Accesso libero

Gas-Particle Partitioning of Formaldehyde in Mainstream Cigarette Smoke

Edward John
Edward John
, 
Steven Coburn
Steven Coburn
, 
Chuan Liu
Chuan Liu
, 
John McAughey
John McAughey
, 
Derek Mariner
Derek Mariner
, 
Kevin G. McAdam
Kevin G. McAdam
, 
István Bakos
István Bakos
 e 
Sandor Dóbé
Sandor Dóbé
   | 23 mag 2020
Contributions to Tobacco & Nicotine Research's Cover Image
INFORMAZIONI SU QUESTO ARTICOLO
Articolo precedente
Articolo Successivo
Cita
Pubblicato online: 23 mag 2020
Pagine: 2 - 20
Ricevuto: 11 nov 2019
Accettato: 20 feb 2020
DOI: https://doi.org/10.2478/cttr-2020-0002
Parole chiave
© 2020 Edward John et al., published by Sciendo
This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.

Figure 1

Experimental set-up used for the preparation of flowing formaldehyde–air gas mixtures. In the apparatus the three-way glass valve is connected to a DNPH impinger to determine the concentration of formaldehyde in the gas stream. In the denuder experiments, the impinger is replaced by a DNPH-coated denuder tube.
Experimental set-up used for the preparation of flowing formaldehyde–air gas mixtures. In the apparatus the three-way glass valve is connected to a DNPH impinger to determine the concentration of formaldehyde in the gas stream. In the denuder experiments, the impinger is replaced by a DNPH-coated denuder tube.

Figure 2

Schematic representation of the denuder apparatus. 1) Denuder tube; 2) Cambridge filter pad; 3) synthetic air cylinder; 4) ultrathermostat; 5) membrane pump; 6) Pyrex® hood; 7) retractable electric igniter; 8) water saturator; 9) and 10) impingers, filled with acidic DNPH solution; 11), 12) and 13) mass flow controllers; 14) mixer to mix dry and wet air flows; 15) humidity sensor; 16) control for mass flow controllers; 17) humidity indicator. Based on Figure 1 of (25).
Schematic representation of the denuder apparatus. 1) Denuder tube; 2) Cambridge filter pad; 3) synthetic air cylinder; 4) ultrathermostat; 5) membrane pump; 6) Pyrex® hood; 7) retractable electric igniter; 8) water saturator; 9) and 10) impingers, filled with acidic DNPH solution; 11), 12) and 13) mass flow controllers; 14) mixer to mix dry and wet air flows; 15) humidity sensor; 16) control for mass flow controllers; 17) humidity indicator. Based on Figure 1 of (25).

Figure 3

Depletion of acetaldehyde, acrolein, crotonaldehyde and formaldehyde along the distance of denuder tubes obtained with aldehyde–air gas mixtures prepared with 0% and 60% RH synthetic air (temperature T = 298 (± 1) K, flow Q273 = 300 (± 6) mL min−1).
Depletion of acetaldehyde, acrolein, crotonaldehyde and formaldehyde along the distance of denuder tubes obtained with aldehyde–air gas mixtures prepared with 0% and 60% RH synthetic air (temperature T = 298 (± 1) K, flow Q273 = 300 (± 6) mL min−1).

Figure 4

Effect of volumetric flow-rate variation on the formaldehyde depletion data in DNPH-coated denuder tubes at 298 K and 60% RH. The curves are two-parameter-fit results to the data using the Gormley-Kennedy equation (26).
Effect of volumetric flow-rate variation on the formaldehyde depletion data in DNPH-coated denuder tubes at 298 K and 60% RH. The curves are two-parameter-fit results to the data using the Gormley-Kennedy equation (26).

Figure 5

Effect of the air flow RH on the formaldehyde depletion data in DNPH-coated denuder tubes at 298 (± 1) K and volumetric air flow Q273 = 300 (± 6) mL min−1. The curves are two-parameter-fit results to the data using the Gormley-Kennedy equation (26).
Effect of the air flow RH on the formaldehyde depletion data in DNPH-coated denuder tubes at 298 (± 1) K and volumetric air flow Q273 = 300 (± 6) mL min−1. The curves are two-parameter-fit results to the data using the Gormley-Kennedy equation (26).

