ALBERT

Description: Alpine glaciers are valuable archives for the reconstruction of human impact on the environment. Besides dating purposes, measurement of radiocarbon (14C) content provides a powerful tool for long-term source apportionment studies on the carbonaceous aerosols incorporated in ice cores. In this work, we present an extraction system for 14C analyses of dissolved organic carbon (DOC) in ice cores. The setup can process ice samples of up to 350 g mass and offers ultra-clean working conditions for all extraction steps. A photo-oxidation method is applied by means of external UV irradiation of the sample. For an irradiation time of 30 min with catalyzation by addition of Fe2+ and H2O2, we achieve an efficiency of 96 ± 6% on average. Inert gas working conditions and stringent decontamination procedures enable a low overall blank of 1.9 ± 1.6 μg C with a F14C value of 0.68 ± 0.13. This makes it possible to analyze the DOC in ice samples with a carbon content of as low as 25 μg C kg−1 ice. For a first validation, the new method was applied to ice core samples from the Swiss Alps. The average DOC concentration and F14C values for the Fiescherhorn ice core samples show good agreement with previously reported data for the investigated period of 1925–1936 AD.

Description: Paleo–atmospheric records of carbon dioxide and its stable carbon isotope composition (δ13C) obtained from polar ice cores provide important constraints on the natural variability of the carbon cycle. However, the measurements are both analytically challenging and time-consuming thus data exist only from a limited number of sampling sites and time periods. Additional analytical resources with high analytical precision and throughput are thus desirable to extend and confirm the existing datasets. Also, consistent measurements derived by independent laboratories and a variety of analytical systems helps to further increase confidence in the global CO2 paleo reconstructions. Here, we describe our new setup for simultaneous measurements of atmospheric CO2 mixing ratios, atmospheric δ13C and δ18O-CO2 in air extracted from ice core samples. The core of the system is a newly designed Needle Cracker for the mechanical release of air entrapped in ice core samples of 8–13 g operated at −45 °C. The small sample size allows for high resolution and replicate sampling schemes. In our method, CO2 is cryogenically and chromatographically separated from the bulk air and the isotopic composition subsequently determined by continuous flow isotope ratio mass spectrometry (IRMS). In combination with thermal conductivity measurement of the bulk air, the CO2 mixing ratio is calculated. The analytical precision determined from standard air sample measurements over ice is ± 1.9 ppm for CO2 and ± 0.09 ‰ for δ13C. In a laboratory intercomparison study with CSIRO (Aspendale, Australia) good agreement between CO2 and δ13C results is found for Law Dome ice core samples. Replicate analysis of these samples resulted in a pooled standard deviation of 2.0 ppm for CO2 and 0.11 ‰ for δ13C. These numbers are good, although rather conservative estimates of the overall analytical uncertainty for a single measurement. Facilitated by the small sample requirement, replicate measurements are feasible and the achievable method precision accordingly higher. Further in this study, new analytical approaches are introduced for the accurate correction of the procedural blank and for the reliable and consistent detection of measurement outliers which is based on δ18O-CO2 and the exchange of oxygen between CO2 and H2O of surrounding ice.

Description: Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1σ Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (Δage) at the firn-ice transition is calculated to be 182+3−9 yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.

Description: Long-term concentration records of carbonaceous particles (CP) are of increasing interest in climate research due to their not yet completely understood effects on climate. Nevertheless, only poor data on their concentrations and sources before the 20th century are available. We present a first long-term record of organic carbon (OC) and elemental carbon (EC) concentrations – the two main fractions of CP – along with the corresponding fraction of modern carbon (fM) derived from radiocarbon (14C) analysis in ice. This allows a distinction and quantification of natural (biogenic) and anthropogenic (fossil) sources in the past. CP were extracted from an ice archive, with resulting carbon quantities in the microgram range. Analysis of 14C by accelerator mass spectrometry (AMS) was therefore highly demanding. We analysed 33 samples of 0.4 to 1 kg ice from a 150.5 m long ice core retrieved at Fiescherhorn glacier in December 2002 (46°33'3.2" N, 08°04'0.4" E; 3900 m a.s.l.). Samples were taken from bedrock up to the firn/ice transition, covering the time period 1650–1940 and thus the transition from the pre-industrial to the industrial era. Before ~1850, OC was approaching a purely biogenic origin with a mean concentration of 24 μg kg−1 and a standard deviation of 7 μg kg−1. In 1940, OC concentration was about a factor of 3 higher than this biogenic background, almost half of it originating from anthropogenic sources, i.e. from combustion of fossil fuels. The biogenic EC concentration was nearly constant over the examined time period with 6 μg kg−1 and a standard deviation of 1 μg kg−1. In 1940, the additional anthropogenic input of atmospheric EC was about 50 μg kg−1.

