Dioxins in Cigarette Smoke

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Dioxins in Cigarette Smoke JoAnn Guest Oct 22, 2005 14:55 PDT

 

 

Archives of Environmental Health,

Pg. 44 (3) : 171-4 May/Jun89

H. Muto

Y. Takazawa

Department of Public Health

Akita University School of Medicine

Akita, Japan

 

http://www.mindfully.org/Pesticide/Dioxins-Cigarette-Smoke.htm

 

Abstract:

Dioxins in cigarettes, smoke, and ash were determined using gas

chromatography/mass spectrometry. The total concentration of

polychlorinated dibenzo-p-dioxins (PCDDs) in cigarette smoke was

approximately 5.0 µ/m3 at the maximum level, whereas various cogeners

from tetra-octa-chlorodibenzo-p-dioxin ( -CDD) were detected.

Particularly, the total concentration of hepta-CDD cogeners was the

highest among these cogeners. Mass fragmentograms of various PCDD

cogeners were similar to those in flue gas samples collected from a

municipal waste incinerator. The PCDD cogeners that were not present in

the cigarettes were found in the smoke samples. The 2, 3, 7, 8-TCDD

toxic equivalent value---an index for effects on humans—for total PCDDs

in smoke was 1.81 nng/m3 using the toxic factor of the United States

Environmental Protection Agency. Daily intake of PCDDs by smoking 20

cigarettes was estimated to be approximately 4.3 pg. kg body/weight/day.

This value was close to that of the ADIs: 1-5 pg. kg body/weight/day

reported in several countries. A heretofore unrecognized health risk was

represented by the presence of PCDDs in cigarette smoke.

 

 

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Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated

dibenzofurans (PCDFs) are hazardous compounds, arid because of their

undisputed highly toxic effects, their presence in the environment

constitutes serious public health problem. Environmental pollution from

PCDDs by disposal of chemical wastes1 and electrical PCB accident2-3 has

been reported the PCDD concentrations in human tissues,4-6 mother's

milk,7 and dietary foods8,9 have also been discussed by many

investigators. The concentrations of PCDDs and PCDFs in daily foods have

been determined and are reported elsewhere.10 The concentration of PCDDs

and PCDFs in fish, eggs, meats, and 'dairy products was higher than

concentrations found in other food items ingested daily.

 

For sources of PCDDs and PCDFs leading to environmental and human

pollution, risk assessments by toxic equivalents predicated from toxic

factors in various countries are being concluded. 11-15 However, the

presence of PCDDs in cigarettes and cigarette smoke has not yet been

reported.

 

Rappe et al.16 reported that PCDDs and PCDFs can be formed in pyrolytic

processes of various incinerators where material containing chlorinated

phenols, polychlorinated biphenyls, polybrominated biphenyls, aid

polyhalogenated diphenyl ethers are incinerated. Cigarette smoke

contains hazardous organic compounds such as benzo(a)pyrene,

dimethylnitrosamine, and N'-nitroso-N-nicotine. Thus, we have conducted

experiments to ascertain whether PCDDs are present in cigarettes or in

cigarette smoke.

 

Methods

 

Apparatus.

A schematic diagram of the sampling method for PCDDs in cigarette smoke

is shown in Figure 1. Smoke was drawn through traps continuously by an

air pump at a flow rate of 1.2-1.5 l/min. A cigarette was burned from

its top to 10 mm from its filter. Polychlorinated dibenzo-p-dioxins in

smoke were trapped with a glass fiber filter (GFP), polyurethane foam

(polyether type, density - 0.016 g/cm3), and XAD-11 resin, successively.

The GFP was set in front of the polyurethane foam. The 30-ml XAD-11

resin was packed in a thimble filter and inserted into another glass

pipe. The glass pipes were sealed with silicone rubber stops covered

with Teflon films and were connected with Teflon pipes (Fig. 1). Ash

resulted from the combustion of 20 cigarettes and was collected for a

period of 30 min. and the weight of an ash sample ranged from 1.4 to 1.6

g.

