tobacco and tobacco products analytes sub-group · lab 1 – 1) no suppressor was used. 2) elution...

Tobacco and Tobacco Products Analytes Sub-Group

Technical Report

2017 Collaborative Study on Ammonia and Benzo[a]pyrene in

Tobacco Products

March 2018

Study Project Leaders:

Regina Ballentine, Altria Client Services LLC, U.S.A.

Anthony Brown, Altria Client Services LLC, U.S.A.

Author:

Regina Ballentine, Altria Client Services LLC, U.S.A.

Co-Author and Statistical Analysis:

Michael Morton, Ph.D., Altria Client Services LLC, U.S.A.

Table of Contents

1. SUMMARY ...................................................................................................................... 3

2. INTRODUCTION ............................................................................................................ 3

2.1 Objective .................................................................................................................. 3

3. ORGANISATION ............................................................................................................ 3

3.1 Participants .............................................................................................................. 3

3.2 Protocol .................................................................................................................... 4

4. DATA – RAW .................................................................................................................. 6

5. DATA – STATISTICAL ANALYSIS ............................................................................. 6

5.1 Exclusion of Outliers ............................................................................................... 6

5.2 Calculation of Repeatability (r) and Reproducibility (R) ........................................ 7

6. DATA INTERPRETATIONS .......................................................................................... 8

7. RECOMMENDATIONS .................................................................................................. 9

8. APPENDICES .................................................................................................................. 9

TTPA-150-1-CTR 2017 Coll. Study on Ammonia and Benzo[a]pyrene – March 2018 3/29

1. Summary

At the May 2017 CORESTA Tobacco and Tobacco Products Analytes Sub-Group (TTPA)

meeting held in Charlottesville, USA, the Sub-Group initiated a collaborative study for the

determination of ammonia and benzo[a]pyrene in smokeless tobacco, cigarette filler, and

ground cigars (wrapper, binder, and filler). The intent of this study was to support laboratory

accreditation and to expand the scopes of CORESTA Recommended Methods (CRMs) N° 79

and N° 82 to include ground cigars.

2. Introduction

At the CORESTA Tobacco and Tobacco Products Analytes Subgroup (TTPA) meeting held

in Charlottesville, USA (May 2017), it was decided to conduct a collaborative study for

Ammonia and Benzo[a]pyrene (B[a]P) using the following CRMs:

CRM N° 79, Determination of Ammonia in Tobacco and Tobacco Products by Ion

Chromatographic Analysis (April 2015)

CRM N° 82, Determination of Benzo[a]pyrene in Tobacco Products by GC-MS

(July 2017)

The collaborative study involved 17 laboratories and will support laboratory accreditation and

a scope expansion of the CRMs to include ground cigars (wrapper, binder, and filler).

Tabulated data are presented along with repeatability (r) and reproducibility (R). The results

of the study demonstrate that the CRMs for Ammonia and B[a]P are suitable for the analysis

of ground cigars. The TTPA recommends that the two CRMs be updated to include ground

cigars.

2.1 Objective

This study was conducted to support laboratory accreditation and scope expansion of the

Ammonia and B[a]P CRMs beyond just tobacco, cigarette filler, and smokeless tobacco to

include ground cigars. This work was conducted using the samples listed in Table 2. Data

were collected from the participating laboratories and statistically evaluated in basic

conformance with the recommendations of ISO 5725-2:1994 and ISO/TR 22971:2005.

3. Organisation

3.1 Participants

A list of the participating laboratories is provided in Table 1. Not all laboratories provided

data for both methods nor did all laboratories analyze all samples. The laboratories are listed

in alphabetical order. Identifying number codes were assigned to each laboratory to protect

confidentiality and do not correspond to the order shown in the table below.


Table 1: List of Participating Laboratories in the 2017 Collaborative Study

Participating Laboratories Ammonia B[a]P

Altria Client Services LLC, United States X X

American Snuff Company, United States X

C.I.T. Montepaz S.A., Uruguay X X

China National Tobacco Quality Supervision and Test Center, China

X X

CNTC, Zhengzhou Tobacco Research Institute, Key Laboratory of Tobacco Flavor Basic Research, China

X X

CNTC, Yunnan Tobacco Quality Supervision and Test Station, China

X X

Enthalpy Analytical, Inc., (Richmond) United States X X

Global Laboratory Services, United States X X

ITG Brands, United States X X

Japan Tobacco Inc., Japan X X

JTI-Ökolab, Austria X

KT&G Research Institute, South Korea X X

Imperial Tobacco, Reemtsma, Germany X

RJ Reynolds Tobacco Company, United States X X

Swedish Match, North America, United States X

Swedish Match, Northern Europe, Sweden X

University of Kentucky, United States X X

3.2 Protocol

Specific details from the protocol are described below:

3.2.1 Sample Shipment

Laboratories were responsible for procuring 1R6F ground cigarette filler from the University

of Kentucky, CRP1.1, CRP2.1, CRP3.1, and CRP4.1 from North Carolina State University,

and Cigar filler #1-05/17 and Cigar M16-05/17 from Altria Client Services LLC.

