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MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting...
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![Page 1: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/1.jpg)
MRPO Nitrate and Organic Speciation Special Studies
Donna Kenski
National RPO Technical Meeting
Dallas, Dec. 3-4, 2002
![Page 2: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/2.jpg)
Bondville
Seney
![Page 3: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/3.jpg)
![Page 4: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/4.jpg)
![Page 5: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/5.jpg)
Key Components at Bondville
• Dasgupta monitor: measures gaseous nitric acid, sulfur dioxide, and ammonia (estimated limits of detection 10, 15 and 100 parts per trillion by volume, respectively) for a 15 min period, and then particulate nitrate, sulfate, and ammonium for the next 15 min period.
• Photolytic (true) NO2 and NOy
• Collocated gravimetric PM2.5, continuous PM2.5, speciated 24-hour PM2.5, continuous EC/OC, ozone, and meteorology (temperature, relative humidity, wind speed
and direction, precipitation). • 24-hour and 6-hour denuder samples
![Page 6: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/6.jpg)
More detail on Dasgupta
• PM2.5 size selector• Particles collected by humidification• Gases collected by wet denuder• Both particles and gases analyzed by IC• Ammonia/ammonium analyzed in
separate detector, using porous membrane and conductivity detector
![Page 7: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/7.jpg)
Current Status and Schedule
• Dasgupta, NO2, Noy will be deployed in January, 2003
• Sampling to continue for at least one calendar year
• Challenges: wintertime measurements with wet denuders, full time use of instruments usually used in shorter-term studies
![Page 8: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/8.jpg)
Air Suction
Air Inlet
Water InWater Out
Particle collector
![Page 9: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/9.jpg)
H2O
H2O2
air out to flow controller and pump
particle sample(aq.)
MB
MB MB
P
P P
Pgas sample(aq) air inlet
Denuder
Particle collector
P
. Liquid and airflow arrangement for the denuder, particle collector
![Page 10: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/10.jpg)
What will we learn?
• What controls the formation of nitrate: HNO3 or NH3:
– HNO3(g) + NH3(g) --> NH4NO3(s)
• What effect will reductions in SO2 and SO4 have on NH4NO3 : additional NH4 available from SO2 reductions could increase NH4NO3
• Diurnal variations in HNO3 and NH4 may lead to answers about sources
![Page 11: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/11.jpg)
Indicator SpeciesExcess Ammonia (Blanchard, et al, 2000) and
Gas Ratio (Ansari and Pandis, 1999)
Excess Ammonia Gas Ratio
EA < 0 NH3-limitedEA > 0.1 HNO3-limited
GR < 0.4 NH3-limitedGR > 1.5 HNO3-limited
![Page 12: MRPO Nitrate and Organic Speciation Special Studies Donna Kenski National RPO Technical Meeting Dallas, Dec. 3-4, 2002.](https://reader035.fdocuments.us/reader035/viewer/2022062804/56649eec5503460f94bfdbb7/html5/thumbnails/12.jpg)
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Organic Carbon at Seney• Organic matter can account for 50% or more of particle mass in
summer at Seney NWR, Boundary Waters, and other remote pristine sites.
• Origin of OCM not obvious:– transported urban pollution– local biogenic– local and/or transported forest fires– other??
• Source apportionment of IMPROVE data isn’t definitive (but efforts continue), hampered by too few species, degraded air far from sources, similarities among combustion sources (for quantified species).
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Seney NWR, Michigan
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What is organic speciation?• Method developed by Glen Cass, Jamie Schauer, many others
• Quartz filters, XAD-coated denuders, or PUF cartridges can be analyzed
• Filters extracted with hexane, then benzene/2-propanol, split, one fraction derivatized (to convert organic acids to methyl esters for GC/MS identification), and both fractions analyzed by GC/MS
• 100s of species can be identified, some unique tracers of sources: – resin acids for soft wood combustion– syringols for hard wood combustion– levoglucosan for wood combustion– cholesterol for meat cooking– hopanes and steranes for diesel combustion
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Sampling plan for Seney NWR• PI: Jamie Schauer at UW-Madison• Quartz filters collected at Seney (2/3 day) will be
composited by month and analyzed for particle phase organic species for Jan ‘02 - Dec ‘02 period
• Source apportionment will be conducted based on tracer species
• Additional daily high-volume samples were collected and a subset of those will be analyzed and apportioned
• Selected molecular markers will be analyzed for single-compound carbon isotope ratios
• Interim report due Jan. 1 2003, final Nov. 1 2003