coresta recommended method no. 70 tobacco - … · 2019-10-02 · crm no. 70 – september 2019...

Cooperation Centre for Scientific Research

Relative to Tobacco

Smoke Analytes Sub-Group

CORESTA Recommended Method

No. 70

TOBACCO - DETERMINATION OF SELECTED

VOLATILE ORGANIC COMPOUNDS IN MAINSTREAM CIGARETTE

SMOKE BY GC-MS

September 2019

CRM No. 70 – September 2019 /21

CORESTA RECOMMENDED METHOD Nº 70

Title:

TOBACCO — DETERMINATION OF SELECTED VOLATILE ORGANIC

COMPOUNDS IN MAINSTREAM CIGARETTE SMOKE BY GC-MS

Status: Valid

Note: CRM developed into ISO 21330

Document history:

Date of review Information

June 2010 Version 1

March 2013 Version 2

July 2014 Version 3

February 2018 Version 4

September 2019 Version 5 - minor revisions to r&R table

CORESTA RECOMMENDED METHOD N° 70

DETERMINATION OF SELECTED VOLATILE ORGANIC COMPOUNDS IN

MAINSTREAM CIGARETTE SMOKE BY GC-MS

(September 2019)

0. INTRODUCTION

The CORESTA Special Analytes Task Force (became CORESTA Smoke Analytes Sub-Group

in 2017) carried out a study in 2005 to compare smoke analyte yield data obtained from different

laboratories using their own preferred methodologies. This study had shown significant and

unacceptable differences in volatiles yields, especially for 1,3-butadiene and acrylonitrile and

suggested that further work was required to understand factors influencing the yield variability.

The Task Force reviewed the key parameters of existing methodologies and further studies were

carried out on selected volatiles between 2008 and 2009 [1, 2]. These studies investigated

critical method steps that required optimisation before incorporation into a CORESTA

Recommended Method (CRM).

The Task Force decided that the CRM would be based on collecting the selected volatile organic

compounds (VOCs) from mainstream cigarette smoke in cryogenically cooled impinger traps

containing methanol. The impinger solutions were fortified with benzene-D6 and analysed by

Gas Chromatography - Mass Spectrometry (GC-MS). Several critical parts of the methodology

were investigated to evaluate their effects on smoke yields before drafting a CRM.

This CRM was initially published after a 2009 collaborative study involving 20 laboratories

from 12 countries using the ISO 3308 smoking regime [2]. Further data were provided for the

same selected volatile substances from 10 samples with different tar yields from a 2012

collaborative study using both ISO 3308 and Health Canada T-115 (HCI) smoking regimes,

which involved 17 laboratories from 11 countries [3]. This method includes recommendations

about critical steps that should be controlled to provide data as robust and consistent as the

repeatability and reproducibility data provided in the CRM. Statistical evaluations carried out

according to ISO 5725 Parts 1 and 2 are included.

At that time, the collaborative study was conducted, the study protocol stipulated the use of

Health Canada Official Method (T-115) for Intense smoking conditions as there was not an ISO

standard that defined Intense smoking conditions. ISO 20778, Routine analytical cigarette-

smoking machine — Definitions and standard conditions was published in 2018 and is

equivalent to Health Canada Intense conditions and is referred to hereafter.

1. FIELD OF APPLICATION

This method is applicable to the quantification of selected VOCs (1,3-butadiene, isoprene,

acrylonitrile, benzene and toluene) in mainstream tobacco smoke from cigarettes with NFDPM

yields between 1 mg/cigarette and 44 mg/cigarette smoked following either ISO 3308 or ISO

20778.

The described method is specified using ISO 3308 and ISO 20778 (i.e. Intense) smoking

parameters. The use of these machine smoking parameters reflects their inclusion in the


reporting requirements of various national regulations rather than an endorsement of their

appropriateness by CORESTA.