Figure 6

Effect of the denuder temperature on formaldehyde depletion data in fully DNPH-coated denuder tubes at 60% RH and Q273 = 200 (± 6) mL min−1. The curves are two-parameter fit results to the data using the Gormley-Kennedy equation (26).
Effect of the denuder temperature on formaldehyde depletion data in fully DNPH-coated denuder tubes at 60% RH and Q273 = 200 (± 6) mL min−1. The curves are two-parameter fit results to the data using the Gormley-Kennedy equation (26).

Figure 7

Formaldehyde depletion in MS from Kentucky 3R4F reference cigarettes; data determined at in DNPH-coated denuder tubes at a temperature of 298 K.
Formaldehyde depletion in MS from Kentucky 3R4F reference cigarettes; data determined at in DNPH-coated denuder tubes at a temperature of 298 K.

Figure 8

Temperature dependence of formaldehyde deposition from cigarette MS in diffusion denuder tubes at a flow rate Q273 = 300 mL min−1.
Temperature dependence of formaldehyde deposition from cigarette MS in diffusion denuder tubes at a flow rate Q273 = 300 mL min−1.

Supplementary Figure S1

Representative HPLC chromatogram. The HPLC peaks are the 2,4-DNPH derivatives of the following carbonyls: #1) formaldehyde; #2) acetaldehyde; #3) acetone; #4) acrolein, #5) propionaldehyde; #6) crotonaldehyde, #7) butyraldehyde; #8) benzaldehyde; #9) isovaleraldehyde.
Representative HPLC chromatogram. The HPLC peaks are the 2,4-DNPH derivatives of the following carbonyls: #1) formaldehyde; #2) acetaldehyde; #3) acetone; #4) acrolein, #5) propionaldehyde; #6) crotonaldehyde, #7) butyraldehyde; #8) benzaldehyde; #9) isovaleraldehyde.

Supplementary Figure S2

HPLC chromatograms of samples from smoking denuder experiments. A)HPLC of a denuder sample obtained with 3R4F cigarette at 298 K and 60% RH. B)addition of acrolein + DNPH reaction mixture to the denuder sample. C)addition of crotonaldehyde + DNPH reaction mixture to A + B. Other DNPH peaks (RT/min): CH2O: ~8.3, CH3CHO(Z): ~11.03, CH3CHO(E): ~11.33, acetone:~14.5.
HPLC chromatograms of samples from smoking denuder experiments. A)HPLC of a denuder sample obtained with 3R4F cigarette at 298 K and 60% RH. B)addition of acrolein + DNPH reaction mixture to the denuder sample. C)addition of crotonaldehyde + DNPH reaction mixture to A + B. Other DNPH peaks (RT/min): CH2O: ~8.3, CH3CHO(Z): ~11.03, CH3CHO(E): ~11.33, acetone:~14.5.

Supplementary Figure S3

Application of the semi-empirical denuder model of Lewis, Colbeck, and Mariner (1994) to model the depletion of formaldehyde from cigarette MS at a flow rate Q273 = 300 mL min−1, and 60% RH with different temperatures (T). Data are non-linear least-squares means.
Application of the semi-empirical denuder model of Lewis, Colbeck, and Mariner (1994) to model the depletion of formaldehyde from cigarette MS at a flow rate Q273 = 300 mL min−1, and 60% RH with different temperatures (T). Data are non-linear least-squares means.

Supplementary Figure S4

Application of the theoretical denuder model of Lipowicz and Piadé (2004) to describe the depletion of formaldehyde from cigarette MS in diffusion denuder tubes. Kentucky 3R4F cigarette MS was assessed at different temperatures (T) at flow rate Q273 = 300 mL min−1 and RH 60%.
Application of the theoretical denuder model of Lipowicz and Piadé (2004) to describe the depletion of formaldehyde from cigarette MS in diffusion denuder tubes. Kentucky 3R4F cigarette MS was assessed at different temperatures (T) at flow rate Q273 = 300 mL min−1 and RH 60%.

Overall formaldehyde masses determined for cigarette MS using the diffusion denuder method.

