Stability of gaseous volatile organic compounds contained in gas cylinders with different internal wall treatments.

Measurements of volatile organic compounds (VOCs) have been ongoing for decades to track growth rates and assist in curbing emissions of these compounds into the atmosphere. To accurately establish mole fraction trends and assess the role of these gas-phase compounds in atmospheric chemistry it is essential to have good calibration standards. A necessity and precursor to accurate VOC gas standards are the gas cylinders and the internal wall treatments that aid in maintaining the stability of the mixtures over long periods of time, measured in years. This paper will discuss the stability of VOC gas mixtures in different types of gas cylinders and internal wall treatments. Stability data will be given for 85 VOCs studied in gas mixtures by National Metrology Institutes and other agency laboratories. This evaluation of cylinder treatment materials is the outcome of an activity of the VOC Expert Group within the framework of the World Meteorological Organization (WMO) Global Atmospheric Watch (GAW) program.

Calibration Strategies for FT-IR and Other Isotope Ratio Infrared Spectrometer Instruments for Accurate δ13C and δ18O Measurements of CO2 in Air.

This paper describes calibration strategies in laboratory conditions that can be applied to ensure accurate measurements of the isotopic composition of the CO2 in ultradry air, expressed as δ13C and δ18O on the VPDB scale, with either FT-IR (in this case a Vertex 70 V (Bruker)) or an isotope ratio infrared spectrometer (IRIS) (in this case a Delta Ray (Thermo Fisher Scientific)). In the case of FT-IR a novel methodology using only two standards of CO2 in air with different mole fractions but identical isotopic composition was demonstrated to be highly accurate for measurements of δ13C and δ18O with standard uncertainties of 0.09‰ and 1.03‰, respectively, at a nominal CO2 mole fraction of 400 µmol mol-1 in air. In the case of the IRIS system, we demonstrate that the use of two standards of CO2 in air of known but differing δ13C and δ18O isotopic composition allows standard uncertainties of 0.18‰ and 0.48‰ to be achieved for δ13C and δ18O measurements, respectively. The calibration strategies were validated using a set of five traceable primary reference gas mixtures. These standards, produced with whole air or synthetic air covered the mole fraction range of (378-420) µmol mol-1 and were prepared and/or value assigned either by the National Institute of Standards and Technology (NIST) or the National Physical Laboratory (NPL). The standards were prepared using pure CO2 obtained from different sources, namely, combustion; Northern Continental and Southern Oceanic Air and a gas well source, with δ13C values ranging between -35‰ and -1‰. The isotopic composition of all standards was value assigned at the Max Planck Institute for Biogeochemistry Jena (MPI-Jena).

Ozone Cross-Section Measurement by Gas Phase Titration.

Elevated values of ground-level ozone damage health, vegetation, and building materials and are the subject of air quality regulations. Levels are monitored by networks using mostly ultraviolet (UV) absorption instruments, with traceability to standard reference photometers, relying on the UV absorption of ozone at the 253.65 nm line of mercury. We have redetermined the ozone cross-section at this wavelength based on gas phase titration (GPT) measurements. This is a well-known chemical method using the reaction of ozone (O3) with nitrogen monoxide (NO) resulting in nitrogen dioxide (NO2) and oxygen (O2). The BIPM GPT facility uses state-of-the-art flow measurement, chemiluminescence for NO concentration measurements, a cavity phase shift analyzer (CAPS) for NO2 measurements, and a UV ozone analyzer. The titration experiment is performed over the concentration range 100-500 nmol/mol, with NO and NO2 reactants/calibrants diluted down from standards with nominal mole fractions of 50 µmol/mol. Accurate measurements of NO, NO2, and O3 mole fractions allow the calculation of ozone absorption cross section values at 253.65 nm, and we report a value of 11.24 × 10-18 cm2 molecule-1 with a relative expanded uncertainty of 1.8% (coverage factor k = 2) based on nitrogen monoxide titration values and a value of 11.22 × 10-18 cm2 molecule-1 with a relative expanded uncertainty of 1.4% (coverage factor k = 2) based on nitrogen dioxide titration values. The excellent agreement between these values and recently published absorption cross-section measurements directly on pure ozone provide strong evidence for revising the conventionally accepted value of ozone cross section at 253.65 nm.

Methane standards made in whole and synthetic air compared by cavity ring down spectroscopy and gas chromatography with flame ionization detection for atmospheric monitoring applications.

There is evidence that the use of whole air versus synthetic air can bias measurement results when analyzing atmospheric samples for methane (CH4) and carbon dioxide (CO2). Gas chromatography with flame ionization detection (GC-FID) and wavelength scanned-cavity ring down spectroscopy (WS-CRDS) were used to compare CH4 standards produced with whole air or synthetic air as the matrix over the mole fraction range of 1600-2100 nmol mol(-1). GC-FID measurements were performed by including ratios to a stable control cylinder, obtaining a typical relative standard measurement uncertainty of 0.025%. CRDS measurements were performed using the same protocol and also with no interruption for a limited time period without use of a control cylinder, obtaining relative standard uncertainties of 0.031% and 0.015%, respectively. This measurement procedure was subsequently used for an international comparison, in which three pairs of whole air standards were compared with five pairs of synthetic air standards (two each from eight different laboratories). The variation from the reference value for the whole air standards was determined to be 2.07 nmol mol(-1) (average standard deviation) and that of synthetic air standards was 1.37 nmol mol(-1) (average standard deviation). All but one standard agreed with the reference value within the stated uncertainty. No significant difference in performance was observed between standards made from synthetic air or whole air, and the accuracy of both types of standards was limited only by the ability to measure trace CH4 levels in the matrix gases used to produce the standards.

