Towards an Optical Gas Standard for Traceable Calibration-Free and Direct NO2 Concentration Measurements

We report a direct tunable diode laser absorption spectroscopy (dTDLAS) instrument developed for NO2 concentration measurements without chemical pre-conversion, operated as an Optical Gas Standard (OGS). An OGS is a dTDLAS instrument that can deliver gas species amount fractions (concentrations), without any previous or routine calibration, which are directly traceable to the international system of units (SI). Here, we report NO2 amount fraction quantification in the range of 100–1000 µmol/mol to demonstrate the current capability of the instrument as an OGS for car exhaust gas application. Nitrogen dioxide amount fraction results delivered by the instrument are in good agreement with certified values of reference gas mixtures, validating the capability of the dTDLAS-OGS for calibration-free NO2 measurements. As opposed to the standard reference method (SRM) based on chemiluminescence detection (CLD) where NO2 is indirectly measured after conversion to NO, titration with O3 and the detection of the resulting fluorescence, a dTDLAS-OGS instrument has the benefit of directly measuring NO2 without distorting or delaying conversion processes. Therefore, it complements the SRM and can perform fast and traceable measurements, and side-by-side calibrations of other NO2 gas analyzers operating in the field. The relative standard uncertainty of the NO2 results reported in this paper is 5.1% (k = 1, which is dominated (98%) by the NO2 line strength), the repeatability of the results at 982.6 µmol/mol is 0.1%, the response time of the instrument is 0.5 s, and the detection limit is 825 nmol/mol at a time resolution of 86 s.

Comparability of calibration strategies for measuring mercury concentrations in gas emission sources and the atmosphere

A primary mercury gas standard was developed at Van Swinden Laboratory (VSL) to establish an International System of Units (SI)-traceable reference point for mercury concentrations at emission and background levels in the atmosphere. The majority of mercury concentration measurements are currently made traceable to the empirically determined vapour pressure of mercury. The primary mercury gas standard can be used for the accurate and precise calibration of analytical systems used for measuring mercury concentrations in air. It has been especially developed to support measurements related to ambient air monitoring (1–2 ng m−3), indoor and workplace-related mercury concentration levels according to health standards (from 50 ng m−3 upwards) as well as stationary source emissions (from 1 µg m−3 upwards). The primary mercury gas standard is based on diffusion according to ISO 6154-8. Calibration gas mixtures are obtained by combining calibrated mass flows of nitrogen and air through a generator holding diffusion cells containing elemental mercury. In this paper, we present the results of comparisons between the primary gas standard and mercury calibration methods maintained by NPL (National Physical Laboratory in the United Kingdom), a National Metrology Institute (NMI), and the Jozef Stefan Institute (JSI), a Designated Institute (DI). The calibration methods currently used at NPL and JSI are based on the bell-jar calibration apparatus in combination with the Dumarey equation or a NIST (National Institute of Standards and Technology in the United States) reference material. For the comparisons, mercury was sampled on sorbent traps to obtain transfer standards with levels between 2 and 1000 ng with an expanded uncertainty not exceeding 3 % (k=2). The comparisons performed show that the results for the primary gas standard and the NIST reference material are comparable, whereas a difference of −8 % exists between results traceable to the primary gas standard and the Dumarey equation.

Comparability of calibration strategies for measuring mercury concentrations in gas emission sources and the atmosphere

A primary mercury gas standard was developed at VSL to establish an SI-traceable reference point for mercury concentrations at emission and background levels in the atmosphere. The majority of mercury concentration measurements are currently made traceable to the empirically determined vapour pressure of mercury. The primary mercury gas standard can be used for the accurate and precise calibration of analytical systems used for measuring mercury concentrations in air. It has been especially developed to support measurements related to ambient air monitoring (1 ng m−3–2 ng m−3), indoor and workplace related mercury concentration levels according to health standards (from 50 ng m−3 upwards) as well as to stationary source emissions (from 1 µg m−3 upwards). The primary mercury gas standard is based on diffusion according to ISO 6154-8. Calibration gas mixtures are obtained by combining calibrated mass flows of nitrogen and air through a generator holding diffusion cells, containing elemental mercury. In this paper, we present the results of comparisons between the primary standard and mercury calibration methods maintained by NPL, a National Metrology Institute (NMI), and JSI, a Designated Institute (DI). The calibration methods currently used at NPL and JSI are based on the bell-jar calibration apparatus in combination with the Dumarey equation or a NIST reference material. For the comparisons, mercury was sampled on sorbent traps to obtain transfer standards with levels between 2 ng and 1000 ng with an expanded uncertainty not exceeding 3 % (k = 2). The comparisons performed show that the results for the primary standard and the NIST reference material are comparable, whereas a difference of −8 % exists between results traceable to the primary standard and the Dumarey equation.

Performance analysis of a pressure swing adsorption unit in removing biogas impurities using zeolite 13X

This study aims to assess the performance of a Pressure Swing Adsorption (PSA) unit in removing the carbon dioxide from biogas by evaluating the breakthrough and adsorption capacity of the adsorption process as well as determining the effects of cyclic regeneration of the adsorbent. The PSA system developed and composed only a main vessel made up of 316 stainless steel components. It was then operated up to 10 bars pressure at ambient temperatures and gas flows at a rate from 0 to 15 L min-1. Use of physical adsorbent (zeolite 13X) will consume the gaseous impurities such as CO2. Product gas was collected into 1 L Tedlar bags and analyzed using SRI gas chromatograph with TCD and HID detector to validate the CO2 and CH4 composition. The results of the pressure swing adsorption (PSA) experiments showed an average increase of 160% in the net heating value over that of a certified gas standard. The amount of methane was also significantly higher although the amount of the other gasses (i.e. nitrogen) remained comparatively the same. The number of other gases was significantly lower and leaving no traces of carbon dioxide was observed in the PSA system product gas indicating that carbon dioxide had been completely adsorbed by the system. This study greatly helps to reduce CO2 emitted to the atmosphere from the anaerobic co-digestion of biogas to produce high energy content bio-methane fuel.

Preparation of Gas Standard Mixture of R134a by an Injection Method

An injection method was proposed for the preparation of R134a in N2 gas standards at 10 nmol/mol. The standard gravimetric method of ISO6142 was used as verification for the injection method. Results showed that good consistence between the injection method and the standard gravimetric method could be obtained. The contribution of the injection method to the standard uncertainty was about 0.92%, almost in the same order of magnitude with contribution of the standard gravimetic method.

The Impact of Raw Material Purity on R142b Standard Gas Mixture Preparation

The impact of purity of raw material on the accuracy of gas standard is studied. The R142b with purity of 99.6% and N2 with purity of 99.996% was used to prepare R142b in N2 gas standard based on gravimetric method. Results showed that if the impurity in R142b raw material was not dectected, it would cause 0.20-0.23% deviation relative to the reference value; if the uncertainty for impurity in R142b reach to 100%, the uncertainty in each step of dilution was amplified for almost 66.9%-144%, seriously reducing the reliability of the gas standard. Conversely, the neglect of 4.85×10-5 mol/mol Ar in dilutent gas N2 would neither significantly affect the mole fraction nor its uncertainty value. These results clarified the importance of purity analysis on standard gas mixture preparation.