S. Szidat

Universität Bern, Berna, Bern, Switzerland

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Publications (95)225.4 Total impact

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    ABSTRACT: Radiocarbon (14C) measurement of water-soluble organic carbon (WSOC) in ambient aerosols is a quantitative tool for unambiguously distinguishing fossil and non-fossil sources. In this study, a fast and reliable method for measuring 14C in micro-scale (μg) WSOC aerosol samples is successfully developed, which includes three steps: (1) extraction (2) freeze drying, and (3) online 14C analysis of CO2 from WSOC combustion. Procedure blanks are carefully assessed by measuring high-purity water and reference materials. Accurate 14C results could be obtained for WSOC with only 10 μg C, and thus the potential applications are substantially broadened because much less filter material is needed compared to previous reported methods. This method is applied to aerosols samples collected during winter from Switzerland and China. The results demonstrate that non-fossil sources are important if not dominant contributors of WSOC. These non-fossil components are consistently enriched in WSOC compared to bulk OC and water-insoluble OC for all samples, due to high water solubility of primary and secondary biomass burning aerosols. However, the presence of fossil WSOC is still considerable indicating a substantial contribution of secondary OC (SOC) formed from precursors emitted by fossil emissions. Larger fossil contributions to WSOC is found in China than in Switzerland and previously reported values in Europe, USA and South Asia, which may be attributed to higher fossil-derived SOC formation in China.
    Atmospheric Environment 11/2014; 97:1–5. · 3.11 Impact Factor
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    ABSTRACT: We conducted a source apportionment and investigated the atmospheric behavior of carbonaceous aerosols during hazy and normal days using radiocarbon (14C) and biomass burning/secondary organic aerosol (SOA) tracers during winter in Guangzhou, China. Haze episodes were formed either abruptly by local emissions or through the accumulation of particles transported from other areas. The average contributions of fossil carbon to elemental carbon (EC), water-insoluble organic carbon (WIOC), and water-soluble organic carbon (WSOC) were 71±10%, 40±6% and 33±3%, respectively. High contributions of fossil carbon to EC (80-90%) were observed for haze samples that were substantially impacted by local emissions, as were the highest (lowest) ratios for NO3-/SO42- (OC/EC), which indicates that these particles mainly came from local vehicle exhaust. Low contributions of fossil carbon to EC (60-70%) were found for haze particles impacted by regional transport. Secondary organic carbon (SOC) calculated using SOA tracers accounts for only ~20% of the SOC estimated by 14C, which is probably because some important volatile organic carbons are not taken into account in the SOA tracer calculation method and because of the large discrepancy in ambient conditions between the atmosphere and smog chambers. A total of 33±11% of the SOC was of fossil origin, a portion of which could be influenced by humidity.
    Environmental science & technology. 09/2014;
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    ABSTRACT: Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.
    Nature 09/2014; · 38.60 Impact Factor
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    ABSTRACT: DAURE (Determination of the sources of atmospheric Aerosols in Urban and Rural Environments in the Western Mediterranean) was a multidisciplinary international field campaign aimed at investigating the sources and meteorological controls of particulate matter in the Western Mediterranean Basin (WMB). Measurements were simultaneously performed at an urban-coastal (Barcelona; BCN) and a rural-elevated (Montseny; MSY) site pair in NE-Spain during winter and summer. State-of-the-art methods such as 14C analysis, Proton-Transfer Reaction Mass Spectrometry and High-Resolution Aerosol Mass Spectrometry were applied for the first time in the WMB as part of DAURE. WMB regional pollution episodes were associated with high concentrations of inorganic and organic species formed during the transport to inland areas and built up at regional scales. Winter pollutants accumulation depended on the degree of regional stagnation of an air mass under anticyclonic conditions and the planetary boundary layer height. In summer, regional recirculation and biogenic secondary organic aerosols (SOA) formation mainly determined the regional pollutant concentrations. The contribution from fossil sources to organic carbon (OC) and elemental carbon (EC) and hydrocarbon-like organic aerosol (HOA) concentrations were higher at BCN compared with MSY due to traffic emissions. The relative contribution of non-fossil OC was higher at MSY especially in summer due to biogenic emissions. The fossil OC/EC ratio at MSY was twice the corresponding ratio at BCN indicating that a substantial fraction of fossil OC was due to fossil SOA. In winter, BCN cooking emissions were identified as important source of modern carbon in primary OA.
