A matrix of reaction conditions is summarized in Table 1. There is a range of number and mass concentrations of organic PM that can be produced depending on the selected α-pinene and ozone concentrations13. For instance, as shown in Table 1, when the ozone concentration is 43 ppm, varying the α-pinene concentration from 0.125-100 ppm could produce (4.4 ± 0.6) × 105 to (9.1 ± 0.3) × 106 particles∙cm3 and mass concentrations of 101 to 104 µg∙m-3, respectively.
The evolution of the dynamic characteristics of the particle population can be studied inside the flow tube reactor. By means of video demonstration, an experiment was conducted using 50 ± 1 ppm of ozone and 125 ppb of α-pinene. The longitudinal position of the particle sampler inside the flow tube allowed sampling at various times from 3.0 ± 0.2 to 38 ± 1 s. Figure 7 shows the number-diameter distributions of the aerosol particle population for this experiment. The total number concentration and the mode diameter of the particles increased with the residence time. For a residence time of 3 s, no particles were detected. For longer residence times, a particle population was obtained and measured. The mode diameter increased from less than 10 nm to about 50 nm for an increase in residence time from 17 ± 0.5 s to 38 ± 1 s. The corresponding number concentration increased from (8.6 ± 0.5) × 104 cm-3 to (2.56 ± 0.07) × 105 cm3.
Examples of the number-mass distributions recorded in three replicate experiments by the APM setup are shown in Figure 8. The particle mass and mobility diameters were used to calculate the dynamic shape factor, χ, across particle subpopulation. The dynamic shape factor χ is the ratio of the drag force on an actual particle divided by the drag force experienced by a volume-equivalent sphere23. Shape factors of nearly spherical particles approach unity whereas highly aspherical particles have significantly larger shape factors. Figure 9 shows the dynamic shape factors of the particles exiting the flow tube at various mobility diameters and humidity levels. The respective χ values for <5% RH were 1.21 ± 0.02, 1.09 ± 0.02, and 1.08 ± 0.02 (one-sigma uncertainty), suggesting that the particle populations were composed largely of non-spherical particles.
As the RH was increased, χ decreased for all three populations, reaching a final value of 1.02 ± 0.01 at 35% RH and corresponding within uncertainty to spherical particles. Figure 10 shows SEM images of the particles exposed to <5% RH (left column) and 80% RH (right column). The images indicate that the non-spherical particles became round after exposure to high RH, as discussed in detail in Zhang et al.7. The results above indicate that the flow tube reactor is capable of performing various kinds of online and offline analysis.

Figure 1. A schematic flow diagram of the flow tube reactor system. The red lines show the flow containing ozone, the light blue lines show the flow containing α-pinene, and the dark blue lines show the flow of the organic PM. The APM system consist of a DMA, an APM, and a CPC that are connected together. This figure previously appeared in Shreatha et al.13 and is reproduced here with permission.

Figure 2. Graphical user interface for the ozone monitoring and recording program.

Figure 3. Graphical user interface for the temperature monitoring and recording program.

Figure 4. Graphical user interface for the pressure monitoring and recording program.

Figure 5. Graphical user interface for the number-diameter distribution program. Please click here to view a larger version of this figure.

Figure 6. Graphical user interface for the APM program.

Figure 7. Size distribution of the particle population from the flow tube at different residence times. The total number concentrations for each size distribution are 1.69 × 10-1, 7.50 × 103, 8.58 × 104, 2.00 × 105, 2.33 × 105, and 2.56 × 105 particles cm-3 for residence times of 3, 10, 17, 25, 32, and 38 s, respectively. The shaded areas are the standard deviation of particle size distribution. This figure previously appeared in Shreatha et al.13 and is reproduced here with permission. Please click here to view a larger version of this figure.

Figure 8. An example of the number-mass distribution, as measured using the DMA-APM system. Results of three replicate experiments are shown to demonstrate reproducibility. Two-sigma uncertainty is represented by the error bars, which are approximately the same size as the data markers. The lines represent fits of a normal distribution to the data. The abscissa is calculated based on the APM rotation speed and the voltage applied between the walls of the APM cylinders. The particles shown in the plot were produced from 700 ppb α-pinene and 14 ppm ozone. A central mobility diameter of 126.0 nm was selected by the DMA. This figure previously appeared in Zhang et al.7 and is reproduced here with permission. Please click here to view a larger version of this figure.

