1 December 2015 - EMPIR Workshop Environment Call 2016
INRiM, Torino, Italy
Ideas in gas chemistry and
gas flow for the EMPIR
Environment Call 2016
Annarita Baldan, VSL
Ideas
1. Sampling-free/ fast measurements in Air
Quality
2. CCS
3. Mercuric Chloride
4. Follow-up on-going projects Environment
Call 2013
Pag. 2
Sampling-free / fast
measurements in Air Quality
Background info
CEN Reference methods available or
under development (CEN/TC264)
Problems are :
Sampling
Lengthy measurement
Costly
Pag. 3
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
Pag. 4
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)
Pag. 5
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
Pag. 6
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
Pag. 7
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
Pag. 8
Project Proposal: COOPeRaTe
CO2 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
STEPWISE Pilot – Luleå, SE
Pag.
P9
Cement
NORCEM CO2 capture pilot, NO
Power
Capture Pilot Maasvlakte, NL
Power & Waste
La Pereda Capture Pilot, ES
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)
Pag. 10
EDGaR Project: Detection of H2S, SO2 and
NO2 in CO2 by using broadband absorption
spectroscopy in the UV/VIS range
Role of NMIs
From an earlier CCS proposal(s)
1.
2.
3.
4.
5.
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 openpath wide area screening of fugitive losses of CO2 from
CCS-facilities
Improve equations of state
Experimental determination of the enhancement factors
for water removal
Pag. 11
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
Pag. 12
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.
Pag. 13
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
Pag. 14 verify data quality.
and
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.
Pag. 15
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.
Pag. 16 However they are currently not accepted.
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
Pag. 17
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
Pag. 18
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
Pag. 19
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.
Pag. 20
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
Pag. 21
instrumentation
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
Pag. 22
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))
Pag. 23
VSL
Thijsseweg 11
2629 JA Delft
Postbus 654
2600 AR Delft
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E
I
015 269 15 00
015 261 29 71
info@vsl.nl
www.vsl.nl
See you at the breakout
session Gas pollutants
and Aerosol !
Abaldan@vsl.nl