Technical Report 2017 Metals Proficiency Study€¦ · Technical Report 2017 Metals Proficiency Study July 2017 Sub-Group Coordinator and Study Coordinator: Karl Wagner, ... week

Tobacco and Tobacco Products Analytes Sub-Group

Technical Report

2017 Metals Proficiency Study

July 2017

Sub-Group Coordinator and Study Coordinator:

Karl Wagner, Ph.D., Altria Client Services LLC, U.S.A.

Author and Study Coordinator:

Derek Bussan, Ph.D., Altria Client Services LLC - ELLPSS, 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

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

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

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

4. DATA – DESCRIPTIVE STATISTICS ........................................................................... 4

5. DATA – STATISTICAL ANALYSIS ............................................................................. 4

6. RESULTS – Z-SCORES .................................................................................................. 6

7. CONCLUSIONS ............................................................................................................ 11

8. APPENDICES ................................................................................................................ 11

TTPA-125-CTR 2017 Metals Proficiency Study – July 2017 3/36

1. Summary

The CORESTA Smokeless Tobacco Sub-Group (STS) (now named Tobacco and Tobacco

Products Analytes Sub-Group, TTPA) conducted a metals proficiency study in the first

quarter of 2017 for arsenic (As), beryllium (Be), cadmium (Cd), chromium (Cr), cobalt (Co),

nickel (Ni), lead (Pb), and selenium (Se) in tobacco and tobacco products. This study

included two cigarette fillers, four smokeless tobacco products (STPs), two cigar fillers, and

one ground flue-cured tobacco. Sixteen laboratories participated in this study.

2. Introduction

The STS conducted the first metals proficiency study in 20151. The objective of this latest

proficiency study was to provide a continuing assessment of laboratory performance for the

analysis of specific trace elements in tobacco and tobacco products. Laboratories were

requested to determine As, Be, Cd, Cr, Co, Ni, Pb, and Se using inductively coupled plasma

mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectroscopy

(ICP-OES).

3. Organisation

3.1 Participants

A list of the participating laboratories is provided in Table 1. The laboratories are listed in

alphabetical order; however the laboratory codes used in this report do not correspond to the

same order as provided in Table 1.

Table 1: List of Participating Laboratories

Participating Laboratories

Altria Client Services LLC, United States

British American Tobacco, Souza Cruz, Brazil

China National Tobacco Quality Supervision and Test Center, Zhengzhou, China

Enthalpy Analytical, Richmond, United States

Essentra Scientific Services, United Kingdom

Global Laboratory Services, United States

Imperial Tobacco, Reemtsma, Hamburg, Germany

ITG Brands LLC, United States

Japan Tobacco Inc., Leaf Tobacco Research Center, Oyama, Japan

JTI Ökolab, Vienna, Austria

KT&G, Daejeon, South Korea

Labstat International ULC, Kitchener, Canada

Philip Morris International, Switzerland

1 STS Technical Report: Proficiency Test Report - The Determination of Arsenic, Beryllium, Cadmium,

Chromium, Cobalt, Nickel, Lead, and Selenium in Reference Materials – September 2015


Participating Laboratories

RJ Reynolds Tobacco, United States

SEITA – Imperial Tobacco, Les Aubrais, France

Swedish Match North Europe, Stockholm, Sweden

3.2 Protocol

Specific details from the protocol are described below and the full protocol is provided in

Appendix A. Participants were required to procure all samples from the University of

Kentucky and North Carolina State University, with the exception of the two cigar fillers and

Flue-Cured #1, which were provided by Altria. Laboratories were requested to store the

samples at approximately 4 °C upon receipt if the analyses would be conducted within one

week or to store the samples at approximately -20 °C if the analyses would be delayed. Three

(3) independent replicate sample digestions and analyses were required per sample and the

data were to be reported in units of ng/g, on an as-is basis (i.e. not corrected for water or

moisture content). Laboratories were requested to submit data by March 15th

2017; however,

data were accepted until March 31st. The samples are identified in Table 2.

Table 2: Sample Identification

Sample Name Description

1R6F Ground Filler Ground, American blended cigarette filler

1R5F Ground Filler Ground, American blended cigarette filler (high burley)

2016 CRP1.1 Swedish style snus pouch

2016 CRP2.1 American-style loose moist snuff

2016 CRP3.1 American-style loose dry snuff powder

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

Flue-Cured #1 Ground, flue-cured tobacco

Cigar Filler #1 Ground, flavoured cigar filler

CIGARM16 Ground, traditional dark air-cured cigar filler

4. Data – Descriptive Statistics

The data tables, with descriptive statistics, are provided in Appendix B. The data are

provided on an as-is basis without any correction for moisture.

