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

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

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

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 x x t-2-butene x x ethyne x x benzene x x methane x x

Sampling Locations (Appledore Island)

1 2 3 Thompson Farm Automated VOC Analysis System 4

Appledore Island: can samples run on a manual VOC analysis system

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 CHBr Compounds Resolved

Toluene Ethyne AI TF Wind DirectionOzone

Isoprene Terpenes AI TF Wind Direction Ozone

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

-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

Thompson Farm Ozone Production Case Study: July 12 & 13

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

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

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