Determination of ultra-low concentrations of gaseous 14C-bearing hydrocarbons produced during corrosion of irradiated steel using accelerator mass spectrometry.

Compound-specific radiocarbon analysis (CSRA) was developed to identify and quantify gaseous 14C-bearing carbon compounds at the pico- to femtomolar concentration range and employed in a corrosion experiment with small specimens of irradiated steel. The approach is based on gas chromatographic separation of single 14C-bearing carbon compounds, their oxidation to 14CO2, sampling with a custom-made fraction collector and quantification by accelerator mass spectrometry (AMS). In addition to CSRA, a method allowing the quantification of the total 14C content of the gas phase was developed and tested. After validation of the two set-ups with standards, the gaseous 14C-bearing carbon compounds produced during alkaline anoxic corrosion of irradiated steel were quantified. Small hydrocarbons (HCs) like methane (14CH4) and ethane (14C2H6) were the only 14C-bearing compounds identified in the gas phase above the detection limit. 14CH4 was the main species (on average 5.4 × 10-14 mol L-1 gas) and contributed >90% to the total 14C content, whereas the concentration of 14C2H6 was much lower (7.9 × 10-16 mol L-1 gas). To our knowledge, this is the first study reporting CSRA of gaseous 14C-bearing HCs produced during anoxic corrosion of irradiated metallic radioactive waste at ultra-low concentrations.

Analysis of 14C-bearing compounds released by the corrosion of irradiated steel using accelerator mass spectrometry.

The combination of ion chromatography (IC) with accelerator mass spectrometry (AMS) was developed to determine the speciation of 14C-(radiocarbon) bearing organic compounds in the femto to pico molar concentration range. The development of this compound-specific radiocarbon analysis (CSRA) of carboxylic acids is reported and the application of the method on a leaching solution from neutron-irradiated steel is demonstrated. The background and the dynamic range of the AMS-based method were quantified. On using 14C-labelled standards, the measurements demonstrate the repeatability of the analytical method and the reproducible recovery of the main target carboxylic acids (i.e., acetate, formate, malonate, and oxalate). The detection limit was determined to be in the mid fmol 14C per L level while the dynamic range of the analytical method covers three orders of magnitude from the low fmol to the mid pmol 14C per L level. Cross contamination was found to be negligible during IC fractionation and was accounted for during eluate processing and 14C detection by AMS. The 14C-bearing carboxylates released from an irradiated steel nut into an alkaline leaching solution were analysed using the CSRA-based analytical method with the aim to check the applicability of the approach and develop appropriate sample preparation. The concentrations of 14C-bearing formate and acetate, the main organic corrosion products, were at a low pmol 14C per L level for convenient dimensions of the alkaline leaching experiment which demonstrates that compound-specific 14C AMS is an extremely sensitive analytical method for analysing 14C-bearing compounds. The content of total organic 14C in solution (TO14C) determined by the direct measurement of an aliquot of the leaching solution agrees well with the sum of the 14C concentrations of the individual carboxylates within the uncertainty of the data. Furthermore, the TO14C content is in good agreement with the calculated value using the corrosion rate determined from the 60Co release and the 14C inventory of the irradiated steel specimen.

Secondary organic aerosol origin in an urban environment: influence of biogenic and fuel combustion precursors.

Source contributions of organic aerosol (OA) are still not fully understood, especially in terms of quantitative distinction between secondary OA formed from anthropogenic precursors vs. that formed from natural precursors. In order to investigate the OA origin, a field campaign was carried out in Barcelona in summer 2013, including two periods characterized by low and high traffic conditions. Volatile organic compound (VOC) concentrations were higher during the second period, especially aromatic hydrocarbons related to traffic emissions, which showed a marked daily cycle peaking during traffic rush hours, similarly to black carbon (BC) concentrations. Biogenic VOC (BVOC) concentrations showed only minor changes from the low to the high traffic period, and their intra-day variability was related to temperature and solar radiation cycles, although a decrease was observed for monoterpenes during the day. The organic carbon (OC) concentrations increased from the first to the second period, and the fraction of non-fossil OC as determined by (14)C analysis increased from 43% to 54% of the total OC. The combination of (14)C analysis and Aerosol Chemical Speciation Monitor (ACSM) OA source apportionment showed that the fossil OC was mainly secondary (>70%) except for the last sample, when the fossil secondary OC only represented 51% of the total fossil OC. The fraction of non-fossil secondary OC increased from 37% of total secondary OC for the first sample to 60% for the last sample. This enhanced formation of non-fossil secondary OA (SOA) could be attributed to the reaction of BVOC precursors with NOx emitted from road traffic (or from its nocturnal derivative nitrate that enhances night-time semi-volatile oxygenated OA (SV-OOA)), since NO2 concentrations increased from 19 to 42 µg m(-3) from the first to the last sample.

