Research of Photochemical Oxidant

Transcription

1 Monitoring and QA/QC system of ozone at EANET sites 4th Tripartite Workshop on Scientific Research of Photochemical Oxidant November, 2011 Tokyo, Japan Keiichi Sato Asia Center for Air Pollution Research 1

2 Location of sites for O3 Monitoring (2010) Mondy (Re) Chiang Mai (Ru) Khanchanaburi (Re) Nakhon Ratchasima Bangkok (Ur) Nakhon Ratchasima (Re) Samutprakarn (Ur) (Ru) ) Tanah Rata (Re) ) Rishiri (Re) Ochiishi (Re) Tappi (Re) Kanghwa (Ru) Sado-seki (Re) Oki (Re) Happo (Re) Imsil(Ru) Ijira (Ru) Cheju Yusuhara (Re) Banryu (Ur) (Re) Hedo (Re) Mt.Sto.Tomas(Re) Ogasawara (Re) 54 sites in EANET Dry: 43 sites O3: 19 sites Reported by 11 sites in Japan, (1 site in Malaysia), 3 sites in ROK, 1 sites in Russia, 4(5) sites in Thailand 2

3 Mondy Rishiri Ochiishi Rishiri Ochiishi Jinyunshan Kanghwa(NO2) Imsil(NO2) Cheju (NO2) Tappi Sado-seki Oki Happo Ijira Yusuhara Banryu Kanghwa Imsil Cheju Tappi Sado-seki Oki Happo Ijira Yusuhara Banryu Hongwen(NO2) Hedo Ogasawara Hedo Ogasawara ChiangMai XiangZhou(NO2) ChiangMai Khanchanaburi Bangkok Samutprakarn Annual NOx, NO2 (2010) Khanchanaburi Bangkok Samutprakarn Annual O3 (2010) Kototabang (NO2) Jakarta(NO2) Bandung(NO2) No data < < (ppb) No data < < (ppb) 3

4 80 40 Annual trend during (O3) R.Korea, Russia Japan Increasing 80 Rishiri Ochiishi Tappi Kanghwa Cheju Imsil Mondy 40 Sado-seki Happo Ijira Oki O3 (ppb) O3 (ppb) Banryu Yusuhara 0 Hedo Ogasawara Thailand Bangkok Samutprakarn Khanchanaburi O3 (ppb) In order to obtain accurate long term monitoring data, QA/QC of O3 monitoring is indispensable. 0 Chiangmai Nakhon Ratchasima

5 Trend of annual O3 conc. (base year 2000) Rishiri Tappi Percentile level mean 95th 75th 50th 25th 5th Percentile level mean 95th 75th 50th 25th 5th Trend (ppb/year) annual R 2 winter R 2 spring R 2 summer R 2 autumn R (± 0.4 ) (± 0.3 ) (± 0.7 ) (± 0.8 ) (± 0.6 ) (± 0.8 ) (± 0.8 ) (± 1.3 ) (± 1.5 ) (± 0.9 ) (± 0.5 ) (± 0.5 ) (± 0.6 ) (± 0.8 ) (± 0.6 ) (± 0.3 ) (± 0.4 ) (± 0.6 ) (± 0.7 ) (± 0.6 ) (± 0.4 ) (± 0.4 ) (± 0.7 ) (± 0.8 ) (± 0.5 ) (± 0.6 ) (± 0.4 ) (± 0.7 ) (± 0.8 ) (± 0.8 ) 0.03 Trend (ppb/year) annual R 2 winter R 2 spring R 2 summer R 2 autumn R (± 0.6 ) (± 0.9 ) (± 0.6 ) (± 0.9 ) (± 0.9 ) (± 0.9 ) (± 0.9 ) (± 1.9 ) (± 1.4 ) (± 1.4 ) (± 0.6 ) (± 1.1 ) (± 0.7 ) (± 1.0 ) (± 0.9 ) (± 0.6 ) (± 1.0 ) (± 0.5 ) (± 1.0 ) (± 0.9 ) (± 0.6 ) (± 1.0 ) (± 0.6 ) (± 0.7 ) (± 0.8 ) (± 0.9 ) (± 0.8 ) (± 0.7 ) (± 1.0 ) (± 0.6 ) 0.73 Most sites demonstrated statically insignificant increasing trend Sadoseki Percentile level mean 95th 75th 50th 25th 5th Trend (ppb/year) annual R 2 winter R 2 spring R 2 summer R 2 autumn u R (± 0.6 ) (± 1.2 ) (± 1.2 ) (± 0.7 ) (± 0.8 ) (± 0.8 ) (± 1.2 ) (± 1.7 ) (± 1.0 ) (± 1.2 ) (± 0.6 ) (± 1.2 ) (± 1.4 ) (± 1.0 ) (± 0.7 ) (± 0.7 ) (± 1.2 ) (± 1.3 ) (± 0.8 ) (± 0.8 ) (± 0.7 ) (± 1.2 ) (± 1.2 ) (± 0.6 ) (± 0.9 ) (± 0.6 ) (± 1.1 ) (± 1.3 ) (± 0.6 ) (± 0.9 ) 0.31 :Not statistically significant (95% confidence level) 5