 

Prior to the experiment, impurities in GFP, urethane foam, and XAD-11

resin used as traps were extracted with acetone and benzene for 24 h

using a Soxhlet extractor. In the combustion experiments, urethane foam

and XAD-11 resin were useful for trapping PCDDs in cigarette smoke and

were used for sampling PCDDs in the atmosphere, and were 88% efficient

for the three traps with 1,2,3,4-TCDD as the standard.

 

Analytical procedure.

A method' of analysis for ash sample is shown in Figure 2. An ash sample

of approximately 1.5 g was treated with acid (1N HCI). The residue was

extracted by a Soxhlet extractor with 200 ml of benzene. The benzene

condensate was treated with sulfuric acid; the PCDDs in condensate were

then separated by column chromatography with 5 g of activated alumina.

Following column chromatography, the PCDDs were purified with HPLC. The

PCDDs in the eluate were extracted with benzene. For gas

chromatography/mass spectrometry (GC/MS) SIM analyses, 5 µg of the

benzene solution were used. The clean up of PCDDs from GFP, urethane

foam, or XAD-11 resin was conducted by subsequent extraction with a

Soxhlet. Cigarette samples were treated similarly. The Teflon tube and

pipe used for sampling were also washed three times with 200 ml of

benzene in a manner similar to that used for the ash sample. A GC/MS

(Shimadzu QP-1000, Tokyo, Japan), equipped with a quadrupole type and a

solvent cut-split system, was used to determine levels of PCDDs.

Guaranteed-grade organic solvents from Wako Pure Chemical, Co. Ltd.

(Tokyo, Japan) were used in this study. Internal Standard materials,

i.e., 1,2,3,4-TCDD (13C6) and octa-CDC) (13C12) [immediately preceding

text blurred on copy] were supplied by Cambridge Isotope Laboratories

(Woburn, MA) ,and were used for tile determination of PCDDs. The

standard of 20 ng was added to the samples. Conditions for high

resolution GC/low resolution MS (HRGC/LRMS) are provided in Table 1.

 

Fig. 1. A schematic diagram of the sampling method used to determine

PCDDs in cigarette smoke.

 

 

 

Results and discussion

 

Our experimental results for PCDD concentrations and abundance ratios of

PCDD isomers in the cigarettes, smoke, and ash sample, which were

obtained from a simple sampling apparatus, may differ from those

obtained in experiments where the autosmoking machine and the smoking

method by international smoking mode are utilized (i.e., 1 puff/min:

puff flow rate, 35 ml/2 sec; length of cigarette end, 30 mm). However,

the detection of PCDD congeners in cigarette smoke may be important.

 

Mass fragmentograms of tetra-CDDs in smoke from urethane foam extracts

corresponding to 20 cigarettes are shown in Figure 3. Approximately 10

peaks for 22 isomers of tetra-CDDs were identified either in urethane

foam extracts or in GFP and XAD-11 resin extracts. However,

2,3,7,11-TCDD was not detected in the smoke, ash, or cigarette samples.

 

Table 2 shows PCDD concentrations and equivalent values for one kind of

cigarette sample and its ash and smoke samples. These results are the

sum of the PCDDs in GFP, urethane foam, and XAD-11 resin. The major

component of total PCDDs in cigarettes and smoke was hepta-CDD

congeners. These hepta-CDD congeners accounted for 84% and 94% of the

total PCDDs in cigarettes and smoke, respectively. The 2,3,7,8-hepta-CDD

was most abundant among the hepta-CDD isomers. However, the abundance

ratio of 2,3,7,8-hepta-CDD was decreased in smoke, whereas that of other

hepta-CDD isomers was increased. Although no penta-CDD congeners were

detected in the cigarettes, the 2,3,7,8-penta-CDD and other penta-CDD

isomers were identified in the smoke samples. These results showed that

penta-CDD congeners were formed during combustion of the cigarettes.

Further, 2,3,7,8-derivatives of pent-hepta-CDDs accounted for 15% of the

total PCDDs.