Characterization of the Axial Jet Separator with a CO2/Helium Mixture: Toward GC-AMS Hyphenation.

Development of interfaces for sample introduction from high pressures is important for real-time online hyphenation of chromatographic and other separation devices with mass spectrometry (MS) or accelerator mass spectrometry (AMS). Momentum separators can reduce unwanted low-density gases and introduce the analyte into the vacuum. In this work, the axial jet separator, a new momentum interface, is characterized by theory and empirical optimization. The mathematical model describes the different axial penetration of the components of a jet-gas mixture and explains the empirical results for injections of CO2 in helium into MS and AMS instruments. We show that the performance of the new interface is sensitive to the nozzle size, showing good qualitative agreement with the mathematical model. Smaller nozzle sizes are more preferable due to their higher inflow capacity. The CO2 transmission efficiency of the interface into a MS instrument is ∼ 14% (CO2/helium separation factor of 2.7). The interface receives and delivers flows of ∼ 17.5 mL/min and ∼ 0.9 mL/min, respectively. For the interfaced AMS instrument, the ionization and overall efficiencies are 0.7-3% and 0.1-0.4%, respectively, for CO2 amounts of 4-0.6 µg C, which is only slightly lower compared to conventional systems using intermediate trapping. The ionization efficiency depends on to the carbon mass flow in the injected pulse and is suppressed at high CO2 flows. Relative to a conventional jet separator, the transmission efficiency of the axial jet separator is lower, but its performance is less sensitive to misalignments.

Fossil and biogenic CO2 from waste incineration based on a yearlong radiocarbon study.

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.

Determination of biogenic and fossil CO(2) emitted by waste incineration based on (14)CO(2) and mass balances.

A field application of the radiocarbon ((14)C) method was developed to determine the ratio of biogenic vs. fossil CO(2) emissions from waste-to-energy plants (WTE). This methodology can be used to assign the Kyoto relevant share of fossil CO(2) emissions, which is highly relevant for emission budgets and emission trading. Furthermore, heat and electricity produced by waste incinerators might be labelled depending on the fossil or biogenic nature of the primary energy source. The method development includes representative on-site CO(2) absorption and subsequent release in the laboratory. Furthermore, a reference value for the (14)C content of pure biogenic waste (f(M,bio)) was determined as 1.130+/-0.038. Gas samples for (14)CO(2) analysis were taken at three WTEs during one month each. Results were compared to an alternative approach based on mass and energy balances. Both methods were in excellent agreement and indicated a fraction of biogenic CO(2) slightly above 50%.

Determination of stable carbon isotopes of organic acids and carbonaceous aerosols in the atmosphere.

A wet oxidation method for the compound-specific determination of stable carbon isotopes (delta(13)C) of organic acids in the gas and aerosol phase, as well as of water-soluble organic carbon (WSOC), is presented. Sampling of the organic acids was done using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to an ion chromatography (IC) system. The method allows for compound-specific stable carbon isotope analysis by collecting different fractions of organic acids at the end of the IC system using a fraction collector. delta(13)C analyses of organic acids were conducted by oxidizing the organic acids with sodium persulfate at a temperature of 100 degrees C and determining the delta(13)C value of the resulting carbon dioxide (CO(2)) with an isotope ratio mass spectrometer. In addition, analysis of delta(13)C of the WSOC was performed for particulate carbon collected on aerosol filters. The WSOC was extracted from the filters using ultrapure water (MQ water), and the dissolved organic carbon was oxidized to CO(2) using the oxidation method. The wet oxidation method has an accuracy of 0.5 per thousand with a precision of +/-0.4 per thousand and provides a quantitative result for organic carbon with a detection limit of 150 ng of carbon.

Iodine-129 in soils from Northern Ukraine and the retrospective dosimetry of the iodine-131 exposure after the Chernobyl accident.

