S. A. Kunasek

Influence of local photochemistry on isotopes of nitrate in Greenland snow

[1] To explore the seasonality in δ 15 N and δ 18 O of nitrate in Greenland snow, we describe a simple box model of local photochemistry. Isotope ratios of HNO 3 are controlled by the nitrogen isotope fractionation between NO and NO 2 , the ratio of NO 2 to NO, and seasonal variations in HNO 3 production. The observed seasonal range in δ 15 N requires either a large net fractionation (∼70‰) associated with NO x cycling or a seasonal change in the δ 15 N of NO x sources. The observed range in δ 18 O of nitrate is smaller than that calculated from HNO 3 production pathways, suggesting that seasonal transport may also be required to explain the seasonality in nitrate δ 18 O.

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate

RATIONALE Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. METHODS Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. RESULTS The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). CONCLUSIONS Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data.

Analysis of oxygen‐17 excess of nitrate and sulfate at sub‐micromole levels using the pyrolysis method

RATIONALE The oxygen-17 excess (Δ(17)O) of nitrate and sulfate contains valuable information regarding their atmospheric formation pathways. However, the current pyrolysis method to measure Δ(17)O requires large sample amounts (>4 µmol for nitrate and >1 µmol for sulfate). We present a new approach employing a Gas Bench interface which cryofocuses O2 produced from sample pyrolysis, enabling the analysis of sub-micromole size samples. METHODS Silver nitrate or sulfate at sub-micromole levels in a sample container was thermally decomposed to O2 and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Byproducts (mainly NO2 for silver nitrate and SO2 for silver sulfate) were removed in a liquid nitrogen trap and the sample O2 was carried by ultra-pure helium (He) gas to a Gas Bench II interface where it was cryofocused prior to entering an isotope ratio mass spectrometer. RESULTS Analysis of the international nitrate reference material USGS35 (Δ(17)O = 21.6‰) within the size range of 300-1000 nmol O2 gave a mean Δ(17)O value of (21.6 ± 0.69) ‰ (mean ±1σ). Three inter-laboratory calibrated sulfate reference materials, Sulf-α, Sulf-β and Sulf-ε, each within the size range of 180-1000 nmol O2, were analyzed and shown to possess mean Δ(17)O values of (0.9 ± 0.10)‰, (2.1 ± 0.25)‰ and (7.0 ± 0.63)‰, respectively. CONCLUSIONS The analyses of nitrate and sulfate reference materials at sub-micromole levels gave Δ(17)O values consistent with their accepted values. This new approach of employing the Gas Bench to cryofocus O2 after the pyrolysis of AgNO3 and Ag2SO4 particularly benefits the effort of measuring Δ(17)O in sample types with a low abundance of nitrate and sulfate such as ice cores.