5. Data – Statistical Analysis

The analysis was carried out in basic conformance with ISO 13528. The assigned values for

each element, and for each sample, were initially developed using the robust Algorithm A

from ISO 13528 on the laboratory values. For comparison, the medians were also computed

and compared to the values calculated using Algorithm A, and the two were in reasonable

agreement for all of the analytes except selenium. Algorithm A appeared to be biased high

because of outlying labs for selenium; consequently the assigned values for selenium were

estimated using the median value.


The standard deviation for proficiency assessment was developed using the Horwitz equation

as described in ISO 13528 and were compared to the standard deviation given in

Algorithm A. Generally speaking the Horwitz equation results were a little higher than, but

broadly similar to, the standard deviation values given by Algorithm A for all of the analytes

except for selenium. Selenium was approximately five times more variable using Algorithm A

than would have been predicted by the Horwitz equation, but that was driven primarily by the

outlying laboratories. For the purposes of z-score calculation, the Horwitz equation was used

to estimate the standard deviations for all of the analytes. These values are shown in Table 3.

Table 3: Data Summary (as-is basis)

1R6F Ground Filler (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 251 18 1013 1245 459 468 1929 54

Standard deviation 49.4 3.89 161.8 192.7 82.6 83.9 279.5 11.9

1R5F Ground Filler (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 305 26 1423 1838 692 1254 2403 84


2016 CRP1.1 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 62 8.9 233 428 376 131 948 57


2016 CRP2.1 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 90 11 687 565 533 214 856 60


2016 CRP3.1 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 213 21 1314 2243 811 542 3215 122


2016 CRP4.1 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 87 8.9 331 925 221 481 981 37


Flue-Cured #1 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 176 8.3 997 591 291 363 505 102


Cigar Filler #1 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 139 21 815 1548 924 394 2094 59



CIGARM16 (ng/g)

As Be

Cd

Cr

Co

Pb Ni Se

Assigned Value 247 30 669 3070 714 613 2361 225

Standard deviation 48.7 6.50 113.6 414.8 120.1 105.6 331.9 45

The assigned value was based upon the estimated group mean using Algorithm A except for selenium which was

estimated by the median of the lab averages.

The standard deviations were estimated from the Horwitz equation.

6. Results – Z-Scores

The values obtained by each laboratory, for each element, are given in Appendix B. The

corresponding z-statistics are given in Tables 4-12. As a general rule, the z-scores are

regarded as reasonable if -2 < z < 2 and generally thought to be unacceptable if |z|>3.

Laboratories should consider |z| between 2 and 3 as a warning signal. Laboratories should

particularly be aware of the pattern of their results. For example a single z-value signal

should be looked into, but a pattern of problematic z-scores in the same direction for the same

analyte should be taken more seriously still.

Table 4: Z-Score Results for 1R6F Ground Filler

Lab Code As Be

Cd

Cr

Co

Pb Ni Se

A -0.42 -0.92 -0.86 -0.45 0.00 -0.25 -0.26 -1.17

B 0.17 -0.20 0.14 -0.61 NA 0.07 -0.72 1.34

C -0.18 <LOD 0.51 -0.27 -0.30 -0.07 -0.06 -0.72a

D -0.09 NA 0.68 0.41 NA -0.12 -0.62 0.00a

E 2.86 NA 0.05 -0.16 1.59 -0.17 0.53 19.76

F 0.20 0.35 0.01 0.60 -0.36 -0.22 -0.39 -0.59

G 0.14 -0.57 -0.41 -1.22 1.59 1.47 1.18 <LOD

H -0.76 0.37 0.52 -0.10 -1.02 -0.12 -0.67 -1.00

I 0.01 0.60a 0.24 0.90 0.08 0.17 -0.55 -0.35

a

J 0.90 NA 0.33 0.65 0.47 -0.95 1.30 20.16

K -0.69 <LOD -0.46 0.50 -1.00 -0.05 -0.51 11.61a

L 0.25 <LOD -0.62 -0.41 -0.76 0.51 -0.70 -0.48

M 0.88 -0.83 0.30 1.64 1.26 NA 1.83 7.86

N <LOQ -0.41 0.01 -0.63 -0.60 0.53a 1.15 107.48

a

O -0.96a 0.63

a -0.05 -0.28 -0.32 0.44 -0.52 -1.89

a

P -0.47 0.97a -0.52 -0.14 -0.33 -0.73 -0.54 12.74

1. “NA” signifies the laboratory did not submit data for this sample/element.