T (K) Formaldehyde mass (μg)
Denuder, mDL Cambridge pad, mc Impinger, mI Total, mΣ fDL
298 1.00 ± 0.33 0.33 ± 0.37 1.54 ± 1.52 2.86 ± 2.02 35 ± 27%
310 1.03 ± 0.35 0.58 ± 0.15 0.80 ± 0.29 2.42 ± 0.54 43 ± 17%
323 1.43 ± 0.22 0.32 ± 0.004 0.58 ± 0.34 2.34 ± 0.79 61 ± 23%
Average 2.530

Summary of physical properties of selected carbonyls in cigarette smoke.

Property Compound
Formaldehyde Acetaldehyde Acrolein Crotonaldehyde
Formula HCHO CH3CHO CH2 = CHCHO CH3CH = CHCHO
Boiling point (K) 254 293 326 377
ISO emissions from KY3R4F (mg/cigarette) 21.5 ± 7.8 (37) 540 ± 135 (37) 49 ± 14 (37) 13 ± 5 (37)
Proportion in particulate phase of mainstream smoke 32% (15, 16) 2% (15) 0% (17, 57) 7% (56)
2% (56)
7% (15)
33% (60)
Total retention on cigarette smoke inhalation 95–99% (61) 94–95% (62,19) > 97% (61)
70–97% (19)
97% (61),
98% (61)
99% (63,64)
Mouth retention from cigarette smoke - 30–60% (19) 72% of 97% total retention (19) -
Predicted main deposition regions in the respiratory tract Mouth and oropharyngeal/laryngeal (21) Mouth and oropharyngeal/laryngeal (21) Mouth and oropharyngeal/laryngeal (21) -
Trachea (22) Deposition past generation 8 (22) Deposition past generation 8 (22)
Toxicity IARC Group 1 human carcinogen (11) IARC Group 2B (58, 59) Inflammatory and cytotoxic effects (2, 65) Mutagenic and carcinogenic (55)

Summary of Gormley-Kennedy analysis of formaldehyde denuder dataa.

Effect of flow rate (temperature = 298 K, RH 60%)
Q273 (mL min−1) 1-parameter fit 2-parameter fit
D298 (cm2 s−1) D298 (cm2 s−1) mD(z0) (μg)
200 0.035 ± 0.016 0.184 499
300 0.049 ± 0.015 0.186 125
400 0.060 ± 0.018 0.188 93
500 0.058 ± 0.014 0.127 33
600 0.064 ± 0.015 0.130 33
Effect of RH (temperature 298 = K, Q273 = 300 mL min−1
RH (%) 1-parameter fit 2-parameter fit
D298 (cm2 s−1) D298 (cm2 s−1) mD(z0) (μg)
0 0.024 ± 0.004 0.042 11.9
10 0.041 ± 0.011 0.112 64.3
20 0.046 ± 0.015 0.162 92.8
60 0.049 ± 0.016 0.192 125.2
Effect of denuder temperature (Q273 = 200 mL min−1, RH 60%)
T (K) 1-parameter fit 2-parameter fit
DT (cm2 s−1) DT (cm2 s−1) mD(z0) (μg)
298 0.035 ± 0.031 0.189 499.2
310 0.035 ± 0.024 0.149 366.6
323 0.032 ± 0.021 0.128 176.5

Comparison of G/P partitioning for formaldehyde and nicotine determined from cigarette MS using the diffusion denuder method.

T (K) Formaldehyde fractiona Nicotine fractionb
Lewis, Colbeck and Mariner model (1994) Lipowicz and Piadé model (2004) Whole length of denuder tube Lewis, Colbeck and Mariner model (1994) Lipowicz and Piadé model (2004) Whole length of denuder tube
298 5.6% 0.49% 35% 1.3% 0.09% 6%
310 7.3% 0.69% 43% 3.0% 0.5% 21%
323 11.6% 1.33% 61% 5.7% 2.5% 53%
Ratio of 323 to 298 K values
2.10 2.71 1.74 4.5 27.8 8.83
eISSN:
2719-9509
Lingua:
Inglese
Frequenza di pubblicazione:
4 volte all'anno
Argomenti della rivista:
General Interest, Life Sciences, other, Physics
Feed RSS della rivista