2. NORMATIVE REFERENCES

2.1 ISO 3308:2012

Routine analytical cigarette-smoking machine – Definition and standard conditions

2.2 ISO 3402:1999

Tobacco and tobacco products – Atmosphere for conditioning and testing

2.3 ISO 4387:2008

Cigarettes – Determination of total and nicotine-free dry particulate matter using a routine

analytical smoking machine

2.4 ISO 8243:2013

Cigarettes – Sampling

2.5 Health Canada Official Method T-115: December 1999

Determination of "Tar", Nicotine and Carbon Monoxide in Mainstream Tobacco Smoke

2.6 ISO 20778:2018

Cigarettes – Routine analytical cigarette-smoking machine – Definitions and standard

conditions with an intense smoking regime

3. METHOD SUMMARY

3.1 VOCs are collected by passing the mainstream smoke of cigarettes through a glass fibre

filter pad (Cambridge Filter Pad, CFP) as specified in ISO 3308 or in ISO 20778 into

cryogenic traps containing methanol.

3.2 The impinger solutions are fortified with benzene-D6 and analysed by GC-MS.

4. APPARATUS AND EQUIPMENT

Laboratory apparatus and equipment, in particular the following items:

• A smoking machine complying with ISO 3308 or ISO 20778. To trap VOCs present in

the vapour phase of mainstream smoke efficiently, an impinger trapping system capable

of being cryogenically cooled is required

• A GC-MS system to obtain chromatographic data to quantify specific ions (Selected Ion

Monitoring mode, SIM or equivalent). The GC must be configured to perform split

injections on a capillary column.

• Gas tight syringes of appropriate volumes

• A fused silica capillary column, for example DB-624, length 60 m with internal diameter

of 0,25 mm and 1,4 μm film thickness, or equivalent

• Laboratory equipment for the preparation of samples, standards and reagents


5. REAGENTS AND SUPPLIES

• Dry ice

• Isopropanol (for Dewar flasks)

• Methanol – HPLC grade or better

Note: Laboratories should check the methanol to ensure the background levels of the analytes will

not negatively affect the analysis.

• Ethanol - reagent grade or equivalent

• Benzene-D6 (99 % D min.; checked for the absence of not-labelled analogue)

• 1,3-Butadiene (99 % min.)

• Isoprene (99 % min.)

• Acrylonitrile (99 % min.)

• Benzene (99 % min.)

• Toluene (99 % min.)

Note: All reagents shall be at least of analytical grade quality unless stated otherwise.

Warning notice: The solvents and chemicals to be used for this method are classified as toxic,

highly toxic, harmful, carcinogenic, mutagenic, sensitising, teratogenic, irritant, corrosive,

easily flammable and dangerous for the environment. The instructions specified in the

individual material safety data sheets concerning safe handling, storage and waste disposal as

well as protective equipment must be followed.

6. PREPARATION OF GLASSWARE

Glassware should be cleaned and dried in such a manner to ensure that contamination from

glassware does not occur.

Note: It is extremely important that all possible sources of contamination are removed from the work

area

7. PREPARATION OF SOLUTIONS

Not applicable.

8. PREPARATION OF STANDARDS

8.1 Preparation of Internal Standard Spiking Solution

8.1.1 Benzene–D6 Stock Solution

Transfer the contents of a 1 g ampoule of benzene-D6 into a 10 ml amber glass volumetric flask.

Dilute to volume with methanol.

8.1.2 Benzene-D6 Spiking Solution

Using a glass volumetric pipette, transfer 4 ml of the benzene-D6 stock solution (section 8.1.1.)

into a 100 ml volumetric flask and dilute to volume with methanol. This solution has an

approximate concentration of 4000 μg/ml.


8.1.3 Storage

Store the diluted solutions in 25 ml vials with PTFE-lined caps in freezer at approximately -20 C.

8.2 Preparation of Working Standards for Isoprene, Acrylonitrile, Benzene, and

Toluene

8.2.1 Primary Isoprene, Acrylonitrile, Benzene and Toluene Stock Solutions

Using gas tight syringes, weigh accurately 100 mg of isoprene, acrylonitrile, benzene, and

toluene into separate 10 ml amber glass volumetric flasks that are half-filled with methanol.

Dilute each compound to volume with methanol. Each solution has a nominal concentration of

10 mg/ml.

Note: Approximate volumes corresponding to 100 mg are: isoprene = 150 μl, acrylonitrile = 140 μl,

benzene = 130 μl, toluene = 120 µl.