6 Comparison of 5 year average monthly O3 conc. between the former (99-04 ) and the latter (04-09 ) 5 years (1) Rishiri Tappi Sadoseki Happo Ijira Oki Seasonal trend did not change between the former and the latter 5 years. 6

7 Comparison of 5 year average monthly O3 conc. between the former (99-04 ) and the latter (04-09 ) 5 years (2) Banryu Yusuhara Hedo Ogasawara 70 kanghwa 60 Kanghwa 70 Cheju 60 Cheju 70 Imsil 60 Imsil O3 [ppb] O3 [ppb] O3 [ppb] Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec month Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec month Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec month Except Ijira, Kanghwa (rural) and Banryu (urban), the average monthly O3 conc. in the latter 5 years (05-09 ) were higher than those in the former 5 years (00-04 ). Increasing in spring was remarkable at Sea of Japan (Rishiri, Tappi Sadoseki and Oki) and Pacific (Yusuhara, Hedo, Ogasawara) sites. 7

8 Instrumental setup of UV absorption method (O3) Ambient air Zero gas generator Reaction Cell A UV light PMT Pump 254nm O3 Scrubber Reaction Cell B Recorder O3 Absorption Spectrum No O3 std. gas cylinder is available. 8

9 Method Principle SI Traceability O3 calibration methods UV Absorption Gas Phase KI Titration Titration Absorption Reaction of Reaction of at nm O3 + NO O3 + KI No Yes NO Uncertainty t Small Relatively l Small Large Uncertainty Factor Cross section of O3, Optical path length, Temperature, Pressure NO standard gas, Gas flow rate, NO measurement Reproducibility of titration UV Absorption method is widely used as international standards. Intercomparison of international O3 std. is essential. 9

10 List of NIST O3 Standard Reference Photometer (SRP) provided in Asian and EANET participating countries SRP# Installation Date Location Organization 30 Nov, 2002 Kaohsiung, Taiwan Taiwan EPA 34 Dec, 2003 Hong Kong Hong Kong EPD 35 Apr, p, Apr, 2006 Tsukuba, Japan St. Petersburg, Russia NIES VNIIM 41 Feb, 2008 Beijing, China NIM 10

11 Current situation of O3 traceability in EANET countries China It is planned that t secondary ozone standards d (treceable to NIST SRP41?) will be installed at some provinces. Ternary standards installed at major cities will be calibrated by the secondary standard, and it will also used for calibration of ozone monitor. Russia O3 monitor at Mondy site was tried to calibrate by ACAP secondary standard, but it was not successful because of custom inspection. It will be calibrated by NIST SRP38 at St. Petersburg. Japan Traceability system was started in April, regional and ACAP ozone secondary standards are calibrated by NIST SRP35. Ternary standards installed at each prefecture are calibrated by the secondary standard, and it is also used for calibration of ozone monitors at air quality and EANET monitoring sites. Other countries There is no NIST SRP, and thus survey of O3 traceability (e.g. KRISS SRP was compared with NIST SRPs) or calibration by the ACAP standard is desirable. 11

12 Establishment of O3 traceability system in Japan Instrumental error: 0.5% Long-term variation: < 1% Primary std. in Japan Secondary std. (ACAP) Ozone Calibrator at EANET sites J. Jpn.Soc. Atmos. Environ (2006) 8 regional and ACAP ozone secondary standards are calibrated by NIST SRP35. Ternary standards installed at each prefecture are calibrated by the secondary standard. 12

13 Example of calibration by O3 secondary standard O3 Secondary std. Air flow of O3 calibration From Secondary std. To O3 Calibrator Overflow Traceable to NIES primary std. (SRP35) Placed at regional center in Japan and ACAP 13