2 .The superscript “a” signifies that one or more of the reported values was between the limit of detection and

the limit of quantitation

3. “<LOD” signifies the data were below the limit of detection.


Table 5: Z-Score Results for 1R5F Ground Filler

Lab Code As Be

Cd

Cr

Co

Pb Ni Se

A -0.58 -0.93 -1.04 -0.41 0.12 -0.10 0.14 -0.84

B -0.21 0.14 -0.07 -0.30 NA 0.30 -0.63 1.20

C -0.27 0.46a 0.49 -0.14 -0.18 -0.08 0.04 -0.55

a

D -0.28 NA 0.29 1.13 NA -0.30 -0.13 0.00a

E 2.40 <LOD -0.50 -1.17 1.15 -0.34 0.39 12.15

F 0.47 0.89 0.10 0.21 -0.19 -0.23 -0.39 -0.19

G 0.15 0.08 -0.30 0.53 1.75 0.76 1.75 <LOD

H -1.20 0.60 0.63 -0.74 -1.25 -0.27 -0.94 -1.05

I -0.08 1.00a 0.19 0.41 0.12 -0.05 -0.34 -0.02

J 0.65 NA 0.55 -0.46 0.20 -1.80 0.53 16.54

K -0.95 <LOD -0.22 -0.39 -1.00 0.30 -0.78 16.96

L -0.03 <LOD -0.57 -0.51 -0.64 0.41 -0.70 -0.28

M 0.83 -1.05 0.52 1.04 1.13 NA 0.74 6.08

N 2.70 -0.46a -0.06 -0.55 -0.69 0.44 1.14 74.34

a

O -1.05 -0.17a -0.03 0.39 -0.06 0.44 0.30 -1.23

a

P -0.02 -0.57 -0.31 0.94 -0.06 -0.52 -0.46 5.73


2. The superscript “a” signifies that one or more of the reported values was between the limit of detection and



Table 6: Z-Score Results for 2016 CRP1.1

Lab Code As Be Cd Cr Co Pb Ni Se

A -1.00 -1.15 -0.83 0.24 -0.18 -0.64 -0.56 -1.46

B -1.10 -0.90 0.04 -0.97 NA -0.32 -1.21 -0.27

C -0.69a <LOD 0.63 0.71 0.01 -0.14

a 0.48 -0.75

a

D NA NA NA NA NA NA NA NA

E 0.70 <LOD -0.01 0.23 0.62 0.50 0.08 5.52

F -0.61 -0.37 0.40 -0.47 -0.04 -0.28 -0.48 -0.72

G 0.14 -0.56 -0.26 -0.97 1.07 1.18 0.31 <LOD

H 1.87 3.19 5.13 2.91 2.86 3.36 3.27 1.72

I -0.37a 0.42

a 0.43 -1.02 -0.07 -0.34 -0.76 -0.77

a

J 5.41 NA -0.53 1.06 -0.33 -0.01 1.51 20.02

K 2.71 <LOD -0.99 0.83 -1.11 -1.29 -0.75 11.51a

L -0.05 <LOD -0.46 -0.90 -1.04 0.74 -0.97 -0.96

M 0.04 -1.93a 0.17 0.74 0.38 NA 1.23 0.27

a

N <LOD 3.18 0.67 0.11 0.12 <LOD 0.89 65.10a

O -1.95a -0.97

a -0.07 -0.69 -0.50 0.25 -0.49 -0.93

a

P -1.69 0.27a -0.20 -0.32 -0.05 -0.98 -0.90 2.00








A -1.37 -0.80 -0.80 -1.17 -0.15 -0.73 -0.39 -0.46

B -0.52 -0.17 0.24 -1.30 NA -0.47 -1.17 -0.82

C -0.59a <LOD 0.68 -0.85 -0.21 -0.24

a 0.34 -1.53

a


E 0.82 <LOD -0.27 2.66 1.00 0.13 0.69 7.23

F -0.34 0.05 0.32 -1.06 -0.31 -0.54 -0.64 -1.42a

G -0.50 0.23 -0.35 -0.76 1.08 1.17 0.70 <LOD

H 1.48 3.51 5.81 2.15 3.11 2.39 3.18 0.46

I -0.56 0.12a 0.25 -1.13 -0.28 -0.51 -0.95 -1.32

a

J 5.08 NA -0.14 2.49 0.86 -0.58 5.49 87.14

K 2.48 <LOD -0.95 3.17 -1.41 -1.00 -0.84 14.67a