Accurate Fourier transform infrared (FT-IR) spectroscopy measurements of nitrogen dioxide (NO2) and nitric acid (HNO3) calibrated with synthetic spectra.

A novel method for determining the accuracy of laboratory-based measurements of nitrogen dioxide (NO2) and nitric acid (HNO3) mole fractions using Fourier transform infrared (FT-IR) spectroscopy 1 cm(-1) resolution instruments calibrated with synthetic spectra has been developed. The traceability of these measurement results is to the reference line strength data contained within the high-resolution transmission molecular absorption (HITRAN) database. Incorporating a proper estimate of the uncertainty of this data into the measurement results will ensure that the SI traceable values are encompassed within the uncertainty of the measurement results. The major contributors to the uncertainties of the results are, in descending order of importance, the uncertainty in the line strength values (HITRAN 2004), the uncertainty attributed to the generation of reference spectra (including knowledge of the optical path length of the FT-IR gas cell), and temperature measurements of the gas. The stability of the FT-IR instrument itself is only a minor contributor to the overall uncertainty of the measurements. FT-IR measurements of NO2 mole fractions at nominal values of 10 µmol mol(-1) calibrated with synthetic spectra lead to standard uncertainties of 0.34 µmol mol(-1) (3.4% relative). In contrast, calibration of the FT-IR instrument with SI traceable gas standards generated by a dynamic weighing system resulted in measurements results with standard uncertainties of 0.04 µmol mol(-1) (0.4% relative). When comparing the consistency of measurement results based on the synthetic calibration method against those obtained by calibrations with SI traceable gas standards, the existence of a potential bias of ~5% was observed, although this was within the stated uncertainties of the results. The FT-IR measurements of HNO3 mole fractions at nominal values of 200 nmol mol(-1) calibrated with synthetic spectra resulted in values with standard uncertainties of 23 nmol mol(-1) (11% relative) with the dominating uncertainty in this case arising from the stabilization of the mole fraction value within the FT-IR gas cell.

Temperature measurement and optical path-length bias improvement modifications to National Institute of Standards and Technology ozone reference standards.

UNLABELLED: Ambient ozone measurements in the United States and many other countries are traceable to a National Institute of Standards and Technology Standard Reference Photometer (NIST SRP). The NIST SRP serves as the highest level ozone reference standard in the United States, with NIST SRPs located at NIST and at many U.S. Environmental Protection Agency (EPA) laboratories. The International Bureau of Weights and Measures (BIPM) maintains a NIST SRP as the reference standard for international measurement comparability through the International Committee of Weights and Measures (CIPM). In total, there are currently NIST SRPs located in 20 countries for use as an ozone reference standard. A detailed examination of the NIST SRP by the BIPM and NIST has revealed a temperature gradient and optical path-length bias inherent in all NIST SRPs. A temperature gradient along the absorption cells causes incorrect temperature measurements by as much as 2 degrees C. Additionally, the temperature probe used for temperature measurements was found to inaccurately measure the temperature of the sample gas due to a self-heating effect. Multiple internal reflections within the absorption cells produce an actual path length longer than the measured fixed length used in the calculations for ozone mole fractions. Reflections from optical filters located at the exit of the absorption cells add to this effect. Because all NIST SRPs are essentially identical, the temperature and path-length biases exist on all units by varying amounts dependent upon instrument settings, laboratory conditions, and absorption cell window alignment. This paper will discuss the cause of and physical modifications for reducing these measurement biases in NIST SRPs. Results from actual NIST SRP bias upgrades quantifying the effects of these measurement biases on ozone measurements are summarized. IMPLICATIONS: NIST SRPs are maintained in laboratories around the world underpinning ozone measurement calibration and traceability within and between countries. The work described in this paper quantifies and shows the reduction of instrument biases in NIST SRPs improving their overall agreement. This improved agreement in all NIST SRPs provides a more stable baseline for ozone measurements worldwide.

Highly accurate nitrogen dioxide (NO2) in nitrogen standards based on permeation.

The development and operation of a highly accurate primary gas facility for the dynamic production of mixtures of nitrogen dioxide (NO(2)) in nitrogen (N(2)) based on continuous weighing of a permeation tube and accurate impurity quantification and correction of the gas mixtures using Fourier transform infrared spectroscopy (FT-IR) is described. NO(2) gas mixtures in the range of 5 µmol mol(-1) to 15 µmol mol(-1) with a standard relative uncertainty of 0.4% can be produced with this facility. To achieve an uncertainty at this level, significant efforts were made to reduce, identify and quantify potential impurities present in the gas mixtures, such as nitric acid (HNO(3)). A complete uncertainty budget, based on the analysis of the performance of the facility, including the use of a FT-IR spectrometer and a nondispersive UV analyzer as analytical techniques, is presented in this work. The mixtures produced by this facility were validated and then selected to provide reference values for an international comparison of the Consultative Committee for Amount of Substance (CCQM), number CCQM-K74, (1) which was designed to evaluate the consistency of primary NO(2) gas standards from 17 National Metrology Institutes.