8.2.2 Secondary Stock Solution (Mixture of Isoprene, Acrylonitrile, Benzene and

Toluene Primary Stock Solutions)

A combined secondary stock solution is prepared by transferring appropriate amounts (Table 1)

of isoprene, acrylonitrile, benzene, and toluene primary stock solutions (section 8.2.1.) into a

50 ml volumetric flask that is a third full with methanol. Dilute to volume with methanol.

Table 1. Preparation of secondary stock solution

Analyte Volume of Primary

Stock (ml)

Approximate Concentration

(μg/ml)

Isoprene 3,0 600

Acrylonitrile 1,0 200

Benzene 1,0 200

Toluene 1,0 200

8.2.3 Calibration Standard Solutions (for Isoprene, Acrylonitrile, Benzene and Toluene)

Prepare seven working standard solutions by mixing appropriate volumes of secondary stock

solution (8.2.2.) and benzene-D6 spiking solution (8.1.2) to cover the concentration range of

interest, i.e. 12 μg/ml - 600 μg/ml (isoprene); 4 μg/ml - 200 μg/ml (acrylonitrile); 4 μg/ml - 200

μg/ml (benzene), 4 μg/ml - 200 μg/ml (toluene) and 40 μg/ml of benzene-D6.

Transfer aliquots of each calibration standard solution into amber GC vials and fill each vial up to

the shoulder of the vial to minimize headspace. Adjust standard concentrations accordingly to

reflect levels of volatiles found in smoke samples.

Note: Concentration ranges of standards may be changed depending on whether ISO or HCI smoking

is conducted.

8.2.4 Storage

Store all solutions in glass vials with PTFE-lined caps in freezer at approximately -20 C.

8.3 Preparation of Working Standards for 1,3-Butadiene

8.3.1 Primary 1,3-Butadiene Stock Solution

Attach a piece of Tygon™ tubing to the valve of a cylinder containing 1,3-butadiene. Place a

Pasteur pipette on the other end of the tubing and immerse the tip of the pipette into a 100 ml

volumetric flask containing methanol up to the base of the neck of the flask. Open the valve


and gently bubble the 1,3-butadiene into the methanol for approximately 5 minutes. Dilute to

volume using methanol and mix well.

8.3.2 Secondary 1,3-Butadiene Stock Solution

Pipette 1 ml of the primary 1,3-butadiene stock solution (section 8.3.1) into a 100 ml amber

glass volumetric flask and dilute to volume with methanol. Mix well.

8.3.3 Determination of Secondary 1,3-Butadiene Stock Concentration

Pipette 1 ml of the secondary 1,3-butadiene stock solution (section 8.3.2) into a 100 ml amber

glass volumetric flask and dilute to volume using ethanol. This solution is used only to check

the concentration of the secondary stock solution and must not be used to prepare the working

standards.

Measure the absorbance of the solution against an ethanol blank on a spectrophotometer.

Conduct a wave scan from 200 nm to 250 nm to determine the wavelength of maximum

absorbance. 1,3-butadiene in hexane absorbs at 217 nm whereas 1,3-butadiene in ethanol may

have a peak shift. Measure the absorbance at the peak maximum.

Repeat the above measurement three more times and calculate the mean absorbance (A, at least

three significant figures). The absorbance should be between 0,2 and 0,6 extinction units. If it

is higher, make a new secondary stock solution using a smaller volume of the primary stock

solution and repeat the spectrophotometer measurements to determine the concentration of the

secondary stock. If the absorbance is lower, make a new secondary stock solution using a larger

volume of the primary stock solution and repeat the spectrometer measurements to determine

the concentration of the secondary stock.

The concentration of the secondary stock solution is calculated as follows:

where

c is the concentration of secondary stock concentration of 1,3-butadiene expressed in µg/ml;

A is the mean absorbance;

20 893 is the molar absorption coefficient of 1,3-butadiene expressed in l/mol/cm;

54 is the molecular weight of 1,3-butadiene expressed in g/mol;

100 is the volume of the solution expressed in ml;

1000 is units conversion factor.

8.3.4 1,3-Butadiene Calibration Standard Solutions

Prepare five working standard solutions by mixing 1,3-butadiene secondary stock solution

(8.3.2.) and benzene-D6 spiking solution (section 8.1.2) that cover the concentration range of

interest, i.e. 5 µg/ml – 50 µg/ml and 40 μg/ml of benzene-D6 (internal standard).

