Abstract Siloxanes are silicon-containing volatile organic compounds that occur in air, biogas and biomethane. Their presence in biogas and biomethane may give rise to silica deposits in gas transmission and distribution infrastructure, as well as in end-user appliances. The silicon concentration in biomethane is therefore regulated, and implementing these regulations requires reliable measurement methods and appropriate certified reference materials (CRMs) to calibrate analytical instruments. In this work, the primary measurement standards of two national metrology institutes are compared to assess their equivalence by means of gas chromatography analysis. The comparison addressed hexamethyldisiloxane (L2), octamethyltrisiloxane (L3), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in methane gas mixtures. Two mixtures were exchanged, one with siloxane amount fractions at the ppb-level as specified in the European specification EN 16723, and a second on ppm-level. The latter CRMs can be dynamically diluted or directly used to process concentrated biomethane samples. The results at both levels demonstrate equivalence in the preparation and analysis of the addressed siloxanes in methane.

Biomethane may contain trace components that can have adverse effects on gas vehicles performances and on the pipelines when injected in the gas grid. Biomethane quality assurance against specifications is therefore crucial for the integrity of the end-users’ appliances. Analytical methods used to assess biomethane conformity assessment must be validated properly and possibly, new methods specifically for biomethane should be developed. This paper provides an overview of the biomethane quality assurance infrastructure and the challenges faced with focus on sampling, analysis methods, reference gas mixtures, and performance evaluation. Currently, requirements for analytical method validation and fit-for-purpose assessments do not exist for biomethane. The industry is in urgent need of a protocol to evaluate the fit-for-purpose of methods in a harmonized manner. Reference gas mixtures to check the accuracy of the instrument and to determine the traceability of the measurement are also urgently required.

Main text CCQM-K118 was an international key comparison on natural gas composition with two types of gases, i.e., a low calorific hydrogen-enriched natural gas and a high calorific LNG type of gas. There were 14 participating laboratories. The traveling standards (i.e., 14 mixtures each) were obtained from an external source and checked for homogeneity and stability before and after the participants' measurements at the two coordinating laboratories. The data evaluation was performed using a consensus value and a laboratory effect model. The results of the participants were benchmarked against a key comparison reference value computed from the largest consistent subset (LCS) of the submitted results, adjusted for the differences between the travelling standards. For the first time in a key comparison in gas analysis, the model included a term to account for excess variability in the LCS. Most of the participants reported one or a few (slightly) discrepant results. Partly this is due to the heterogeneity and heteroscedasticity of the datasets. In all, the results in this key comparison demonstrate the good comparability of the national measurement standards for natural gas composition maintained by the participating NMIs. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA). To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Novel traceable analytical methods and reference gas standards were developed for the detection of trace-level ammonia in biogas and biomethane. This work focused on an ammonia amount fraction at an upper limit level of 10 mg m-3 (corresponding to approximately 14 μmol mol-1) specified in EN 16723-1:2016. The application of spectroscopic analytical methods, such as Fourier transform infrared spectroscopy, cavity ring-down spectroscopy, and optical feedback cavity-enhanced absorption spectroscopy, was investigated. These techniques all exhibited the necessary ammonia sensitivity at the required 14 μmol mol-1 amount fraction. A 29-month stability study of reference gas mixtures of 10 μmol mol-1 ammonia in methane and synthetic biogas is also reported.

European Commission targets specify that 32% of the European energy consumption should come from renewable sources by 2030. One of the most promising options to reach this target is gas generation from biomass, especially biomethane, for injection into natural gas grid. EN 16723 presents specifications for VOCs, corrosive components and compressor oil in biomethane, impurities monitored because of integrity of gas infrastructure and for health and safety reasons. Currently, it proposes test methods that are neither harmonized nor validated, and usually not dedicated to biomethane. Launched in June 2017, the EMPIR project 16ENG05 Metrology for Biomethane is aimed for specific, robust and standardized analytical methods development, along with novel and improved reference standards. The present paper focusses on the developed methods for the monitoring of amines, terpenes and ammonia involving μGC-TCD, TD-GC-MS and OFCEAS.

Biogas is a renewable energy source with many different production pathways and various excellent opportunities to use, for example as vehicle fuel (biomethane). Reliable analytical methodologies for assessing the quality of the gas are critical to ensure that the gas can technically and safely be used. An essential part of any procedure aiming to determine the quality is the sampling and the transfer to the laboratory. One of the greatest challenges is then to ensure that the composition of the sample collected does not change between the time of sampling and the analysis. The choice of the sampling vessel to be used must be made only after fully assessing its short-term stability. In this paper, the results from short-term stability studies in different vessels (cylinders, bags and sorbents) are presented for siloxanes, BTEX, halogenated hydrocarbons and sulfur compounds. Storage of dry gas at high pressure (> 6 MPa) appears to be a good alternative however it is currently challenging to find an optimal treatment of the cylinders for all species to be assessed in biogas/biomethane. At lower pressure, adsorption effects on the inner surface of the cylinders have been observed. The use of bags and sorbent tubes also shows limitation. No existing sorbent tubes are sufficiently universal as to trap all possible impurities and high boiling compounds may adsorbed on the inner surface of the bags walls. Moreover, the presence of water when storing biogas most certainly impacts the storage stability of compounds in most vessels. Using at least two sampling methods for a given compound and comparing results will allow taking into account the eventual effects of water vapour, and adsorption on the inner surface of the vessels. (C) 2017 Elsevier Ltd. All rights reserved.

Dimethyl sulfide (DMS) is an important compound in monitoring climate change and is monitored by the World Meteorological Organization Global Atmospheric Watch Volatile Organic Compounds (WMO-GAW VOC) program at several monitoring sites. It is essential that measurement results are accurate and consistent among the assigned values for primary gas mixtures to meet the WMO requirement. The purpose of this comparison is to compare the measurement capability of DMS at approximately 10 μ­mol/mol and expectation to contribute the establishment of traceability to single measurement scale for DMS between NMIs. Main text To reach the main text of this paper, click on Final Report . Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/ . The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

•We review the stability of sulfur-containing compounds in standard gas mixtures.•Trace levels of sulfur-containing compounds exhibit good stability in passivated cylinders.•Stability of sulfur-containing compounds in commercial sampling vessels is variable.•There are significant losses of sulfur-containing compounds stored in sample bags.•We make suggestions to improve the accuracy of measuring sulfur-containing compounds.

The first reference gas mixtures of sulfur-free natural gas odorants that are traceable to the International System of Units (SI) have been produced and their compositions validated. These mixtures, which contain methyl acrylate and ethyl acrylate at amount fractions between 1.1 and 2.1 μmol mol(-1), can be used to underpin measurements of sulfur-free odorants, which are increasingly being used to odorize natural gas in transmission networks as they have less harmful properties than traditional sulfur-containing odorants. The reference gas mixtures produced have been shown to be stable in passivated aluminum cylinders for at least 8 months and have been validated (to within 6% or less) by interlaboratory measurements at three National Measurement Institutes. The stability of methyl acrylate and ethyl acrylate in gas sampling bags has been investigated, and the challenges of analyzing 2-ethyl-3-methylpyrazine, which is used as a stabilizer in sulfur-free odorants, are also briefly discussed.