    Journal of Geophysical Research: Atmospheres. 04/2014;
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    ABSTRACT: Radiocarbon (14C) analysis is a unique tool to distinguish fossil/non-fossil sources of carbonaceous aerosols. We present 14C-measurements of organic and total carbon (OC, TC) on highly time resolved filters (3–4 h, typically 12 h or longer have been reported) from 7 days collected during CalNex-2010, in Pasadena. Average non-fossil contributions of 58% ± 15% and 51% ± 15% were found for OC and TC, respectively. Results indicate that non-fossil carbon is a major constituent of the background aerosol, evidenced by its nearly constant concentration (2–3 μgC m−3). Cooking is estimated to contribute at least 25% to non-fossil OC, underlining the importance of urban non-fossil OC sources. In contrast, fossil OC concentrations have prominent and consistent diurnal profiles, with significant afternoon enhancements (~3 μgC m−3), following the arrival of the western Los Angeles (LA) basin plume with the sea breeze. A corresponding increase in semi-volatile oxygenated OC and organic vehicular emissions markers and their photochemical reaction products occurs. This suggests that the increasing OC is mostly from fresh anthropogenic secondary OC (SOC) from mainly fossil precursors formed in the western LA basin plume. We note that in several European cities where the diesel passenger car fraction is higher, SOC is 20% less fossil, despite 2–3 times higher elemental carbon concentrations, suggesting that SOC formation from gasoline emissions most likely dominates over diesel in the LA basin. This would have significant implications for our understanding of the on-road vehicle contribution to ambient aerosols and merits further study.
    Journal of Geophysical Research: Atmospheres. 04/2014;
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    ABSTRACT: To assign fossil and non-fossil contributions to carbonaceous particles, radiocarbon (14C) measurements were performed on organic carbon (OC), elemental carbon (EC) and water-insoluble OC (WINSOC) of aerosol samples from a regional background site in South China under different seasonal conditions. The average contributions of fossil sources to EC, OC and WINSOC were 38±11%, 19±10% and 17±10%, respectively, indicating generally a dominance of non-fossil emissions. A higher contribution from fossil sources to EC (~51%) and OC (~30%) was observed with air-mass pathway from Southeast China during low fire periods, associated to large fossil-fuel combustion and vehicle emissions in highly urbanized regions of China. In contrast, an increase of the non-fossil contribution by 5-10% was observed during the periods with enhanced open biomass-burning activities in Southeast Asia or Southeast China. A modified EC tracer method was used to estimate the fossil-derived SOC by determining 14C-derived fossil WINSOC and fossil EC. This approach indicates a dominating secondary component (70±7%) of fossil OC. Furthermore, contributions of biogenic and biomass-burning emissions to contemporary OC were estimated to be 56±16% and 44±14%, respectively.
    Environmental Science & Technology 02/2014; · 5.48 Impact Factor
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    ABSTRACT: In 2005, two ice cores with lengths of 58.7 and 57.6 m respectively to bedrock were recovered from the Miaoergou flat-topped glacier (43°03′19′′ N, 94°19′21′′ E; 4512 m a.s.l.), eastern Tien Shan. 210Pb dating of one of the ice cores (57.6 m) was performed, and an age of AD 1851±6 at a depth of 35.2 m w.e. was determined. For the periodAD 1851–2005, a mean annual net accumulation of 229±7 mm w.e.a–1 was calculated. At the nearby oasis city of Hami (∼80 km from the Miaoergou flat-topped glacier) the annual precipitation rate is 38 mm w.e.a–1, hence glacial meltwater is a major water supply for local residents. The surface activity concentration of 210Pbex was found to be ∼400 mBq kg–1, which is higher than observed at other continental sites such as Belukha, Russia, and Tsambagarav, Mongolia, which have surface activity concentrations of 280 mBq kg–1. The 210Pb dating agrees well with the chronological sequence deduced from the annual-layer counting resulting from the seasonalities of δ18O and trace metals for the period AD 1953–2005, and β-activity horizons resulting from atmospheric nuclear testing during the period AD 1962–63. We conclude that 210Pb analysis is a suitable method for obtaining a continuous dating of the Miaoergou ice core for ∼160 years, which can also be applied to other ice cores recovered from the mountains of western China.
