emerging challenges in gas and particle measurements for atmospheric, air quality and emissions...
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Emerging challenges in gas and particle measurements for atmospheric, air quality and emissions science
Dr Richard BrownNational Physical Laboratory [email protected]
Welcome to the National Physical Laboratory
Metrology for Environment
Covers traditional and progressive NMI activities
From the laboratory to the end user
Traceability chain is harder to ensure
Emerging requirements are more apparent
Legislation is more important
New technologies are more important
The Results of Metrology
Provides a measurement infrastructure which is stable over time, comparable between locations, and coherent, allowing measurements of different properties using different methods to be combined (without scaling factors)
Removes barriers to trade, improves efficiency and competitiveness, enables technological development, encourages global agreement and collaboration
Generates systems and frameworks for quantification and through these underpins consistency and assurance in all measurement
Gives a quantified level of confidence in the measurement through an uncertainty statement
Provides a measurement infrastructure which is stable over time, comparable between locations, and coherent, allowing measurements of different properties using different methods to be combined (without scaling factors)
confidence in trendsconfidence in spatial data
confidence that data can be used directly in the equations of chemical
physics – unique to the SI
Richard Brown
Ownership of the whole traceability chain & the variety of end user measurements
Reduction of uncertainties throughput the measurement process
Support for long term monitoring and assessment
Direct impact on end user requirements: often different for those in the laboratory
Providing traceability link from lab to field
Stronger interaction between NMIs and monitoring organisations (inc. comparison studies)
Best practice guidelines Data quality improvement
and verification Metrological uncertainty
analysis Experimental design
Improvement of existing capabilities
Lower concentratio
nsReduced
uncertainties
Improved samplingReduced
uncertainties
Development of new
capabilities
Isotopic measureme
ntEmerging pollutants
Standard methods
Novel calibration
End user dissemination
& best practice
Micro-cylindersParticle transfer
standards
Dilution technologies
Quality control
Novel technologies & methods
Cylinder technology
High res spectroscop
y
High spatial and
temporal resolutionSensors
Labo
rato
ryFi
eld
REGULATIONGLOBAL MONITORING NEW ENVIRONMENTS
TECHNOLGY PULLEMERGING POLLUTANTS ECONOMIC PRESSURE
Topics in Gas Metrology
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Environment Call:Metrology for High Impact Greenhouse Gases 2HIGHERGAS
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Background need Improve our understanding of the global atmosphere, control the increasing
influence of human activity on it and address the effects of climate change. Meet EU directives (including air quality 2008/50/EC), Kyoto protocol Support WMO/GAW maintain long term stable values of GHGs at very high
levels of precision for analysis trends in the atmosphere.
Metrological challenges and proposed work
• Traceable standards with long-term stability for the highest impact greenhouse gases (CO2, CH4, N2O, CO) with uncertainties that support global monitoring of background levels - factor of four lower than achieved in HIGHGAS
• Reference standards to underpin urban measurements• Dynamic methods for emerging requirements (ie. F-gases, H2, halocarbons)• Development of a high accuracy zero gas reference standard for field use• Develop and validate suitable transfer standards to facilitate comparability
studies, support international traceability and validate field measurement techniques (including in-situ calibration methodologies)
Environment Call:Metrology for Hydrogen ChlorideMETHCl
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Background need
Emission sources (manufacturing: paper, petrochemical, cement, electronics steel treatment, power plants: coal and oil fired, waste incineration)
Meet Industrial Emissions Directive, 2015 EPA regulations for cement and paper, human health requirements
Requirements for trace detection from advanced manufacturing – detrimental to product as fabrication sizes scale down
Metrological challenges and proposed work• Challenging molecule due to it reactive nature• Evaluate existing methods (10 µmol/mol to 1 cmol/mol), to include the
development of at least two independent methods (e.g. CRDS, IMS)• Develop open path optical techniques for absolute measurement• Develop high accuracy static reference standards of HCl, focus on improving
stability, reducing loses on preparation and quantification of influencing impurities in the matrix (e.g. water).
