Ideas in gas chemistry and gas flow for the EMPIR Environment Call 2016 Annarita Baldan, VSL

1. Ideas in gas chemistry and gas flow for the EMPIR Environment Call 2016Annarita Baldan, VSL

2. Ideas • Sampling-free/ fast measurements in Air Quality • CCS • Mercuric Chloride • Follow-up on-going projects Environment Call 2013

3. Sampling-free / fast measurements in Air Quality • Background info • CEN Reference methods available or under development (CEN/TC264) • Problems are : • Sampling • Lengthy measurement • Costly

4. Problems associated with sampling in Air Quality • Reference methods both in ambient and stationary source emissions measurements need sampling. • Sampling lines/filters/pumps can cause problems: 1 -Adsorption/reactions of the analyte (such as ammonia, hydrogen chloride, nitrogen dioxide) 2-Condensation of moisture 3-Mold / Insects / Particles

5. Problems in fugitive emissions • Concawe (ad-hoc group OGI) and US EPA are looking for alternatives for the LDAR* sniffing standard method as it is: 1) Time consuming & Costly: in a major petrochemical facility > 10.000 LDAR testing points to assess leaks 2) Quality issue: Occurrence of false positive (small leak, high concentration) and false negatives (large leak, low concentration) Sniffing device (TVA- FID) *LDAR: Leak Detection and Repair (US EPA method 21)

6. Role of NMIs • There are several techniques that can be applied in the field and that are in “advanced research stage”. These techniques should fulfill the metrological requirements of accuracy and traceability. • Metrological validation of sampling-free/fast measurement methods for air quality applications thanks to a multi-disciplinary approach • Examples: • Optical Gas imaging (OGI) • (low-cost) gas sensors

7. Impact • Quantitative and reliable data for industry and policy makers thanks to development of calibration approaches for ‘sampling free instruments’ (e.g. gas sensors and OGI camera) • Faster route to the market for new emerging technologies (speed up of the acceptance process) thanks to the metrological validation • Fast, effective and less expensive measurement techniques for users working in Air Quality monitoring and LDAR measurements

8. Carbon Capture and Storage Background info • Carbon Capture and Storage (CCS) could be used to (temporarily) lower CO2 emissions • CCS has a significant power consumption • There are several EU pilot plants (being) realised that aim at investigating/ demonstrating more efficient sequestration methods

9. Project Proposal: COOPeRaTeCO2 Pilot Ratification for Transport • Directly using CO2 produced by the pilots of new technology being demonstrated across Europe for transport related testing, e.g. corrosion • These capture technologies will produce different CO2 streams (composition) that will also require metering Iron and Steel Cement Power Power & Waste STEPWISE Pilot – Luleå, SE NORCEM CO2 capture pilot, NO Capture Pilot Maasvlakte, NL La Pereda Capture Pilot, ES

10. Need • The pilot plants result in CO2 streams of ~96% purity, other components are NOx, SOx, N2 • Current transport and storage strategies may not work for (all) different CO2 streams • Some CO2 streams are quite aggressive (e.g. corrosion) • Need for gas composition and gas flow measurements of CO2 streams: • to achieve uncertainty 1.5% on mass • for Safety in CC Storage (fugitive losses) EDGaR Project: Detection of H2S, SO2 and NO2 in CO2 by using broadband absorption spectroscopy in the UV/VIS range

11. Role of NMIsFrom an earlier CCS proposal(s) • Develop improved metering of flow and (on-line) composition for high pressure and supercritical/ dense CO2 streams • Measure and assess the challenges related to CO2 transport by pipeline as a result of internal corrosion • Develop field proven measuring instruments and open-path wide area screening of fugitive losses of CO2 from CCS-facilities • Improve equations of state • Experimental determination of the enhancement factors for water removal

12. Impact • Facilitate the discussion on the safety of CCS • Facilitate ETS (emission trading schemes, EU ETS Directive 2003/87/EC) • Facilitate the implementation of CCS

13. Mercuric Chloride • Background info • Mercury and its various compounds have a range of serious health impacts including brain and neurological damage, especially among the young. • Ratification of the Minamata Convention is currently in operation. At the end of September 2015, 128 countries and the European Union have signed. The Minamata Convention on Mercury provides controls and reductions across a range of products, processes and industries where mercury is used, released or emitted. • The Global Mercury Partnership of the Minamata Convention is supporting the development of Hg measurement/ monitoring capabilities which require Hg reference materials and standards.