    Annals of Glaciology 01/2014; 55(66). · 1.87 Impact Factor
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    ABSTRACT: Measurement of the radioactive carbon isotope 14C in aerosols can provide a direct estimate of the contribution of fossil fuel sources to aerosol carbon. In aerosol science, measurements of 14C/12C ratios are usually reported as fraction modern (fm). The radiocarbon signature gives a clear distinction between 'modern' carbon sources (fm around 1.1-1.2 for biomass burning and around 1.05 for biogenic secondary organic aerosol) and 'fossil' carbon sources (fm =0 for primary and secondary formation from fossil fuel combustion). Due to the high cost of 14C analyses very few long-term studies have been conducted to date. The data that will be presented offer a unique insight into the seasonal variation of source contributions to the carbonaceous aerosol in a highly industrialized region. High volume filter samples have been collected roughly twice per month from February 2011 - July 2012 at Cabauw, a rural location in the Netherlands surrounded by major urban centers and highways. This site provides a regional background aerosol contamination in the Netherlands. We report measurements of fm for total carbon (TC), organic carbon (OC), water insoluble OC (WIOC) and thermally refractory carbon (RC) as a proxy for elemental carbon. The fraction modern of OC lies between 0.65 - 1 and shows only a moderate seasonal variation with highest values in the spring and lowest values in the summer. Elemental carbon is generally dominated by fossil fuel emissions, but shows a distinct seasonal variation with higher contribution of modern sources from November - Mai. This contribution is attributed to wood combustion. It is low when air masses arrive from the ocean and high for air masses with European continental origin, pointing to a main source outside the Netherlands. Water soluble organic carbon is dominated by modern sources throughout the year. For TC concentrations between 1.2 and 8 μg/m3, fm(TC) increases with TC concentration. A Keeling plot implies that synoptic scale variation in fm(TC) are mainly due to a modern source, imposed on a regional background with a relatively high contribution from fossil sources. TC concentrations > 8 μg/m3 are associated with pollution events transported from Germany/Eastern Europe and can have much high fossil contributions. However, fm in all carbon fractions is usually reduced in day time compared to night time, most likely due to traffic variations, which modify the carbonaceous aerosol on shorter time scales. Using a simple model the contributions of fossil emissions, biomass burning, and biogenic emissions will be estimated for all carbon fractions. The seasonal variation in the source contributions will be presented and discussed.
    04/2013;
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    ABSTRACT: Carbonaceous particles (total carbon, TC) are a major fraction of the fine aerosol and affect climate and human health. TC is classified into the sub-fractions elemental carbon (EC) and organic carbon (OC). EC originates only from fossil fuel combustion and biomass burning. OC can be emitted directly as primary organic aerosol from biogenic emissions, wood burning and fossil fuel combustion or can be formed in-situ in the atmosphere (secondary organic aerosol) (Szidat et al. 2006). Radiocarbon (14C) analysis is a direct and quantitative tool for distinguishing fossil and non-fossil sources, since 14C in fossil fuels is completely depleted whereas other sources have a contemporary 14C level. This study presents source apportionment results from the winter season over a time period of 5 years (2007/2008-2011/2012) using 14C measurements on aerosol filters collected simultaneously at 16 air quality monitoring stations across Switzerland. For every year 5 winter smog episode days were selected from which filters from all stations were analyzed. To resolve a good spatial variability 11 stations north and 5 stations south of the Alps were selected. This 14C data set is unique around the world concerning the number of analyzed filters and the duration. The filter sampling was conducted using high volume samplers with PM10 inlets and a time resolution of 24h. Separation of OC and EC was carried out using the THEODORE system (Szidat et al. 2004) and a Sunset EC/OC analyzer (Zhang et al. 2012), respectively. The resulting CO2 was cryo-trapped and sealed in glass ampoules for 14C measurements, performed with the Mini Carbon Dating System MICADAS (Ruff et al. 2007) at the Swiss Federal Institute of Technology (ETH) Zürich. The results for non-fossil (NF) OC (5 year average) are 81% ± 10% for north and 85% ± 8% for south of the Alps. ECNF values range from 31% to 53% north and from 36% to 66% south of the Alps. Both, the OCNF and ECNF show higher values south of the Alps. The highest values were found in alpine valleys with OCNF of max. 100% and ECNF of max. 87%. The station-to-station variation north of the Alps is low, whereas in the south a spatial trend was found with an increase of the non-fossil values towards the north showing the influence of more fossil air masses advected from the Po-valley. No real time trend over the 5 winters was found. The high ECNF and OCNF values together with a good correlation with levoglucosan show that wood burning is the major source of TC in Switzerland during winter smog episodes. This work was funded by the Swiss Federal Office for the Environment, inNet Monitoring AG, Liechtenstein and the Swiss cantons Basel-Stadt, Basel-Landschaft, Graubünden, Solothurn, Valais and Ticino. Ruff, M. et al (2007) Radiocarbon 49(2), 307-314 Szidat, S. et al. (2004) Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 223-224: 829-836 Szidat, S. et al. (2006) J. Geophys. Res. 111, D07206 Zhang, Y.L. et al. (2012), Atmos. Chem. Phys. 12(22): 10841-10856
