characterization-quantification-compound-specific-isotopic-analysis

Characterization, Quantification and Compound-specific Isotopic Analysis of Pyrogenic Carbon Using Benzene Polycarboxylic Acids (BPCA)

Fire-derived, pyrogenic carbon (PyC), sometimes called black carbon (BC), is the carbonaceous solid residue of biomass and fossil fuel combustion, such as ...

ETH Zurich

Ice cores from glaciers situated near anthropogenic sources of air pollution provide important archives of the emissions of species with short atmospheric lifetimes. Here we present the history of atmospheric Pu fallout reconstructed from an ice core from the Belukha glacier in the Siberian Altai. Fourteen ice core samples covering the time period 1941-1986 were selected for Pu analysis, chemically processed, and measured using accelerator mass spectrometry. The Pu concentration peaks in 1963, coinciding with the maximum of the nuclear weapons tests and in concordance with the 3H activity concentration peak. The shapes of the 239Pu and 3H profiles reflect two main periods of atmospheric nuclear test activity: premoratorium testing before 1958 and postmoratorium testing in 1961 and 1962. Premoratorium tests contribute about 45% of the integrated Pu inventory. The average 240Pu/239Pu isotopic ratio is 0.18 +/- 0.05, indicating that a large majority of the Pu in the Belukha glacier originates from global stratospheric fallout rather than from direct tropospheric input.

Plutonium from global fallout recorded in an ice core from the Belukha glacier, Siberian Altai.

Real-time measurements of submicrometer aerosol were performed using an Aerodyne aerosol mass spectrometer (AMS) during three weeks at an urban background site in Zurich (Switzerland) in January 2006. A hybrid receptor model which incorporates a priori known source composition was applied to the AMS highly time-resolved organic aerosol mass spectra. Three sources and components of submicrometer organic aerosols were identified: the major component was oxygenated organic aerosol (OOA), mostly representing secondary organic aerosol and accounting on average for 52-57% of the particulate organic mass. Radiocarbon (14C) measurements of organic carbon (OC) indicated that approximately 31 and approximately 69% of OOA originated from fossil and nonfossil sources, respectively. OOA estimates were strongly correlated with measured particulate ammonium. Particles from wood combustion (35-40%) and 3-13% traffic-related hydrocarbon-like organic aerosol (HOA) accounted for the other half of measured organic matter (OM). Emission ratios of modeled HOA to measured nitrogen oxides (NOx) and OM from wood burning to levoglucosan from filter analyses were found to be consistent with literature values.

Source attribution of submicron organic aerosols during wintertime inversions by advanced factor analysis of aerosol mass spectra.

Trace element records from glacier and ice sheet archives provide insights into biogeochemical cycles, atmospheric circulation changes, and anthropogenic pollution history. We present the first continuous high-resolution thallium (Tl) record, derived from an accurately dated ice core from tropical South America, and discuss Tl as a tracer for volcanic eruptions. We identify four prominent Tl peaks and propose that they represent signals from the massive explosive eruptions of the "unknown 1258" A.D. volcano, of Kuwae ( approximately 1450 A.D.), Tambora (1815 A.D.), and Krakatoa (1883 A.D.). The highly resolved record was obtained with an improved setup for the continuous analysis of trace elements in ice with inductively coupled plasma sector field mass spectrometry (ICP-SFMS). The new setup allowed for a stronger initial acidification of the meltwater and shorter tubing length, thereby reducing the risk of memory effects and losses of analytes to the capillary walls. With a comparison of the continuous method to the established conventional decontamination and analysis procedure for discrete samples, we demonstrate the accuracy of the continuous method for Tl analyses.

Thallium as a tracer for preindustrial volcanic eruptions in an ice core record from Illimani, Bolivia.

Steroids are potent hormones that are found in many environments. Yet, contributions from synthetic and endogenous sources are largely uncharacterized. The goal of this study was to evaluate whether carbon isotopes could be used to distinguish between synthetic and endogenous steroids in wastewater and other environmental matrices.

Carbon isotopic (13C and 14C) composition of synthetic estrogens and progestogens.