Laboratories were requested to store the samples at approximately 4 °C upon receipt. If

samples were not analysed within one week, they were to be stored in a freezer at

approximately −20 °C until the analyses were performed. Laboratories were requested to

conduct the study July through August and report data by August 15, 2017. The samples are

identified in Table 2. The protocol incorrectly identified Cigar Filler #1-05/17 as only ground

filler; however, this sample was a ground finished cigar that included the wrapper, binder, and

filler.


Table 2: Sample Identification

Product Type

CRP1.1 - Swedish-style snus pouch

CRP2.1 - American-style loose moist snuff

CRP3.1 - American-style loose dry snuff powder

CRP4.1 - American-style chopped loose-leaf chewing tobacco

1R6F Ground Filler-RT1 - American blend cigarette filler

Cigar Filler #1-05/17 - Flavoured ground cigar (wrapper, binder, and filler)

Cigar M16-05/17 - Traditional dark-air cured ground cigar (wrapper, binder, and filler)

3.2.2 Within Laboratory Sample Preparation

The laboratories were directed to remove samples from the −20 °C freezer and place the

unopened samples in a refrigerator for a minimum of 24 hours to ensure that the water in the

sample had been fully equilibrated. Samples could then be removed from the refrigerator for

a minimum of 2 hours prior to opening for analysis. Once samples were opened, the samples

could be stored in a tightly sealed container at approximately 4 ºC for up to one week.

Additional handling requirements are described below:

CRP1.1: The Snus pouches should be cut into 2 halves and both parts added directly

into the extraction vessel. Both Snus and pouch material (paper) are to be analyzed.

All other samples should be mixed with a spatula before removing aliquots for

analysis.

3.2.3 Sample Analysis and Data Reporting

The participating laboratories were instructed to conduct three replicate analyses (individual

tobacco weighing) for Ammonia and B[a]P using the current versions of the CRMs.

Ammonia: CRM N° 79, Determination of Ammonia in Tobacco and Tobacco Products

by Ion Chromatographic Analysis (April 2015)

B[a]P: CRM N° 82, Determination of Benzo[a]pyrene in Tobacco Products by GC-MS

(July 2017)

Participating laboratories were requested to document any deviations from the protocol and

the CRMs and submit the deviations with their results. As stated in the protocol, data

submitted with significant deviations from the applicable CRM would be excluded from the

study. Deviations reported by the laboratories are identified below.

The following deviations for Ammonia CRM N° 79 were reported:

Lab 1 – 1) No suppressor was used. 2) Elution was done with 3 mM Oxalic acid

solution containing 1 mM 18-Crown-6 ether.

Lab 2 – A segmented flow analyzer was used for analysis.

Lab 3 – The amount of sample and volume of extraction solution was changed.

Lab 5 – A chilled auto-sampler tray was not used.

Lab 8 – No suppressor was used.

Lab 14 – 1) Modified the mobile phase gradient because a CS19 column was used.

2) Several sample dilutions were performed prior to analysis.


The following deviations for B[a]P: CRM N° 82 were reported:

Lab 1 – 1) ultrasonic extraction was used instead of an orbital shaker or wrist action

shaker. 2) Hexane was used for calibration standards instead of 50:50

toluene:isooctane. 3) There was no filtration of the sample extract 4) Evaporated

solvent before washing the SPE cartridge 5) Hexane was the only wash solvent used

for solvent phase extraction even though methanol: water and isopropyl alcohol were

also specified.

Lab 2 – Used a DB-5MS (30 m x 0.25 mm x 1.0 µm) column.

Lab 10 – Used a DB-35MS column.

Lab 11 – Used a DB-35MS column.

Lab 12 – 1) Used a DB-5MS Ultra Inert column. 2) Concentration differed from

protocol because neat B[a]P-d12 material was used to prepare the Working Internal

Stock Solutions.

The protocol deviations for ammonia analysis of Labs 1 and 2 were considered significant

(i.e. likely to impact testing results) and their ammonia data were excluded from the r&R

portion of the study. Similarly the protocol deviation for B[a]P analysis of Lab 1 was

considered significant and their B[a]P data were also excluded from the r&R portion of the

study. All other deviations were considered of minor significance and therefore, the data

were included. All test results were to be reported to three decimal places. The study results

and the comments were sent by e-mail to the study coordinators.

4. Data – Raw

The full data set for the study is provided in Appendix B. The results are presented on an as-

is basis, without correction for moisture. Each analysis includes three replicates. Not all

laboratories provided data for all analyses or all samples. Data sets were removed from the

repeatability (r) and reproducibility (R) (r&R) portion of the study if the data were identified

as outlying data or the lab was excluded for protocol deviations. All data are included in

Appendix B, but the excluded data were eliminated prior to the r&R analysis. Raw data plots

that include all replicates, without removal of outliers, are given in Appendix C.

