Hydrogen Peroxide Methylhydroperoxide Formaldehyde Peroxide Methylhydroperoxide Formaldehyde (Peroxyacetic Acid) ... OOH, ppt CH 2 O(NCAR), ppb Formaldehyde Acetaldehyde, Acetone, Methanol, ...

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Hydrogen PeroxideMethylhydroperoxideFormaldehyde & (Peroxyacetic Acid)Brian G. Heikes & Haiwei Shen, URIDaniel W. OSullivan, USNAJulie A. Snow, Slippery Rock U. Tropospheric Ozone Radical Oxidants: HO, HO2, CH3OO, CH3C(O)OO ? Carbon Processing: HCs -> CH2O -> CO ; CH2O lifetime and carbon flux through CH2O CH3OOH or CH2O ; methane world vs nonmethane world CH3C(O)OOH (HO2 vs NO2) ; Extension of Trop-Chem Measurements by Satellite: CH2O directly Combined with other compounds and campaigns Vertical Transport & Mixing Tracers, Yes Working on being quantitative Instrument Development & Comparison H2O2 : URI, CIT & BAE146 CH2O: URI, NCAR & WP3Our INTEX ObjectivesIn Measuring Title CompoundsInstrument Changes and Comparison CH2O pre-mission, during, & prototype Simplified FIA system; improved noise Modified signal processing; noise vs response time Stability allows for continuous measurements Last Five Flights (16-20; 8/6,7,11,13 &14) 1 minute resolution with continuous sampling 25 pptv level of detection CH2O Relationships with Other Compounds 0 1 2 3 4 5 6 701234567CH2O, ppb (URI)CH2O, ppb (NCAR) DC-8 Flt06 07/10/04Major Axis Reg.(All); DottedIntercept = -7.7781 16.4423 Slope = 1.4846 0.016654corr-coef = 0.95706MatLab Robust Fit; Solidb(robfit) = 58.048m(robfit) = 1.41830 1 2 3 4 5 6 701234567CH2O, ppb (URI)CH2O, ppb (NCAR) DC-8 Flt19 08/13/04Major Axis Reg.(All); DottedIntercept = -97.5188 9.0237 Slope = 1.1835 0.01175corr-coef = 0.95563MatLab Robust Fit; Solidb(robfit) = -54.7793m(robfit) = 1.0647Direct comparison, URI & NCAR, 10-s Merge Productred ascent/descent green level blue Xw > 1%~1.1~1.5Formaldehyde Robust Fit Regression: NCAR = URI*slope + intercept0.000.200.400.600.801.001.201.401.601.806/22/2004 7/2/2004 7/12/2004 7/22/2004 8/1/2004 8/11/2004 8/21/2004Date of FlightSlope-80-60-40-20020406080100120Interceptm-robustb-robustLinear (m-robust)Formaldehyde Relationships with Parents & Daughter Carbon Monoxide, Ethane, Propane, & Benzene0 200 40001234CO, ppbCH2O(URI), ppb DC-8 Flt6 07/10/040 5000 1000001234C2H6, pptCH2O(URI), ppb0 2000 400001234C3H8, pptCH2O(URI), ppb0 100 20001234benzene, pptCH2O(URI), ppb0 200 400-202468CO, ppbCH2O(NCAR), ppb0 5000 10000-202468C2H6CH2O(NCAR), ppb0 2000 4000-202468C3H8, pptCH2O(NCAR), ppb0 100 200-202468benzene, pptCH2O(NCAR), ppb0 50001234C2H2, ppbCH2O(URI), ppb DC-8 Flt6 07/10/040 200 