On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

Stable carbon isotope analysis of methane (delta C-13 of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr) can severely interfere during the mass spectrometric measurement, leading to significant biases in delta C-13 of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged Kr-86 peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in delta C-13. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

Validation of a modified AVHRR aerosol optical depth retrieval algorithm over Central Europe

The Advanced Very High Resolution Radiometer (AVHRR) carried on board the National Oceanic and Atmospheric Administration (NOAA) and the Meteorological Operational Satellite (MetOp) polar orbiting satellites is the only instrument offering more than 25 years of satellite data to analyse aerosols on a daily basis. The present study assessed a modified AVHRR aerosol optical depth τa retrieval over land for Europe. The algorithm might also be applied to other parts of the world with similar surface characteristics like Europe, only the aerosol properties would have to be adapted to a new region. The initial approach used a relationship between Sun photometer measurements from the Aerosol Robotic Network (AERONET) and the satellite data to post-process the retrieved τa. Herein a quasi-stand-alone procedure, which is more suitable for the pre-AERONET era, is presented. In addition, the estimation of surface reflectance, the aerosol model, and other processing steps have been adapted. The method's cross-platform applicability was tested by validating τa from NOAA-17 and NOAA-18 AVHRR at 15 AERONET sites in Central Europe (40.5° N–50° N, 0° E–17° E) from August 2005 to December 2007. Furthermore, the accuracy of the AVHRR retrieval was related to products from two newer instruments, the Medium Resolution Imaging Spectrometer (MERIS) on board the Environmental Satellite (ENVISAT) and the Moderate Resolution Imaging Spectroradiometer (MODIS) on board Aqua/Terra. Considering the linear correlation coefficient R, the AVHRR results were similar to those of MERIS with even lower root mean square error RMSE. Not surprisingly, MODIS, with its high spectral coverage, gave the highest R and lowest RMSE. Regarding monthly averaged τa, the results were ambiguous. Focusing on small-scale structures, R was reduced for all sensors, whereas the RMSE solely for MERIS substantially increased. Regarding larger areas like Central Europe, the error statistics were similar to the individual match-ups. This was mainly explained with sampling issues. With the successful validation of AVHRR we are now able to concentrate on our large data archive dating back to 1985. This is a unique opportunity for both climate and air pollution studies over land surfaces.

Simultaneous stable isotope analysis of methane and nitrous oxide on ice core samples

Methane and nitrous oxide are important greenhouse gases which show a strong increase in atmospheric mixing ratios since pre-industrial time as well as large variations during past climate changes. The understanding of their biogeochemical cycles can be improved using stable isotope analysis. However, high-precision isotope measurements on air trapped in ice cores are challenging because of the high susceptibility to contamination and fractionation. Here, we present a dry extraction system for combined CH4 and N2O stable isotope analysis from ice core air, using an ice grating device. The system allows simultaneous analysis of δD(CH4) or δ13C(CH4), together with δ15N(N2O), δ18O(N2O) and δ15N(NO+ fragment) on a single ice core sample, using two isotope mass spectrometry systems. The optimum quantity of ice for analysis is about 600 g with typical "Holocene" mixing ratios for CH4 and N2O. In this case, the reproducibility (1σ ) is 2.1‰ for δD(CH4), 0.18‰ for δ13C(CH4), 0.51‰ for δ15N(N2O), 0.69‰ for δ18O(N2O) and 1.12‰ for δ15N(NO+ fragment). For smaller amounts of ice the standard deviation increases, particularly for N2O isotopologues. For both gases, small-scale intercalibrations using air and/or ice samples have been carried out in collaboration with other institutes that are currently involved in isotope measurements of ice core air. Significant differences are shown between the calibration scales, but those offsets are consistent and can therefore be corrected for.