Baltimore Supersite. Measurements of Elemental and Organic Carbon in PM2.5 at Ponca St. Feb./Mar. Nov. 2002
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1 Baltimore Supersite Measurements of Elemental and Organic Carbon in PM2.5 at Ponca St. Feb./Mar. Nov. 22 Seung Shik Park, David Harrison, Narayanan Nair, and John Ondov Department of Chemistry and Biochemistry University of Maryland, College Park, MD 2742 ;
2 Objective/Scope Present Summary Statistics for EC,OC - Feb. Dec. 22 Characterize EC, OC, and Organic Markers during worst PM2.5 Episodes - Ramifications for Urban Excess vs Regional control strategies Data discussed Project period, Episodes EC, OC Sunset Labs, thermal optical, 6 min PM2.5 3 o TEOM, 3 min Met WD, WS various, 5 min Two worst episodes Molecular Organic Markers 3-hr, Filter/PUF-GCMS (Rogge & Bernardo- Bricker) Baltimore Ponca St., East Balt. Can local stationary or area source control reduce urban excess?
3 Sources affecting Ponca St. Measurements 3 o 3 o 24 o 24 o 19 o to 2 19 o to o 2 o o o
4 PM2.5 Summary Statistics 316 days, 22 3-min concentrations, µg/m 3 all data w/out Canadian Smoke Mean = 16.9± ± 11 Max = Numbers of 24-hr means (w/out Canadian Smoke): 65 µg/m Frequency of incidences (>3 µg/m 3 ) by type (5% traffic related; 42% sulfate haze; 8% Canadian Smoke) Observations: - Barely out of attainment for annual PM2.5 Standard - 24-hr exceedences rare
5 3-min PM 2.5 Concentrations: Reveal 29 Episodes Episodes A F discussed in Park et al., 24 PM2.5, µg/m 3 PM2.5, µg/m 3 PM2.5, µg/m 3 PM2.5, µg/m E Mar Mar Apr Apr Apr May May Jun Jun Jul Jul Jul D reconstructed A B C Aug Aug Sep Sep Sep Oct Oct Nov Nov Dec Dec Dec F Canadian Smoke (off scale)
6 Hourly EC and OC were adjusted to STN Units: µg C/m hr integrated MetOne EC (µg C/m 3 ) Sunset EC vs. MetOne EC Regression line After 4 outliers removed (c) y = 1.13 x +.44 (R 2 =.91) 24-hr integrated MetOne OC (µg C/m 3 ) Sunset OC vs MetOne OC Regression line After 3 outliers removed (d) y = 1.28 x +.71 (R 2 =.95) hr average Sunset EC (µg C/m 3 ) hr average Sunset EC (µg C/m 3 ) EC STN = 1.13 EC SL +.44 R 2 =.91 OC STN = 1.28 OC SL +.71 R 2 =.95
7 OC statistics, Ponca st., 22 (hourly data) Study mean, Range 5.7 µg C/m to 9 µg C/m 3 (33.6±1.6% of PM2.5) Organic carbon conc (µg C/m 3 ) 1 Box-W hisker plot (OC) (a) 1 1 Horizontal lines and two circles : 5th ~ 95th percentiles Dashed line : mean value Canadian Smoke 7 AM Nov. 2 th Feb M ar Apr M ay June July Aug Sept Oct Nov M easurement month (22) OC was consistently a substantial fraction of PM2.5
8 EC statistics Ponca st., 22 Study mean: 1.1 µg C/m 3 (7.3±3.8% of PM2.5) range.4 to 12 µg C/m3 Elemental carbon conc (µg C/m 3 ) 1 1 (b) Box-W hisker plot (EC) Horizontal lines and two circles : 5th ~ 95th percentiles Dashed line : mean value Includes Canadian Smoke Episode 7 AM Nov. 2 th.1 Feb M ar Apr M ay June July Aug Sept Oct Nov Measurement month (22) Max 1-hr EC and OC 7: AM EST, Nov. 2th 22
9 Diurnal profiles indicate large traffic Influence OC (µg C/m 3 ) W hole period OC EC CO EC (µg C/m 3 ) or CO(x2 ppm) T im e of the day (hr) OC (µg C/m 3 ) August Time of the day (hr) OC EC CO EC (µg C/m 3 ) or CO(x2 ppm) November Time of the day (hr) Features: AM traffic peak; OC increases earlier than EC, CO OC increases relative to EC during mid-day ozone excursions, e.g., June and August OC (µg C/m 3 ) OC EC CO EC (µg C/m 3 ) or CO(x2 ppm)
10 Selected Episodes Episode C: July Regional Haze Episode F: Nov Traffic dominated
11 Episode C: July Regional Haze PM 2.5 mass conc (µg/m 3 ) Wind speed (m/sec) PM2.5 mass Sulfate Organic carbon Measurement period Episode C 7/17/2 7/18/2 7/19/2 7/2/ Wind speed Wind direction stagnation Episode C 7/17/2 7/18/2 7/19/2 7/2/2 M easurement period Wind direction (deg) Sulfate and OC conc (µg/m 3 ) Main episode: Local winds from W to NW, shifting to NW to N
12 Episode C: OC and EC moderate ozone OC/EC ratio OC/EC-O 3 OC/EC ratio O O3 conc (ppb) 7/17/2 7/18/2 7/19/2 7/2/2 7/21/2 OC:EC =
13 Primary and Secondary OC Episode C (OC)pri, (OC)sec (µg C/m 3 ) Pri OC Sec OC 7/17/2 7/18/2 7/19/2 7/2/2 7/21/2 traffic induced Measurement period Mostly Secondary OC except for traffic induced excursions!