40001234C2H4, pptCH2O(URI), ppb0 2000 400001234isoprene, pptCH2O(URI), ppb0 50 10001234C3H6, pptCH2O(URI), ppb0 500-202468C2H2, ppbCH2O(NCAR), ppb0 200 400-202468C2H4, pptCH2O(NCAR), ppb0 2000 4000-202468isoprene, pptCH2O(NCAR), ppb0 50 100-202468C3H6, pptCH2O(NCAR), ppbFormaldehyde Relationships Continued Ethyne, Ethene, Isoprene, & Propene0 1000 200001234CH3CHO, ppbCH2O(URI), ppb DC-8 Flt6 07/10/040 5000 1000001234CH3COCH3, pptCH2O(URI), ppb0 5000 1000001234CH3OH, pptCH2O(URI), ppb0 1000 200001234CH3OOH, pptCH2O(URI), ppb0 1000 2000-202468CH3CHO, ppbCH2O(NCAR), ppb0 5000 10000-202468CH3COCH3, pptCH2O(NCAR), ppb0 5000 10000-202468CH3OH, pptCH2O(NCAR), ppb0 1000 2000-202468CH3OOH, pptCH2O(NCAR), ppbFormaldehyde Acetaldehyde, Acetone, Methanol, Methylhydroperoxide0 50 10001234HO2, pptCH2O(URI), ppb DC-8 Flt6 07/10/040 50 10001234O3, ppbCH2O(URI), ppb10210410601234H2O(proj), ppmCH2O(URI), ppb10-210-110001234HO, pptCH2O(URI), ppb0 50 100-202468HO2, pptCH2O(NCAR), ppb0 50 100-202468O3, ppbCH2O(NCAR), ppb102 104 106-202468H2O(proj), ppmCH2O(NCAR), ppb10-2 10-1 100-202468HO, pptCH2O(NCAR), ppbFormaldehyde Perhydroxyl, Ozone, Water, & Hydroxyl0 2 42004006008001000P, hPaCH2O(URI), ppb DC-8 Flt6 07/10/040 50 10001234RH(water), %CH2O(URI), ppb10010210401234NO2, pptCH2O(URI), ppb0 1 2x 10401234SO2, pptCH2O(URI), ppb0 52004006008001000P, hPaCH2O(NCAR), ppb0 50 100-202468RH(water), %CH2O(NCAR), ppb100102104-202468NO2, pptCH2O(NCAR), ppb0 1 2x 104-202468SO2, pptCH2O(NCAR), ppbFormaldehyde vsPressure, RH, Nitrogen Dioxide, Sulfur DioxideInstrument Changes & Comparison H2O2 / CH3OOH / CH3C(O)OOH Initial setup for H2O2 / CH3OOH alone StL Samples Indicated 3rd ROOH; PAA on CIT New HPLC Column online in Portsmouth Tests for hydroxymethylhydroperoxide negative Tests for peroxyacetic acid positive Modify mode and run times to resolve PAA, PAA is a work in progress (~3 months more) Hence, less frequent sampling from NH on. 0 2 4 6 8 10-1012345678910H2O2, ppb (URI)H2O2, ppb (CalTech) DC-8 Flt06 07/10/04M-A RegressionM-A Regression, Hydrogen Peroxide Robust Fit: CIT = URI * slope + intercept00.20.40.60.811.21.47/7 7/12 7/17 7/22 7/27 8/1 8/6 8/11 8/16Flight DateSlope050100150200250Interceptm-robustb-robust0 20 4001234HO2, pptH2O2(URI), ppb DC-8 Flt8 07/15/040 100 20001234O3, ppbH2O2(URI), ppb10010501234H2O(proj), ppmH2O2(URI), ppb10-210-110001234HO, pptH2O2(URI), ppb0 20 4001234HO2, pptH2O2(CIT), ppb0 100 20001234O3, ppbH2O2(CIT), ppb10010501234H2O(proj), ppmH2O2(CIT), ppb10-210-110001234HO, pptH2O2(CIT), ppbHydrogen Peroxide RelationshipsPerhydroxyl, Ozone, Water, & HydroxylHydrogen Peroxide Pressure, RH, Nitrogen