    04/2013;
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    ABSTRACT: In 2010 more than 600 radiocarbon samples were measured with the gas ion source at the MIni CArbon DAting System (MICADAS) at ETH Zurich and the number of measurements is rising quickly. While most samples contain less than 50 μg C at present, the gas ion source is attractive as well for larger samples because the time-consuming graphitization is omitted. Additionally, modern samples are now measured down to 5 per-mill counting statistics in less than 30 min with the recently improved gas ion source.In the versatile gas handling system, a stepping-motor-driven syringe presses a mixture of helium and sample CO2 into the gas ion source, allowing continuous and stable measurements of different kinds of samples. CO2 can be provided in four different ways to the versatile gas interface. As a primary method, CO2 is delivered in glass or quartz ampoules. In this case, the CO2 is released in an automated ampoule cracker with 8 positions for individual samples. Secondly, OX-1 and blank gas in helium can be provided to the syringe by directly connecting gas bottles to the gas interface at the stage of the cracker. Thirdly, solid samples can be combusted in an elemental analyzer or in a thermo-optical OC/EC aerosol analyzer where the produced CO2 is transferred to the syringe via a zeolite trap for gas concentration. As a fourth method, CO2 is released from carbonates with phosphoric acid in septum-sealed vials and loaded onto the same trap used for the elemental analyzer. All four methods allow complete automation of the measurement, even though minor user input is presently still required. Details on the setup, versatility and applications of the gas handling system are given.
    Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms 01/2013; 294:315–319. · 1.19 Impact Factor
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    ABSTRACT: Radiocarbon offers a unique possibility for unambiguous source apportionment of carbonaceous particles due to a direct distinction of non-fossil and fossil carbon. In this work, particulate matter of different size fractions was collected at 4 sites in Switzerland to examine whether fine and coarse carbonaceous particles exhibit different fossil and contemporary sources. Elemental carbon (EC) and organic carbon (OC) as well as water-soluble OC (WSOC) and water-insoluble OC (WINSOC) were separated and determined for subsequent C-14 measurement. In general, both fossil and non-fossil fractions in OC and EC were found more abundant in the fine than in the coarse mode. However, a substantial fraction (similar to 20 +/- 5%) of fossil EC was found in coarse particles, which could be attributed to traffic-induced non-exhaust emissions. The contribution of biomass burning to coarse-mode EC in winter was relatively high, which is likely associated to the coating of EC with organic and/or inorganic substances emitted from intensive wood burning. Further, fossil OC (i.e. from vehicle emissions) was found to be smaller than non-fossil OC due to the presence of primary biogenic OC and/or growing in size of wood-burning OC particles during aging processes. C-14 content in WSOC indicated that the second organic carbon rather stems from non-fossil precursors for all samples. Interestingly, both fossil and non-fossil WINSOC concentrations were found to be higher in fine particles than in coarse particles in winter, which is likely due to primary wood burning emissions and/or secondary formation of WINSOC.
    Radiocarbon 01/2013; 55(2-3):1510-1520. · 1.07 Impact Factor
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    ABSTRACT: Establishing precise age-depth relationships of high-alpine ice cores is essential in order to deduce conclusive paleoclimatic information from these archives. Radiocarbon dating of carbonaceous aerosol particles incorporated in such glaciers is a promising tool to gain absolute ages, especially from the deepest parts where conventional methods are commonly inapplicable. In this study, we present a new validation for a published C-14 dating method for ice cores. Previously C-14-dated horizons of organic material from the Juvfonne ice patch in central southern Norway (61.676 degrees N, 8.354 degrees E) were used as reference dates for adjacent ice layers, which were C-14 dated based on their particulate organic carbon (POC) fraction. Multiple measurements were carried out on 3 sampling locations within the ice patch featuring modern to multimillennial ice. The ages obtained from the analyzed samples were in agreement with the given age estimates. In addition to previous validation work, this independent verification gives further confidence that the investigated method provides the actual age of the ice.