14 Episode F: November 2 7:AM, stagnation November stagnation (OC +EC) PM2.5 mass contribution (ug/m 3 ) 11/2/2 : 11/2/2 1: 11/2/2 2: 11/2/2 3: 11/2/2 4: 11/2/2 5: 11/2/2 6: 11/2/2 7: 11/2/2 8: 11/2/2 9: 11/2/2 1: 11/2/2 11: 11/2/2 12: 11/2/2 13: 11/2/2 14: 11/2/2 15: 11/2/2 16: 11/2/2 17: 11/2/2 18: 11/2/2 19: 11/2/2 2: 11/2/2 21: 11/2/2 22: 11/2/2 23: Measurement period Undetermined Organics EC (NH4)2SO4 NH4NO3 Episode F Excellent Correlation: EC,OC, NOx, CO
15 Episode F: Low ozone, low Mixing height, cool OC (µg C/m 3 ), OC/EC ratio (-) Nov 19~21 OC OC/EC ratio EC EC (µg C/m 3 ) OC=2.98 EC (R 2 =.86) 11/19/2 11/2/2 11/21/2 11/22/2 Measurement period OC/EC = ~3 OC and EC well correlated in cool, low mixing height periods
16 Episode F subsidence venting of the I895/I95 corridor Occurred after winds slowed, turned northerly, allowing subsidence venting of the I895/I95 corridor to the monitoring site WS WD(1-min) Wind direction (deg) Col 43 vs NOx Col 43 vs CO /19/2 11/2/2 11/21/ CO (ppm)
17 2 o Toll Booths
18 Primary and Secondary OC (OC) pri, (OC)sec (µg C/m 3 ) pri OC sec OC 11/19/2 11/2/2 11/21/2 11/22/2 Measurement period Primary OC Secondary OC
19 Organic Markers ( Rogge( data ) Episode F
20 Episode F Traffic Markers? n-alkanes norm conc n-alkanes Alkylcyclohexanes PAHs Oxy-PAHs Pentacyclic Triterpanes (Hopanes).2. 11/19/22 11/2/22 time 11/21/22 11/22/22 7: AM Peak CPI = 1. (C27-C35) and 1.3 (C19-26) for n-alkanes, consistent with DIESEL 7.6 (C24-C33) for n-alkanoic acids; consistent with VASCULAR PLANTS! n-alkanes: 39 ng/m3 n-alkanoic acids: 2 ng/m3 PAH: 114 ng/m3 Fraction of Sunset OC identified: ~3%
21 Heterocyclic PAH n-alkanes conc n-alkanes S-Hetero-PAH (Dibenzothiphene) S Dibenzothiophene High S diesel? or coke plant? S-Hetero-PAH conc 11/19/22 11/2/22 time 11/21/22 11/22/22.12 N-Hetero-PAH conc N 7,8-Benzoquinoline N-Hetero-PAH. 11/19/22 11/2/22 time 11/21/22 11/22/22 Thiazoles conc Thiazoles dibenzothiazole N S Benzothiazole (tire wear) 5 11/19/22 11/2/22 time 11/21/22 11/22/22
22 Thiazoles conc Resin acids and steroids vs. Benzothiazole Thiazoles dibenzothiazole 6: to 9: AM N S Benzothiazole (tire wear) Resin Acids conc Steroids conc 11/19/22 11/2/22 11/21/22 11/22/22 time /19/22 11/2/22 time 11/21/22 11/22/ Resin Acids Steroids Cholesterol + b-sitosterol 11/19/22 11/2/22 time 11/21/22 11/22/22
23 General wood burning marker 6: to 9: AM Sugars conc Sugars Levoglucosan 11/19/22 11/2/22 11/21/22 11/22/22 time Phenolic Woodmarkers conc Phenolic Woodmarkers 11/19/22 11/2/22 11/21/22 11/22/22 time Syringaldehyde (as 3,4,5-trimethoxy benzaldehyde) + Acetosyringone (as 3,4,5-trimethoxyacetophene) + Syringic acid ME (as 3,4,5-trimethoxybenzoic acid, ME)
24 Gasoline oxidation products? Aliphatic Dicarboxylic Acids conc Aliphatic Dicarboxylic Acids C5 C9 e.g. Propandioic Acid. 11/19/22 11/2/22 time 11/21/22 11/22/22 Aromatic Polycarboxylic Acids conc Aromatic Polycarboxylic Acids Mostly phthalic acid 6,1,14-trimethyl-2-pentadecanone 11/19/22 11/2/22 time 11/21/22 11/22/22
25 Secondary terpene oxidation products Norpinone + Norpinonic acid + cispinonic acid Secondary Biogenic Oxidation Products conc Secondary Biogenic Oxidation Products 11/19/22 11/2/22 time 11/21/22 11/22/22
26 Conclusions Part II. Despite the hard work, only 3 to 5% of OC has been characterized! What we thought was a largely a traffic induced episode, appears to have biomass combustion, meat cooking, and secondary terpene oxidation products, as well! CMB would be needed to sort this out! The 6: to 9: AM excursion may have resulted from the subsidence of highly polluted air along the I895/I95 corridor at 3 o Such hot spots likely exist at various locations in and around Baltimore Part I. The EC:OC method suggests secondary POC is ~5% of total POC, even during what we thought was largely a traffic induced episode. Wood combustion and meat cooking may have contributed oxygenated OM to this, but it is doubtful that these sources could have accounted for so much OC. Unidentified Mass responsible?
GAMINGRE 8/1/ of 7
FYE 09/30/92 JULY 92 0.00 254,550.00 0.00 0 0 0 0 0 0 0 0 0 254,550.00 0.00 0.00 0.00 0.00 254,550.00 AUG 10,616,710.31 5,299.95 845,656.83 84,565.68 61,084.86 23,480.82 339,734.73 135,893.89 67,946.95
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