Oxygen isotope analysis of levoglucosan, a tracer of wood burning, in experimental and ambient aerosol samples.

RATIONALE: Levoglucosan is formed from cellulose during biomass burning. It is therefore often used as a specific tracer to quantify the contribution of wood burning to the aerosol loading. The stable oxygen isotope composition (δ18 O value) of biomass is determined by the water cycle and varies regionally, and hence the δ18 O value of levoglucosan could help to identify source regions of organic aerosols. METHODS: After solvent extraction of the organic fraction and concentration steps, a recently developed methylation derivatisation technique was applied on experimental (i.e. controlled wood-burning experiments) and on ambient aerosol samples from Switzerland and Lithuania. The method achieves sufficient compound separation for isotope analysis in atmospheric particulate matter, enabling δ18 O analysis of levoglucosan by gas chromatography/pyrolysis-isotope ratio mass spectrometry (GC/Pyr-IRMS), with a precision better than 1.0 ‰ and an accuracy of 0.3 ‰. RESULTS: The δ18 O value of the levoglucosan released during controlled wood-burning experiments was not significantly different from the cellulose δ18 O values, which implies very little or no isotope fractionation during wood burning under the given conditions. While the δ18 O values of levoglucosan in Swiss samples were as expected for the source region, those in Lithuania were 1-4 ‰ lower than expected. This may be due to differences in vegetation (grass vs wood) or burning conditions (high vs low temperatures). CONCLUSIONS: Low oxygen isotope fractionation between cellulose and levoglucosan and clear differences in levoglucosan δ18 O values between the Swiss and Lithuanian ambient samples demonstrate that our new method is useful for source appointment studies on wood-burning-derived aerosols.

A novel methylation derivatization method for δ(18)O analysis of individual carbohydrates by gas chromatography/pyrolysis-isotope ratio mass spectrometry.

RATIONALE: The oxygen isotope ratio (δ(18)O) of carbohydrates derived from animals, plants, sediments, and soils provides important information about biochemical and physiological processes, past environmental conditions, and geographical origins, which are otherwise not available. Nowadays, δ(18)O analyses are often performed on carbohydrate bulk material, while compound-specific δ(18)O analyses remain challenging and methods for a wide range of individual carbohydrates are rare. METHODS: To improve the δ(18)O analysis of individual carbohydrates by gas chromatography/pyrolysis-isotope ratio mass spectrometry (GC/Pyr-IRMS) we developed a new methylation derivatization method. Carbohydrates were fully methylated within 24 h in an easy-to-handle one-pot reaction in acetonitrile, using silver oxide as proton acceptor, methyl iodide as methyl group carrier, and dimethyl sulfide as catalyst. RESULTS: The precision of the method ranged between 0.12 and 1.09‰ for the δ(18)O values of various individual carbohydrates of different classes (mono-, di-, and trisaccharides, alditols), with an accuracy of a similar order of magnitude, despite high variation in peak areas. Based on the δ(18)O values of the main isomers, important monosaccharides such as glucose and fructose could also be precisely analyzed for the first time. We tested the method on standard mixtures, honey samples, and leaf carbohydrates extracted from Pinus sylvestris, showing that the method is also applicable to different carbohydrate mixtures. CONCLUSIONS: The new methylation method shows unrivalled accuracy and precision for δ(18)O analysis of various individual carbohydrates; it is fast and easy-to-handle, and may therefore find wide-spread application.

Field-scale labelling and activity quantification of methane-oxidizing bacteria in a landfill-cover soil.

Aerobic methane-oxidizing bacteria (MOB) play an important role in soils, mitigating emissions of the greenhouse gas methane (CH(4)) to the atmosphere. Here, we combined stable isotope probing on MOB-specific phospholipid fatty acids (PLFA-SIP) with field-based gas push-pull tests (GPPTs). This novel approach (SIP-GPPT) was tested in a landfill-cover soil at four locations with different MOB activity. Potential oxidation rates derived from regular- and SIP-GPPTs agreed well and ranged from 0.2 to 52.8 mmol CH(4) (L soil air)(-1) day(-1). PLFA profiles of soil extracts mainly contained C(14) to C(18) fatty acids (FAs), with a dominance of C(16) FAs. Uptake of (13) C into MOB biomass during SIP-GPPTs was clearly indicated by increased δ(13)C values (up to c. 1500‰) of MOB-characteristic FAs. In addition, (13)C incorporation increased with CH(4) oxidation rates. In general, FAs C(14:0) , C(16:1ω8), C(16:1ω7) and C(16:1ω6) (type I MOB) showed highest (13)C incorporation, while substantial (13)C incorporation into FAs C(18:1ω8) and C(18:1ω7) (type II MOB) was only observed at high-activity locations. Our findings demonstrate the applicability of the SIP-GPPT approach for in situ quantification of potential CH(4) oxidation rates and simultaneous labelling of active MOB, suggesting a dominance of type I MOB over type II MOB in the CH(4)-oxidizing community in this landfill-cover soil.