Abstract. We report results from our atmospheric flask sampling network for three European sites: Lutjewad in the Netherlands, Mace Head in Ireland and the North Sea F3 platform. The air samples from these stations are analyzed for their CO2 and O2 concentrations. In this paper we present the CO2 and O2 data series from these sites between 1998 and 2009, as well as the atmospheric potential oxygen (APO). The seasonal pattern and long term trends agree to a large extent between our three measurement locations. We however find a changing gradient between Mace Head and Lutjewad, both for CO2 and O2. To explain the potential contribution of fossil fuel emissions to this changing gradient we use an atmospheric transport model in combination with CO2 emission data and information on the fossil fuel mix per region. Using the APO trend from Mace Head we obtain an estimate for the global oceanic CO2 uptake of 1.8 ± 0.8 PgC/year.
The Ansanto Valley (southern Italy) is characterized by vents and boiling mud lakes that emit typical volcanic exhalations (mostly fossil CO 2 ). This fossil dilution spreads over the Ansanto Valley and its impact on local trees is investigated in this study. Six trees at increasing distance from the emitting sources and 2 aliquots of gas were sampled. Dendrochronological analysis was performed on tree cores in order to check the accuracy of the tree-ring sequences; the results indicate no anomalies in the curves of the analyzed trees. δ 13 C and radiocarbon ( 14 C) analyses were performed on the α-cellulose extracted from some selected tree rings. The main aim of δ 13 C analysis was to gain information about the origin of CO 2 arising from the source; the results support the hypothesis of a carbonatic origin, with respect to a volcanic origin. 14 C analysis was performed to evaluate the influence and to quantify the percentage of fossil dilution characterizing the local atmosphere and affecting the trees at different distances from the source during the years. The results show the presence of a strong fossil dilution affecting the trees, increasing toward the sources (from ∼6% at 80 m distance to ∼30% at 20 m from the nearest vent) with quite stable values over the examined period.
The chemical and stable carbon isotopic composition of the organic aerosol particles (OA) emitted by a shuttle passenger ship between mainland Naples and island Capri in Italy were investigated. Various methylsiloxanes and derivatives were found in particulate ship emissions for the first time, as identified in the mass spectra of a thermal desorption - proton transfer reaction - mass spectrometer (TD-PTR-MS) based on the natural abundance of silicon isotopes. Large contributions of methylsiloxanes to OA (up to 59.3%) were found under inefficient combustion conditions, and considerably lower methylsiloxane emissions were observed under cruise conditions (1.2% of OA). Furthermore, the stable carbon isotopic composition can provide a fingerprint for methylsiloxanes, as they have low δ13C values in the range of -44.91‰ ± 4.29‰. The occurrence of methylsiloxanes was therefore further supported by low δ13C values of particulate organic carbon (OC), ranging from -34.7‰ to -39.4‰, when carbon fractions of methylsiloxanes in OC were high. The δ13C values of OC increased up to around -26.7‰ under cruise conditions, when carbon fractions of methylsiloxanes in OC were low. Overall, the δ13C value of OC decreased linearly with increasing carbon fraction of methylsiloxanes in OC, and the slope is consistent with a mixture of methylsiloxanes and fuel combustion products. The methylsiloxanes in ship emissions may come from engine lubricants.