Transfer aliquots of each calibration standard solution into amber GC vials and fill each vial up

to the shoulder of the vial to minimize headspace.

Note: Certified concentrations of 1,3-butadiene in methanol can be purchased and used to prepare the

standards.

8.3.5 Storage

Store all calibration standard solutions in freezer until use.


Note: Stability of all standard solutions for all components should be assessed by laboratories under

their own in-house conditions before use as stability is dependent on the actual storage

conditions of each laboratory.

9. SAMPLING

Take samples in accordance with ISO 8243:2013.

10. TOBACCO PRODUCT PREPARATION

Condition the cigarettes in accordance with ISO 3402:1999.

11. SAMPLE GENERATION – SMOKING OF CIGARETTES

The smoking regimes for which the method has been studied are defined in ISO 3308 and in

ISO 20778 (Table 2).

Table 2. Smoking parameters for ISO 3308 and ISO 20778 smoking regimes

Smoking regime Puff volume

(ml)

Puff frequency

(seconds)

Puff duration

(seconds)

Ventilation

blocking (%)

ISO 3308 35 60 2 0

ISO 20778 55 30 2 100

11.1 Smoking Machine Setup

• An analytical cigarette-smoking machine complying with the requirements of ISO 3308

or ISO 20778 is required. Additionally, the smoking machine must be equipped with a

liquid trapping system filled with methanol that is capable of being cryocooled. Figure 1

shows an example using two impingers connected in series, which were used by

laboratories who participated in collaborative studies. However other trapping systems

may be used as long as sufficient trapping efficiency is demonstrated.

• Fill all Dewar flasks one-third full with isopropanol and add dry ice until each flask is

filled halfway. The number of flasks required is dependent on the impinger design and

has to be optimized to ensure all volatiles are trapped effectively.

• Add 10 ml of methanol to each impinger and place the impingers into the Dewar flasks

containing the dry ice / isopropanol solution. Check each Dewar flask to ensure that the

temperature is at or below -70 °C. A sufficient time must be given to impingers and

impinger contents to cool below -70 °C before starting smoke collection.

Note: If a different style impinger is used, modification of methanol volume may be required.

• Connect the impingers to the smoking machine (Figure 1).


• Check and adjust the puff volume drawn by the smoking machine at all channels

Figure 1. An example of connection of two impingers connected in series.

Note: When applying a more intense smoking regime with a higher smoke velocity through the

impingers, the volume of methanol needs to be adjusted. For example, for the ISO 20778

smoking regime, 20 ml of methanol is added to each impinger.

Note: To determine whether a leak has occurred in the smoking machine impinger setup, use a leak

tester. If the fluid column does not maintain its position but drops then there is a leak in the

system.

It is recommended that tubing other than silicone tubing is used for connections between the

smoking machine and the impingers (i.e. polyethylene, polyvinyl chloride e.g. Tygon™,

polypropylene). Methyl silicone tubing is not recommended since adsorption of the analytes can

occur. Tubing should be as short as possible to minimize the potential for any adsorption.

Connectors made of either glass or stainless steel are preferred.

It is recommended that the trapping efficiency is checked when validating this method. To

check the trapping efficiency of the method, add an additional impinger and follow the method

accordingly. Analyse each impinger individually for the VOCs of interest. If no compounds

are detected in the additional impinger then only the prescribed number of impingers is required

to trap all VOCs effectively.

Note: If carryover occurs, it is a responsibility of each laboratory to assess this with respect to the

trapping system design and decide how to manage it. Carryover should be small (less than 5 %,

ideally less than 1 %) and repeatable [2]. If greater, it should be reported, investigated for

improvement and considered in calculations.


11.2 Smoking

The cigarettes are smoked according to ISO 3308 and/or ISO 20778 regimes with the

following modifications:

11.2.1 Linear Smoking (ISO 3308)

• Five or ten cigarettes are smoked per trap.

• Before the maximum amount of TPM that the CFP is capable to retain is exceeded, the

CFP shall be changed to prevent breakthrough. When changing the CFP no clearing

puffs shall be taken.

• When all cigarettes are smoked take six clearing puffs.

