Assessing the Long-Term Performance of the UK Emissions Monitoring Industry from PT Scheme Data
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1 Assessing the Long-Term Performance of the UK Emissions Monitoring Industry from PT Scheme Data Dr Marc Coleman AQE 2013, 13 th 14 th March, Telford UK
2 Contents Description of NPL Proficiency Testing schemes Stack Simulator facility How proficiency is expressed in terms of a z-score for each participant Evaluation of industry performance since inception of each scheme Z-score distributions Subsequent performance of outlier participants Conclusions
3 NPL Operated Schemes There are 3 ANNONYMISED Proficiency Testing (PT) schemes operated at NPL Calibration Gas Gas bottle certified reference materials Tests calibration proficiency Gas Measurement Utilises NPL s Stack Simulator facility Sampling apparatus required Tests not only quantification proficiency but importantly also sampling proficiency Particulate Shims to simulate filters NaCl solutions to simulate probe washings
4 NPL Stack Simulator Facility 2m tall recirculating stack Four 127mm (BSP) ports Temperatures of up to 180 C and flows of up to 12m.s -1 Up to 25% H 2 O can be introduced along with a broad range of analytes / interferents (e.g. HCl, SO 2, NOx, CO, CO 2, O 2, etc.)
5 NPL PT Schemes Coverage Calibration Gas longest running scheme ~70 organizations have participated Representing vast majority of UK stack testing industry
6 Expression of Results Results are expressed in terms of z-scores Consistent with ISO z-scores are segregated into 3 categories 2 & -2 = satisfactory >2 & <3 or <-2 & >-3 = warning 3 & -3 = unsatisfactory On the balance of probabilities it s unlikely that a participant would achieve these levels without there being a real issue to address Consequence of not achieving a satisfactory score is that at the annual surveillance visit UKAS are likely to expect to see evidence of an internal investigation as to the cause
7 Analysis Approach (1) Motivation for work was to determine if any trends had started to emerge across the schemes Is the proficiency of the industry being maintained / improving / deteriorating? Comparing data between rounds Issue evaluating across rounds is that test concentrations and allowable deviations change Selected a fixed concentration present in all rounds Recalculated z-scores using allowable deviations from 2011 Have focused on NO, SO 2 & particulates only as more difficult to measure compared to other species in the schemes (e.g. CO)
8 Analysis Approach (2) Allowable deviations and assigned values for recalculated participant z-scores Scheme Measurand Assigned value Calibration Gas Gas Measurement Allowable deviation SO 2 100ppm ±5ppm 5% NO 100ppm ±5ppm 5% SO 2 40ppm ±5ppm 12% NO 30ppm ±3.5ppm 12% Particulate Shims 140mg ±14mg 10% NaCl 5mg ±1mg 20% Allowable deviation / % For SO 2 & NO the IED requires measurement uncertainty of ±10%, k=1 of the ELV For particulates IED requires ± 15%, k=1 of ELV
9 CALIBRATION GAS (Gas Bottles)
10 Z-Score Distributions for SO 2 and NO Calibration Gas Scheme Outlier at z=12 SO 2 NO Box encompasses 25-75% quartiles Whiskers extend out to farthest score within 25% of box limit * = outlier z-score Greater number of unsatisfactory (>3 & <-3) participant scores for SO 2 than NO Frequency of unsatisfactory scores & outliers decreases with time
11 Tracking Performance SO 2 Plots show subsequent score for any participant achieving a z-score >3 & <- 3 All participants unsatisfactory by 2011 requirements are seen to improve Scheme appears to be having the desired effect NO
12 Interquartile (25-75%) Z-Score Ranges for Calibration Gas SO Round NO Decreased interquartile distribution seen for NO over SO 2 Combined with boxplots implies a greater proficiency of the industry for NO over SO 2 No obvious trend with time in interquartile range Round
13 GAS MEASUREMENT (Stack Simulator)
14 Z-Score Distributions for Gas Measurement Scheme SO NO Narrower NO distributions However, some evidence of a negative bias in SO 2 scores Consistent with sample loss in sampling apparatus but not sufficient to lead to unsatisfactory scores Highlights importance of schemes where sampling is included in the proficiency test To accurately assess proficiency the entire measurement must be tested
15 Interquartile (25-75%) Z-Score Ranges for Gas Measurement SO 2 As for Calibration Gas scheme decreased interquartile distribution seen for NO over SO 2 No trend with time NO
16 PARTICULATES (Shims and NaCl Washings)
17 Z-Score Distributions for Particulates Scheme Shims Round Outlier at z=-40 Washings Shims performance has been maintained Washings appears to have improved EN requires a weighing accuracy of ±5% Are only testing weighing in scheme so could argue this should be the allowable deviation Washing distributions would increase 4-fold, performance would be poorer Round
18 Tracking Performance Post Unsatisfactory Score As with gases, participants who would be unsatisfactory by 2011 requirements all improve
19 Conclusions The number of unsatisfactory scores for NO & SO 2 has decreased since the inception of the Calibration Gas scheme showing that the proficiency testing is having the desired effect The Stack Simulator (Gas Measurement scheme) data evidenced a negative bias in SO 2 scores (i.e. participant underreading) not seen with the gas bottle (Calibration Gas) scheme Bias not sufficient to lead to unsatisfactory scores Highlighted importance of testing proficiency of entire measurement For particulates number of unsatisfactory scores for washings has decreased The Future PT testing for HCl using the Stack Simulator commenced in Feb 2013 Particulate Stack Simulator (enabling particulate sampling to be directly tested, i.e. as opposed to NaCl solutions to simulate washings) Stack Simulator PT on only wet chemistry SRMs (SO 2, HCl) Speciated VOCs
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