14 O3 calibration record sheet at Japanese sites Ozone monitor calibration record sheet Prefectu Tokyo Site: Ogasawara Date: 2010/11/15 Operator: ** ** Ternary standard Block: ACAP ManufactureHORIBA Model: OZGU360 Serial #: Span: Zero: Ozone monitor information ManufacHORIBA Model: APOA-360 Serial #: X881JTSJ Temp. and Press. Corre Yes Minus signal: Yes Previous span: Previous zero: Ozone calibration result Span p and Zero Calibration Span after calib. Repeatability 1st 2nd 3rd Span value (ppb) Zero value (ppb) SD for span Zero after calib SD for zero Linearity Setting O3 conc. Zero ca. 60ppb ca. 120ppb span gas (180~250ppb) Ozone std. (X)(ppb) Ozone monitor (Y)(ppb) Linear regression y = x R 2 = Correlation Coeff. 14

15 O3 calibration results at 5 Japanese EANET sites in 2010 [Change in span factor after calibration] Average of relative span difference = -3.1% (-12.3 ~ +8.3%) [Repeatability] Average RSD of 3 measurements of span gas ( ppbv) =0.1% ( ~ 0.19%) Average SD of 3 measurements of zero gas = ppbv (0.047 ~ ppbv) [Linearity] Linear regression: y(o3 monitor) = Ax(O3 std.) + B A(slope): ~ ; B(offset): ~ Correlation: R 2 = ~

16 Questioner sheet sent to EANET participating countries Questioner sheet for investigating traceability on automatic air concentration monitoring Asia Center for Air Pollution Research 1.Country: 2.Name of site; 3.Questioner for automatic air monitor calibration Please fill the cells in the following ow table. Monitoring Parameter Name of Equipment Installation date Ownership Main purpose of monitoring Calibration method Traceability of standards (gases or solutions) Calibration frequency Organization responsible for calibration SO 2 SO 2 O 3 NO X PM 1.Problems on automatic air concentration monitoring (if there are any problems, please describe major ones in the following parts) 1)Sample inlet: 2)Electricity: 3)Maintenance system: 4)Financial support: 5)Others: Counterpart name (Organization) 16

17 Results of questioner for O3 traceability China O3 monitor has been calibrated by NIST SRP41 every three months. (since 2009) Russia O3 monitor has not been calibrated as of It will be calibrated by NIST SRP38 at St. Petersburg. Technical training for O3 calibration was implemented at ACAP in Dec., Thailand O3 monitor was calibrated everyday by calibrator installed in the station. The staffs confirm the span factors are within ±5%. O3 calibrators are checked by maintenance company once a year. It is planned that O3 SRP will be installed in (Thai Meteorological Department) TMD in future. Malaysia O3 monitor was equipped at two EANET sites, and it was calibrated by every 3 months. Secondary O3 standard was calibrated by EMPA at Switzerland (NIST SRP 15?) once a two years. 17

18 Schedule for calibration of O3 monitors at EANET sites November December, Calibration of O3 monitor by ACAP 2011 ternary std. at Bangkok, Thailand December 2011 February, 2012 January, 2012 In FY2012 Calibration of O3 monitor at 4 EANET sites in Thailand Parallel O3 monitoring for 2 weeks Survey on O3 monitoring and calibration system in Indonesia Calibration of O3 monitor at Tanah Rata in Malaysia Parallel O3 monitoring for 2 weeks Survey at monitoring sites in Philippines 18

19 Strategy Paper on Future Direction of Monitoring for Dry Deposition of EANET ( ) 2015) vi) Promotion of an ozone monitoring network and review of its current status t in East tasia Each ozone monitor in EANET shall be calibrated using an ozone calibrator traceable to the NIST Ozone Reference standard at least once every two years. Within the next two years, the NC will acquire an ozone secondary standard calibrator, to be available to participating countries upon the request. Detailed conditions of O3 traceability will be described in the EANET Technical Manual for Air Concentration Monitoring. 19

20 Draft table of contents of the EANET Technical Manual for Air Concentration Monitoring [To be published in 2013] (Chapter 1 Introduction) (Chapter 2 Monitoring design) (Chapter 3 Manual monitoring) (Chapter 4 Automatic monitoring) 4.1. Calibration (including standard gases of SO2 and NOx, O3 SRP, zero gas ) SO2 monitor [DOAS, Point measurement] 4.3. NOx monitor [DOAS, Point measurement] 4.4. O3 monitor [DOAS, Point measurement] 4.5. PM10 and PM2.5 monitors 4.6. Meteorology (Chapter 5 Maintenance) (Chapter 6 Data reporting and validation) (Chapter 7 Quality Control and Quality Assurance) (Chapter 8 Future issues) 20