5. Data – Statistical Analysis

The statistical analysis was conducted in basic conformance with ISO 5725-2:1994 and

ISO/TR 22971:2005. A summary of the results from outlier detection and the calculated

results for repeatability (r) and reproducibility (R) are given below in sections 5.1 and 5.2,

respectively. Raw data plots that include all replicates, without removal of outliers, are shown

in Appendix C.

5.1 Exclusion of Outliers

Procedures outlined in ISO 5725-2:1994 and ISO/TR 22971:2005 were generally used for the

exclusion of outliers. An adaptation of Levene’s Test1 was used for eliminating laboratories

with overly large repeatability standard deviations and Grubbs’ Test was used to eliminate

laboratories with outlying mean values.

1 The approach is discussed in detail by Michael Morton in “Within-Laboratory Variance Outlier Detection: An

Alternative to Cochran’s Test” in Beitrage zur Tabakforschung International, Vol 27 No. 7, pp 135-144.


ISO 5725-2:1994 also recommends the use of Mandel’s h and k plots. Mandel’s h statistic is

the same as the statistic used in Grubbs’ Test. Similarly Mandel’s k statistic, associated with

within lab standard deviation, is statistically equivalent to the c-value calculated in Cochran’s

Test )( cnk labs . However, the critical values associated with Mandel’s h and k statistics

do not make allowance for multiple testing and can therefore, give a false impression of

statistical significance. Thus, Mandel’s h and k statistics do not add fundamentally new

information and may lead to incorrect conclusions. For those reasons, we do not include

Mandel’s h and k plots.

The results of the outlier tests are shown in Table 3. In addition to the outliers shown in

Table 3, one of the Lab 16 Cigar Filler #1-05/17 B[a]P replicates was a single-point outlier

and that B[a]P replicate was deleted and not included in the r&R calculations.

Table 3: Outliers

Product Analyte Levene’s Outlier Lab Grubbs’ Outlier Lab

CRP3.1 B[a]P ̶ 17

Cigar M16-05/17 B[a]P 17 ̶

The (–) symbol indicates an outlier was not detected.

5.2 Calculation of Repeatability (r) and Reproducibility (R)

After removal of outlying data based on numerical data consistency methods (Grubbs’ Test

and Levene’s Test), the final repeatability and reproducibility (r&R) results were calculated.

The r&R results for ammonia are shown in Table 4 and B[a]P r&R results are shown in Table

5. The r&R results reflect both laboratory variability and product consistency.

Table 4: Ammonia Repeatability (r) and Reproducibility (R) Limits

Product N° of

Labs*

Mean

Ammonia (µg/g)

Repeatability Reproducibility

r r (%) R R (%)

CRP1.1 - Swedish-style snus pouch 12 982 63,6 6,5 687 70

CRP2.1 - American-style loose moist snuff 12 2400 161 6,7 1248 52


12 7159 469 6,5 1647 23


12 2003 142 7,1 536 27


12 1005 85,1 8,5 260 26

Cigar Filler #1-05/17 - Flavoured cigar (ground wrapper, binder, and filler)

9 786 117 15 203 26

Cigar M16-05/17 - Traditional dark-air cured cigar (ground wrapper, binder, and filler)

9 2813 262 9,3 1026 36

* This is the number of laboratory data sets reported as values and after removal of outliers.


Table 5: Benzo[a]pyrene Repeatability (r) and Reproducibility (R) Limits

Product N° of

Labs*

Mean

B[a]P (ng/g)

Repeatability Reproducibility

r r (%) R R (%)

CRP1.1 - Swedish- style snus pouch 14 0,86 0,496 58 0,902 105

CRP2.1 - American-style loose moist snuff 14 154 13,1 8,5 42,4 28


13 147 9,94 6,8 41,7 28


14 1,21 0,638 53 0,82 67


14 4,88 1,161 24 3,44 71

Cigar Filler #1-05/17 - Flavoured cigar (ground wrapper, binder, and filler)

11 10,4 2,20 21 5,89 57

Cigar M16-05/17 - Traditional dark-air cured cigar (ground wrapper, binder, and filler)

10 4,38 0,42 10 1,97 45

6. Data Interpretations

Overall, the percent repeatability (% r) and percent reproducibility (% R) results from this

study compare well to the results presented in the CRMs. Notable differences include the

following:

The ammonia % reproducibility values were higher than anticipated for CRP1.1 and

CRP2.1. However that seemed largely a result of Lab 12 being near outlier

classification. Excluding Lab 12 would result in reproducibility values for CRP1.1

and CRP2.1 similar to the previous study.

