US EPA

1228599 

Book/Book Chapter 

Development and Modification of a GC-IRMS System for Ambient Atmospheric Studies of Low-Molecular Weight Oxygenated Volatile Organic Compounds 

Giebel, BM; Riemer, DD; Swart, PK 

2007 

American Geophysical Union 

Determining δ super(13)C values for reduced hydrocarbons in atmospheric samples is emerging as an important area of interest in isotopic analytical chemistry. The importance of stable isotopic data stems from its usefulness to differentiate between multiple sources and allows for an assessment of changing source structure and source strength in a constantly changing environment. Though much stable isotopic work is available on CH sub(4) and other VOCs, particularly NMHCs, few studies have focused on oxygenated volatile organic compounds (OVOCs) such as methanol, ethanol, acetone, and propanal. Both anthropogenic and biogenic sources exist for these OVOCs and their role in atmospheric chemistry is important. The OVOCs of interest here are found in very low concentrations in ambient air (low ppbv to high pptv) and thus provide unique challenges for analysis by GC-C-IRMS. To address the challenges of measuring OVOCs, a Hewlett Packard 6890 gas chromatograph interfaced with a Europa Scientific Geo 20-20 IRMS was modified to accept ambient atmospheric samples. To sharpen peak shape all dead volume within the system was minimized; starting with the addition of a fused silica combustion tube (0.25 mm i.d.) containing Cu, Pt, or Ni wires (0.1 mm dia.). To assist water removal from the sample stream before delivery to the IRMS a small volume nafion dryer (0.20 mm i.d.) and a water-trap submersed in a dry-ice / acetone slurry were tested individually. Deactivated fused silica (0.1 mm i.d.) joins the custom designed open split to the ion source and effectively decreases dead volume while maintaining chromatographic separation and desired source pressure. To decrease the variability of the instrumentation, and to increase the total amount of carbon at the ion source, total carrier gas flow is reduced to 0.7 mL/min. Reference gas addition is manually facilitated by a six port rotary valve upstream of the open split and delivers diluted CO sub(2) reference gas (0.1% CO sub(2) in He) directly to the ion source while maintaining continuous flow conditions from the gas chromatograph. Experimental results of initial biogenic source sampling will be presented and future directions will be discussed. 

(Oct 2007)