Evolution of Ozone Precursor Measuring and the PAMs Project from 1992 to Present
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1 Evolution of Ozone Precursor Measuring and the PAMs Project from 1992 to Present Carol Meyer, Orsat, LLC Ozone Precursor Analyzer Lee Marotta, PerkinElmer
2 US Clean Air Act of 1992 US Mandated to the states in nonattainment of their ozone precursors that they monitor for four summer months a sample every hour. Essentially unattended operation: generators for combustion gases, controlled off-site to both collect data and to control system. A visit to the site every month to change carrier and fuel gases. An Ozone Precursor?
3 3 Current PAMS Sites
4 Current PAMS Sites Where I live YIKES! 4
5 System Configuration Continuous Ambient Air Sampling Sample Manifold Online Sampling Accessory Sample Calibrant Nafion drier Sample Pump Clarus 500 Gas Chromatograph Turbomatrix Thermal Deserbor Calibrant System 8/1 PerkinElmer INspiring INnovation Event November 15, 2012
6 Focusing 600mL of Sample (15mL/min for 40 min) Optional inlet split (off) Desorb flow xxxxxx Peltier-cooled focusing trap no liquid cryogen required to meet -35 o C Injection every hour Chromatography of previous sample is occurring as next sample is being collected onto the trap Carrier gas
7 Trap desorption in opposite direction of sampling Optional outlet split Analytical column FID heated trap Carrier gas in Analytical column Trap heats at 99 degrees / sec to efficiently desorb cold trap
8 Cold Trap Reduced diameter outlet reduces analyte dispersion or band broadening for narrower, focused peaks Trap is backflushed during desorption to recovery components Sorbent(s) Glass Wool Sample In/Out 0.7 mm xxxxxxxxx xxxxxxxxx xxxxxxxxx xxxxxxxxx Glass Tube Disks Packing Retaining Spring 2.8 mm
9 Air Toxics and Ozone Precursor Cold Trap graphitized carbon black sample in/out carbon molecular sieve
10 n-hexane C 2 hydrocarbons n-undecane Heart cut via Dean Switch All components eluting from methyl silicone column to determine heart cut time 30ppb canister standard at 15mL/min for 40min 600 ml sample cut
11 Volatiles onto PLOT split P1 trap P2 FID 1 50m x 0.22mm x 1µm methyl silicone column 50m x 0.32mm alumina/na 2 SO 4 PLOT column FID 2
12 C6 plus BP-1 split P1 trap P2 FID 1 50m x 0.22mm x 1µm methyl silicone column 50m x 0.32mm alumina/na 2 SO 4 PLOT column FID 2
13 Chromatography Alumina PLOT Chromatogram Methyl Silicone Chromatogram
14 Target Analyte List PLOT Column BP1 Column Methane** 1,3-Butadiene n-hexane 2-Methylheptane n-decane Ethane 2-Methyl-1-Butene* Trans-2-Hexene* 3-Methylheptane 1,2,3-trimethylbenzene Ethylene Cyclopentene Cis-2-Hexene* N-Octane m-diethylbenzene* Propane Trans-2-Pentene Methylcyclopentane Ethyl Benzene p-diethylbenzene* Propylene 2-Methyl-2-Butene* 2,4-Dimethylpentane m + p-xylene n-undecane* Isobutane 1-Pentene Benzene Styrene α-pinene* n-butane Cis-2-Pentene Cyclohexane o-xylene β-pinene* Acetylene 2,2-Dimethylbutane 2-Methylhexane n-nonane Trans-2-Butene 2,3-Dimethylbutane* 2,3-Dimethylpentane Isopropyl Benzene 1-Butene 2-Methylpentane 3-Methylhexane n-propylbenzene Isobutene 3-Methylpentane* 2,2,4-Trimethylpentane m-ethyltoluene* Cis-2-Butene Isoprene n-heptane p-ethyltoluene* Cyclopentane 4-Methyl-1-Pentene* Methylcyclohexane 1,3,5- trimethylbenzene Isopentane 2-Methyl-1-Pentene* 2,3,4-Trimethylpentane o-ethyltoluene* n-pentane 1-Hexene* Toluene 1,2,4-trimethylbenzene * Components no longer reported by TCEQ ** not quantitatively trapped 8/10/2013