 

Table 1. Conditions for High Resolution GC/Low Resolution MS

 

GC/column packing and temperature:

Supelco sp-2331, 0.25 mm x 30 l/min

1800° C - 270° C. rate 6° C/min (internal STD and tetra-CDDs)

200° C - 270° C. rate 5° C/min (penta- and hexa-CDDs)

Shimadzu HiCap-CBP-5, 0.25 mm x 15 l/min

(5% phenylmethylsilicone)

220° C - 300° C. rate 7° C/min (internal STD, hepta- and octa-CDD)

GC/Injection temp. and carrier gas: 270° C

He gas, 60 ml/min

MS/ion source and temp.: El mode. 70eV, 250° C

MS/separator temp.: 270° C

Monitor ion: M°, (M + 2)° (isotope ratio: + < 30%)

GC/injection vol.: 5 µl

 

 

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Fig. 3. Mass fragmentograms of tetrachlorodibenzo-p-dioxins in cigarette

smoke (urethane foam extracts).

 

 

 

 

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Fig.2. Analytical procedure used to determine dioxins in ash sample.

PCDDs in urethane foam, GFP, and XAD-11 resin were extracted with 200 ml

of benzene using a Soxhlet extractor; PCDDs in cigarettes were extracted

directly three times with 200 ml benzene.

 

Ash sample (ca. 1.5 g/20 cigarettes)

 

Treatment with acid 1N HCI, 200 ml

(shaking)

 

Filtration

air-dry

 

Soxhlet extraction benzene, 200 ml: 24 h

condensation (1 ml)

n-Hexane, 150 ml

1,2,3,4-TCDD (13C6). 20 ng

 

Treatment with sulfuric acid

washing

K.D. condensation

N, gas purge (200 µl)

n-Hexane, 5 ml

 

Column chromatography activated alumina. 5 g

n-hexane, 50 ml

n-Hexane + dichloromethane, 70 ml

distillate of n-hexane + dichloromethane

K.D. condensation

 

HPLC Zolbax SIL col.

n-Hexane, 1 ml/min (4-8 min)

condensation final: benzene, 100 µl

 

GC-MS

 

 

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To evaluate human effects of PCDDs found in the present samples, the

2,3,7,8-TCDD toxic equivalent values were calculated using U.S.

Environmental Protection Agency toxic factors.12 The values were 1.88

pg/g, 1.81 ng/m3, and 0.102 ng/g for the cigarette, smoke, and ash

sample, respectively. In the smoke sample, the ratio of equivalent value

of 2,3,7,8-penta-CDD isomer produced by combustion accounted for

approximately 12% of the total equivalent value. The equivalent value of

total PCDDs in cigarette smoke was in agreement with that in flue gas

from municipal waste incinerators.17 Further, the daily intake of PCDDs

by smoking 20 cigarettes was estimated to be 4.3 pg - kg body weight/day

for the 60-kg (132-lb.+) adult. This intake rate was close to those of

acceptable daily intakes (ADIs), i.e., 5 pg - kg/day, reported in

several countries.18-20 Because the smoker or passive smoker might also

inhale and ingest dioxins from other sources, PCDD in. take by smokers

or passive smokers may exceed the ADIs for dioxins. A heretofore

unrecognized health hazard resulting from the presence of PCDDs,

especially lower PCDD congeners, in cigarettes should be considered.

 

Conclusions

 

The concentration of PCDDs in cigarette smoke was similar to that found

in the flue gas-of a municipal waste incinerator. However, the presence

of PCDDs in cigarette smoke is more significant than that in tile flue

pas because cigarette smoke is inhaled directly into the lungs without

diffusion and/or dilution. Although PCDDs concentration in cigarette

smoke is lower than formaldehyde or benzo(a)pyrene concentrations, daily

intake of PCDDs by smoking 20 cigarettes was estimated to be about 4.3

pg - kg body weight/day. The value obtained was close to those of the

ADIs: 1-5 pg kg body weight/day reported in several countries. the

presence of tetra-CDD isomers, except 2,3,7,8.TCDD, was notable.