• Development of dynamic reference standards• Improve international comparability via organised comparisons with NMIs
Environment Call:Metrology for Stable Isotope Reference StandardsSIRS
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Improve our understanding of the global atmosphere, control the increasing influence of human activity on it and address the effects of climate change 2/3 of RF is by CO2 and N2O
N2O pre-cursor for upper atmosphere NOX and regulates stratospheric ozone
Meet EU directives (including air quality 2008/50/EC), Kyoto protocol, COP21
Support WMO/GAW and IAEA to maintain long term high-quality observations of GHGs for analysis of trends and atmospheric burdens
Improve understanding of the sources and sinks of N2O and CO2
Improve quality of data for policy making and regulation and underpin other environmental research initiatives
Background need
No existing metrology infrastructure for stable (except 14CO2) isotope reference standards
Development of static reference standards of CO2 to meet WMO compatibility goals (13C-CO2 0.01 ‰ 18O-CO2 0.05 ‰ 14C-CO2 0.5 ‰)
Static reference standards of N2O (14N15N16O, 15N15N16O and 14N14N18O) Provide traceability to the primary scale and study stability and fractionation
of standards Develop dynamic methods to validate reference mixtures (mixing of pure
12CO2 and 13CO2 to be compared to the developed reference standards and mixing of two reference standards to cover the range of isotopic compositions)
Development of laser spectroscopic and mass spectrometry techniques Provide recommendations for the use of stable isotope laser spectrometers
to trace production pathways Doubly substituted (clumped) isotopes, e.g. 13C18O16O or 14N15N18O by laser
spectroscopy
Metrological challenges and proposed work
Environment Call:Metrology for Nitrogen DioxideMETNO2
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Background need Rise in NO2 emissions mainly from diesel vehicles Selective techniques for NO2 becoming available so the requirement for
reference standards is significantly pronounced Meet EU directives (2008/50/EC) 17 European member states currently exceeding limits
Metrological challenges and proposed work NO2 is a challenging molecule due to its reactive nature Develop high accuracy dynamic reference standards (10 – 500 nmol/mol)
with a target uncertainty of 1 % Develop higher concentration static reference standards to underpin
dynamic systems with a target uncertainty of 0.5 % Develop selective techniques for measuring NO2 (i.e. CRDS) Develop methods and reference standards for measuring main impurities in
NO2 reference standards (e.g. nitric acid and other oxides) Quantification of impurities in zero gas Study stability and passivation chemistry of cylinders
Environment Call:Metrology for VOC tracers of air pollution and climate change (KeyVOC II)
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Background need Improve our understanding of the climatic and air quality impacts of future
changes in land use, biogenic and anthropogenic emissions and meteorology. Quality of life / public health (EU Air Quality Directive 2008/50/EC, National
Emissions Ceiling Directive 2001/81/EC) Support WMO/GAW to achieve accurate and precise long term global
measurements of VOCs for characterizing spatial and temporal trends.
Metrological challenges and proposed work• Develop high accuracy static reference standards (10 – 500 nmol/mol) of VOC
tracers (CH3CN, DMS, Acetaldehyde, MEK, MVK, Methacrolein and β-pinene) with a target uncertainty of < 5 % and a stability of > 1 year.
• Develop high accuracy dynamic methods for calibration of reactive species that are appropriate for in field instrument calibrations
• Determine dependence of stability on nature of matrix gas (air vs nitrogen)• Better characterization of the effects of water and ozone management
systems on accuracy and precision of ambient measurements• Study stability and passivation chemistry of cylinders
Topics in particle metrology and air quality
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Low Cost Sensors for gas, particle and air quality monitoring
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Low Cost Sensors for Air Quality
New improvements in low cost powered sensors have the potential to revolutionise the ambient air quality monitoring market
Reduced device costs will enable measurements to be carried out over a wider target geographical area than is currently possible with existing instrumentation making reference measurements
Such an increase in sensors will generate substantially more data in real time
Could be employed to deliver useful information for citizen science projects or policy development by governments and legislators
The performance of many low cost sensors is not well understood, even though they are being extensively marketed
Use of the air quality data generated by such technologies will only come about if it can be demonstrated to be credible and validated at appropriate a fit for purpose level
Low Cost Sensors for Air Quality 2
This project aims to develop a suitable protocol that could be used as the basis for evaluating the emerging new sensor technologies
Active participation of sensor manufacturers as part of the collaboration, together with other NMIs and other organisations
This includes characterising the performance of sensors in the laboratory using exposure chambers, and in the field (both as individual sensors and as part of a sensor network) to underpin the work of CEN TC264 WG42
The use of mathematical modelling to add value to individual low cost sensor data by treating it as part of a large network, and helping to identify which relevant metadata is required
This will impact on air pollution monitoring, fence line monitoring, personal exposure monitoring, and community or individual monitoring activities
Could cover a number of ambient components: gases, particles, mercury vapour, and could be extended to real time particle composition measurement: metals by XRF and PAHs by TD-GC-MS
Drivers in the particle metrology area
CCQM GAWG workshop in 2015 on particles
Produced roadmap for a number of key quantities
First CMCs for particle number count accepted in 2015
Particle metrics and composition now widely implicated in health effects
Role in radiative forcing
Black Carbon
• A key air pollutant for human health and also climate change• Identified as needing metrological support at the BIPM
GAWG particulate metrology workshop in April 2015• Would build on pre-co-normative project JRP-n06, if this is
