Online coupling of pure O2 thermo-optical methods – 14C AMS for source apportionment of carbonaceous aerosols

This paper reports on novel separation methods developed for the direct determination of 14C in organic carbon (OC) and elemental carbon (EC), two sub-fractions of total carbon (TC) of atmospheric air particulate matter. Until recently, separation of OC and EC has been performed off-line by manual and time-consuming techniques that relied on the collection of massive CO2 fractions. We present here two on-line hyphenated techniques between a Sunset OC/EC analyzer and a MICADAS (MIni radioCArbon DAting System) accelerator mass spectrometer (AMS) equipped with a gas ion source. The first implementation facilitates the direct measurement in the low sample size range (<10 lg C) with high throughput on a routine basis, while the second explores the potential for a continuous-flow real-time CO2 gas feed into the ion source. The performance achieved with reference materials and real atmospheric samples will be discussed to draw conclusions on the improvement offered in the field of 14C aerosol source apportionment

Age of the Mt. Ortles ice cores, the Tyrolean Iceman and glaciation of the highest summit of South Tyrol since the Northern Hemisphere Climatic Optimum

In 2011 four ice cores were extracted from the summit of Alto dell'Ortles (3859 m), the highest glacier of South Tyrol in the Italian Alps. This drilling site is located only 37 km southwest from where the Tyrolean Iceman, similar to 5.3 kyrs old, was discovered emerging from the ablating ice field of Tisenjoch (3210 m, near the Italian-Austrian border) in 1991. The excellent preservation of this mummy suggested that the Tyrolean Iceman was continuously embedded in prehistoric ice and that additional ancient ice was likely preserved elsewhere in South Tyrol. Dating of the ice cores from Alto dell'Ortles based on Pb-210, tritium, beta activity and C-14 determinations, combined with an empirical model (COPRA), provides evidence for a chronologically ordered ice stratigraphy from the modern glacier surface down to the bottom ice layers with an age of similar to 7 kyrs, which confirms the hypothesis. Our results indicate that the drilling site has continuously been glaciated on frozen bedrock since similar to 7 kyrs BP. Absence of older ice on the highest glacier of South Tyrol is consistent with the removal of basal ice from bedrock during the Northern Hemisphere Climatic Optimum (6-9 kyrs BP), the warmest interval in the European Alps during the Holocene. Borehole inclinometric measurements of the current glacier flow combined with surface ground penetration radar (GPR) measurements indicate that, due to the sustained atmospheric warming since the 1980s, an acceleration of the glacier Alto dell'Ortles flow has just recently begun. Given the stratigraphic-chronological continuity of the Mt. Ortles cores over millennia, it can be argued that this behaviour has been unprecedented at this location since the Northern Hemisphere Climatic Optimum

European source and sink areas of CO2 retrieved from Lagrangian transport model interpretation of combined CO2 and CO2 measurements at the high alpine research station Jungfraujoch

The University of Bern monitors carbon dioxide (CO2) and oxygen (O2) at the High Altitude Research Station Jungfraujoch since the year 2000 by means of flasks sampling and since 2005 using a continuous in situ measurement system. This study investigates the transport of CO2 and O2 towards Jungfraujoch using backward Lagrangian Particle Dispersion Model (LPDM) simulations and utilizes CO2 and O2 signatures to classify air masses. By investigating the simulated transport patterns associated with distinct CO2 concentrations it is possible to decipher different source and sink areas over Europe. The highest CO2 concentrations, for example, were observed in winter during pollution episodes when air was transported from Northeastern Europe towards the Alps, or during south Foehn events with rapid uplift of polluted air from Northern Italy, as demonstrated in two case studies. To study the importance of air-sea exchange for variations in O2 concentrations at Jungfraujoch the correlation between CO2 and APO (Atmospheric Potential Oxygen) deviations from a seasonally varying background was analyzed. Anomalously high APO concentrations were clearly associated with air masses originating from the Atlantic Ocean, whereas low APO concentrations were found in air masses advected either from the east from the Eurasian continent in summer, or from the Eastern Mediterranean in winter. Those air masses with low APO in summer were also strongly depleted in CO2 suggesting a combination of CO2 uptake by vegetation and O2 uptake by dry summer soils. Other subsets of points in the APO-CO2 scatter plot investigated with respect to air mass origin included CO2 and APO background values and points with regular APO but anomalous CO2 concentrations. Background values were associated with free tropospheric air masses with little contact with the boundary layer during the last few days, while high or low CO2 concentrations reflect the various levels of influence of anthropogenic emissions and the biosphere. The pronounced cycles of CO2 and O2 exchanges with the biosphere and the ocean cause clusters of points and lead to a seasonal pattern

