BEE-TEX Field Study. Aerodyne Mobile Laboratory May Berk Knighton (PTRMS) Tara Yacovitch, Rob Roscioli, John Nowak (QCL) Cody Floerchinger (EE)

Transcription

1 BEE-TEX Field Study Aerodyne Mobile Laboratory May Berk Knighton (PTRMS) Tara Yacovitch, Rob Roscioli, John Nowak (QCL) Cody Floerchinger (EE)

2 BEETEX

3 BEE-TEX Given the monitoring and modeling technologies to be deployed during BEE-TEX, what are the major scientific hypotheses that should be examined during the field study? How can the mobile labs best be deployed to address the aforementioned hypotheses? What synergies can be exploited from the mix of monitoring technologies? What ancillary information will be required to properly interpret the data from the cultured human lung cell exposure device? What should the role of real-time data broadcasting be in the project? How can uncertainties in source attribution be quantified and minimized?

4 BEE-TEX Given the monitoring and modeling technologies to be deployed during BEE-TEX, what are the major scientific hypotheses that should be examined during the field study? The open path tomographic measurement and analysis will be a diagnostic for quantifying fluxes and exposures. Sophisticated emission plume models will be more accurate than simple gaussian plume models. How can the mobile labs best be deployed to address the aforementioned hypotheses? Collect accurate, rapid (1 Hz) measurement suite to identify source of perturbation (emission type). Use mobile monitor to build exposure map to accompany open path. Employ Tracer Release?

5 BEE-TEX What synergies can be exploited from the mix of monitoring technologies? Open path and in-situ comparisons. Local wind field for micromet dynamics. Rapid PTR and comprehensive VOC via GC What ancillary information will be required to properly interpret the data from the cultured human lung cell exposure device? What should the role of real-time data broadcasting be in the project? Aerodyne mobile lab will produce data with 1 day lag How can uncertainties in source attribution be quantified and minimized? 1. Cooperation with industrial partners in focus area 2. Broad suite of compounds, combustion tracers, ethane, GC 3. Wind, wind, wind

6 Overview and Conclusions Measurement Payload Mobile laboratory basics BEE-TEX The aromatics are: Benzene, toluene, ethyl benzene + xylene(s), tri-methyl benzenes Remote wind units Analysis of time-series/spatial data Mode or median probably more useful to represent area Differences in observed mixing ratios within study region Industrial Plumes in Channelview (Discover AQ) Ethene Benzene comparisons

7 non-proton Transfer Reaction Mass Spectrometer Measurements UTC, Latitude, Longitude, UTM Northing, Easting, Zone Specific bearing of the truck Wind measured at the truck CO 2, CO, NO 2, NOx, NO, O 3 CH 4, C 2 H 6, C 2 H 2 Dry Zero Air heart Mask, companion valve on times wet NMHC free Air heart Mask, companion valve on times Remote wind measurements Measurements Data Analysis Industrial Plumes Future Work

8 Proton Transfer Reaction Mass Spectrometer Species Listing PTR data UTC, acetic acid, acetonitrile, benzene, toluene, C2-benzene, C3-benzene, methanol, styrene, terpene, concmass59, concmass69, concmass71 Measurements Data Analysis Industrial Plumes Future Work

9 Proton transfer reaction H 3 O + + benzene H 2 O + benzene*h + mass spectrometer N 2 /O 2 and other sample gas && benzene*h + electric field draws ions to detector differential pumping stages draw neutral sample away

