Development of graphitization method for low carbon aerosol filter samples with Automated Graphitization System AGE-3.

The wide applications of the radiocarbon (14C) approach in environmental, archeological, and geological research often necessitates the analysis of microgram-sized samples. The ability to measure low carbon samples is particularly relevant for aerosol particle filters, especially for samples from pristine environments. For this purpose, we investigated the sample dilution method for graphitization of low-carbon samples (20-200 µg C) with an Automated Graphitization System (AGE-3), and applied a mass balance equation for the calculation of 14C values. Materials with known 14C values (standards NIST-OXII and IAEA-C7) were diluted with 14C-free phthalic anhydride (PhA) until sufficient mass (500 µg C) for graphitization with the AGE-3 system was acquired. Reliable 14C values were obtained for samples with carbon amount in the range of 40-200 µg. Next, we adapted the dilution method for estimation of aerosol sample 14C values. Using it, we attained a precision of 0.71 ± 0.83 pMC for 14C measurements of aerosol samples containing 40-200 µg C. A shift of radiocarbon values to 5.07 pMC (average 3.08 ± 1.7 pMC) was observed for samples with low carbon content (<20 µg C). We determined that a precision of 2-3 pMC is acceptable for aerosol particle source apportionment studies. Using the sample dilution method, graphitization with AGE-3 of aerosol samples with carbon content >40 µg becomes a viable and efficient way of sample preparation for 14C analysis.

Aerosol source (biomass, traffic and coal emission) apportionment in Lithuania using stable carbon and radiocarbon analysis.

In the present study, a combination of the stable carbon isotope ratio (13C/12C) with radiocarbon data (14C) allowed us to perform the aerosol source apportionment. Filter samples of PM1 were collected during the warm and cold periods in rural and urban sites in Lithuania. The 14C/12C ratio of total carbon (TC) was measured using the single stage accelerator mass spectrometer quantifying of fossil and non-fossil derived aerosol emissions. The δ13C value was measured using an elemental analyser interfaced with an isotope ratio mass spectrometer. We have found that the highest fraction of contemporary carbon (fc = 0.82) was measured during a warm period in a rural location. A higher fraction of fossil fuel-derived carbon was observed for air masses transported from highly industrialized Western European regions during both seasons. Isotope mass balance calculations revealed that the traffic emissions composed 15 and 25 % in rural and urban sites, respectively, and did not change during either season. Input from coal-derived aerosol particles was estimated to be 15 % at an urban site during the cold period. The combination of the stable carbon isotope ratio with the radiocarbon data allowed us to distinguish coal, liquid fossil fuel combustion, and non-fossil derived aerosol particle emissions.