Dioxide, Sulfur Dioxide0 2 42004006008001000P, hPaH2O2(URI), ppb DC-8 Flt8 07/15/040 50 10001234RH(water), %H2O2(URI), ppb10-5 100 10501234NO2, pptH2O2(URI), ppb0 1000 200001234SO2, pptH2O2(URI), ppb0 2 42004006008001000P, hPaH2O2(CIT), ppb0 50 10001234RH(water), %H2O2(CIT), ppb10-5 100 10501234NO2, pptH2O2(CIT), ppb0 1000 200001234SO2, pptH2O2(CIT), ppb0 500 100001234CH3CHO, ppbH2O2(URI), ppb DC-8 Flt8 07/15/040 5000 1000001234CH3COCH3, pptH2O2(URI), ppb0 5000 1000001234CH3OH, pptH2O2(URI), ppb0 1000 200001234CH3OOH, pptH2O2(URI), ppb0 500 100001234CH3CHO, ppbH2O2(CIT), ppb0 5000 1000001234CH3COCH3, pptH2O2(CIT), ppb0 5000 1000001234CH3OH, pptH2O2(CIT), ppb0 1000 200001234CH3OOH, pptH2O2(CIT), ppbHydrogen Peroxide Acetaldehyde, Acetone, Methanol, MethylhydroperoxideCase Study: August 11, 2004; DC-8 Flight 1812345678910New Brunswick Far Off N. CarolinaSt Louis Far Off N. Carolina2040 60 801001200510Altitude(GPS), kmO3, ppb DC-8 Flt18 08/11/0422040 60 801001200510O3, ppb32040 60 8010012005104O3, ppb2040 60 8010012005105O3, ppb20 40 60 8010012005106O3, ppb2040 60 80100120024681012Altitude(GPS), km10O3, ppb2040 60 801001200246810129O3, ppb2040 60 801001200246810128O3, ppb2040 60 801001200246810127O3, ppb20 40 60 801001200246810126O3, ppbNew Brunswick Far Off N. CarolinaSt Louis Far Off N. Carolina50 100 1500510Altitude(GPS), kmCO, ppb DC-8 Flt18 08/11/04250 100 1500510CO, ppb350 100 15005104CO, ppb50 100 15005105CO, ppb50 100 15005106CO, ppb50 100 1500510Altitude(GPS), km10CO, ppb50 100 15005109CO, ppb50 100 15005108CO, ppb50 100 15005107CO, ppb50 100 15005106CO, ppb0 5000 100000510Altitude(GPS), kmCH3OOH (CH2O or H2O2), ppt DC-8 Flt18 08/11/0420 50000510CH3OOH (CH2O or H2O2), ppt30 500005104CH3OOH (CH2O or H2O2), ppt0 500005105CH3OOH (CH2O or H2O2), ppt0 500005106CH3OOH (CH2O or H2O2), ppt0 5000024681012Altitude(GPS), km10CH3OOH (CH2O or H2O2), ppt0 50000246810129CH3OOH (CH2O or H2O2), ppt0 50000246810128CH3OOH (CH2O or H2O2), ppt0 50000246810127CH3OOH (CH2O or H2O2), ppt0 50000246810126CH3OOH (CH2O or H2O2), pptNew Brunswick Far Off N. CarolinaSt Louis Far Off N. Carolinagrn H2O2 blk CH3OOH red CH2O(URI) mag CH2O(NCAR)New Brunswick Far Off N. CarolinaSt Louis Far Off N. Carolinagrn H2O2 blk CH3OOH red CH2O(URI) mag CH2O(NCAR)0 500 10000510Altitude(GPS), kmCH3OOH (CH2O or H2O2), ppt DC-8 Flt18 08/11/0420 500 10000510CH3OOH (CH2O or H2O2), ppt30 500 100005104CH3OOH (CH2O or H2O2), ppt0 500 100005105CH3OOH (CH2O or H2O2), ppt0 500 10000510CH3OOH (CH2O or H2O2), ppt0 500 10000510Altitude(GPS), km10CH3OOH (CH2O or H2O2), ppt0 500 100005109CH3OOH (CH2O or H2O2), ppt0 500 100005108CH3OOH (CH2O or H2O2), ppt0 500 100005107CH3OOH (CH2O or H2O2), ppt0 500 10000510CH3OOH (CH2O or H2O2), pptSummaryCH2O MeasurementsURI to NCAR comparison factor of 1.1 to 1.6Highly correlatedIndicate same functional relationships to other compoundsH2O2 MeasurementsURI to CIT comparison factor of 0.7 to 1.2Well correlated with outliers, better when XvCase Study: August 2, 2004; DC-8 Flight 151234567 8910111213140 100 200024681012Altitude(GPS), kmO3, ppb DC-8 Flt15 08/02/0430 100 200024681012O3, ppb40 100 2000246810125O3, ppb0 100 2000246810126O3, ppb0 100 2000246810127O3, ppb0 100 200024681012Altitude(GPS), km8O3, ppb0 100 20002468101214O3, ppb0 100 20002468101213O3, ppb0 100 20002468101212O3, ppb0 100 20002468101211O3, ppb0 100 20002468101210O3, ppb0 100 2000246810129O3, ppbS. Quebec N. New FoundlandS. Maine S. New FoundlandS. Quebec N. New FoundlandS. Maine S. New Foundland50 100150024681012Altitude(GPS), kmC O , ppb D C -8 F lt15 08/02/04350 100150024681012C O , ppb450 1001500246810125C O , ppb50 1001500246810126C O , ppb50 100 1500246810127C O , ppb50100150024681012Altitude(GPS), km8C O , ppb50 10015002468101214C O , ppb50 10015002468101213C O , ppb50 10015002468101212C O , ppb50 10015002468101211C O , ppb50 100 15002468101210C O , ppb501001500246810129C O , ppbS. Quebec N. New FoundlandS. Maine S. New Foundland0 5000024681012Altitude(GPS), kmCH3OOH (CH2O or H2O2), ppt DC-8 Flt15 08/02/0430 5000024681012CH3OOH (CH2O or H2O2), ppt40 50000246810125CH3OOH (CH2O or H2O2), ppt0 50000246810126CH3OOH (CH2O or H2O2), ppt0 50000246810127CH3OOH (CH2O or H2O2), ppt0 5000024681012Altitude(GPS), km8CH3OOH (CH2O or H2O2), ppt0 500002468101214CH3OOH (CH2O or H2O2), ppt0 500002468101213CH3OOH (CH2O or H2O2), ppt0 500002468101212CH3OOH (CH2O or H2O2), ppt0 500002468101211CH3OOH (CH2O or H2O2), ppt0 500002468101210CH3OOH (CH2O or H2O2), ppt0 50000246810129CH3OOH (CH2O or H2O2), pptgrn H2O2 blk CH3OOH red CH2O(URI) mag CH2O(NCAR)S. Quebec N. New FoundlandS. Maine S. New Foundlandgrn H2O2 blk CH3OOH red CH2O(URI) mag CH2O(NCAR)0 50010000510Altitude(GPS), kmCH3OOH (CH2O or H2O2), ppt DC-8 Flt15 08/02/0430 50010000510CH3OOH (CH2O or H2O2), ppt40 500100005105CH3OOH (CH2O or H2O2), ppt0 500100005106CH3OOH (CH2O or H2O2), ppt0 500100005107CH3OOH (CH2O or H2O2), ppt0 50010000510Altitude(GPS), km8CH3OOH (CH2O or H2O20 5001000051014CH3OOH (CH2O or H2O2), ppt0 5001000051013CH3OOH (CH2O or H2O2), ppt0 5001000051012CH3OOH (CH2O or H2O2), ppt0 5001000051011CH3OOH (CH2O or H2O2), ppt0 5001000051010CH3OOH (CH2O or H2O2), ppt0 500100005109CH3OOH (CH2O or H2O2

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