10 PTR-MS Measurement Detail m/z 33 methanol (calibrated) m/z 42 acetonitrile (calibrated) some interference from C13 contribution of m/z41 m/z 43 propene (calibrated) many interferences from larger hydrocarbons should be used with caution. High concentration plumes in the absence of other HCs can generally be assumed to be propene. m/z 45 acetaldehyde (measured by not reported) Interference from ethylene glycol from mobile lab cooling system m/z 59 concmass59 (calibrated as acetone) Lyondellbasel facility produces propylene oxide which is an isomer of acetone and can not be distinguished. m/z 61 acetic acid (based on reaction kinetics and measured product branching ratio) Ethylacetate is an interference m/z 69 concmass69 (calibrated as isoprene) In combustion plumes (ie. auto exhaust) don t consider m/z 69 to be isoprene. There are industrial sources of isoprene in Houston m/z 71 concmass71 (calibrated as methacrolein/methyvinylketone) Ion is not unique at least in Houston. Pentene/cyclopentane, gasoline and other HC mixtures (paving) produce intensity at this mass. m/z 79 benzene (calibrated) Some interference from the fragmentation of ethylbenzene, propylbenzene and isopropylbenzene. m/z 93 toluene (calibrated) Generally free of interference except in the presence of cumenes (isopropyltoluene) which fragments to m/z 93. m/z 105 styrene (based on p-xylene calibration) Styrene monomer is used extensively in Houston area m/z 107 C2benzene (calibrated p-xylene) Assumes all isomers have the same response. Not compensation for fragmentation of ethylbenzene m/z 121 C3benzene (calibrated as 1,2,4-trimethylbenzene) Assumes all isomers have the same response. No correction has been made for fragmentation of propyl or isopropylbenzene. m/z 137 terpenes (calibrated as alpha pinene) Assumes all terpenes have the same response.

11 Additional Measurements CAPS extinction UTC, Extinction InverseMegaMeters, Mm-1 The human instrument QA/QC start/stop times classifying events industrial plume, car or truck exhaust, special event self sampling, blacklist chat logs Measurements Data Analysis Industrial Plumes Future Work

12 Airmar wind units 12

13 Overview and Conclusions Measurement Payload Mobile laboratory basics BEE-TEX The aromatics are: Benzene, toluene, ethyl benzene + xylene(s), tri-methyl benzenes Remote wind units Analysis of time-series/spatial data Mode or median probably more useful to represent area Differences in observed mixing ratios within study region Industrial Plumes in Channelview (Discover AQ) Ethene Benzene comparisons

14 Data timeseries Winds easterly Measurements Data Analysis Industrial Plumes Future Work

15 A Study Region Measurements Data Analysis Industrial Plumes Future Work

16 Channelview Measurements Data Analysis Industrial Plumes Future Work

17 CO 2 CO HCHO NO 2 Measurements Data Analysis Industrial Plumes Future Work

18 Measurements Data Analysis Industrial Plumes Future Work

19 CO 2 CO HCHO NO 2 Measurements Data Analysis Industrial Plumes Future Work

20 NO 2 medians Measurements Data Analysis Industrial Plumes Future Work

21 Drivetime/daytime NO 2 mixing ratio in study region NO 2 Mode Box Name ppbv Point 1.8 Llyondell Road 5.0 MarSec 4.3 inner 0.3 west 7.3 ksolve 6.6 body ±2.5 Home base 8.0* * Includes nighttime measurements Measurements Data Analysis Industrial Plumes Future Work

22 Overview and Conclusions Measurement Payload Mobile laboratory basics BEE-TEX The aromatics are: Benzene, toluene, ethyl benzene + xylene(s), tri-methyl benzenes Remote wind units Analysis of time-series/spatial data Mode or median probably more useful to represent area Differences in observed mixing ratios within study region Industrial Plumes in Channelview (Discover AQ) Ethene Benzene comparisons

23 Industrial Plumes in Channelview Yellow/Red enhancement in Benzene

24 The north side ethene, propene, butadiene, benzene south side uses feedstocks produced on the north plant to make propene oxide, styrene and other monomers Measurements Data Analysis Industrial Plumes Future Work

25 Pass 2 Winds easterly Measurements Data Analysis Industrial Plumes Future Work

26 Pass 3 Winds easterly Measurements Data Analysis Industrial Plumes Future Work

27 Ethene from Lyondell Measurements Data Analysis Industrial Plumes Future Work

28 The north side ethene, propene, butadiene, benzene south side uses feedstocks produced on the north plant to make propene oxide, styrene and other monomers Measurements Data Analysis Industrial Plumes Future Work

29 Industrial Plumes in Channelview Measurements Data Analysis Industrial Plumes Future Work

30 Measurements Data Analysis Industrial Plumes Future Work

31 Observed Benzene Emission Plume Events Source Date and Time SC WS m/s WD Dist km Benzene Emission Rate (g/s) Barge Area 9/4/13 17:10 B K-Solve 9/6/13 17:20 C Lyondell South 9/7/13 21:19 D Lyondell South 9/7/13 23:20 C Lyondell South 9/8/13 07:00 C Lyondell North1 9/8/13 20:10 C/D /6.5 Barge Area 9/8/13 22:50 C K-Solve 9/8/13 23:10 C K-Solve 9/9/13 23:30 C Lyondell South 9/11/13 12:12 C Lyondell South 9/11/13 13:04 C

