ALBERT

Description: Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal–optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to a vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average, 91 % of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our setup, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our setup were 0.8 ± 0.4 and 0.67 ± 0.34 μg C, respectively, based on multiple measurements of ultra-small samples. The extraction procedure (Swiss_4S protocol and cryo-trapping only) contributed 0.37 ± 0.18 μg of modern carbon and 0.13 ± 0.07 μg of fossil carbon to the total blank of our system, with consistent estimates obtained for the two laboratories. There was no difference in the background correction between the OC and EC fractions. Our setup allowed us to efficiently isolate and trap each carbon fraction with the Swiss_4S protocol and to perform 14C analysis of ultra-small OC and EC samples with high accuracy and low 14C blanks.

Description: Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make its deployment at sufficient sites to determine regional characteristics impractical. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, and PM10, i.e., PM with aerodynamic diameters smaller than 1, 2.5, and 10 µm, respectively), collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g., AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60–91 %) achieved using this technique, together with low detection limits (0.8 µg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon ions, ions containing oxygen, and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning, and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g., filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially resolved long-term data sets.