Quantifying the uncertainties in thermal-optical analysis of carbonaceous aircraft engine emissions: an interlaboratory study

Carbonaceous particles, such as soot, make up a notable fraction of atmospheric particulate matter and contribute substantially to anthropogenic climate forcing, air pollution, and human health impacts. Thermal-optical analysis (TOA) is one of the most widespread methods used to speciate carbonaceous particles and divides total carbon (TC) into the operationally defined quantities of organic carbon (OC; carbon that has evolved during slow heating in an inert atmosphere) and elemental carbon (EC). While multiple studies have identified fundamental scientific reasons for uncertainty in distinguishing OC and EC, far fewer studies have reported on between-laboratory reproducibility. Moreover, existing reproducibility studies have focused on complex atmospheric samples. The real-time instruments used for regulatory measurements of the mass concentration of aircraft engine non-volatile particulate matter (nvPM) emissions are required to be calibrated to the mass of EC, as determined by TOA of the filter-sampled emissions of a diffusion flame combustion aerosol source (DFCAS). However, significant differences have been observed in the calibration factor for the same instrument based on EC content determined by different calibration laboratories. Here, we report on the reproducibility of TC, EC, and OC quantified using the same TOA protocol, instrument model (Model 5L, Sunset Laboratory), and software settings (auto-split-point: Calc405) across five different laboratories and instrument operators. Six unique data sets were obtained, with one laboratory operating two instruments. All samples were collected downstream of an aircraft engine after treatment with a catalytic stripper to remove volatile organics. Between-laboratory contributions made up a majority of the within-filter uncertainties for EC and TC, even for these relatively well-controlled samples. Overall, expanded (k = 2) uncertainties due to measurement reproducibility correspond to 17 %, 15 %, and 13 % of the nominal values for EC, OC, and TC, respectively, and 7.3 % in the EC / TC ratio. These values are lower than previous studies, including atmospheric samples without volatile organic removal; therefore, they likely represent lower limits for the uncertainties of the TOA method.