Figure 9. Dynamic shape factor for increasing relative humidity. Panel A: Particles produced from 700 ppb α-pinene and 14, 25, and 30 ppm ozone for particle populations having central mobility diameters of 126.0, 175.0, and 190.0 nm, respectively. The exposure time to relative humidity was 310 s. The error bars in each panel represent two sigma of standard deviation. This figure previously appeared in Zhang et al.7 and is reproduced here with permission. Please click here to view a larger version of this figure.

Figure 10. SEM images of the particles obtained from 700 ppb α-pinene and sampled for a central mobility diameter of 180.0 nm. The aerosol particles were collected on the silica substrate for 12 h and then coated with 5 nm of Pt/Pd. The voltage for the electron beam was 5 kV, and the working distance was 2.3 mm. Column 1 shows dimer, trimer, and higher-order agglomerates of the granular monomers for <5% RH. Red circles identify the monomers. Column 2 shows nearly spherical particles that were collected after exposure to 80% RH followed by drying to <5% RH. This figure previously appeared in Zhang et al.7 and is reproduced here with permission.
| O3 (ppm) | | 0.15±0.02 | 0.9±0.1 | 5.7±0.2 | 43±1 | 194±2 |
|
| α-pinene |
| (ppm) |
| 0.125 ± 0.003 | Num. Conc. | 0 | (1±1)×102 | (1.0±0.6)×105 | (4.4±0.6)×105 | (3.2±0.2)×105 |
| Mass. Conc. | 0 | (3±5)×10-2 | 15±5 | 11±3 | 20±2 |
| Mode Diameter | 0 | 22±4 | 60±5 | 35±3 | 34±2 |
| Geo. St. Deviation | N/A | 1.2 | 1.3 | 1.3 | 1.5 |
| 1.00 ± 0.03 | Num. Conc. | 0 | (3.1±0.9)×102 | (1.5±0.2)×105 | (5.5±0.2)×105 | (5.8±0.4)×105 |
| Mass. Conc. | 0 | (9±3)×10-3 | 61±9 | (52±0.1)×102 | (66±0.1)×102 |
| Mode Diameter | 0 | 33±7 | 86±6 | 84±3 | 85±19 |
| Geo. St. Deviation | N/A | 1.3 | 1.4 | 1.5 | 1.7 |
| 10.0 ± 0. 3 | Num. Conc. | (2±2)×101 | (4.0±0.2)×105 | (6.0±0.7)×105 | (6.3±0.7)×105 | (1.8±0.2)×106 |
| Mass. Conc. | 0* | (1.6±0.2)×102 | (2.5±0.2)×103 | (1.19±0.02)×104 | (1.57±0.02)×104 |
| Mode Diameter | 8±9 | 81±2 | 147±9 | 245±38 | 155±5 |
| Geo. St. Deviation | 1 | 1.4 | 1.4 | 1.4 | 1.5 |
| 100 ± 3 | Num. Conc. | (4.4±0.3)×105 | (8.3±0.3)×105 | (8.3±0.4)×106 | (9.1±0.2)×106 | (1.3±0.02)×107 |
| Mass. Conc. | 35±3 | (8.6±0.1)×102 | (1.3±0.1)×104 | (1.6±0.04)×105 | (4.0±0.1)×105 |
| Mode Diameter | 48±2 | 88±5 | 134±8 | 262±12 | 334±4 |
| Geo. St. Deviation | 1.4 | 1.6 | 1.5 | 1.7 | 1.9 |
Table 1. Number concentrations (cm-3), mass concentrations (µg m-3), mode diameter (nm), and geometric diameter standard deviation of the particles produced by α-pinene ozonolysis. A material density of 1200 kg∙m3 was used for conversion of volume concentrations to mass concentrations and the residence time was 38 s for all experiments. *Although particles were present, the mass concentration was below the detection limit. This table previously appeared in Shreatha et al.13 and is reproduced here with permission.