Similarly the B[a]P % reproducibility value is somewhat larger for Cigar Filler

#1-05/17 than would have been expected. That is largely driven by Lab 17 that is near

outlier classification for this sample and was classified as an outlier or near outlier

classification for several other products. If that laboratory were excluded from the

study, the % reproducibility for Cigar Filler #1-05/17 would be approximately 38 %,

in line with the expected levels.

The ammonia value for 1R6F Ground Filler-RT1 is in good agreement with the certified value

of 956 μg/g published by the University of Kentucky Center for Tobacco Reference

Products2.

2 Certificate of Analysis for 1R6F Certified Reference Cigarette, Certificate Number 2017-002CTRP, University

of Kentucky Center for Tobacco Reference Products.


7. Recommendations

The CRMs listed below were originally developed for the analysis of tobacco, cigarette filler,

and smokeless tobacco products:

Ammonia: CRM N° 79, Determination of Ammonia in Tobacco and Tobacco Products

by Ion Chromatographic Analysis (April 2015)

B[a]P: CRM N° 82, Determination of Benzo[a]pyrene in Tobacco Products by GC-MS

(July 2017)

The results of this study demonstrate that the methods are also fit for purpose for the analysis

of cigar filler. The TTPA recommends the scope of the CRMs to be updated to include the

additional matrices not included in the previous studies and that the applicable r&R data for

these new matrices be added to the CRMs.

8. Appendices

Appendix A: Study Protocol

Appendix B: Full Data Set

Appendix C: Raw Data Plots


APPENDIX A: Study Protocol

CORESTA TOBACCO AND TOBACCO PRODUCTS ANALYTES SUB-GROUP

Project Title: Collaborative study for Ammonia and Benzo[a]pyrene in Tobacco

Products

Type of Document: Collaborative Study Protocol

Date: July 5, 2017

Study Coordinators: Regina Ballentine and Anthony Brown

Confidentiality Notice: All data submitted by participating laboratories will be coded and kept

confidential.


1. Introduction

At the CORESTA Tobacco and Tobacco Products Analytes Sub-Group (TTPA) meeting held

on May 2017 in Charlottesville, the group decided to conduct a collaborative study for

ammonia and benzo[a]pyrene (B[a]P) in tobacco products.

2. Objective

The objectives of the study are: (1) support laboratory accreditation and (2) expand the scope

of the following CORESTA Recommended Methods (CRMs) to include cigars:

• Ammonia: CRM N° 79, Determination of Ammonia in Tobacco and Tobacco

Products by Ion Chromatographic Analysis (April 2015)

• B[a]P: CRM N° 82, Determination of Benzo[a]pyrene in Tobacco Products by

GC-MS (July 2017)

The final output will be one technical report and the corresponding updates to CRM N°79 and

CRM N° 82 to include cigars. Results will be discussed at the next TTPA meeting scheduled

for October 7, 2017 in Kitzbühel, Austria.

Note: Use of methods other than those specified will not support the study objectives.

3. Time schedule

Table 1: Study timeline

Date Activity

May 31, 2017 Laboratories state their intention to participate and provide the shipping information in order to receive two cigar fillers from Altria

May 31, 2017 Distribute the study protocol and data reporting sheet (the methods are the CRMs)

June 2017 Altria distributes ground cigar samples to participants

July 2017 Participants order 1R6F ground cigarette filler (RT1) from the University of Kentucky.

July-August Laboratories conduct the study

August 15, 2017 Laboratories submit results by this date

October 7, 2017 Discuss results at TTPA meeting in Kitzbühel, Austria

4. Participating Laboratories:

The laboratories listed in Table 2 have kindly agreed to take part in the study using the most

recent versions of the specified CRMs. Other laboratories are encouraged to participate and

should notify Regina Ballentine [email protected] and Anthony Brown

[email protected] of their interest to participate.


Table 2: Participating Laboratories

Participating Laboratories Ammonia B[a]P

Altria Client Services LLC, United States X X

American Snuff Company, United States X

British American Tobacco, Brazil X

British American Tobacco, Germany X

C.I.T. Montepaz S.A., Uruguay X X

China National Tobacco Quality Supervision and Test Center, China

X X

CNTC, Zhengzhou Tobacco Research Institute,

Key Laboratory of Tobacco Flavor Basic Research, China X X

CNTC, Yunnan Tobacco Quality Supervision and test Station, China

X X

Enthalpy Analytical, United States X X

Eurofins, Sweden X X

Global Laboratory Services, United States X X

ITG Brands, United States X X

Japan Tobacco Inc., Japan X

JTI-Ökolab AUSTRIA TABAK, Austria X X

KT&G Research Institute, South Korea X X

Labstat International ULC, Canada X X

Reemtsma (Imperial Tobacco Limited) X X

RJ Reynolds tobacco Company, United States X X

Swedish Match, Northern Europe, Sweden X X

University of Kentucky, United States X

5. Samples

The samples should be ordered from the suppliers listed in Table 3. Altria will provide the

two ground cigar samples to all participants. For long-term storage, it is critical that the

samples be stored at the recommended temperature of −20 °C. Upon receipt, the samples

may be stored at approximately 4 °C if the analyses will be conducted within 1-week. If

samples will not be analysed within 1-week, they shall be stored in a freezer at approximately

−20 °C until the analyses are performed.