    Radiocarbon 01/2013; 55(2-3):571-578. · 1.07 Impact Factor
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    ABSTRACT: For more than 4 years, gaseous samples of 1–50 μg carbon have been routinely measured with the gas ion source of the small AMS (Accelerator Mass Spectrometer) facility MICADAS (MIni CArbon DAting System) at ETH Zurich. The applied measurement technique offers a simple and fast way of 14C measurements without the need of sample graphitization. A major drawback of gaseous 14C measurements, however, is the relatively low negative ion current, which results in longer measurement times and lower precision compared to graphitized samples. In December 2009, a new, improved Cs sputter ion source was installed at MICADAS and we began to optimize conditions for the measurement of gaseous samples. 12C− currents from the new ion source were improved from initially 3 to 12–15 μA for routine measurements and the negative ion yield was increased by a factor of 2, reaching 8% on average during routine operation. Moreover, the new measurement settings enable a doubled CO2 flow, thus substantially reducing measurement times. The achieved performance allows closing the sample size gap between gaseous and solid samples and makes the gas ion source a promising tool for dating with a measurement precision of 5‰ on samples as small as 50 μg carbon.
    Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms 01/2013; 294:320–327. · 1.19 Impact Factor
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    ABSTRACT: Carbonaceous particles that comprise organic carbon (OC) and elemental carbon (EC) are of increasing interest in climate research because of their influence on the radiation balance of the Earth. The radiocarbon determination of particulate OC and EC extracted from ice cores provides a powerful tool to reconstruct the long-term natural and anthropogenic emissions of carbonaceous particles. However, this C-14-based source apportionment method has not been applied for the firn section, which is the uppermost part of Alpine glaciers with a typical thickness of up to 50 m. In contrast to glacier ice, firn samples are more easily contaminated through drilling and handling operations. In this study, an alternative decontamination method for firn samples consisting of chiselling off the outer parts instead of rinsing them was developed and verified. The obtained procedural blank of 2.8 +/- 0.8 mu g C for OC is a factor of 2 higher compared to the rinsing method used for ice, but still relatively low compared to the typical OC concentration in firn samples from Alpine glaciers. The EC blank of 0.3 +/- 0.1 mu g C is similar for both methods. For separation of OC and EC for subsequent C-14 analysis, a thermal-optical method instead of the purely thermal method was applied for the first time to firn and ice samples, resulting in a reduced uncertainty of both the mass and C-14 determination. OC and EC concentrations as well as their corresponding fraction of modern for firn and ice samples from Fiescherhorn and Jungfraujoch agree well with published results, validating the new method.
    Radiocarbon 01/2013; 55(2-3):383-390. · 1.07 Impact Factor
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    ABSTRACT: Radiocarbon analysis of the carbonaceous aerosol allows an apportionment of fossil and non-fossil sources of airborne particulate matter (PM). A chemical separation of total carbon (TC) into its subfractions organic carbon (OC) and elemental carbon (EC) refines this powerful technique, as OC and EC originate from different sources and undergo different processes in the atmosphere. Although 14C analysis of TC, EC, and OC has recently gained increasing attention, interlaboratory quality assurance measures have largely been missing, especially for the isolation of EC and OC. In this work, we present results from an intercomparison of 9 laboratories for 14C analysis of carbonaceous aerosol samples on quartz fiber filters. Two ambient PM samples and 1 reference material (RM 8785) were provided with representative filter blanks. All laboratories performed 14C determinations of TC and a subset of isolated EC and OC for isotopic measurement. In general, 14C measurements of TC and OC agreed acceptably well between the laboratories, i.e. for TC within 0.015–0.025 F14C for the ambient filters and within 0.041 F14C for RM 8785. Due to inhomogeneous filter loading, RM 8785 demonstrated only limited applicability as a reference material for 14C analysis of carbonaceous aerosols. 14C analysis of EC revealed a large deviation between the laboratories of 28–79% as a consequence of different separation techniques. This result indicates a need for further discussion on optimal methods of EC isolation for 14C analysis and a second stage of this intercomparison.
