis of spectral coverage and absorption band shape. Both aqueous and glass Ho2O3 reference materials are available commercially and through various National Metrology Institutes (NMIs). Three NMIs of the North American Cooperation in Metrology (NORAMET) have evaluated the performance of Ho3-(aq)-based Certified Reference Materials (CRMs) under "routine" operating conditions using commercial instrumentation. The study was not intended to intercompare national wavelength scales but to demonstrate comparability of wavelength measurements among the participants and between two versions of the CRMs. It was also designed to acquire data from a variety of spectrophotometers for use in a NIST study of wavelength assignment algorithms and to provide a basis for a possible reassessment of NIST-certified Ho3+(aq) band locations. The resulting data show a substantial level of agreement among laboratories, instruments, CRM preparations, and peak-location algorithms. At the same time, it is demonstrated that the wavelength comparability of the five participating instruments can actually be improved by calibrating all of the instruments to the consensus Ho3+(aq) band locations. This finding supports the value of absorption-based wavelength standards for calibrating absorption spectrophotometers. Coupled with the demonstrated robustness of the band position values with respect to preparation and measurement conditions, it also supports the concept of extending the present approach to additional NMIs in order to certify properly prepared dilute acidic Ho2O3 solution as an intrinsic wavelength standard.