Gas-Particle Partitioning of Formaldehyde in Mainstream Cigarette Smoke Cover

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Gas-Particle Partitioning of Formaldehyde in Mainstream Cigarette Smoke

Contributions to Tobacco & Nicotine Research

Volume 29 (2020): Issue 1 (April 2020)

By: Edward John, Steven Coburn, Chuan Liu, John McAughey, Derek Mariner, Kevin G. McAdam, István Bakos and Sandor Dóbé

Open Access

|May 2020

Figures & Tables

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.

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).

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).

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 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 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).

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

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

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.

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.

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 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, m_DL	Cambridge pad, m_c	Impinger, m_I	Total, m_Σ	f_DL
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
Property	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)	-
Predicted main deposition regions in the respiratory tract	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)	m_D(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)	m_D(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
	D_T (cm² s⁻¹)	D_T (cm² s⁻¹)	m_D(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 fraction^a			Nicotine fraction^b

	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

DOI: https://doi.org/10.2478/cttr-2020-0002 | Journal eISSN: 2719-9509

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Language: English

Page range: 2 - 20

Submitted on: Nov 11, 2019

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Accepted on: Feb 20, 2020

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Published on: May 23, 2020

Published by: Institut für Tabakforschung GmbH

In partnership with: Paradigm Publishing Services

Publication frequency: 4 issues per year

Keywords:

Mainstream cigarette smoke,

crotonaldehyde,

gas-particle partitioning,

diffusion denuder,

2,4-dinitrophenylhydrazine

Related subjects:

General interest,

Life sciences, other,

© 2020 Edward John, Steven Coburn, Chuan Liu, John McAughey, Derek Mariner, Kevin G. McAdam, István Bakos, Sandor Dóbé, published by Institut für Tabakforschung GmbH
This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 4.0 License.

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