Note: CFPs of 44 mm diameter are capable of retaining up to 150 mg of TPM. The CFP is typically

changed after five cigarettes to prevent breakthrough.

11.2.2 Linear Smoking (ISO 20778)

• Three or six cigarettes are smoked per trap.

• Before the maximum amount of TPM that the CFP is capable to retain is exceeded, the

CFP shall be changed to prevent breakthrough. When changing the CFP no clearing

puffs shall be taken.

• When all cigarettes are smoked take six clearing puffs.

Note: CFPs of 44 mm diameter are capable of retaining up to 150 mg of TPM. The CFP is typically

changed after three cigarettes to prevent breakthrough.

11.2.3 Rotary Smoking (ISO 3308)

• Ten cigarettes are smoked per trap.

11.2.4 Rotary Smoking (ISO 20778)

• Five cigarettes are smoked per trap.

• When the maximum amount of TPM that the CFP is capable to retain is likely to be

exceeded, the number of cigarettes shall be reduced and a calculation made to allow for

the reduced number of cigarettes smoked.

Note: CFPs of 44 mm diameter are capable of retaining up to 150 mg of TPM and pads of 92 mm

diameter are capable of retaining 600 mg of TPM.

12. SAMPLE ANALYSIS

12.1 Sample preparation

After all samples have been smoked, the TPM should be determined on the CFP as a quality

control measure and the CFP discarded. The connecting tubes between the filter pad holder

and impingers should be rinsed with trapping solutions. It is good practice to rinse connecting

tubes and as quickly as possible to avoid any loss of analytes. It is recommended that the

trapping solution remains at the cold trap temperature at all times.

Note: Laboratories should evaluate the trapping system for losses in the tubing connecting pad holder

and the impinger(s) and the connection between impingers when more than one impinger is

used.


After all samples have been smoked following ISO 3308, each impinger is spiked with 100 μl

of benzene-D6 spiking solution. For the Intense regime (ISO 20779), each impinger is spiked

with 200 μl of benzene-D6 spiking solution.

The impingers are stoppered and gently mixed to ensure that the extract is well mixed. If the

impinger set up requires more than one impinger then the trapping solutions are combined in

such a way to ensure complete mixing of both impingers. The impingers should be kept in the

Dewar flasks until sampling is complete. Transfer an aliquot of the combined impinger

solutions into amber GC vial and analyse for volatiles using GC-MS. Fill each vial up to the

shoulder of the vial to minimise headspace and cap tightly. Prepare all samples in duplicate

and keep a set in the freezer in case repeated analysis is required.

Note: Samples are stable when stored in the freezer (temperature below -20 C) for a maximum of 48

hours.

12.2 Determination

12.2.1 GC-MS operating conditions

Set up and operate the GC-MS system in accordance with the manufacturer’s instruction.

The following parameters have been found to be suitable for separation:

GC Separation Conditions:

Injector temperature: 150 °C

Column temperature: 40 °C (6 minutes)

20 °C / min to 225 °C (6 minutes)

Injection mode: Split

Injection split ratio: 30:1

Injection split flow: 30 ml/min

Injection volume: 3 μl

MS Detection Conditions:

Transfer line temperature: 240 °C

MS source temperature: 240 °C

Acquisition mode: SIM (or SCAN)

Solvent delay: column dependent

Low mass: 40,0

High mass: 200,0

Ion Traces (m/z): Quantification Confirmation

1,3-butadiene 54 53

Isoprene 67 68

Acrylonitrile 52 53

Benzene 78 77

Benzene-D6 84 83

Toluene 91 92

Chromatographic separation should be similar to example chromatograms shown in

Appendices 1-4.

Note: The choice of chromatographic conditions and data acquisition parameters may differ for

different instrument configurations.


12.2.2 Calibration

Analyse successively each working standard solution (sections 8.2.3 and 8.3.4) by GC-MS.

Record the area of each of the analysed compounds and the internal standard peaks. Generate

a calibration curve for each of the compounds by calculating a linear regression equation of the

peak area ratios of the analysed compounds to the internal standard against their concentration.

The intercept of these regression lines should be close to zero.