Table 3: Samples

Sample Name Description Supplier Quantity to

Request

Cigar Filler #1-05/17 1 Flavoured cigar filler,

ground Altria Client Services 1 bottle

Cigar M16-05/17 1

Traditional dark-air cured cigar, ground wrapper, and filler

Altria Client Services 1 bottle

1R6F Ground Filler-RT1 2 American blended cigarette

filler University of Kentucky 1 bottle

2016 CRP1.1 Swedish-style snus pouch North Carolina State University

4 cans

2016 CRP2.1 American-style loose moist snuff

North Carolina State University

4 cans

2016 CRP3.1 American-style loose dry snuff powder


4 cans

2016 CRP4.1 American-style chopped loose-leaf chewing tobacco


4 cans

1: The cigar filler distributed for the previous study should not be used for this study. The

sample name provided above should match that on the sample bottle.

2: The 1R6F ground filler must be ordered from the University of Kentucky. Do not use

filler that has been removed from cigarettes.

6. Analysis

6.1 Methods:

Report ammonia and B[a]P in each sample using the current versions of the specified

CRMs. Data collected with other methods, or with methods that have significant

deviations from the CRMs will not be included in the study.

• Ammonia: CRM N° 79, Determination of Ammonia in Tobacco and Tobacco

Products by Ion Chromatographic Analysis (April 2015)

• B[a]P: CRM N° 82, Determination of Benzo[a]pyrene in Tobacco Products by

GC-MS (July 2017)

Note: The following three samples will exceed the calibration range for ammonia and

will need to be diluted as described in CRM N° 79: 1R6F ground filler (RT1), Cigar

Filler #1-05/17, and Cigar M16-05/17.

Note: CRP2.1 and CRP3.1 will exceed the calibration range for B[a]P and will need to

be prepared with a reduced sample mass as described in the current version of

CRM N° 82.

6.2 Replicates:

Conduct three (3) independent replicate analyses for each sample. The replicates should

be determined from independent tobacco extractions.


6.3 Sample equilibration:

Samples held at −20 °C should be placed unopened in a refrigerator for a minimum of

24 hours to ensure water has fully equilibrated within the product. Samples shall be

removed from the refrigerator a minimum of 2 hours prior to opening for analysis. The

samples should not be opened during the time the samples are equilibrating to ambient

temperature. Once samples are equilibrated to ambient temperature, the samples shall

be stored at approximately 4 °C for up to one week if the analyses will not be conducted

immediately. Sample retains shall be stored at −20 °C. Additional handling

requirements are described below:

• CRP1.1: The Snus pouches shall be cut into 2 halves and added directly into the

extraction vessel. Both Snus and pouch material (paper) are to be analyzed.

• All other samples should be mixed with a spatula before removing aliquots for

analysis.

6.4 Data Reporting:

The data report spreadsheet provided with this protocol should be used for data

reporting. Send the completed data reporting spreadsheet to the study coordinators

(Regina Ballentine [email protected], Anthony Brown

[email protected]) and Karl Wagner [email protected].)

Additionally:

• Data shall be reported to three decimal places for Ammonia and Benzo[a]pyrene.

• If data are below the LOQ, but above the LOD, report the estimated analytical

result and note that the analytical result is an estimate beside the cell.

• If the result is below the LOD, report the actual LOD value using the format (e.g.

<LOD (##)).

• All test results shall be reported as-is (with no correction for moisture content).

• Report any deviations from the CRMs.

7. Statistical Analysis

A statistical analysis in general conformance with ISO 5725-2:1994 and ISO/TR 22971:2005

will be conducted.

8. Presentation of the Results

The results will be presented for discussion at the TTPA meeting, which is scheduled to be

held in Kitzbühel, Austria on October 7, 2017.

mailto:[email protected]


APPENDIX B: Full Data Set

Full Data Set (results are presented on an as-is basis)

Lab Code Sample Ammonia B[a]P

(µg/g) (ng/g)

1 1R6F Ground Filler 1045,77 4,964

1 1R6F Ground Filler 1033 4,997











5 1R6F Ground Filler 953,71 –



6 1R6F Ground Filler – 4,609





















(µg/g) (ng/g)


