Description: Radiocarbon enables a distinction between contemporary and fossil carbon, which can be used for the apportionment of biogenic and anthropogenic sources in environmental studies. In order to apply this approach to carbonaceous atmospheric aerosols, it is necessary to adapt pretreatment procedures to the requirements of 14C measurements. In this work, we followed an approach in which total carbon (TC) is subdivided into fractions of different chemical and physical properties. 14C data of ambient aerosols from Zürich (Switzerland) are presented for the 2 sub-fractions of TC, organic carbon (OC) and elemental carbon (EC). Furthermore, OC is separated into water-insoluble OC (WINSOC) and water-soluble OC (WSOC). Results demonstrate the importance to differentiate between these fractions for 14C-deduced source apportionment, as the contributions can range between both extremes, nearly exclusively biogenic and anthropogenic.

Description: Water stable isotope ratios and net snow accumulation in ice cores are commonly interpreted as temperature or precipitation proxies. However, only in a few cases has a direct calibration with instrumental data been attempted. In this study we took advantage of the dense network of observations in the European Alpine region to rigorously test the relationship of the annual and seasonal resolved proxy data from two highly resolved ice cores with local temperature and precipitation. We focused on the time period 1961–2001 with the highest amount and quality of meteorological data and the minimal uncertainty in ice core dating (±1 year). The two ice cores were retrieved from the Fiescherhorn glacier (northern Alps, 3900 m a.s.l.), and Grenzgletscher (southern Alps, 4200 m a.s.l.). A parallel core from the Fiescherhorn glacier allowed assessing the reproducibility of the ice core proxy data. Due to the orographic barrier, the two flanks of the Alpine chain are affected by distinct patterns of precipitation. The different location of the two glaciers therefore offers a unique opportunity to test whether such a specific setting is reflected in the proxy data. On a seasonal scale a high fraction of δ18O variability was explained by the seasonal cycle of temperature (~60% for the ice cores, ~70% for the nearby stations of the Global Network of Isotopes in Precipitation – GNIP). When the seasonality is removed, the correlations decrease for all sites, indicating that factors other than temperature such as changing moisture sources and/or precipitation regimes affect the isotopic signal on this timescale. Post-depositional phenomena may additionally modify the ice core data. On an annual scale, the δ18O/temperature relationship was significant at the Fiescherhorn, whereas for Grenzgletscher this was the case only when weighting the temperature with precipitation. In both cases the fraction of interannual temperature variability explained was ~20%, comparable to the values obtained from the GNIP stations data. Consistently with previous studies, we found an altitude effect for the δ18O of −0.17‰/100 m for an extended elevation range combining data of the two ice core sites and four GNIP stations. Significant correlations between net accumulation and precipitation were observed for Grenzgletscher during the entire period of investigation, whereas for Fiescherhorn this was the case only for the less recent period (1961–1977). Local phenomena, probably related to wind, seem to partly disturb the Fiescherhorn accumulation record. Spatial correlation analysis shows the two glaciers to be influenced by different precipitation regimes, with the Grenzgletscher reflecting the characteristic precipitation regime south of the Alps and the Fiescherhorn accumulation showing a pattern more closely linked to northern Alpine stations.