successful• Content linked to GAWG roadmap (under development)• Could fit in nicely with a wider ‘AQ sensors’ project• Surrogate measurement for other quantities – for instance
PAH concentration
Draft Traceability Hierarchy SI
Aerosol-based Equivalent Black Carbon (EBC) measurements:
extinction minus scattering (reported as Mm-1)
Standard near-black aerosol source (JRP-n06 ?) with low volatility and low water content
(to allow mass concentration measurements to be interpreted as EBC mass concentration)
Filter-based EBC measurements, eg aethalometer, MAAP
EC/OC CRMs (powder or filter-based; EC
component linked to the near-black aerosol)
Aerosol mass concentration measurements (eg gravimetry or
TEOM, reported as μg.m-3)
Elemental Carbon (EC) measurements
Equivalent Refractory Carbon measurements
Particle metrics 1
a) Mass concentration (PM10 and PM2.5)
• Traceability is still via parallel trials with the reference method
• Development of a controlled mixed source (with a realistic range of hygroscopic and semi-volatile particles) would allow direct calibration
• Further possibility for combination with sensor-based projects
Particle metrics 2
b) Size distribution
• Simple number concentration, via Condensation Particle Counters, is becoming mature (CMCs exist)
• Size distribution, e.g. with Mobility Particle Size Spectrometers (~10 – 1000 nm diameter) is becoming standardised and needs calibration facilities
Air quality data
Do we make the best use of the huge quantity of data produced by air quality measurements? (‘Big Data’)
Could a more detailed analysis allow us to add value: Improve quality assurance Predict missing data in time and space Spot patterns and correlations Source apportionment Data checking The role of uncertainty and bias in the
above Much of this research has never had a
rigorous metrological approach Very consistent with the sensors agenda
Mercury
Measurement of Hg remains a significant challenge in environmental compartments
Work already done under EMRP on elemental Hg in air (but not related to sensors)
No work done on oxidised and reactive gaseous mercury and standards for these
Most toxic components in terms of human health and accumulation in the environment
Loading in air and emissions is poorly understood
Topics in emissions metrology and atmospheric science
Welcome to the National Physical Laboratory
IMPRESS 2: Project Need The need to reduce industrial emissions to air is
continuous: Best Available Technique Reference documents
(BREFs) will be adopted under the Industrial Emissions Directive (2010/75/EU)
This will bring in emission limits even more stringent than those currently coming into force under the IED
Measurement techniques and associated methods standardised at CEN will become no longer fit for purpose
A project is needed to: Assess future measurement needs due to increasingly stringent regulation Critique existing techniques and associated standardised methods against
current and near future requirements Develop far-future techniques and associated methods Carry out uncertainty work and provide guidance documents to help the
industry in complying with regulation and applying new techniques
IMPRESS 2: Proposed Work
Address a broad range of sampling issues cutting across the suite of periodic measuring methods e.g. water vapour removal from streams containing acidic measurands
Continuing investigation into limits of current standardised approaches for key pollutants as increasingly stringent emissions limits come on-line Proposed Medium Combustion Plant Directive – are current suite of
SRMs fit for enforcement? Impact on plant operators of existing QA/QC regulatory requirements
e.g. trade off between cost of implementing EN 14181 and uncertainty improvements as a consequence
Regulatory and standardisation activities Contributions to BREF drafting process Development of SRMs for HF and NH3, and harmonisation of PT
Development of future techniques E.g. TDL, cascade lasers, 3D pitot tubes?
New Source Terms for GHG Inventory: Project Need
Many EU states have put exploitation of new gas sources (e.g. shale gas) on hold pending further understanding of the environmental impact The European Commissions Energy Roadmap 2050 identifies gas as a
critical fuel for the transformation of the energy system. The substitution of coal and oil with gas in the short term could help
reduce emissions with existing technologies until at least 2030 2035‐ Europe is committed to CCS to transition to a low carbon economy via the
EC’s strategic initiative ‘Preventing dangerous climate change’ To gain this understanding application of existing and development of new
techniques is required to allow: A capability for periodic monitoring at key industrial sites Improved emissions factors for calculation of estimated emissions Well characterised, robust data to regulate new activities Improved public confidence in environmental impact
New Source Terms for GHG Inventory: Proposed Work
Work ensuring involvement in the project of key industrialists and regulatory authorities involved in unconventional gas exploitation
Laboratory development and characterisation of techniques: Including development of procedures for operation of such techniques
in accordance with standard to be published by CEN / TC264 / WG38 (applicable to fugitive emissions)
Field demonstration work at two unconventional gas sites if possible, ideally CCS plant and shale gas site: To include assessment of capability of techniques to enable compliance
and impact of techniques uncertainties Comparison of calculation based estimates of emissions
Key output to include joint document with regulators and industrial partners summarising findings and best practise conclusions to be used as a reference document by the industry
Metrology in Environmental Extremes
Tom Gardiner will talk about this in a separate presentation later in the session
Work Areas for Partnering
Optical remote sensing Lidar, optical gas imaging (OGI), FTIR, laser absorption
Follow on to MetNH3
Other species the project could move onto include formaldehyde Spectroscopy
Field application of EUMETRISPEC spectroscopy? Atmospheric compositional and radiative balance measurements
Marine emissions On-vessel and in port measurement techniques for enforcement of
the MARPOL City-scale emissions CEN / ISO standardisation activities
Significant involvement at CEN, in particular in TC264 Air Quality Applied metrology
Laboratory and field validation exercises
Gas Metrology ● ●Particle Metrology & Air Quality ● ●Sensors and data analysis ● ●Emissions Metrology ●Atmospheric science ●
Some NPLContacts:[email protected]
Paul Brewer Richard Brown Paul Quincey Nick Martin Marc Coleman Tom Gardiner