1. Trace Gas Measurements at Appledore Island and Thompson Farm during the ICARTT 2004 Campaign Karl Haase New Mexico Tech holstien@nmt.edu Advisor: Dr. Barkley Sive

2. What Is ICARTT? International Consortium for Atmospheric Research on Transport and Transformation The largest air quality study ever: 15 Aircraft, 1 ship, many ground monitoring stations; over 100 different groups and institutions. Goal: A better understanding of how air masses move and transform chemically between North America and Western Europe

3. Question: Are ozone levels observed at UNH’s Thompson Farm and Appledore Island observing stations are enhanced by anthropogenic non-methane hydrocarbon (NMHC) emissions?

4. The Formation of Ozone in the Troposphere RH + OH  R + H 2 O R + O 2  RO 2 RO 2 + NO  RO + NO 2 NO 2 + h  NO + O O + O 2 + M  O 3 + M Determination of the relative importance of NMHCs in ozone production Compound (ppbv) [RH] (mol/cm 3 ) k OH (cm 3 /mol-sec) [RH] x k OH (s -1 ) ethane 102.6 x 10 11 2.7 x 10 -13 0.07 t-2-butene 2.5 6.2 x 10 10 6.4 x 10 -11 3.97 ethyne 20 4.9 x 10 11 7.8 x 10 -13 0.37 benzene 3.5 8.8 x 10 10 1.3 x 10 -12 0.11 methane1800 4.4 x 10 13 6.3 x 10 -15 0.28

5. Sampling Locations (Appledore Island)

6. 1 2 3 Thompson Farm Automated VOC Analysis System 4

7. Appledore Island: can samples run on a manual VOC analysis system 1 3 4 5 2

8. NMHCs ethane ethene propane propene i-butane n-butane ethyne trans-2-butene 1-butene i-butene cis-2-butene cylclopentane i-pentane n-pentane 1,3-butadiene propyne cyclopentene 3-methyl-1-butene trans-2-pentene 2-methy-2-butene 1-pentene cis-2-pentene methylcyclopentane 2,2-dimethylbutane cyclohexane 2,3 dimethylbutane 2-methylpentane 3-methylpentane n-hexane isoprene trans-2-hexene 1-hexene cis-2 hexene 2,4-dimethylpentane methylcyclohexane 2,3-demethylpentane 2-methylhexane 3-methylhexane n-heptane benzene 2,2,4 trimethylheptane 2-methylheptane 2,3,4-trimethylpentane 3-methylheptane n-octane toluene p-xylene ethylbenzene o-xylene styrene i-propylbenzene n-decane n-propylbenzene 3-ethyltoluene 1,2,3-trimethylbenzene 1,3-diethylbenzene 1,4 diethylbenzene Alkyl Nitrates Methyl Nitrate Ethyl Nitrate i-Propyl Nitrate n-Propyl Nitrate 2-Butyl Nitrate 3-Pentyl Nitrate 2-Pentyl Nitrate Halocarbons Methyl Chloride Methyl Bromide Methyl Iodide CFC-12 CFC-112 CFC-113 CFC-114 H-1301 H-1211 H-2402 CH2Cl2 CHCl3 MeCCl3 CCl4 C2Cl4 CH2Br2 CHBrCl2 CHBr3 200+ Compounds Resolved

9. Toluene Ethyne AI TF Wind DirectionOzone

10. Isoprene Terpenes AI TF Wind Direction Ozone

11. Back-Trajectories: Clean Period 8am EDT 7/15/04 Polluted Nocturnal Period 9pm EDT 7/15/04 Appledore Island NMHC Reactivity Case Study: July 14 & 15, 2004

13. -NMHC influx late in day, so less ozone formation -Both days, biogenic compounds comprise roughly 1/2 reactivity Anthropohenic emissions comprise about half of the ozone production potential

14. Thompson Farm Ozone Production Case Study: July 12 & 13

15. O3 FormationO3 DestructionPredictedObserved Both situations show that Ozone is transported to the Thompson Farm site

16. Summary: -Anthropogenic NMHCs significantly impact ozone levels at Thompson Farm and Appledore Island -Most anthropogenic NMHCs and ozone are transported in to this region, not produced locally -Biogenics relative importance decreases after morning at Thompson Farm because of transport - VOC rich/NO x limited region

17. Acknowledgements -Dr. Barkley Sive -Dr. George Hurtt & Research and Discover Program -Dr. Oliver Wingenter -Dr. Ruth Varner -Rachel Russo, Jesse Ambrose, Yong Zhou, Patrick Veres, Hillary Graves, Justine Kombarakkaran, Asako Enomoto, and Carsten Nielsen -NOAA AML HYSPLIT model http://www.arl.noaa.gov/ready/