Validation of ammonia diffusive and pumped samplers in a controlled atmosphere test facility using traceable Primary Standard Gas Mixtures

We report the determination of ammonia (NH3) diffusive sampling rates for six different designs of commercial diffusive samplers (CEH ALPHA sampler, Gradko diffusion tube, Gradko DIFRAM-400, Passam ammonia sampler,and ICS Maugeri Radiello radial sampler (blue and white turbulence barriers)), together with the validation test results for a pumped sampler (CEH DELTA denuder). The devices were all exposed in the UK's National Physical Laboratory's (NPL) controlled atmosphere test facility (CATFAC). For each of the seven diffusive sampler exposure tests there were traceable concentrations of ammonia (in the range 3–25 μgm−3) generated under well-defined conditions of temperature, relative humidity and wind speed, which are applicable to a variety of ambient monitoring environments. The sampler exposure time at each concentration was 28 days, except for the radial devices, which were exposed for 14 days. The work relied on the dilution of newly developed stable Primary Standard Gas Mixtures (PSMs) prepared by gravimetry in passivated gas cylinders as a method of improving the metrological traceability of ammonia measurements. The exposed diffusive samplers were sent blind to the participants for analysis and the reported NH3 concentrations were then compared against the known reference concentration. From the results for each sampler type a diffusive sampling rate was calculated and compared against the rate used routinely by the participants. Some measurement results were in good agreement with the known traceable reference concentration (particularly for one diffusive sampler design (ALPHA)), while other devices exhibited over-reading and under-reading (each with a clear bias). The new diffusive sampling rates determined in the laboratory study were then applied to measurements in a field comparison campaign, and this was found to deliver an improvement in agreement between the different devices deployed

Metrology for Ammonia in Ambient Air. Final publishable JRP report

This project developed reference standards and measurement techniques for traceable measurements of NH3 in air. These will enable validated high quality ammonia measurement data which will help monitor and compare NH3 levels and ensure compliance with environmental protection policies and legislation

THE USE OF GC-MS TO SUPPORT STABILITY ASSESSMENT OF DENSITY REFERENCE LIQUIDS

Abstract − Density measurements are frequently associated to specific requirements in order to evaluate the quality of a process or to determine mass and/or volume of the material. Certified reference liquids can be used to assure metrological traceability of density measurements to the International System of Units (SI) with uncertainty lower than 0.005 %. This paper presents the new approac

Investigation of cylinder pre-treatments for the stability of ammonia gas reference materials

This report describes work to evaluate the performance of different commercial and proprietary cylinder treatments in improving the stability of ammonia reference materials in high pressure cylinders. Gas mixtures of 100 µmol/mol and 10 µmol/mol ammonia in nitrogen were prepared gravimetrically at both NPL and VSL. Comparative measurements at each amount-of-substance fraction were used to assess which passivation technique minimised the loss of ammonia upon preparation. The results indicate little difference between the commercial treatments, except at lower amount-of-substance fractions (10 μmol/mol). The variation observed in performance might be explained by the different abilities of the various treatments to prevent the adsorption of ammonia molecules on the internal surfaces of the cylinder, although the role of residual water on the cylinder surface in reacting with ammonia is unclear

Characterization of Fourier transform infrared, cavity ring-down spectroscopy, and optical feedback cavity-enhanced absorption spectroscopy instruments for the analysis of ammonia in biogas and biomethane

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

Development of standardized methods for the analysis of amines, terpenes and ammonia in biomethane

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