L -0.25 <LOD -0.49 -1.06 -1.06 0.21 -0.30 -1.75

M -0.30 -0.79a -0.23 -0.54 -0.22 NA -0.37 3.98

N <LOD 0.33a 0.16 -0.61 -0.85 3.42

a 0.84 79.08

a

O -1.57a -0.93

a 0.18 -1.04 -0.23 0.44 -0.54 -2.07

a

P -0.01 0.78a 0.44 -0.46 0.35 -0.61 -0.26 7.52







A -0.63 -0.73 -0.88 0.01 0.09 -0.04 0.10 -0.94

B 0.21 0.00 0.70 -0.33 NA 0.16 -0.36 0.00

C 0.00 <LOD 0.92 0.46 -0.06 0.14 0.23 -1.11


E 1.30 <LOD -0.69 -0.23 0.95 -0.16 0.51 9.35

F 0.56 0.32 0.37 0.18 -0.23 -0.10 -0.33 -0.93

G -0.31 -0.05 -0.68 -2.02 1.33 0.45 0.69 3.29a

H -0.90 0.10 0.61 -0.16 -1.09 -0.15 -0.65 -1.42

I 0.17 1.40a 0.50 0.40 0.12 0.02 -0.11 -0.82

J 1.73 NA -0.27 1.87 1.47 -0.27 1.64 51.48

K -0.68 <LOD -0.55 -0.37 -1.26 0.21 -1.20 5.52a

L 0.08 <LOD -0.73 -1.29 -1.20 -0.37 -1.12 -1.35

M -0.02 -2.05a -0.45 0.06 -0.28 NA -0.48 2.81

N <LOD 0.31 0.10 -0.07 -0.69 -0.05a 0.53 39.44

a

O -1.09a -0.03

a 0.31 0.06 -0.04 0.58 0.17 -1.42

a

P 0.27 0.07a 0.74 1.87 0.90 -0.18 0.83 4.47








A -0.62 -1.87 -0.53 -0.94 -0.37 0.23 -1.14 -1.29

B -0.11 -0.79 0.24 -2.04 NA 0.03 -1.57 0.84

C 0.05a <LOD 0.67 0.08 -0.30 0.12 0.37 -1.22


E 1.92 <LOD -0.33 -0.60 0.81 -0.25 0.07 12.68

F 0.17 0.47 0.06 1.14 -0.28 -0.22 -0.05 -1.21a

G 0.15 -1.21 -0.38 -1.62 1.23 0.99 0.10 <LOD

H 0.09 0.82a 1.22 0.00 -0.07 0.69 -0.58 -1.02

I -0.03 1.03a 0.29 0.04 0.28 -0.13 -0.52 -1.49

a

J 1.33 NA -0.34 1.70 1.13 -0.56 3.69 145.93

K -0.79 <LOD -0.56 2.09 -0.81 -0.14 -0.57 <LOD

L 0.19 <LOD -0.50 -2.22 -1.22 -0.60 -0.45 <LOD

M 0.07 <LOD -0.34 0.02 -0.24 NA -0.36 1.75a

N <LOD -0.01a 0.17 0.96 -0.55 1.02

a 2.16 110.18

a

O -2.44a -0.29

a 0.03 1.89 -0.30 -0.94 3.56 -0.84

a

P -0.04 1.84a 0.71 -0.49 0.69 -0.12 -0.40 15.43





Table 10: Z-Score Results for Flue-Cured #1


A -0.39 -0.50 -0.86 0.47 0.06 0.04 -0.06 -0.64

B 0.32 0.01 0.25 -0.89 NA 0.22 -0.95 1.15

C -0.09 <LOD 0.41 -0.10 -0.15 -0.01 0.71 -0.67

D -0.10 NA 0.52 0.88 NA 0.06 -1.16 0.33

E NA NA NA NA NA NA NA NA

F 0.74 -0.49 0.17 -0.59 -0.42 -0.02 -0.97 -0.45

G 0.23 0.10 -0.21 -0.90 1.52 1.26 0.60 <LOD

H -0.53 0.54a 0.79 -0.17 -0.56 0.15 -0.83 -0.72

I 0.26 1.25a 0.21 0.50 -0.07 -0.07 -0.77 -0.33

J 0.60 NA -0.36 0.67 1.21 -0.22 6.18 45.75

K -1.14 <LOD -0.42 1.34 -1.21 0.10 0.31 2.13a

L NA NA NA NA NA NA NA NA

M 0.35 0.11a -0.49 -0.79 -0.14 NA -0.43 6.71

N NA NA NA NA NA NA NA NA

O -3.47a -0.22

a -0.72 -3.85

a -1.21 -1.59 3.97 -3.10

a

P 0.53 -0.26a 0.71 1.10 0.96 -0.24 0.28 7.70