Forty-eight soil profiles down to a depth of 40 cm were taken in Russia and Ukraine in 1995 and 1997, respectively, in order to investigate the feasibility of retrospective dosimetry of the 131I exposure after the Chernobyl accident via the long-lived 129I. The sampling sites covered areas almost not affected by fallout from the Chernobyl accident such as Moscow/Russia and the Zhitomir district in Ukraine as well as the highly contaminated Korosten and Narodici districts in Ukraine. 129I was analyzed by radiochemical neutron activation analysis (RNAA) and accelerator mass spectrometry (AMS). 127I was measured for some profiles by RNAA or ion chromatography (IC). The results for 127I demonstrated large differences in the capabilities of the soils to store iodine over long time spans. The depth profiles of 129I and of 137Cs showed large differences in the migration behavior between the two nuclides but also for each nuclide among the different sampling sites. Though it cannot be quantified how much 129I and 137Cs was lost out of the soil columns into deeper depths, the inventories in the columns were taken as proxies for the total inventories. For 129I, these inventories were at least three orders of magnitude higher than a pre-nuclear value of 0.084+/-0.017 mBq m(-2) derived from a soil profile taken in 1939 in Lutovinovo/Russia. From the samples from Moscow and Zhitomir, a pre-Chernobyl 129I inventory of (44+/-24) mBq m(-2) was determined, limiting the feasibility of 129I retrospective dosimetry to areas where the 129I inventories exceed 100 mBq m(-2). Higher average 129I inventories in the Korosten and Narodici districts of 130 and 848 mBq m(-2), respectively, allowed determination of the 129I fallout due to the Chernobyl accident. Based on the total 129I inventories and on literature data for the atomic ratio of 129I/131I=13.6+/-2.8 for the Chernobyl emissions and on aggregated dose coefficients for 131I, the thyroid exposure due to 131I after the Chernobyl accident was estimated for the inhabitants of four villages in the Korosten and of three villages in the Narodici districts. The limitations and uncertainties of the 129I retrospective dosimetry are discussed.

Relative influence of 129I sources in a sediment core from the Kattegat area.

The depth profiles of the (129)I concentration and the (129)I/(127)I ratio in a surface sediment core from the Kattegat area have been analyzed in order to obtain information about the different sources of (129)I in that core. Therefore, a mathematical model that relates the measured values to the available emission data from the nuclear fuel reprocessing plants and nuclear weapons tests has been applied. Results show that the reprocessing plants at La Hague and Sellafield are the main sources of (129)I in the sediment. Results about the transfer from the release points at the reprocessing plants to the sampling zone agree with other literature data. The model calculates quite fast the sedimentation of (129)I in the sampling place, probably attached to organic matter. Finally, an estimation of approximately 89 kg of (129)I released by Sellafield between 1952 and 1968 has been obtained from the model.

Wet and dry deposition of 129I in Seville (Spain) measured by accelerator mass spectrometry.

Iodine-129 (T1/2 = 1.57 x 10(7) yr) concentrations have been determined by accelerator mass spectrometry in rainwater samples taken at Seville (southwestern Spain) in 1996 and 1997. This technique allows a reduction in the detection limits for this radionuclide in comparison to radiometric counting and other mass spectrometric methods such as ICP-MS. Typical 129I concentrations range from 4.7 x 10(7) 129I atoms/l (19.2%) to 4.97 x 10(9) 129I atoms/l (5.9%), while 129I depositions are normally in the order of 10(8)-10(10) atoms/m2d. These values agree well with other results obtained for recent rainwater samples collected in Europe. Apart from these, the relationship between 129I deposition and some atmospheric factors has been analyzed, showing the importance of the precipitation rate and the concentration of suspended matter in it.

Enhanced selectivity in the determination of delta9-tetrahydrocannabinol and two major metabolites in serum using ion-trap GC-MS-MS.

Cannabinoids were extracted from serum with C18 SPE cartridges and analyzed as their trimethylsilyl (TMS) derivatives. A benchtop gas chromatography-tandem mass spectrometry (GC-MS-MS) system based on an ion trap with external ionization was used. Quantitation was done in relation to trideuterated internal standards in dual MS-MS mode. Confirmation of the identity for the three compounds of interest, delta9-tetrahydrocannabinol (THC), 11-hydroxy-delta9-tetrahydrocannabinol (11-OH-THC), and 11-nor-9-carboxy-delta9-tetrahydrocannabinol (THCCOOH), was achieved by registering the daughter spectra in full scan mode. It was possible to identify the three compounds at concentrations down to 0.25 microg/L for THC, 0.5 microg/L for 11-OH-THC, and < 2.5 microg/L for THCCOOH by comparison with reference spectra. The limits of quantitation are better than 2 microg/L for THC, 5 microg/L for 11-OH-THC, and 8 microg/L for THCCOOH. The within-run and day-to-day precision for the three analytes were very similar and ranged from 4.2 to 10.4%.