1 Cigar Filler #1-05/17 810,17 9,704

1 Cigar Filler #1-05/17 821,71 9,603

1 Cigar Filler #1-05/17 823,48 9,973

2 Cigar Filler #1-05/17 937,05 8,416

2 Cigar Filler #1-05/17 1039,44 8,116

2 Cigar Filler #1-05/17 981,92 9,264

3 Cigar Filler #1-05/17 716,54 11,212

3 Cigar Filler #1-05/17 710,65 10,528

3 Cigar Filler #1-05/17 707,63 10,972

4 Cigar Filler #1-05/17 859,17 11,186

4 Cigar Filler #1-05/17 854,51 11,393

4 Cigar Filler #1-05/17 862,93 11,174

5 Cigar Filler #1-05/17 786,16 –

5 Cigar Filler #1-05/17 720,11 –

5 Cigar Filler #1-05/17 737,72 –

6 Cigar Filler #1-05/17 – 11,307

6 Cigar Filler #1-05/17 – 10,772

6 Cigar Filler #1-05/17 – 10,891

7 Cigar Filler #1-05/17 813,01 8,986



(µg/g) (ng/g)

7 Cigar Filler #1-05/17 875,25 9,029

7 Cigar Filler #1-05/17 988,79 9,101

8 Cigar Filler #1-05/17 740,81 11,033

8 Cigar Filler #1-05/17 735,09 11,163

8 Cigar Filler #1-05/17 766,94 10,871

9 Cigar Filler #1-05/17 – 10,906

9 Cigar Filler #1-05/17 – 10,018

9 Cigar Filler #1-05/17 – 9,988

10 Cigar Filler #1-05/17 – –

10 Cigar Filler #1-05/17 – –

10 Cigar Filler #1-05/17 – –

11 Cigar Filler #1-05/17 – –

11 Cigar Filler #1-05/17 – –

11 Cigar Filler #1-05/17 – –

12 Cigar Filler #1-05/17 – –

12 Cigar Filler #1-05/17 – –

12 Cigar Filler #1-05/17 – –

13 Cigar Filler #1-05/17 721,59 –

13 Cigar Filler #1-05/17 726,28 –

13 Cigar Filler #1-05/17 779,94 –

14 Cigar Filler #1-05/17 843,63 10,429

14 Cigar Filler #1-05/17 819,47 10,872

14 Cigar Filler #1-05/17 831,79 10,742

15 Cigar Filler #1-05/17 – 11,855

15 Cigar Filler #1-05/17 – 11,562

15 Cigar Filler #1-05/17 – 11,264

16 Cigar Filler #1-05/17 808,15 26,731

16 Cigar Filler #1-05/17 814,46 14,139

16 Cigar Filler #1-05/17 815,62 13,718

17 Cigar Filler #1-05/17 811,68 8,331

17 Cigar Filler #1-05/17 703,52 4,537

17 Cigar Filler #1-05/17 678,07 4,079

1 Cigar M16-05/17 2881,75 4,652

1 Cigar M16-05/17 2856,41 4,945

1 Cigar M16-05/17 2895,77 4,83

2 Cigar M16-05/17 2796,85 3,252



(µg/g) (ng/g)

2 Cigar M16-05/17 2842,69 3,6

2 Cigar M16-05/17 2859,52 3,827

3 Cigar M16-05/17 2525,26 4,718

3 Cigar M16-05/17 2509,2 4,51

3 Cigar M16-05/17 2482,86 4,736

4 Cigar M16-05/17 2665,28 4,354

4 Cigar M16-05/17 2724,03 4,358

4 Cigar M16-05/17 2716,98 4,393

5 Cigar M16-05/17 2416,82 –

5 Cigar M16-05/17 2479,34 –

5 Cigar M16-05/17 2387,09 –

6 Cigar M16-05/17 – 3,643

6 Cigar M16-05/17 – 3,843

6 Cigar M16-05/17 – 3,696

7 Cigar M16-05/17 3233,03 3,499

7 Cigar M16-05/17 3078,61 3,442

7 Cigar M16-05/17 2854,04 3,516

8 Cigar M16-05/17 2706,31 4,601

8 Cigar M16-05/17 2703,03 4,475

8 Cigar M16-05/17 2768,89 4,725

9 Cigar M16-05/17 – 4,569

9 Cigar M16-05/17 – 4,75

9 Cigar M16-05/17 – 4,66

10 Cigar M16-05/17 – –

10 Cigar M16-05/17 – –

10 Cigar M16-05/17 – –

11 Cigar M16-05/17 – –

11 Cigar M16-05/17 – –

11 Cigar M16-05/17 – –

12 Cigar M16-05/17 – –

12 Cigar M16-05/17 – –

12 Cigar M16-05/17 – –

13 Cigar M16-05/17 2592,97 –

13 Cigar M16-05/17 2573,59 –

13 Cigar M16-05/17 2544,75 –

14 Cigar M16-05/17 3707,77 4,13



(µg/g) (ng/g)