Table 11: Z-Score Results for Cigar Filler #1


A -0.60 -0.69 -0.95 0.43 -0.03 0.15 -0.06 -1.90

B 0.04 0.12 0.19 -0.60 NA 0.41 -0.73 1.73

C 0.07 <LOD 0.53 0.15 1.43 0.32 0.14 -0.69a

D -0.46 NA 0.91 -0.12 NA -0.33 -0.75 0.16a


F 0.96 -0.14 0.23 0.34 -0.36 -0.05 -0.41 -0.16

G 0.17 0.33 -0.31 -0.10 1.70 0.89 1.16 <LOD

H -0.95 0.43 0.84 -1.05 -1.13 0.28 -1.22 -1.06

I 0.20 1.05a 0.43 0.13 0.00 0.56 -0.33 -0.25

a

J 1.20 NA 0.00 1.01 1.40 -0.38 1.64 72.03

K -1.53 <LOD -0.53 0.00 -1.50 -0.12 -1.22 3.65a

L 0.70 <LOD -0.36 -0.64 -0.92 -0.06 -0.65 -0.46

M 0.24 -1.59a -0.56 -0.21 -0.38 NA -0.64 7.78

N <LOD -0.10 -0.08 -0.11 -0.83 -0.35a 1.20 77.86

a

O -1.53a 0.16

a -4.35 -0.09 -0.16 -3.53

a 1.43 -0.51

a

P 1.48 -0.10a 0.72 1.26 0.78 -0.43 0.46 16.87


2 The superscript “a” signifies that one or more of the reported values was between the limit of detection and



Table 12: Z-Score Results for CIGARM16


A -0.40 -0.78 -0.97 -0.12 0.20 -0.12 0.15 -1.51

B -0.12 0.04 0.08 -0.28 NA 0.61 -0.51 0.36

C 0.03 0.53a 0.47 0.65 0.10 0.25 0.49 -0.60

D -0.46 NA 0.65 0.18 NA 0.06 -0.48 -0.30


F 0.56 0.36 0.20 0.84 0.08 0.03 -0.07 0.00

G 0.10 -0.53 -0.50 -1.44 1.66 1.19 0.99 1.28

H -1.12 0.69 0.67 -1.29 -1.17 0.04 -1.52 -1.39

I -0.03 0.87a 0.21 1.10 0.39 -0.04 -0.07 -0.49

J 1.05 NA -0.28 1.48 1.87 -0.31 2.48 18.26

K -0.98 <LOD -0.45 -0.58 -1.10 0.46 -0.69 2.41

L 0.34 <LOD -0.40 -0.89 -0.67 0.00 -0.28 -0.63

M -0.20 -1.69 -0.63 0.29 -0.16 NA -0.25 1.36

N 6.02a 5.05 -0.04 0.24 -0.30 -0.93

a 1.63 29.84

a

O -0.84a 0.08

a 0.71 -6.28 -1.68 -3.60 -4.76 -0.31

P 0.86 -1.26a 0.17 1.62 0.89 -0.24 0.62 0.01






7. Conclusions

The overall results of the proficiency study, showing the percentage of acceptable results

where |z|≤2, are given in Table 13. Notable observations include the following:

The results demonstrate that participating laboratories showed the least agreement

with the determination of selenium in all samples. It is worth noting that more

laboratories had unacceptable zscore results for selenium as compared to the other

elements and also selenium showed the greatest deviation from |z|=2 as compared

to the other elements. For example nearly half of the laboratories that measured

selenium for sample CRP3.1 had values of |z|≥2, one laboratory (N) for CRP4.1 had

a |z|=145.93.

Elements that have a higher number of polyatomic and spectral interferences such

as arsenic, chromium, selenium, and nickel had more values of |z|≥2.