    Radiocarbon 01/2013; 55(2-3):1496. · 1.07 Impact Factor
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    ABSTRACT: Radiocarbon (14C) measurements of elemental carbon (EC) and organic carbon (OC) separately (as opposed to only total carbon, TC) allow an unambiguous quantification of their non-fossil and fossil sources and represent an improvement in carbonaceous aerosol source apportionment. Isolation of OC and EC for accurate 14C determination requires complete removal of interfering fractions with maximum recovery. The optimal strategy for 14C-based source apportionment of carbonaceous aerosols should follow an approach to subdivide TC into different carbonaceous aerosol fractions for individual 14C analyses, as these fractions may differ in their origins. To evaluate the extent of positive and negative artefacts during OC and EC separation, we performed sample preparation with a commercial Thermo-Optical OC/EC Analyser (TOA) by monitoring the optical properties of the sample during the thermal treatments. Extensive attention has been devoted to the set-up of TOA conditions, in particular, heating program and choice of carrier gas. Based on different types of carbonaceous aerosols samples, an optimised TOA protocol (Swiss_4S) with four steps is developed to minimise the charring of OC, the premature combustion of EC and thus artefacts of 14C-based source apportionment of EC. For the isolation of EC for 14C analysis, the water-extraction treatment on the filter prior to any thermal treatment is an essential prerequisite for subsequent radiocarbon measurements; otherwise the non-fossil contribution may be overestimated due to the positive bias from charring. The Swiss_4S protocol involves the following consecutive four steps (S1, S2, S3 and S4): (1) S1 in pure oxygen (O2) at 375 °C for separation of OC for untreated filters and water-insoluble organic carbon (WINSOC) for water-extracted filters; (2) S2 in O2 at 475 °C followed by (3) S3 in helium (He) at 650 °C, aiming at complete OC removal before EC isolation and leading to better consistency with thermal-optical protocols like EUSAAR_2, compared to pure oxygen methods; and (4) S4 in O2 at 760 °C for recovery of the remaining EC. WINSOC was found to have a significantly higher fossil contribution than the water-soluble OC (WSOC). Moreover, the experimental results demonstrate the lower refractivity of wood-burning EC compared to fossil EC and the difficulty of clearly isolating EC without premature evolution. Hence, simplified techniques of EC isolation for 14C analysis are prone to a substantial bias and generally tend towards an overestimation of fossil sources. To obtain the comprehensive picture of the sources of carbonaceous aerosols, the Swiss_4S protocol is not only implemented to measure OC and EC fractions, but also WINSOC as well as a continuum of refractory OC and non-refractory EC for 14C source apportionment. In addition, WSOC can be determined by subtraction of the water-soluble fraction of TC from untreated TC. Last, we recommend that 14C results of EC should in general be reported together with the EC recovery.
    ATMOSPHERIC CHEMISTRY AND PHYSICS 11/2012; 12(22):10841-10856. · 5.51 Impact Factor
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    ABSTRACT: Radiocarbon (14C) measurements of elemental carbon (EC) and organic carbon (OC) separately (as opposed to only total carbon, TC) allow an unambiguous quantification of their non-fossil and fossil sources and represent an improvement in carbonaceous aerosol source apportionment. Isolation of OC and EC for accurate 14C determination requires complete removal of interfering fractions with maximum recovery. To evaluate the extent of positive and negative artefacts during OC and EC separation, we performed sample preparation with a commercial Thermo-Optical OC/EC Analyser (TOA) by monitoring the optical properties of the sample during the thermal treatments. Extensive attention has been devoted to the set-up of TOA conditions, in particular, heating program and choice of carrier gas. Based on different types of carbonaceous aerosols samples, an optimised TOA protocol (Swiss_4S) with four steps is developed to minimise the charring of OC, the premature combustion of EC and thus artefacts of 14C-based source apportionment of EC. For the isolation of EC for 14C analysis, the water-extraction treatment on the filter prior to any thermal treatment is an essential prerequisite for subsequent radiocarbon; otherwise the non-fossil contribution may be overestimated due to the positive bias from charring. The Swiss_4S protocol involves the