15 1994 C.O.A.S.T Project State of Texas Program Supported by Orsat
16 November 15, 2012 Several Requirements Capable of separating 56 hydrocarbon species each hour. Fully automated to allow automatic introduction of a daily check standard and system blank Daily Calibration Verification Standard (CVS) 15 components across boiling point range 3-point calibration curve Additional second source standards and retention time standards run weekly Automated file handling generating 144 data files each day/site Current Network of 35 sites reporting hourly data (31 public) Current Target list of 46 compounds Concentrations reported as ppbc 8/10/2013 PerkinElmer INspiring INnovation Event
17 Multi-point Calibration Propane and Benzene 8/1 PerkinElmer INspiring INnovation Event November 15, 2012
18 Air Monitoring Stations in Texas Dallas Hinton Region 4 - Dallas - Fort Worth Dallas PAMS 1999 Fort Worth Northwest Fort Worth PAMS 2003 Eagle Mountain Lake Fort Worth - Barnett Shale CATMN 2010 DISH Fort Worth - Barnett Shale CATMN 2010 Decatur Fort Worth - Barnett Shale CATMN 2010 Flower Mound Fort Worth - Barnett Shale CATMN 2010 Everman Fort Worth - Barnett Shale CATMN 2011 Kennedale Fort Worth - Barnett Shale CATMN 2012 Mansfield Fort Worth - Barnett Shale CATMN 2012 Rhome (TBD) Fort Worth - Barnett Shale CATMN 2012 OD Wyatt (TBD) Fort Worth - Barnett Shale CATMN 2012 UT Arlington Campus Fort Worth - Barnett Shale CATMN 2012 Dallas County (TBD) Fort Worth - Barnett Shale CATMN 2013 Johnson County (TBD) Fort Worth - Barnett Shale CATMN 2013 Tarrant County (TBD) Fort Worth - Barnett Shale CATMN 2013 El Paso Chamizal Region 46 - El Paso - Juarez El Paso PAMS 1997 El Paso Delta El Paso CATMN 2011 Region 7 - Odessa - Midland Odessa Hays Odessa CATMN 1999 Dallas/Ft. Worth: 15 Houston/Galveston/Brazoria: 12 Corpus Christi: 3 Beaumont/Pt. Arthur: 2 El Paso: 2 Odessa : 1 8/1 PerkinElmer INspiring INnovation Event November 15, 2012
19 Air Monitoring Stations in Texas, continue Nederland Region 10 - Beaumont - Port Arthur Beaumont-Pt. Arthur PAMS 2006 Beaumont Downtown Beaumont-Pt. Arthur PAMS 2006 Clinton Region 12 - Houston - Galveston - Brazoria Houston PAMS 1997 Deer Park Houston PAMS 1997 Channelview Houston PAMS 2001 HRM3 Houston EIMS 2003 Lynchburg Ferry Houston EIMS 2003 Wallisville Houston EIMS 2003 Texas City Texas City EIMS 2003 Lake Jackson Lake Jackson EIMS 2003 Danciger Danciger EIMS 2003 Cesar Chavez Houston CATMN 2004 Milby Park Houston CATMN 2005 HRM16 Houston Industry 2010 Region 14 - Corpus Christi - Victoria Oak Park Corpus Christi CATMN 2005 Solar Estates Corpus Christi CATMN 2005 CC Palm Corpus Christi CATMN 2010 PAMS 8 EIMS/Industry 7 CATMN 20 Total 35 11/ PerkinElmer INspiring INnovation Event November 15, 2012 EIMS Extended Industry Monitoring Site CATMN Community Air Toxics Monitoring Site
20 Automated file handling!!! generating 144 data files each day/site! Managing the data
21 TCEQ Web Based Data Reporting and Validation The key to handling large amounts of data consistently over long periods of time is Automation of Data Handling Consistent Application of Validation Rules Control of System Performance 8/ PerkinElmer INspiring INnovation Event November 15, 2012