Laboratories with poor z-scores should consider developing the digestion and instrumental

methods using plant tissue standard reference materials in order to have some assurance that

interferences from polyatomic and doubly charged ions are effectively managed. As a

potential guide for the participants, the isotopes measured for each element by the

participating laboratories are provided in Appendix C while the reaction and collision cell

gases used are tabulated in Appendix D.

Table 13: Overall Proficiency Study Results

Element Number of Scores

|z|≤2 Total Number of

Scoresǂ Percent |z|≤2

As 119 129 92 %

Be 85 90 94 %

Cd 132 135 98 %

Cr 124 135 92 %

Co 119 121 98 %

Pb 120 125 96 %

Ni 125 135 93 %

Se 78 126 62 %

ǂ: Laboratories that reported <LOD or did not determine the element in the matrix were not included in the sum.

8. Appendices

Appendix A: Study Protocol

Appendix B: Data Tables

Appendix C: Isotopes

Appendix D: Reaction and Collision Cell Gases


Appendix A: Study Protocol

Tobacco and Tobacco Products Analytes Sub-Group

Metals Proficiency Study

Protocol

December 15, 2016

Authors and Study Coordinators:

Derek Bussan and Karl Wagner (Altria Client Services Inc.), U.S.A

Confidentiality Notice: All data in this Collaborative Study should be handled in the strictest

of confidence by all participating laboratories.


1. Introduction

The purpose of interlaboratory proficiency testing is to provide participating laboratories with

an objective means of assessing laboratory capability. Additionally, proficiency testing is an

important component of a quality system and is a requirement of ISO 17025 accreditation.

2. Objective

The objective of this proficiency study is to provide an assessment of laboratory capabilities

for the analysis of specific trace elements in tobacco and tobacco products. Arsenic,

beryllium, cadmium, chromium, cobalt, lead, nickel, and selenium will be determined in the

matrices using inductively coupled plasma mass spectrometry (ICP-MS). If laboratories do

not have the capability to use ICP-MS, they may also use inductively coupled plasma optical

emission spectroscopy (ICP-OES).

3. Time schedule

Date Activity

November 30, 2016 Laboratories state their intention to participate

December 2016 Participants order samples from North Carolina State University and the University of Kentucky

December 2016 Finalize protocol and distribute cigar samples to participants

March 15, 2017 Laboratories submit results by this date

May 3, 2017 Discuss results at SG STS meeting in Charlottesville, VA, USA

4. Participating Laboratories

Following receipt of this protocol, the participating laboratories in the 2016 Metals

Proficiency Study will confirm or notify Derek Bussan and Karl Wagner of their active

participation. Laboratories are encourage, but not required to submit data for all samples

and/or elements.

5. Samples

5.1 Selection

Participants should order the samples shown in the following table at their earliest

convenience. The University of Kentucky reference materials are available at

(https://ctrp.uky.edu/) and the North Carolina State University reference materials are

available at (http://www.tobacco.ncsu.edu/strp.html). Altria Client Services will distribute

two ground cigar samples and one ground flue-cured tobacco sample to the participating

laboratories.

Sample Name Description Source

1R6F Ground Filler American blended cigarette filler University of Kentucky

1R5F Ground Filler American blended cigarette filler (high burley) University of Kentucky

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

2016 CRP2.1 American-style loose moist snuff North Carolina State University

https://ctrp.uky.edu/

http://www.tobacco.ncsu.edu/strp.html


Sample Name Description Source

2016 CRP3.1 American-style loose dry snuff powder North Carolina State University

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

North Carolina State University

Flue-Cured #1 Ground flue-cured tobacco Altria

Cigar Filler #1 Ground, flavoured cigar filler Altria

CIGARM16 Ground, traditional dark air-cured cigar filler Altria

5.2 Storage

Upon receipt, the samples must immediately be stored at approximately 4 °C. 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.

5.3 Within Laboratory Sample Preparation

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 should 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.

6. Analysis

6.1 Analytes

The following analyses should be determined by each participating laboratory using ICP-MS:

Arsenic, Beryllium, Cadmium, Chromium, Cobalt, Lead, Nickel, and Selenium.

6.2 Sample Handling Requirements

The Snus pouches (CPR1.1) shall be cut into 2 halves and both the paper and tobacco shall be

added directly into the digestion vessel. If inclusion of a whole pouch results in a larger

sample aliquot than is normally digested, participants should scale the digestion appropriately.

All other samples shall be mixed immediately before removing aliquots for digestion.

6.3 Methods

Laboratories should use their in house instrumental method.