12.2.3 Calculation

The results are reported in µg/cigarette. Use the following calculation:

where

C is the concentration of target analyte expressed in µg/cigarette;

c is the concentration of the target analytes in the sample extract expressed in µg/ml;

V is the volume of the extract expressed in ml;

n is the number of cigarettes smoked.

13. REPEATABILITY AND REPRODUCIBILITY

This Recommended Method contains repeatability and reproducibility in five replicate analysis

values from collaborative studies conducted in 2009 and 2012. In 2009 a collaborative study

involving 20 laboratories and five replicate analyses of two reference cigarettes from University

of Kentucky (3R4F and 1R5F), the CORESTA Monitor Test Piece CM6 and five cigarette

samples covering a wide range of blends and designs smoked under ISO conditions was

organised [2]. The samples used in this study are shown in Table 3. The statistical evaluation

was conducted according to ISO 5725 Parts 1 and 2. The repeatability and reproducibility

results are provided in Tables 4 – 9.

Table 3. 2009 Collaborative Study Sample Identification [2]

Sample ID ISO 3308 NFDPM

Yield (mg/cig) Product/ Blend Type

Sample 1 10 Dark air-cured blended

Sample 2 6 American blended

Sample 3 8 Virginia blended

Sample 4 1 American blended, charcoal filter

Sample 5 10 American blended, charcoal filter

CM6 15 CORESTA Monitor, Virginia blend

1R5F 2 Kentucky Reference, American blended

3R4F 8 Kentucky Reference, American blended

In the 2012 collaborative study, mean yield, r (repeatability) and R (reproducibility) data were

obtained from 17 laboratories. This study provided data on the measurement of the same

selected volatiles substances in five replicate analyses of 10 samples (seven commercial

products and 3R4F, 1R5F, and CORESTA Monitor Test Piece CM6) performed under both the


ISO 3308 and ISO 20778 smoking regimes. The samples used in this study are shown in

Table 4. The statistical evaluation was conducted according to ISO 5725 Parts 1 and 2. The

repeatability and reproducibility results are provided in Tables 10 – 14.

Table 4. 2012 Collaborative Study Sample Identification [3]

Sample ID

ISO 3308 TPM Yield

(mg/cig)

ISO 20778 TPM Yield

(mg/cig)

Product/ Blend Type

CM6 18,0 43,7 CORESTA Monitor 6 Test Piece

1R5F 2,5 27,2 Kentucky Reference 1R5F

3R4F 10,6 41,7 Kentucky Reference 3R4F

Sample 1 12,3 39,5 Dark air-cured

Sample 2 10,5 35,9 American blended

Sample 3 7,8 31,9 American blended

Sample 4 4,6 27,7 Virginia blended



Sample 7 1,7 22,4 Charcoal filtered

13.1 Results from 2009 Collaborative Study [2]

Calculated statistical data of the individual selected VOCs are summarised in the Tables 5 – 9.

Table 5. 1,3-Butadiene (2009 Collaborative Study, ISO 3308 Smoking)

Sample description

NFDPM

(mg/cigarette) N*

Mean sr** r sR*** R

(µg/cigarette)

1 10 19 33,3 4,2 11,8 8,9 25

2 6 19 32,1 3,9 11,0 8,9 25

3 8 18 32,5 4,8 13,3 8,0 22

4 1 19 7,5 1,8 4,9 2,5 7

5 10 19 39,0 3,9 10,9 10 28

CM 6 15 18 60,3 7,6 21,2 13,5 38

1R5F 2 19 12,2 1,9 5,3 2,9 8

3R4F 8 19 41,4 4,7 13,3 10,6 30

% Reported 95 %

% Removed 1,3 %

Abbreviations: *N – number of data sets taken for statistical analysis after removing of

outliers, **sr – repeatability variance, ***sR – reproducibility variance


Table 6. Isoprene (2009 Collaborative Study, ISO 3308 Smoking)

Sample description

NFDPM

(mg/cigarette) N*

Mean sr** r sR*** R

(µg/cigarette)

1 10 20 216 16 46 32 89

2 6 20 256 17 48 39 108

3 8 20 245 15 43 36 102

4 1 19 58 5 15 11 31

5 10 20 281 18 52 44 122

CM 6 15 20 553 35 98 71 198

1R5F 2 20 120 14 38 27 74

3R4F 8 20 362 21 57 48 134

% Reported 100 %

% Removed 0,6 %



Table 7. Acrylonitrile (2009 Collaborative Study, ISO 3308 Smoking)