Description: Water stable isotope ratios and net snow accumulation in ice cores are usually interpreted as temperature and precipitation proxies. However, only in a few cases a direct calibration with instrumental data has been attempted. In this study we took advantage of the dense network of observations in the European Alpine region to rigorously test the relationship of the proxy data from two highly-resolved ice cores with local temperature and precipitation, respectively, on an annual basis. We focused on the time period 1961–2001 with the highest amount and quality of meteorological data and the minimal uncertainty in ice core dating (±1 yr). The two ice cores come from Fiescherhorn glacier (Northern Alps, 3900 m a.s.l.) and Grenzgletscher (Southern Alps, 4200 m a.s.l.). Due to the orographic barrier, the two flanks of the Alpine chain are affected by distinct patterns of precipitation. Therefore, the different location of the two ice cores offers the unique opportunity to test whether the precipitation proxy reflects this very local condition. We obtained a significant spatial correlation between annual δ18O and regional temperature at Fiescherhorn. Due to the pronounced intraseasonal to interannual variability of precipitation at Grenzgletscher, significant results were only found when weighting the temperature with precipitation. For this site, disentangling the temperature from the precipitation signal was thus not possible. Significant spatial correlations between net accumulation and precipitation were found for both sites but required the record from the Fiescherhorn glacier to be shifted by −1 yr (within the dating uncertainty). The study underlines that even for well-resolved ice core records, interpretation of proxies on an annual or even sub-annual basis remains critical. This is due to both, dating issues and the fact that the signal preservation intrinsically depends on precipitation.

Description: Air bubbles in ice core samples represent the only opportunity to study the mixing ratio and isotopic variability of palaeoatmospheric CH4 and N2O. The highest possible precision in isotope measurements is required to maximize the resolving power for CH4 and N2O sink and source reconstructions. We present a new setup to measure δ13C-CH4, δ15N-N2O and δ18O-N2O isotope ratios in one ice core sample and with one single IRMS instrument, with a precision of 0.09, 0.6 and 0.7‰, respectively, as determined on 0.6–1.6 nmol CH4 and 0.25–0.6 nmol N2O. The isotope ratios are referenced to the VPDB scale (δ13C-CH4), the N2-air scale (δ15N-N2O) and the VSMOW scale (δ18O-N2O). Ice core samples of 200–500 g are melted while the air is constantly extracted to minimize gas dissolution. A helium carrier gas flow transports the sample through the analytical system. We introduce a new gold catalyst to oxidize CO to CO2 in the air sample. CH4 and N2O are then separated from N2, O2, Ar and CO2 before they get pre-concentrated and separated by gas chromatography. A combustion unit is required for δ13C-CH4 analysis, which is equipped with a constant oxygen supply as well as a post-combustion trap and a post-combustion GC column (GC-C-GC-IRMS). The post-combustion trap and the second GC column in the GC-C-GC-IRMS combination prevent Kr and N2O interferences during the isotopic analysis of CH4-derived CO2. These steps increase the time for δ13C-CH4 measurements, which is used to measure δ15N-N2O and δ18O-N2O first and then δ13C-CH4. The analytical time is adjusted to ensure stable conditions in the ion source before each sample gas enters the IRMS, thereby improving the precision achieved for measurements of CH4 and N2O on the same IRMS. The precision of our measurements is comparable to or better than that of recently published systems. Our setup is calibrated by analysing multiple reference gases that were injected over bubble-free ice samples. We show that our measurements of δ13C-CH4 in ice core samples are generally in good agreement with previously published data after the latter have been corrected for krypton interferences.

Description: Long-term concentration records of carbonaceous particles (CP) are of increasing interest in climate research due to their not yet completely understood effects on climate. Nevertheless, only poor data on their concentrations and sources in the past is available. We present a first long-term record of organic carbon (OC) and elemental carbon (EC) concentrations - the two main fractions of CP – along with the corresponding fraction of modern carbon (fM) derived from radiocarbon (14C) analysis. The combination of concentration measurements with 14C analysis of CP allows a distinction and quantification of natural, biogenic and anthropogenic fossil sources in the past. CP were extracted from an ice archive, with resulting carbon quantities in the microgram range. Analysis of 14C by accelerator mass spectrometry (AMS) was therefore highly demanding. We analysed 33 samples of 0.4 to 1 kg ice from a 150.5 m long ice core retrieved at Fiescherhorn glacier in December 2002 (46°33'3.2" N, 08°04'0.4'' E; 3900 m a.s.l.). Samples were taken from below the firn/ice transition down to bedrock, covering the time period 1650–1940 and thus the transition from the pre-industrial to the industrial era. Before 1800, OC was of pure biogenic origin with a mean concentration of 21±2 μg kg−1}. In 1940, OC concentration was more than a factor of 3 higher than this biogenic background, almost half of it originating from anthropogenic sources, i.e. from combustion of fossil fuels. The biogenic EC concentration was nearly constant over the examined time period with 6±1 μg kg−1. In 1940, the additional anthropogenic input of atmospheric EC was about 50 μg kg−1.