Mobilization of Arctic permafrost carbon is expected to increase with warming-induced thawing. However, this effect is challenging to assess due to the diverse processes controlling the release of various organic carbon (OC) pools from heterogeneous Arctic landscapes. Here, by radiocarbon dating various terrestrial OC components in fluvially and coastally integrated estuarine sediments, we present a unique framework for deconvoluting the contrasting mobilization mechanisms of surface vs. deep (permafrost) carbon pools across the climosequence of the Eurasian Arctic. Vascular plant-derived lignin phenol (14)C contents reveal significant inputs of young carbon from surface sources whose delivery is dominantly controlled by river runoff. In contrast, plant wax lipids predominantly trace ancient (permafrost) OC that is preferentially mobilized from discontinuous permafrost regions, where hydrological conduits penetrate deeper into soils and thermokarst erosion occurs more frequently. Because river runoff has significantly increased across the Eurasian Arctic in recent decades, we estimate from an isotopic mixing model that, in tandem with an increased transfer of young surface carbon, the proportion of mobilized terrestrial OC accounted for by ancient carbon has increased by 3-6% between 1985 and 2004. These findings suggest that although partly masked by surface carbon export, climate change-induced mobilization of old permafrost carbon is well underway in the Arctic.

Differential mobilization of terrestrial carbon pools in Eurasian Arctic river basins.

Activation measurements of materials exposed to nuclear bomb explosions are widely used to reconstruct the neutron flux for retrospective dosimetry. In this study the applicability of coral CaCO3 as a biogenic neutron fluence dosimeter is tested. The long-lived radioisotopes (41)Ca, (14)C and (10)Be, which had been produced in nuclear bomb explosions, are measured in several coral sand samples from the Bikini atoll at the 600 kV and 200 kV AMS facilities of ETH Zurich. Elevated concentrations of all studied isotopes are found in a sample from the crater that was initially formed by the high-yield nuclear explosion Castle Bravo in 1954 and that had been used as site for several tests afterward. The observed (14)C concentration is considered too large to originate from neutron irradiation of CaCO3 alone. The relatively low concentration of (10)Be found in the crater sample indicates that production of (10)Be during nuclear bomb testing is generally minor. A simple neutron fluence reconstruction is performed on basis of the (41)Ca/(40)Ca ratio.

41Ca, 14C and 10Be concentrations in coral sand from the Bikini atoll.

To assign fossil and nonfossil contributions to carbonaceous particles, radiocarbon ((14)C) 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 nonfossil emissions. A higher contribution from fossil sources to EC (∼51%) and OC (∼30%) was observed for air-masses transported from Southeast China in fall, associated with large fossil-fuel combustion and vehicle emissions in highly urbanized regions of China. In contrast, an increase of the nonfossil 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 secondary organic carbon from fossil emissions by determining (14)C-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.

Radiocarbon-based source apportionment of carbonaceous aerosols at a regional background site on Hainan Island, South China.

By focusing high-intensity laser pulses on carbonate samples carbon dioxide is generated and can be directly introduced into the gas ion source (GIS) of an Accelerator Mass Spectrometer (AMS). This new technique allows rapid radiocarbon analyses at high spatial resolution. The design of the deignated laser ablation cell as well as first results on a stalagmite sample are presented.

Article	Year
Plutonium from global fallout recorded in an ice core from the Belukha glacier, Siberian Altai. Environmental science & technology\| PubMed ID: 15669306	2004
Source attribution of submicron organic aerosols during wintertime inversions by advanced factor analysis of aerosol mass spectra. Environmental science & technology\| PubMed ID: 18350899	2008
Thallium as a tracer for preindustrial volcanic eruptions in an ice core record from Illimani, Bolivia. Environmental science & technology\| PubMed ID: 20050662	2010
Carbon isotopic (13C and 14C) composition of synthetic estrogens and progestogens. Rapid communications in mass spectrometry : RCM\| PubMed ID: 23059878	2012
Differential mobilization of terrestrial carbon pools in Eurasian Arctic river basins. Proceedings of the National Academy of Sciences of the United States of America\| PubMed ID: 23940354	2013
41Ca, 14C and 10Be concentrations in coral sand from the Bikini atoll. Journal of environmental radioactivity\| PubMed ID: 24378732	2014
Radiocarbon-based source apportionment of carbonaceous aerosols at a regional background site on Hainan Island, South China. Environmental science & technology\| PubMed ID: 24506282	2014
Rapid revelation of radiocarbon records with laser ablation Accelerator Mass Spectrometry. Chimia\| PubMed ID: 24983600	2014

Lukas Wacker

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