Sample description

NFDPM

(mg/cigarette) N*

Mean sr** r sR*** R

(µg/cigarette)

1 10 19 10,2 0,9 2,4 1,5 4

2 6 18 5,3 0,6 1,7 1,0 3

3 8 19 7,5 0,7 1,9 1,2 4

4 1 15 1,0 0,1 0,4 0,4 1

5 10 19 6,3 0,6 1,7 1,1 3

CM 6 15 19 12,3 1,2 3,2 2,1 6

1R5F 2 18 2,1 0,3 0,7 0,5 1

3R4F 8 19 8,6 0,8 2,1 1,3 4

% Reported 96 %

% Removed 5,5 %




Table 8. Benzene (2009 Collaborative Study, ISO 3308 Smoking)

Sample description

NFDPM

(mg/cigarette) N*

Mean sr** r sR*** R

(µg/cigarette)

1 10 20 38,6 2,6 7,2 5,2 15

2 6 20 31,6 2,4 6,7 4,7 13

3 8 20 34,9 2,1 5,9 4,9 14

4 1 19 6,7 0,7 2,0 1,7 5

5 10 20 28,5 2 5,7 4,9 14

CM 6 15 20 60,3 3,8 10,6 7,5 21

1R5F 2 19 14,3 0,9 2,5 2,6 7

3R4F 8 20 41,9 2,2 6,3 5,5 15

% Reported 100 %

% Removed 1,3 %



Table 9. Toluene (2009 Collaborative Study, ISO 3308 Smoking)

Sample description

NFDPM

(mg/cigarette) N*

Mean sr** r sR*** R

(µg/cigarette)

1 10 20 57,8 4,7 13,3 9,7 27

2 6 20 44,5 4,4 12,4 7,4 21

3 8 20 49,3 3,5 9,7 8,4 24

4 1 20 8,5 1,3 3,5 3,5 10

5 10 20 37,4 3,5 9,7 7,3 21

CM 6 15 20 85,4 6,9 19,4 14,6 41

1R5F 2 19 18,5 1,7 4,7 3,5 10

3R4F 8 20 64,8 4,4 12,2 11 31

% Reported 100 %

% Removed 0,6 %




13.2 Results from the 2012 Collaborative Study [3]

Calculated statistical data of the individual select VOCs are summarised in the Tables 10 - 14.

Table 10. 1,3-Butadiene (2012 Collaborative Study)

Sample description

ISO 3308 smoking ISO 20778 smoking

N* Mean r R

N* Mean r R

(µg/cigarette) (µg/cigarette)

CM6 16 61,1 12,2 35 14 108,1 17,1 59

1R5F 16 12,1 3,3 7 16 91,1 19,2 66

3R4F 17 40,5 9,1 20 15 100,5 17,5 55

1 13 31,0 6,9 16 12 73,8 12,7 30

2 13 39,0 10,1 18 11 94,9 18,2 49

3 12 35,1 7,5 16 10 105,8 17,4 41

4 12 18,0 4,1 8 11 85,4 18,2 49

5 13 10,1 2,7 4 11 62,7 13,0 51

6 13 46,1 11,7 22 11 89,9 17,9 41

7 12 8,2 2,4 5 12 89,7 20,6 68


outliers

Table 11. Isoprene (2012 Collaborative Study)

Sample description


N* Mean r R

N* Mean r R


CM6 16 563,9 89,5 246 15 995,1 147,0 356

1R5F 16 117,8 26,0 67 16 885,8 131,0 590

3R4F 16 349,3 65,3 125 15 912,5 113,2 392

1 13 176,2 45,0 117 11 415,8 64,7 114

2 13 278,9 70,6 143 12 647,3 112,8 197

3 11 271,6 36,8 137 11 814,0 97,1 261

4 13 150,1 39,3 85 12 688,7 166,5 329

5 12 65,3 13,3 29 12 394,9 95,2 225

6 13 278,4 50,6 182 12 499,7 73,2 170

7 13 63,1 15,4 41 12 632,8 134,6 410


outliers


Table 12. Acrylonitrile (2012 Collaborative Study)