Further, the total concentration of 2,3,7,8-derivatives of

penta-hepta-CDD accounted for 15% of the total PCDDs, whereas hepta-CDD

congeners were most abundant in smoke (94°/0) and in the original

cigarettes (84°/o). The dioxins in the cigarette smoke appear to be

volatilized from the cigarettes themselves. Further work needs to be

done to characterize the magnitude of the public health problem.

 

Table 2. Concentrations and Toxic Equivalents of Dioxins in Cigarettes,

Smoke, and Ash*

 

Concentrations Toxic equivalents E

Cigarettes

(pg/g)

Smoke

(ng/ml)

Ash

(pg/g)

Cigarettes

(pg/g)

Smoke

(ng/m3)

Ash

(pg/g)

 

2,3.7,8-TCDD ND L ND ND 0 0 0

Other TCDDs 44.9 68.0 4.63 0 4-49 0.68 0.046

2,3,7,8-PeCDO ND 0.43 ND 0 0.215 0

Other PeCDDs ND 1.08 ND 0 0.005 0

2.3,7,8-HxCDDs 2.01 2.15 0.56 0.08 0.086 0.022

Other HxCDDs 11.4 5.36 4.45 0.005 0.002 0.002

2.3,7,8-HpCDOs 1343 783 ND 1.343 0.783 0

Other HpCDDs 286 4156 3211 0.003 0.042 0.032

OCDD 257 240 ND 0 0 0

Total PCDDs 1944 5256 3221 1.88 1.81 0.102

 

* Values were calculated from 20 cigarettes.

E Equivalent factor, United States Environmental Protection Agency,12

L Lower than the limit of detection (0.5 pg/g; 0.22 ng/ml).

 

Submitted for publication April 5, 1988; revised; accepted for

publication August 24, 1988.

 

Requests for reprints should be sent to: H. Muto, Dept. of Public

Health. Akita University School of Medicine, Hondo 1-1-1, Akita 010.

Japan.

 

References

 

1. Smith RH, O'Keffe PW, Aldous KM, Hilker DR. O'Brien IE. 2,3,7,8-TCDD

in sediment samples from Love Canal storm sewers and creeks. Environ Sci

Tech 1983;17(1):6-10.

 

2. Hutzinger O, Choudhry GG, Chittim BG, Johnston LE. Formation of

polychlorinated dibenzofurans and dioxins during combustion, electrical

equipment tires and PCB incineration. Research Triangle Park, NC:

Proceedings of conference on potential health effects of PCBs and

related persistent halogenated hydrocarbons, September 12-14, 1983.

 

3. Rappe C, Kjeller L-O, Marklund 5, Nygrene M. Electrical PCB

accidents: an update. Chemosphere 1985;15:1291-95.

 

4. Schecter A, Ryan JJ, Lizotte R, Sun W-F, Miller 1, Gitlitz G,

Bogdasarian M. 1985. Chlorinated dibenzodioxins and dibenzofurans in

human adipose tissue from exposed and control New York State patients.

Chemosphere 1985;14:933-37.

 

5. Ryan JJ, Schecter A, Masuda Y, Kikuchi M. Comparison of PCDDs and

PCDFs in the general population in Japan and China. Chemosphere

1987;16:2017-25.

 

6. Sielken RL. Statistical evaluations reflecting the skewness in the

distribution of TCDD levels in human adipose tissue. Chemosphere

1987;16:2135-40.

 

7. Schecter A, Gasiewicz TA. Health hazard assessment of chlorinated

dioxins and dibenzofurans contained in human milk. Chemosphere

1987;16:2147-54.

 

8. Ono M, Kashima Y, Wakimoto T, Tatsukawa R. Daily intake of PCDDs and

PCDFs by Japanese through food. Chemosphere. 1987;16:1823-28.

 

9. Ogaki J, Takayama K, Miyata H, Kashimoto T. Levels of PCDDs and PCDFs

in human tissues and various foodstuffs in Japan. Chemosphere

1987:16:2047-56.

