Trace Gas Measurements at Appledore Island and Thompson Farm during the ICARTT 2004 Campaign

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 + H2O R + O2 RO2 RO2 + NO  RO + NO2 NO2 + hn NO + O O + O2 + M  O3 + M Determination of the relative importance of NMHCs in ozoneproduction Compound (ppbv) [RH] (mol/cm3) kOH (cm3 /mol-sec) [RH] x kOH (s-1) ethane 10 2.6 x 1011 2.7 x 10-13 0.07 t-2-butene 2.5 6.2 x 1010 6.4 x 10-11 3.97 ethyne 20 4.9 x 1011 7.8 x 10-13 0.37 benzene 3.5 8.8 x 1010 1.3 x 10-12 0.11 methane 1800 4.4 x 1013 6.3 x 10-15 0.28

5. Sampling Locations (Appledore Island)

6. 1 2 3 4 Thompson Farm AutomatedVOC Analysis System

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

8. 200+ Compounds Resolved 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 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 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 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

9. AI TF Wind Direction Ozone Ethyne Toluene

10. AI TF Wind Direction Terpenes Ozone Isoprene Ozone

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

12. Appledore Island NMHC Reactivity Case Study: July 14 & 15, 2004

13. Appledore Island NMHC Reactivity Case Study: July 14 & 15, 2004 -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 Formation O3 Destruction Predicted Observed Thompson Farm Ozone Production Case Study: July 12 & 13 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/NOx 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/