Date of Award

12-1999

Degree Name

Master of Arts

Department

Chemistry

First Advisor

Dr. Steven Bertman

Second Advisor

Dr. Jay Means

Third Advisor

Dr. John B. Miller

Access Setting

Masters Thesis-Open Access

Abstract

As part of the PROPHET intensive held at the University of Michigan Biological Station in northern Michigan, a gas chromatography system for making fast-turnaround measurements of C1 to C5 alkyl nitrates was developed and deployed from July 19 to August 21, 1998. Every 30 minutes, samples were automatically acquired on a small Tenax trap made from silicosteel column and injected on a GC column by thermal desorption prior to ECD detection. Tests performed to measure breakthrough and on-trap destruction indicated no breakthrough for C3, C4, and C5 nitrates and excellent stability for these compounds on the trap. Chromatographic resolution of C3, C4, and CS nitrates was better than the resolution of C1 and C2 nitrates. The detection limit of the instrument was less than 1 pptv. The sum of C3- C5 alkyl nitrates measured during this intensive ranged from 3.45-65.8 pptv, with a mean of 18.6 pptv. C3-C5 alkyl nitrates contributed 1% on average to total NOy, with a range of >0.5% to 3%, but differences are found when the data are filtered according to air mass origin. The relationship of alkyl nitrate isomers from the same parent hydrocarbon was investigated. A kinetic model to describe a relationship between n-propyl nitrate and peroxypropionyl nitrate was developed.

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Chemistry Commons

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