 

10. Takizawa Y, Muto H. PCDDs and PCDFs carried to human body from the

diet. Chemosphere 1987;16:1971-75.

 

11. Birmingham B, Clement T, Harding O, Pearson R, Rokosh D, Smithies W,

Szakolcai A, Thorpe BH, Tosine H, Wells D. Chlorinated dioxins and

dibenzofurans in Ontario: analysing and controlling the risks

development of scientific criteria document leading to multimedia

standards for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzo

polychlorinated dibenzofurans (PCDFs). Chemosphere 1986;15:1835-50.

 

12. Barners DG, Bellin J, Cleverly D. Interim procedures for estimating

risks associated with exposures to mixtures of chlorinated

dibenzodioxins and dibenzofurans (CODs and CDFs). Chemosphere

1986:15:1895-1903.

 

13. Jones KH, Walsh J, Alston D. The statistical properties of available

world-wide MSW combustion dioxin/furan emissions data as they apply to

the conduct of risk assessments. Chemosphere 1987;16:218386.

 

14. Hiremath C, Bayliss D, Bayard S. Qualitative and quantitative cancer

risk assessment of 2,3,7,8tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD.

Chemosphere 1986:15:1815-23.

 

15. Tanaka M, Takeshita R. Evaluation of 2,3,7,8-TCDD and PCDDs in fly

ash from refuse incinerators. Chemosphere 1987;16: 1865-68.

 

16. Rappe C, Buser HR, Bosshardt H-P. Dioxins, dibenzofurans and other

polyhalogenated aromatics: production, use, formation, and destruction.

Ann NY Acad Sci 1979:320:1-18.

 

17. Rappe C, Marklund 5, Kjeller L-O, Tysklind M- PCDDs and PCDFs in

emissions from various incinerators. Chemosphere 1986;15:12 13-17.

 

18. Ahlborg UG. Organohalogen compounds in human milk and related

hazards. Copenhagen, Denmark: Report on a WHO Consultation Bilthouven

9-11 January, 1985; WHO European Programme on Chemical Safety, Annex 9.

(ICP/CEH 501/m O5.)

 

19. Appel KE, Hildebrandt AG, Lingk WL, Kunz HW. Approaches to the

health risk assessment of PCDD/PCDF. Chemosphere 1986;15:1825-34.

 

20. Nygren M, Rappe C, Lindstrom G, Hansson M, Bergqvist P-A, Marklund

5, Hardell L, Olsson M. In: Rappe C, Choudhary G, Keith LH, eds.

Chlorinated dioxins and dibenzofurans in perspective. Michigan: Lewis

Publishers, Inc., 1986; 17-34.

 

- END OF PAPER -

 

 

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Comments by John Jonik

Chlorinated parts of typical cigs.

The paper.

 

About a third of the 450 tobacco pesticides...about two doz. pesticide

residues per cig...about a third of them, one estimates, are

chlorinated.

 

Any of the many agricultural products in the list of non-tobacco

additives.

 

Likely ALL of the non-tobacco cellulose materials used to make

fake-tobacco. This includes the Loblolly pine, which may be contaminated

pine waste. (I thought they just ground up trees to make the paper-like

stuff they...and our media and officials AND phony " anti smoking " groups

call " Tobacco " .)

 

This study was cited by Lois Gibbs in her book, “Dying From Dioxin”. The

Environmental Protection Agency’s 1995 “Re-evaluating Dioxin” cited this

study as well. Both pointed out that studies are scarce. This could be

due to widespread influence of chlorine industries. The EPA, in

“Re-evaluating Dioxin”, acknowledged that dioxins are not considered

likely in nature (i.e., not in tobacco) but are from man-made

(Dow-invented) chlorine. Note also that, according to Greenpeace dioxin

experts, inhalation of incinerated dioxins presents a health risk over a

thousand times greater than other exposure routes. Still legal in US

cigarettes.

 

 

 

 

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