<p class="Abstract"><span lang="EN-US">In historical contexts, analyses of carbon and nitrogen stable isotopes can be useful to answer different question on dietary behavior and to crosscheck information, drawn from texts and classical archaeological investigations. In this study the Isotope Ratio Mass Spectrometry (IRMS) facility installed at the IRMS-SUN Laboratory of the Second University of Naples is presented. Moreover, results coming from application of stable isotope analyses to bone collagen extracted from human remains of the necropolis of “Porta Sirena” in Paestum will be discussed. </span><span lang="EN-US">Finally, a combined analyses of archaeological and historical record and stable isotope measurements permits to expand our knowledge on diet in Roman Paestum.</span></p>
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Analysis of the stable carbon isotope 13C in organic carbon (OC) can give insight into sources and atmospheric processing of carbonaceous aerosols, provided the 13C source signatures are known. However, only few data on 13C signatures of OC emitted by common sources of carbonaceous aerosol are available in Europe. We present and evaluate an improved version of a measurement method to obtain δ13C signatures on organic aerosols desorbed from filter samples at three different desorption temperatures (200 °C, 350 °C and 650 °C) and apply it in a source study. With our calibration approach, the reproducibility of a L-Valine reference material desorbed at a single temperature step of 650 °C shows a standard deviation of 0.19‰ over a period of more than one year. The average δ13C value for this reference material over 248 measurements is −24.10‰, which shows only a slight bias to the nominal value of −24.03‰. Repeated analysis of ambient filter samples desorbed at three temperature steps show typical standard deviations of about 0.3‰ for all temperature steps (200 °C, 350 °C and 650 °C). Isotopic fractionation due to partial thermal desorption during the individual temperature steps was tested on single compound reference materials. It showed significant isotopic fractionation only at temperature steps, in which a very minor fraction of the compound was desorbed. Possible isotope effects caused by charring of organic material were investigated and found to be not significant. The thermal desorption method was applied to various source filter samples from the region of Naples, Italy. We analyzed two different biomass burning sources, exhaust from a city bus and traffic emissions collected in a tunnel and compared these to ambient filter samples from the same region. δ13C signatures of the total OC show values in a narrow range of about −28‰ to −26‰ for all sources, which does not allow a source apportionment only based on 13C. Nevertheless, the results add information to a source inventory of δ13C, where information of 13C in organic aerosol from specific emission sources are rare. City bus emissions show little variation of δ13C over the temperature steps, whereas biomass burning aerosol is enriched in 13C for OC desorbed at 650 °C. For PM10 samples in the urban tunnel an enrichment in δ13C at the 650 °C temperature steps was observed, which is likely caused by the contribution of carbonate carbon to the carbonaceous material desorbed at this temperature step.
A better knowledge of the local and regional sources of the atmospheric particulate matter provides policy makers with the proper awareness when acting to improve air quality, in order to protect public health. A source apportionment study of the carbonaceous aerosol in Naples (Italy) is presented here, in order to improve this understanding in a vulnerable urban area. The aim of this study is quantifying directly fossil and non-fossil contributions to carbonaceous aerosol, by means of radiocarbon measurements. This is the first time that such an approach is implemented in this area. Fine particles with diameter ≤ 2.5 µm (PM2.5) were collected daily on top of a building in the city center, from November 2016 until January 2017. The carbonaceous aerosol was separated into organic carbon (OC) and elemental carbon (EC), by a two-step thermal desorption method. Subsequent radiocarbon analysis enabled the partitioning of the major sources of carbonaceous aerosol into fossil and non-fossil ones by applying radiocarbon isotopic mass balance. The PM2.5 concentration was on average 29 ± 3 µg⁄m3 (mean ± standard error; n = 18), with a maximum of 68.6 ± 0.7 µg⁄m3 on a day when air masses back-trajectories suggest a local origin and stagnant airflow conditions in the region. The carbonaceous component accounts for roughly half of the PM2.5 mass. Fossil fuel emissions are a minor source of OC (23%), but the dominant source of EC (66%), which is directly emitted during combustion processes. However, overall only 30% of the total carbon is of fossil origin, accounting for 14% of PM2.5 mass. Surprisingly, a comparable contribution is due to primary biomass burning carbon, which accounts in total for 15% of PM2.5 mass. Traffic pollution, the main cause of fossil fuel emissions in urban areas, is a significant, but not the predominant source of carbonaceous particle concentration. These findings support the conclusion of a predominant contribution from non-fossil sources to the carbon in airborne particulate matter, which policy makers should take into account when planning mitigation strategies to improve urban air quality.