32 Measurements Data Analysis Industrial Plumes Future Work Observed Benzene Emission Plume Events Source Date and Time SC WS m/s WD Dist km Benzene Emission Rate (g/s) Lyondell South 9/11/13 21:05 C Lyondell South 9/11/13 21:28 C Lyondell South 9/12/13 12:31 C Lyondell South 9/12/13 14:20 C Lyondell South 9/12/13 20:47 C Lyondell North2 9/13/13 19:14 C Lyondell North2 9/13/13 20:30 C

33 Overview and Conclusions Measurement Payload Mobile laboratory basics BEE-TEX The aromatics are: Benzene, toluene, ethyl benzene + xylene(s), tri-methyl benzenes Remote wind units Analysis of time-series/spatial data Mode or median probably more useful to represent area Differences in observed mixing ratios within study region Industrial Plumes in Channelview (Discover AQ) Ethene Benzene comparisons Tracer Release Bonus! Measurements Data Analysis Industrial Plumes Future Work

34 Flow Controller DAQ Computer GPS x2 Met. Station Wireless Trans. CB Radio Dual Tracer Release: C 2 H 2, N 2 O tracer A tracer B - Effective method to determine when site- wide measurements are being performed - Close plume transects provide rapid localization and semi-quantification of emission vectors local emitter identification MET MET Flow Controller DAQ Computer GPS x2 Met. Station Wireless Trans. CB Radio facility-level emissions 34

35 Tracer Release Overview Prevailing Wind Plume Intercept Area Tracer gases N 2 O and C 2 H 2 Released at fixed rates Fixed location (fence-line release) Mobile Lab Ambient sampling on downwind roads Multiple passes through multispecies plume

36 Instruments In The Mobile Laboratory TILDAS CO CH 4 C 2 H 6 N 2 O C 2 H 2 Li-COR CO 2 <100 ppt sensitivity 36

37 Why We Care About C 2 H 6 (Ethane) Different CH 4 sources exhibit different C 2 H 6 /CH 4 ratios Source C 2 H 6 /CH 4 Natural Gas 0.5% - 20% Cows 0% % 37

38 Spatially averaged Ethane/Methane (all plume events) compressor facility compressor facility cooperating processing facility wind all facility plumes Ethane/Methane Spatial cut to 50 m Ethane is a valuable corroborating species for source attribution

39 Aerosol and PTR-MS VOCs not observed at any Marcellus site Tracer Release Example

40 BEE-TEX Given the monitoring and modeling technologies to be deployed during BEE-TEX, what are the major scientific hypotheses that should be examined during the field study? The open path tomographic measurement and analysis will be a diagnostic for quantifying fluxes and exposures. Sophisticated emission plume models will be more accurate than simple gaussian plume models. How can the mobile labs best be deployed to address the aforementioned hypotheses? Collect accurate, rapid (1 Hz) measurement suite to identify source of perturbation (emission type). Use mobile monitor to build exposure map to accompany open path. Employ Tracer Release?

41 BEE-TEX What synergies can be exploited from the mix of monitoring technologies? Open path and in-situ comparisons. Local wind field for micromet dynamics. Rapid PTR and comprehensive VOC via GC What ancillary information will be required to properly interpret the data from the cultured human lung cell exposure device? What should the role of real-time data broadcasting be in the project? Aerodyne mobile lab will produce data with 1 day lag How can uncertainties in source attribution be quantified and minimized? 1. Cooperation with industrial partners in focus area 2. Broad suite of compounds, combustion tracers, ethane, GC 3. Wind, wind, wind

42 Future Work Determine Measurement Plan integrate PTRMS into mobile lab shakedown and recalibration Execute Measurement Plan last three weeks of May 2014

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45 Industrial Plumes in Channelview

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47 Llyondel North and South, Benzene Emission Estimates Dataset Channelview Data Industrial Plumes Future Work

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