Sample description


N* Mean r R N* Mean r R


CM6 15 12,3 2,1 6 14 25,3 4,1 10

1R5F 14 2,1 0,7 2 16 28,0 4,5 23

3R4F 17 8,5 2,5 4 14 27,0 3,5 11

1 13 10,2 2,3 5 12 27,2 5,0 10

2 13 7,9 1,8 4 12 24,3 5,2 11

3 12 5,8 1,5 3 11 24,2 5,3 12

4 11 2,2 0,5 2 12 15,8 3,5 11

5 12 1,3 0,3 1 11 13,4 2,4 12

6 13 7,9 1,8 4 11 18,1 2,8 8

7 11 1,0 0,3 1 11 20,1 4,7 9


outliers

Table 13. Benzene (2012 Collaborative Study)

Sample description


N* Mean r R

N* Mean r R


CM6 15 60,4 7,6 26 15 108,5 15,2 37

1R5F 16 13,9 2,9 8 16 79,3 10,6 35

3R4F 16 41,6 8,1 19 16 97,4 9,9 35

1 13 34,5 5,9 15 12 77,7 11,8 31

2 12 37,3 6,1 16 12 85,3 15,2 30

3 11 32,9 4,2 15 11 91,1 10,4 35

4 13 17,1 4,2 9 11 65,0 10,7 34

5 13 10,5 2,5 7 12 51,2 7,3 31

6 13 41,0 7,2 18 11 80,4 10,1 33

7 13 7,5 2,0 7 11 63,8 11,6 32


outliers


Table 14. Toluene (2012 Collaborative Study)

Sample description


N* Mean r R

N* Mean r R


CM6 15 87,3 12,9 35 14 174,4 23,5 62

1R5F 15 19,2 5,1 12 15 135,6 21,0 70

3R4F 16 67,4 16,4 33 15 174,2 19,7 64

1 12 59,7 11,9 28 11 142,3 22,3 50

2 12 58,8 10,6 28 11 142,7 24,4 51

3 11 47,1 9,9 22 10 148,3 18,6 56

4 12 23,9 5,3 13 11 96,0 18,5 43

5 12 14,3 3,9 9 11 78,5 11,2 43

6 12 56,0 10,6 26 11 119,4 19,3 46

7 12 9,7 4,0 10 11 99,0 16,6 49


outliers

14. REPORT

• The expression of the laboratory data depends on the purpose for which the data are

required, and the level of laboratory precision. Any further statistical analyses should be

calculated and expressed on the basis of the laboratory data before any rounding has taken

place.

• The amount of individual selected volatile compounds in the mainstream smoke of

cigarettes is reported in µg/cigarette to the nearest 0,1 µg/cigarette.


15. REFERENCES

[1] Intorp, M., Purkis, S.W., 2011a. Determination of Selected Volatiles in Cigarette

Mainstream Smoke. The CORESTA 2008 Joint Experiment. Beiträge zur Tabakforsch.,

24(4), 174-186.

[2] Intorp, M., Purkis, S.W., Wagstaff, W., 2011b. Determination of Selected Volatiles in

Cigarette Mainstream Smoke. The CORESTA 2009 Collaborative Study and

Recommended Method. Beiträge zur Tabakforsch., 24(5), 243-251.

[3] CORESTA Smoke Analytes Sub-Group Technical Report – ‘2012 Collaborative Study

on B[a]P, VOCs, and Carbonyls in Mainstream Cigarette Smoke”, August 2019.

[4] ISO 5725-1:1994 – Accuracy (trueness and precision) of measurement methods and

results – Part 1: General principles and definitions

[5] ISO 5725-2:1994 – Accuracy (trueness and precision) of measurement methods and

results – Part 2: Basic method for the determination of repeatability (r) and reproducibility

(R) of a standard measurement method


Appendix 1 - Example of a chromatogram of toluene, isoprene, benzene and

acrylonitrile calibration standard

Appendix 2 - Example of a chromatogram of a 1,3-butadiene calibration standard


Appendix 3 - Example of a 1R5F chromatogram

Appendix 4 - Example of a 3R4F chromatogram

coresta recommended method no. 70 tobacco - … · 2019-10-02 · crm no. 70 – september 2019...

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