Extraction of CO2 from air samples for isotopic analysis and limits to ultra high precision delta O-18 determination in CO2 gas

The determination of delta O-18 values in CO2 at a precision level of +/-0. 02 parts per thousand (delta -notation) has always been a challenging, if n ot impossible, analytical task. Here, we demonstrate that beyond the usuall y assumed major cause of uncertainty - water contamination - there are othe r, hitherto underestimated sources of contamination and processes which can alter the oxygen isotope composition Of CO2. Active surfaces in the preparation line with which CO2 comes into contact, as well as traces of air in the sample, can alter the apparent delta O-18 v alue both temporarily and permanently. We investigated the effects of diffe rent surface materials including electropolished stainless steel, Duran (R) glass, gold and quartz, the latter both untreated and silanized. CO2 froze n with liquid nitrogen showed a transient alteration of the O-18/O-16 ratio on all surfaces tested. The time to recover from the alteration as well as the size of the alteration varied with surface type. Quartz that had been ultrasonically cleaned for several hours with high pur ity water (0.05 muS) exhibited the smallest effect on the measured oxygen i sotopic composition of CO2 before and after freezing. However, quartz prove d to be mechanically unstable with time when subjected to repeated large te mperature changes during operation. After several days of operation the gas released from the freezing step contained progressively increasing trace a mounts Of O-2 probably originating from inclusions within the quartz, which precludes the use of quartz for cryogenically trapping CO2. Stainless stee l or gold proved to be suitable materials after proper pre-treatment. To ensure a high trapping efficiency Of CO2 from a flow of gas, a cold trap design was chosen comprising a thin wall 1/4 " outer tube and a 1/8 " inne r tube, made respectively from electropolished stainless steel and gold. Du e to a considerable O-18 specific isotope effect during the release Of CO2 from the cold surface, the thawing time had to be as long as 20 min for hig h precision delta O-18 measurements. The presence of traces of air in almost all CO2 gases that we analyzed was another major source of error. Nitrogen and oxygen in the ion source of our mass spectrometer (MAT 252, Finnigan MAT, Bremen, Germany) give rise to th e production of NO2 at the hot tungsten filament. NO2+ is isobaric with (CO O+)-O-16-O-18 (m/z 46) and interferes with the delta O-18 measurement. Trac e amounts of air are present in CO2 extracted cryogenically from air at -19 6 degreesC. This air, trapped at the cold surface, cannot be pumped away qu antitatively. The amount of air present depends on the surface structure an d, hence, the alteration of the measured delta O-18 value varies with the s urface conditions. For automated high precision measurement of the isotopic composition Of CO2 of air samples stored in glass flasks an extraction interface ('BGC-AirTra p') was developed which allows 18 analyses (including standards) per day to be made. For our reference CO2-in-air, stored in high pressure cylinders, the long term (>9 months) single sample precision was 0.012%. for delta C-1 3 and 0.019 parts per thousand for delta O-18. Copyright (C) 2001 John Wile y & Sons, Ltd.