following consecutive four steps (S1, S2, S3 and S4): (1) S1 in pure oxygen (O2) at 375 °C for separation of OC for untreated filters, and water-insoluble organic carbon (WINSOC) for water-extracted filters; (2) S2 in O2 at 475 °C, followed by (3) S3 in helium (He) at 650 °C, aiming at complete OC removal before EC isolation and leading to better consistency with thermal-optical protocols like EUSAAR_2, compared to pure oxygen methods; and (4) S4 in O2 at 760 °C for recovery of the remaining EC. WINSOC was found to have a significantly higher fossil contribution than the water-soluble OC (WSOC). Moreover, the experimental results demonstrate the lower refractivity of wood-burning EC compared to fossil EC and the difficulty of clearly isolating EC without premature evolution. Hence, simplified techniques of EC isolation for 14C analysis are prone to a substantial bias and generally tend towards an underestimation of the non-fossil sources. Consequently, the optimal strategy for 14C-based source apportionment of carbonaceous aerosols should follow an approach to subdivide TC into different carbonaceous aerosol fractions for individual 14C analyses, as these fractions differ in their origins. To obtain the comprehensive picture of the sources of carbonaceous aerosols, the Swiss_4S protocol is not only implemented to measure OC and EC fractions, but also WINSOC as well as a continuum of refractory OC and non-refractory EC for 14C source apportionment. In addition, WSOC can be determined by subtraction of the water-soluble fraction of TC from untreated TC. Last, we recommend that 14C results of EC should in general be reported together with the EC recovery.
    Atmospheric Chemistry and Physics 07/2012; 12(7):17657-17702. · 4.88 Impact Factor
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    ABSTRACT: We describe the first long-term implementation of the radiocarbon (¹⁴C) method to study the share of biogenic (%Bio C) and fossil (%Fos C) carbon in combustion CO₂. At five Swiss incinerators, a total of 24 three-week measurement campaigns were performed over 1 year. Temporally averaged bag samples were analyzed for ¹⁴CO₂ by accelerator mass spectrometry. Significant differences between the plants in the share of fossil CO₂ were observed, with annual mean values from 43.4 ± 3.9% to 54.5 ± 3.1%. Variations can be explained by the waste composition of the respective plant. Based on our dataset, an average value of 48 ± 4%Fos C was determined for waste incineration in Switzerland. No clear annual trend in %Fos C was observed for four of the monitored incinerators, while one incinerator showed considerable variations, which are likely due to the separation and temporary storage of bulky goods.
    Waste Management 04/2012; 32(8):1516-20. · 3.16 Impact Factor
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    ABSTRACT: Although laboratory experiments have shown that organic compounds in both gasoline fuel and diesel engine exhaust can form secondary organic aerosol (SOA), the fractional contribution from gasoline and diesel exhaust emissions to ambient SOA in urban environments is poorly known. Here we use airborne and ground-based measurements of organic aerosol (OA) in the Los Angeles (LA) Basin, California made during May and June 2010 to assess the amount of SOA formed from diesel emissions. Diesel emissions in the LA Basin vary between weekdays and weekends, with 54% lower diesel emissions on weekends. Despite this difference in source contributions, in air masses with similar degrees of photochemical processing, formation of OA is the same on weekends and weekdays, within the measurement uncertainties. This result indicates that the contribution from diesel emissions to SOA formation is zero within our uncertainties. Therefore, substantial reductions of SOA mass on local to global scales will be achieved by reducing gasoline vehicle emissions.
    Geophysical Research Letters 03/2012; 39(6):L06805. · 3.98 Impact Factor

Publication Stats

1k Citations
225.40 Total Impact Points

Institutions

  • 2004–2014
    • Universität Bern
      • Department of Chemistry and Biochemistry
      Berna, Bern, Switzerland
  • 2012
    • Empa - Swiss Federal Laboratories for Materials Science and Technology
      • Laboratory for Air Pollution/Environmental Technology
      Duebendorf, Zurich, Switzerland
  • 2000–2010
    • Paul Scherrer Institut
      • Laboratory of Atmospheric Chemistry (LAC)
      Aargau, Switzerland
  • 2005
    • Leibniz Universität Hannover
      Hanover, Lower Saxony, Germany
  • 2001
    • Universidad de Sevilla
      Hispalis, Andalusia, Spain