14 Cigar M16-05/17 3386,25 4,049

14 Cigar M16-05/17 3653,2 4,061

15 Cigar M16-05/17 – 4,725

15 Cigar M16-05/17 – 5,01

15 Cigar M16-05/17 – 4,913

16 Cigar M16-05/17 2726,03 6,044

16 Cigar M16-05/17 2684,11 5,686

16 Cigar M16-05/17 2742,67 5,529

17 Cigar M16-05/17 3117,13 1,777

17 Cigar M16-05/17 2999,46 1,395

17 Cigar M16-05/17 2965,94 2,496

1 CRP1.1 1117,11 0,774

1 CRP1.1 1100,79 0,724

1 CRP1.1 1105,95 0,82

2 CRP1.1 1210,06 1,256

2 CRP1.1 1201,53 1,393

2 CRP1.1 1226,61 1,203

3 CRP1.1 708,65 0,709

3 CRP1.1 739,93 0,738

3 CRP1.1 710,64 0,695

4 CRP1.1 1201,23 0,672

4 CRP1.1 1133,95 0,707

4 CRP1.1 1182,06 0,876

5 CRP1.1 945 –

5 CRP1.1 911,71 –

5 CRP1.1 888,49 –

6 CRP1.1 – 0,246

6 CRP1.1 – 0,467

6 CRP1.1 – 0,405

7 CRP1.1 854.14 0,551

7 CRP1.1 897,3 0,497

7 CRP1.1 898,73 0,513

8 CRP1.1 1058,02 0,726

8 CRP1.1 1020,61 1,31

8 CRP1.1 1016,34 1,138

9 CRP1.1 – 0,782



(µg/g) (ng/g)

9 CRP1.1 – 0,958

9 CRP1.1 – 0,678

10 CRP1.1 1144,67 1,001

10 CRP1.1 1113,59 1,17

10 CRP1.1 1095,14 0,964

11 CRP1.1 1095,62 0,811

11 CRP1.1 1107,86 0,869

11 CRP1.1 1060,79 0,96

12 CRP1.1 512,3 1,11

12 CRP1.1 515,73 1,85

12 CRP1.1 520,57 1,34

12 CRP1.1 523,28 –

12 CRP1.1 530,87 –

12 CRP1.1 519,24 –

13 CRP1.1 1103,42 –

13 CRP1.1 1112,02 –

13 CRP1.1 1140,03 –

14 CRP1.1 1308,67 0.881

14 CRP1.1 1368.87 1,099

14 CRP1.1 1327,8 1,193

15 CRP1.1 – 0.696

15 CRP1.1 – 0,689

15 CRP1.1 – 0,678

16 CRP1.1 957,53 0,641

16 CRP1.1 963,7 0,986

16 CRP1.1 915,96 0,756

17 CRP1.1 949,59 0,736

17 CRP1.1 947,28 0,374

17 CRP1.1 926,71 0,917

1 CRP2.1 2520,15 145,236

1 CRP2.1 2511,12 148,117

1 CRP2.1 2520,71 150,547

2 CRP2.1 2672,21 133,016

2 CRP2.1 2727,74 133,632

2 CRP2.1 2634,37 131,035

3 CRP2.1 2009,55 163,373



(µg/g) (ng/g)

3 CRP2.1 2014,95 170,672

3 CRP2.1 1980,89 152,943

4 CRP2.1 2523,4 159,776

4 CRP2.1 2541,8 159,071

4 CRP2.1 2527,55 158,191

5 CRP2.1 2083,32 –

5 CRP2.1 2094,26 –

5 CRP2.1 2146,41 –

6 CRP2.1 – 157,203

6 CRP2.1 – 152,759

6 CRP2.1 – 147,352

7 CRP2.1 2624,88 123,418

7 CRP2.1 2431,03 122,48

7 CRP2.1 2694,11 126,62

8 CRP2.1 2399,37 162,087

8 CRP2.1 2387,88 159,981

8 CRP2.1 2343,25 163,741

9 CRP2.1 – 159,369

9 CRP2.1 – 165,754

9 CRP2.1 – 155,566

10 CRP2.1 2666,11 164,219

10 CRP2.1 2644,22 164,466

10 CRP2.1 2606,03 168,755

11 CRP2.1 2577,02 171,31

11 CRP2.1 2529,91 175,78

11 CRP2.1 2635,55 163,369

12 CRP2.1 1456,94 134,767

12 CRP2.1 1487,69 126,206

12 CRP2.1 1487,32 128,646

12 CRP2.1 1559,84 –

12 CRP2.1 1577,55 –

12 CRP2.1 1569,83 –

13 CRP2.1 2482,97 –

13 CRP2.1 2431,96 –

13 CRP2.1 2474,68 –

14 CRP2.1 2991,42 153,808



(µg/g) (ng/g)