6.4 Replicates

Conduct three (3) independent replicate sample digestions and analyses per sample.

7. Data Reporting

1) The analytes should be reported in units of ng/g, on an as-is basis.

2) Data above the LOD, but below the LOQ shall be reported and footnoted to

indicate the value was below the LOQ, but above the LOD.

3) If the instrumental result is less than the LOD, the numerical LOD should be

reported with a “<” symbol (e.g. <0.201).

4) The completed data sheet that includes instrumental and acquisition parameters

should be sent to [email protected]; and [email protected]


Microsoft Excel Worksheet

8. Statistical Analysis

Z-Scores will also be calculated for all samples.

9. Presentation of the Results

The final output will be a presentation for discussion at the spring STS meeting which is

scheduled to be held in Charlottesville, VA, USA on May 3, 2017. A technical report will be

prepared for publication.


Appendix B: Data Tables

Data values in ng/g as-is

Sample Lab Rep As Be

Cd

Cr

Co

Pb Ni Se

1R6F Filler A 1 240.9 14.26 876.4 1168 466.4 458.5 1957 31.49

1R6F Filler A 2 224.1 13.78 874.8 1106 464.8 437.9 1793 44.34

1R6F Filler A 3 225.2 14.3 871.4 1199 446.2 442.9 1821 44.81

1R6F Filler B 1 261.7 17.86 1004 1152 NA 471 1713 74.72

1R6F Filler B 2 251.4 16.29 1044 1145 NA 454.5 1713 65.28

1R6F Filler B 3 264.3 16.54 1058 1084 NA 494.4 1760 70.02

1R6F Filler C 1 239.5 <LOD 1069 1307 420.7 456.3 1806 45.64a

1R6F Filler C 2 255.5 <LOD 1111 1190 448.1 468 2036 45.51a

1R6F Filler C 3 230.3 <LOD 1109 1082 435.5 460.3 1894 45.42a

1R6F Filler D 1 247.1 NA 1130.8 1327.5 NA 428.4 1800.2 51.8a

1R6F Filler D 2 262.4 NA 1126.2 1417.4 NA 508.6 1825.7 51.7a

1R6F Filler D 3 230.2 NA 1114.2 1229.0 NA 436.6 1638.8 58.8a

1R6F Filler E 1 416.8 <LOD 1112 1263 642.3 485.5 1914 264.7

1R6F Filler E 2 370.2 <LOD 930.8 1189 527 408.8 2048 282.5

1R6F Filler E 3 389.6 <LOD 1021 1189 602.8 464.9 2270 320.5

1R6F Filler F 1 266.4 18.94 992.4 1269 426.2 449.8 1825 47.39

1R6F Filler F 2 246 20.91 1040 1412 434.8 453.3 1772 47.35

1R6F Filler F 3 269.1 17.32 1013 1402 427.2 443.6 1866 46.34

1R6F Filler G 1 259.7 15.46 956.3 994.2 590.2 553 2246 <LOD

1R6F Filler G 2 253.8 14.32 936.7 1021 577.1 520.5 2176 <LOD

1R6F Filler G 3 259.1 16.63 945.9 1017 605.6 700 2349 <LOD




Cd

Cr

Co

Pb Ni Se

1R6F Filler H 1 214.8 19.6 1119.2 1233.9 365.7 479.6 1732.8 42.4

1R6F Filler H 2 211.6 19.29 1088.4 1216.5 382.7 450.6 1777.5 44.51

1R6F Filler H 3 212.9 18.52 1085.7 1228.5 377.8 443.6 1711.7 39.84

1R6F Filler I 1 268.6 18.12a 1052 1510 464.6 473.1 1828 52.28

a

1R6F Filler I 2 240.5 20.62a 1040 1394 467.8 484.6 1779 49.55

a

1R6F Filler I 3 244 21.32a 1065 1353 465.1 488.4 1718 47.95

a

1R6F Filler J 1 305 NA 1135 1379 515 365 2469 256

1R6F Filler J 2 288 NA 1015 1344 487 401 2051 319

1R6F Filler J 3 292 NA 1051 1389 492 398 2355 307

