Rhoderick, GC, et al. 2019. Stability of gaseous volatile organic compounds contained in gas cylinders with different internal wall treatments. Elem Sci Anth, 7: 28.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.
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.
Studies of climate change increasingly recognize the diverse influences of hydrocarbons in the atmosphere, including roles in particulates and ozone formation. Measurements of key nonmethane hydrocarbons (NMHCs) suggest atmospheric mole fractions ranging from low picomoles per mol (ppt) to nanomoles per mol (ppb), depending on location and compound. To accurately establish mole fraction trends and to relate measurement records from many laboratories and researchers, it is essential to have accurate, stable, calibration standards. In February of 2008, the National Institute of Standards and Technology (NIST) developed and reported on picomoles per mol standards containing 18 nonmethane hydrocarbon compounds covering the mole fraction range of 60 picomoles per mol to 230 picomoles per mol. The stability of these gas mixtures was only characterized over a short time period (2 to 3 months). NIST recently prepared a suite of primary standard gas mixtures by gravimetric dilution to ascertain the stability of the 2008 picomoles per mol NMHC standards suite. The data from this recent chromatographic intercomparison of the 2008 to the 2011 suites confirm a much longer stability of almost 5 years for 15 of the 18 hydrocarbons; the double-bonded alkenes of propene, isobutene, and 1-pentene showed instability, in line with previous publications. The agreement between the gravimetric values from preparation and the analytical mole fractions determined from regression illustrate the internal consistency of the suite within ±2 pmol/mol. However, results for several of the compounds reflect stability problems for the three double-bonded hydrocarbons. An international intercomparison on one of the 2008 standards has also been completed. Participants included National Metrology Institutes, United States government laboratories, and academic laboratories. In general, results for this intercomparison agree to within about ±5% with the gravimetric mole fractions of the hydrocarbons.
Abstract. The measurement of gaseous pollutants in air is a sensitive and priority issue that has a large impact on human health and environment. The European Directive on "Ambient air quality and cleaner air for Europe" (2008/50/EC) sets limit values and data quality objectives for the measurement in EU member states of air pollutants in ambient air. Although no harmonized legislation is currently present for the monitoring of indoor air, the concern on the exposure to indoor chemical pollutants is clearly increasing. The Joint Research Project MACPoll (Metrology for Chemical Pollutants in Air), running under the European Metrology Research Program, addresses the need to improve the metrological traceability and comparability of measurements using current air monitoring techniques and the need to set up a metrological bases for the new sensor technologies used in air quality applications.
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