22 What s different about Texas sampling? Year round sampling The use of two data bases for information LEADS Oracle
23 8/ November 15, 2012 TCEQ Web Based Data Reporting and Validation LEADS Database* Repository of hourly data collected directly from monitoring sites Updated with data which has been validated Database used for real-time Public Display of monitoring values Oracle Database Data is loaded daily by QC Validation staff System for the display and review of all quality control data Allows reload of reprocessed data Allows for flagging invalid data Allows calculation of Data Recovery Generation of EPA AQS files Review of operator and validator logs Other miscellaneous database management functions PerkinElmer INspiring INnovation Event * LEADS - Leading Environmental Analysis & Display software developed by IPS Meteostar
24 8/ November 15, 2012 TCEQ Web Based Data Reporting and Validation System for Display and Review of Quality Controls Display CVS, LCS, RTS and Blank Data Shows QC failures Shows Status Information Calibration Standards (LCS and CVS) with Dilution Factors Operator and Validator contact information Generation of Control Charts for LCS and CVS data Indicators for Audit Samples which have been run Shows Precision Each Sunday two CVS runs Day-to-day precision calculations Comparative results for CVS/LCS PerkinElmer INspiring INnovation Event
25 Will go through these quickly Example of reports from oracle The results!
26 TCEQ Web Based Data Reporting and Validation 8/ PerkinElmer INspiring INnovation Event November 15, 2012
27 Quicklook Daily Data Report Page 1 Collection Hour Sample Type File Name Reprocess Date Missing Targets TNMHC Total UnID d Wind Speed Wind Direction 8/ PerkinElmer INspiring INnovation Event November 15, 2012
28 Quicklook Daily Data Report Page 2 Ambient Data Flags PLOT Column 8/ PerkinElmer INspiring INnovation Event November 15, 2012
29 Quicklook Daily Data Report Page 3 Ambient Data Flags BP-1 Column 8/ PerkinElmer INspiring INnovation Event November 15, 2012
30 Quality Control Reports Quality Control Navigation 8/ PerkinElmer INspiring INnovation Event November 15, 2012
31 Quality Control Reports Date Range and Site Selection 8/ PerkinElmer INspiring INnovation Event November 15, 2012
32 Quality Control Reports Weekly RTS 8/ PerkinElmer INspiring INnovation Event November 15, 2012
33 Quality Control Reports Weekly LCS 8/ PerkinElmer INspiring INnovation Event November 15, 2012
34 Quality Control Reports Graph Weekly LCS 8/ PerkinElmer INspiring INnovation Event November 15, 2012
35 Quality Control Reports Daily CVS 8/ PerkinElmer INspiring INnovation Event November 15, 2012
36 Quality Control Reports Graph Daily CVS 8/ PerkinElmer INspiring INnovation Event November 15, 2012
37 Quality Control Reports Daily Blanks 8/ PerkinElmer INspiring INnovation Event November 15, 2012
38 Site Operator Log Reports 8/ PerkinElmer INspiring INnovation Event November 15, 2012
39 Summary Automated Online Sampling - for sample and calibrant Remote Access Control Overlapping - Analytical Run Time Low Volume Cold Trap Auto Log - data integrity Automatic Leak Check per Injection Focusing and Chromatography without liquid cryogen Get info on web when you want it Total Solution
40 ??? Ozone Precursor Analyzer Contact Carol Information Meyer, Orsat, LLC Lee Marotta, PerkinElmer
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