Comparison between real time and flask measurements of atmospheric O2 and CO2 performed at the High Altitude Research Station Jungfraujoch, Switzerland

First real time CO2 and O2 measurements on the High Altitude Research Station Jungfraujoch (Switzerland) are compared with corresponding flasks samples. Whereas CO2 measurements show a good agreement, O2 compares only moderately. Real time O2 measurements are performed using two different methods, i.e. by paramagnetic and fuel cells. Fuel cell values exhibit significantly higher scatter, but they compare acceptably well with the paramagnetic values when averaging over 228 min (20 point running mean). Continuous measurements are powerful in many respects in contrast to spot-like flask sampling. They help to set up data selection criteria and to improve the robustness of trend calculations. Further, real time measurements help to partition the anthropogenic CO2 increase into ocean and terrestrial biosphere for short-time variations of minutes, hours, days, which are not covered by flask sampling

Measurements and trend analysis of O2, CO2 and δ13C of CO2 from the high altitude research station Junfgraujoch, Switzerland - A comparison with the observations from the remote site Puy de Dôme, France

Atmospheric O2 and CO2 flask measurements from the high altitude research station Jungfraujoch, Switzerland, and from the observatory at Puy de Dôme, France, are presented. Additionally, the Jungfraujoch δ13C record of CO2 is discussed. The observations on flask samples collected at the Jungfraujoch station show, since 2003, an enhancement of the oxygen trend which amounts to about 45 per meg/year with a corresponding CO2 increase of around 2.4 ppm/year. This enhancement is comparable with that observed at the Puy de Dôme station where oxygen, since mid 2002, has decreased with a rate of about 50 per meg/year whilst the CO2 increase was of around 1.7 ppm/year but exhibiting a higher variability. Several processes influence δO2/N2. However, these processes are marked with different oxidation ratios (O2:CO2) that can be used to distinguish them. The apparent slopes calculated from correlation plots between de-trended CO2 and δO2/N2 records as well as between corresponding trends are significantly larger than the observed terrestrial exchange and fossil fuel emission slopes indicating a strong oceanic influence. Since ocean–atmosphere exchange can have very variable O2:CO2 ratios depending on processes within the ocean, it is to our understanding the only possibility to explain our observations. The stability of the δO2/N2 scale is critical in this regard, therefore, it is addressed here and we found no significant scale drift which would influence our trend calculations. In our view more important are criterions on the data selection before trend analysis

Chromatographic Separation and Wet Oxidation of Oxalic Acid from Aerosols for Radiocarbon Source Apportionment

Radiocarbon analysis is a powerful technique for the apportionment of fossil and non-fossil sources of carbonaceous aerosols. This technique can be applied to total carbon, organic carbon and elemental carbon, as well as more specific fractions of aerosols. We aim at compound-specific radiocarbon analyses (CSRA) of dicarboxylic acids (DCAs) using a one-step chromatographic separation followed by a chemical wet oxidation and subsequent radiocarbon measurement with an accelerator mass spectrometer (AMS). DCAs have received much attention because of their role as cloud condensation nuclei and are found in urban, rural, and marine sites. This raises questions about their sources, precursors, and formation processes. Gaseous precursors can react in the atmosphere forming secondary organic aerosols (SOA). Both primary organic aerosols (POA) and SOA can undergo aging processes, from which low-molecular-weight DCAs are produced. The dominant DCAs in aerosols are by a large margin oxalic acid, followed by malonic and succinic acid. Previously, the sources of formic, acetic, and oxalic acid in aerosols were investigated using stable carbon isotopes (Fisseha et al., 2009). In contrast, owing to their low prevalence, radiocarbon measurements of DCAs are seldom conducted. Fahrni et al. (2010) performed CSRA of DCAs using a two-step chromatographic separation. There, water-soluble organic compounds were separated by ion chromatography (IC), followed by high-performance liquid chromatography (HPLC). The fractions were collected, water removed on a vacuum line, and the compounds oxidised to CO2at 950°C with cupric oxide in a quartz glass tube for AMS measurement. In this work, chemical wet oxidation (Lang et al., 2016) was used to oxidise oxalic acid directly after IC separation without a second chromatographic separation and an additional concentration step. Wet oxidation directly forms CO2from carbonaceous compounds in the eluate whereas inorganic compounds such as sulphates remain unaffected. This simplifies the procedure while achieving lower blanks by omitting additional concentration and separation steps. We focus on the apportionment of fossil and non-fossil sourcesof oxalic acid extracted from filters sampled at urban and rural sites. As a consequence of their low content, pooled fractions of malonic and succinic acid will be measured additionally. Fahrni et al., Radiocarbon 52, 752-760 (2010) Fisseha et al., Atmos. Environ. 43, 431-437 (2009) Lang et al., Radiocarbon 58, 1-11 (2016

