Greetings,
    Two more cents for the group.  We have had accurate and precise results for isotope
measurements of N2O by gas tight syringe injection through butyl rubber stoppers (0.5
per mil for 15N, 1.0 per mil for 18O, 1.5 per mil for d31/30... for the isotopomerists).  We
do use needles with side ports.  Having said this I do not like to use syringe needles
if at all possible.  We have not analyzed O2 by syringe injection but have excellent
results for O2 and N2 using an evacuated gas sampling loop locatec between two Valco
valves that avoids having to use syringes (see Roberts et al., 2000 Env. Sci. Tech. 34: 2337-2341).
Cheers,
Nathaniel


At 01:46 PM 6/6/2003 +0100, you wrote:
Dear fellow Listmembers,

Has anyone else experienced non-reproducible (and 'light' by as much as 1
per mil) isotope values as a result of using a gas-tight syringe and septum
arrangement to remove gas aliquots from a sample bottle (with contents at
approx. 1 bar pressure)? My specific application is O2, but any information
gained using e.g. N2 or CO2 would be equally valid. Perhaps it is because of
the size of the aliquots (500 microlitres, from a 750mL vessel) in the case
in question. The 'large' size is necessary to provide sufficient gas for
dual inlet IRMS.

Gas transfer into a syringe, through a septum, seems to be a fairly routine
procedure for many isotope measurement applications; perhaps there is a
relatively small (<<500 microlitres) upper limit on the size of gas aliquot
that can be removed without significant fractionation - the latter
presumably being caused by diffusion effects into the syringe. One possible
contributory cause could be the occasional 'coring' of the septum during
injection of the syringe, thereby narrowing even further the bore of the
needle. But I'd be glad of any advice that others may have to offer...

Thanks,
Martin

==============================================
Martin Miller
Planetary & Space Sciences Research Institute,
The Open University,
Walton Hall,
Milton Keynes MK7 6AA
United Kingdom

E-mail: [log in to unmask]
Web (departmental): http://pssri.open.ac.uk
==============================================

Nathaniel E. Ostrom, Ph.D.
Professor
Dept. of Geological Sciences
206 Natural Sciences Building
Michigan State University
East Lansing MI 48824-1115
517-355-4661