14. Need • According to US EPA: • Gaseous Mercuric Chloride (HgCl2), the primary oxidized form of mercury, is an environmental concern, primarily due to its high water solubility and ultimate role in the availability of organic mercury. • HgCl2 is released directly to the environment from combustion processes (e.g. coal-fired utilities, hazardous and municipal waste combustors) but is also formed atmospherically through the oxidation of atmospheric elemental mercury. • The direct measurement of gaseous HgCl2 has become a major focus of international continuous source emission and ambient measurement and monitoring programmes. These measurements are dependent on the availability of reliable HgCl2 gaseous reference standards and materials to assess and verify data quality.

15. Role of NMIs • In many cases, HgCl2 must be reduced to the detectable, elemental form in order to be quantified. Reliable HgCl2 reference gases are needed to quantify this conversion as well as assess the ability to quantitatively transfer the reactive HgCl2 through the entire measurement system. • Reliable HgCl2 reference gases with known uncertainty do not yet exist. Research topics include: • Quantitative confirmation of the output of liquid evaporative HgCl2 generators. • Development real-time/on-site HgCl2 measurement technique or HgCl2 transfer standard. • Development of reliable, portable HgCl2 reference gas materials/sources.

16. Impact • Quantitative confirmation of the output of liquid evaporative HgCl2 generators • A fundamental difference is found between the absolute output of Hg0 and HgCl2 reference gases of the same concentration. A measurement study to determine the output of liquid evaporative HgCl2 generators and agreement with Hg0 reference gases would enable an understanding of how liquid evaporative HgCl2 generators can be used as reference gases. • Development of a real-time direct HgCl2 measurement technique or HgCl2 transfer standard • To this point, all measurements are based on Hg0 measurements (analyzers) where the HgCl2 must first be reduced in order to be measured. This reduction or conversion step is of unknown efficiency and has to be investigated. • Development of reliable, portable HgCl2 reference gas materials/sources • Currently the liquid evaporative HgCl2 generators are the only technology available. However they are currently not accepted.

17. Follow up of ENV56 KEY-VOCs • Background info • VOCs are a multitude of organic chemicals present in traces in the air. They include both anthropogenic and biogenic compounds. VOCs are relevant because: • Involved in atmospheric processes (WMO-GAW) • Air pollutants (regulation emission and ambient air) • Indoor Air (Construction Products regulation) • KEY-VOCs project aims at building a metrological infrastructure (traceability and accuracy) for measuring a selected group of VOCs by conventional and gas sensing analytical techniques

18. Role of NMIs • The work initiated in KEY-VOCs needs to be further addressed. Specifically: • Focus on Toxic Organic Air Pollutants (US EPA TO-14 and TO-15) • Evaluation of new high accurate real-time analytical techniques: PTR-MS/ SIFT-MS • Continue the studies on the interaction of VOCs on surface materials for the preparation of stable Reference Materials

19. Impact • Provide traceability and accuracy so that reliable data can be obtained • Facilitate the implementation of new analytical techniques • Support policy makers in preparation of regulation on VOCs • Protect environment and climate, health and safety

20. Follow up of ENV52 HIGHGAS • Background info • There is a direct link between climate change and the increasing levels of greenhouse gases (GHG) in the atmosphere. The IPCC has established that man-made emissions of GHG’s have become dominant over the natural cycles of e.g. CO2, CH4 and N2O. • Good measurement of GHG’s is pivotal to understanding changes in the earth climate and are required to underpin legislation to reduce the emission of GHG.

21. State-of-the-art • Accurate and reliable measurements require accurate instruments and metrologically traceable calibration standards (reference gases). • State of the art: • Within the WMO-GAW, GHG’s in the atmosphere have been monitored with high quality for many years • To maintain, improve and expend the activities on GHG measurements, the WMO and the metrology institutes have joined their forces within the CCQM • Within the 2013 EMRP programme the ENV52 HIGHGAS project has started to improve the level of the NMI’s on the production of GHG calibration gases, field measurements and instrumentation

22. Role of NMIs • One of the outcomes of HIGHGAS is that the current (and future) measurement techniques, especially spectroscopic, are biassed by the presence of different isotopologues in the sample or in the calibration gas • What can NMIs do: • Work together on the investigation and quantification of different isotopes in the reference materials • Collaborate with universities and instrument manufacturers to develop measurement techniques which can correct for the presence of different isotopic abundance or techniques that are not biassed by different isotopes

23. Impact • Maintain stable values of Greenhouse Gas trend analysis • Underpin the quality of future data sets • Transparent basis for developing and implementing policies for the control of anthropogenic emissions (based on e.g. the Kyoto protocol, Cancun agreement, or the COP21 Climate Conference meeting in Paris that is held right now (dec 2105))

24. VSL Thijsseweg 11 2629 JA Delft Postbus 654 2600 AR Delft T F E I See you at the breakout session Gas pollutants and Aerosol ! Abaldan@vsl.nl 015 269 15 00 015 261 29 71 info@vsl.nl www.vsl.nl