Widespread pollution of the South American atmosphere predates the industrial revolution by 240 y

In the Southern Hemisphere, evidence for preindustrial atmospheric pollution is restricted to a few geological archives of low temporal resolution that record trace element deposition originating from past mining and metallurgical operations in South America. Therefore, the timing and the spatial impact of these activities on the past atmosphere remain poorly constrained. Here we present an annually resolved ice core record (A.D. 793–1989) from the high-altitude drilling site of Quelccaya (Peru) that archives preindustrial and industrial variations in trace elements. During the precolonial period (i.e., pre-A.D. 1532), the deposition of trace elements was mainly dominated by the fallout of aeolian dust and of ash from occasional volcanic eruptions, indicating that metallurgic production during the Inca Empire (A.D. 1438−1532) had a negligible impact on the South American atmosphere. In contrast, a widespread anthropogenic signal is evident after around A.D. 1540, which corresponds with the beginning of colonial mining and metallurgy in Peru and Bolivia, ∼240 y before the Industrial Revolution. This shift was due to a major technological transition for silver extraction in South America (A.D. 1572), from lead-based smelting to mercury amalgamation, which precipitated a massive increase in mining activities. However, deposition of toxic trace metals during the Colonial era was still several factors lower than 20th century pollution that was unprecedented over the entirety of human history

Extraction of Dissolved Organic Carbon from Glacier Ice for Radiocarbon Analysis

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

Radiocarbon dating of glacier ice: overview, optimisation, validation and potential

High-altitude glaciers and ice caps from midlatitudes and tropical regions contain valuable signals of past climatic and environmental conditions as well as human activities, but for a meaningful interpretation this information needs to be placed in a precise chronological context. For dating the upper part of ice cores from such sites, several relatively precise methods exist, but they fail in the older and deeper parts, where plastic deformation of the ice results in strong annual layer thinning and a non-linear age–depth relationship. If sufficient organic matter such as plant, wood or insect fragments were found, radiocarbon (14C) analysis would have thus been the only option for a direct and absolute dating of deeper ice core sections. However such fragments are rarely found and, even then, they would not be very likely to occur at the desired depth and resolution. About 10 years ago, a new, complementary dating tool was therefore introduced by our group. It is based on extracting the μg-amounts of the water-insoluble organic carbon (WIOC) fraction of carbonaceous aerosols embedded in the ice matrix for subsequent 14C dating. Since then this new approach has been improved considerably by reducing the measurement time and improving the overall precision. Samples with ~10 μg WIOC mass can now be dated with reasonable uncertainty of around 10–20% (variable depending on sample age). This requires about 300 to 800 g of ice for WIOC concentrations typically found in midlatitude and low-latitude glacier ice. Dating polar ice with satisfactory age precision is still not possible since WIOC concentrations are around 1 order of magnitude lower. The accuracy of the WIOC 14C method was validated by applying it to independently dated ice. With this method, the deepest parts of the ice cores from Colle Gnifetti and the Mt Ortles glacier in the European Alps, Illimani glacier in the Bolivian Andes, Tsambagarav ice cap in the Mongolian Altai, and Belukha glacier in the Siberian Altai have been dated. In all cases a strong annual layer thinning towards the bedrock was observed and the oldest ages obtained were in the range of 10 000 years. WIOC 14C dating was not only crucial for interpretation of the embedded environmental and climatic histories, but additionally gave a better insight into glacier flow dynamics close to the bedrock and past glacier coverage. For this the availability of multiple dating points in the deepest parts was essential, which is the strength of the presented WIOC 14C dating method, allowing determination of absolute ages from principally every piece of ice