14 CRP2.1 3017,1 152,262

14 CRP2.1 3175,13 146,656

15 CRP2.1 – 157,562

15 CRP2.1 – 167,926

15 CRP2.1 – 163,784

16 CRP2.1 2405,32 165,799

16 CRP2.1 2352,07 160,052

16 CRP2.1 2418,71 175,17

17 CRP2.1 2580,9 152,001

17 CRP2.1 2522,26 153,986

17 CRP2.1 2526,41 153,764

1 CRP3.1 7344,96 142,849

1 CRP3.1 7329,82 146,41

1 CRP3.1 7319,63 145,202

2 CRP3.1 7294,05 119,106

2 CRP3.1 7287,65 122,879

2 CRP3.1 7224,06 125,733

3 CRP3.1 6532,32 156,368

3 CRP3.1 6361,06 154,617

3 CRP3.1 6436,62 161,26

4 CRP3.1 7082,86 146,702

4 CRP3.1 7080,79 142,284

4 CRP3.1 7123,86 143,024

5 CRP3.1 6676,37 –

5 CRP3.1 6702,43 –

5 CRP3.1 6843,66 –

6 CRP3.1 – 151,207

6 CRP3.1 – 145,27

6 CRP3.1 – 147,931

7 CRP3.1 6440,07 120,235

7 CRP3.1 6713,6 122,277

7 CRP3.1 6801,99 120,154

8 CRP3.1 7091,37 145,096

8 CRP3.1 7176,77 147,63

8 CRP3.1 7346,6 144,275

9 CRP3.1 – 145,21



(µg/g) (ng/g)

9 CRP3.1 – 150,198

9 CRP3.1 – 155,745

10 CRP3.1 7951,23 160,023

10 CRP3.1 7744,26 171,229

10 CRP3.1 7343,13 173,402

11 CRP3.1 7729,27 168,759

11 CRP3.1 7814,94 164,649

11 CRP3.1 7726,82 171,533

12 CRP3.1 6433,61 135,382

12 CRP3.1 6453,56 138,869

12 CRP3.1 6447,31 132,973

13 CRP3.1 6673,57 –

13 CRP3.1 6787,51 –

13 CRP3.1 6780,75 –

14 CRP3.1 7975,7 139,686

14 CRP3.1 8393,99 140,034

14 CRP3.1 8125,24 137,056

15 CRP3.1 – 153,822

15 CRP3.1 – 153,017

15 CRP3.1 – 153,694

16 CRP3.1 7234,61 155,941

16 CRP3.1 7232,5 147,217

16 CRP3.1 7297,75 151,32

17 CRP3.1 7900,98 70,969

17 CRP3.1 7328,67 72,195

17 CRP3.1 7950,23 72,595

1 CRP4.1 2115,08 1,194

1 CRP4.1 2128,45 1,302

1 CRP4.1 2137,17 1,175

2 CRP4.1 2075,87 0,808

2 CRP4.1 2044,87 1,038

2 CRP4.1 2042,05 0,945

3 CRP4.1 1778,65 0,927

3 CRP4.1 1797,27 1,026

3 CRP4.1 1719,34 1,057

4 CRP4.1 2141,95 1,262



(µg/g) (ng/g)

4 CRP4.1 2144,86 1,284

4 CRP4.1 2178,76 1,139

5 CRP4.1 1712,11 –

5 CRP4.1 1692,45 –

5 CRP4.1 1762,69 –

6 CRP4.1 – 0,921

6 CRP4.1 – 0,951

6 CRP4.1 – 1,041

7 CRP4.1 2108,25 0,972

7 CRP4.1 2322,89 1,403

7 CRP4.1 2281,23 1,118

8 CRP4.1 2008,75 1,397

8 CRP4.1 2082,33 1,684

8 CRP4.1 2000,75 1,451

9 CRP4.1 – 1,097

9 CRP4.1 – 0,95

9 CRP4.1 – 1,056

10 CRP4.1 2080,32 1,295

10 CRP4.1 2072,56 1,751

10 CRP4.1 2133,38 1,498

11 CRP4.1 2124,74 1,564

11 CRP4.1 2168 1,366

11 CRP4.1 1998,32 1,559

12 CRP4.1 1724,8 1,215

12 CRP4.1 1727,8 0,973

12 CRP4.1 1731,19 1,106

13 CRP4.1 1892,9 –

13 CRP4.1 1882,51 –

13 CRP4.1 1900,89 –

14 CRP4.1 2245,51 0,982

14 CRP4.1 2278,07 0,98

14 CRP4.1 2194,66 0,792

15 CRP4.1 – 1,347

15 CRP4.1 – 1,688

15 CRP4.1 – 1,273

16 CRP4.1 1992,05 1,161



(µg/g) (ng/g)

16 CRP4.1 1977,55 1,65

16 CRP4.1 1969,84 1,292

17 CRP4.1 2067,97 2,027

17 CRP4.1 2075,96 0,785

17 CRP4.1 2141,72 1,102

The (–) symbol indicates the laboratory did not submit a result for that sample analysis

TTPA-150-1-CTR 2017 Collaborative Study on Ammonia and Benzo[a]pyrene – March 2018 26/29

APPENDIX C: Raw Data Plots

tobacco and tobacco products analytes sub-group · lab 1 – 1) no suppressor was used. 2) elution...

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