1R6F Filler K 1 214 <LOD 951 1332 383 462 1789 191a

1R6F Filler K 2 221 <LOD 935 1353 370 470 1793 175a

1R6F Filler K 3 215 <LOD 933 1341 376 459 1773 211a

1R6F Filler L 1 270 <LOD 900 1200 390 490 1800 49

1R6F Filler L 2 270 <LOD 950 1200 410 520 1700 50

1R6F Filler L 3 250 <LOD 890 1100 390 520 1700 46

1R6F Filler M 1 266.9 15.85 965.8 1476 521.6 NA 2156 136.5

1R6F Filler M 2 304.9 11.71a 1102 1475 575 NA 2386 140.8

1R6F Filler M 3 310.8 15.85 1119 1735 592.7 NA 2781 165.5

1R6F Filler N 1 <LOD 15.85 1001 1190 423.9 469.1a 2326 1254

a

1R6F Filler N 2 <LOD 15.5 1029 1080 401.7 542.6a 2242 1358

a

1R6F Filler N 3 <LOD 16.95 1017 1100 404.4 525.7a 2185 1388

a

1R6F Filler O 1 202.6 19.42a 1000 1138 431.2 501.5 1747 36.18

a

1R6F Filler O 2 212.5 20.99a 1028 1249 457.7 520.4 1907 30.22

a




Cd

Cr

Co

Pb Ni Se

1R6F Filler O 3 194.7a 20.01

a 986 1185 409.9 491.5 1695 28.31

a

1R6F Filler P 1 230.2 20.49 857.3 1120 410.9 392.7 1660 169.3

1R6F Filler P 2 223.6 27.91 962.8 1202 394.2 404.3 1736 217

1R6F Filler P 3 228.3 16.02a 966.9 1330 489.9 421.8 1941 230.8

1R5F Filler A 1 267.2 20.43 1179 1878 698.7 1184 2598 66.23

1R5F Filler A 2 266.4 20.83 1184 2008 711.5 1203 2476 65.75

1R5F Filler A 3 279.2 19.74 1233 1297 708.7 1313 2275 72.22

1R5F Filler B 1 292.5 26.01 1400 1671 NA 1285 2163 102.5

1R5F Filler B 2 299 26.81 1396 1880 NA 1328 2091 106.2

1R5F Filler B 3 287.4 26.16 1431 1725 NA 1322 2322 108.2

1R5F Filler C 1 283 28.77a 1533 1825 658.9 1224 2384 73.66

a

1R5F Filler C 2 294.5 26.88a 1516 1662 674.9 1234 2495 73.39

a

1R5F Filler C 3 289.6 28.72a 1537 1915 679.7 1256 2372 73.39

a

1R5F Filler D 1 289 NA 1481.5 2305.2 NA 1206.1 2390.9 80.1a

1R5F Filler D 2 287.1 NA 1500.6 2018.2 NA 1205.9 2363.2 86a

1R5F Filler D 3 289.8 NA 1472.9 2101.7 NA 1171.7 2320.4 84.6a

1R5F Filler E 1 466 <LOD 1368 1619 850.2 1166 2634 277.2

1R5F Filler E 2 442.4 <LOD 1333 1513 822.7 1287 2582 321.4

1R5F Filler E 3 426.2 <LOD 1244 1441 806.1 1108 2387 322.3

1R5F Filler F 1 330.2 29.6 1428 1819 667.3 1175 2284 79.51

1R5F Filler F 2 336.3 31.73 1437 1962 667.7 1202 2233 79.68

1R5F Filler F 3 331.2 30.29 1468 1905 674.1 1251 2293 80.94

1R5F Filler G 1 300.5 25.28 1320 2021 905.5 1378 2914 <LOD




Cd

Cr

Co

Pb Ni Se

1R5F Filler G 2 313.4 25.91 1379 1910 903.7 1474 2897 <LOD

1R5F Filler G 3 326.8 26.79 1375 2012 881.1 1349 3163 <LOD

1R5F Filler H 1 230.9 29.26 1597.9 1552.8 545.1 1228.8 1957.4 63.59

1R5F Filler H 2 235.3 29.2 1546.5 1678.8 542 1199.3 2123 67.56

1R5F Filler H 3 239.7 28.3 1535.6 1685.1 547.9 1176.7 2177 61.81

1R5F Filler I 1 300.3 28.55a 1462 1925 696.8 1226 2279 85.44

1R5F Filler I 2 305.9 31.46a 1460 1834 714.8 1208 2285 83.08

1R5F Filler I 3 294.9 33.52a 1470 2087 706.7 1300 2300 81.16

1R5F Filler J 1 334 NA 1585 1796 743 808 2982 325

1R5F Filler J 2 340 NA 1419 1572 668 968 2110 456

1R5F Filler J 3 354 NA 1621 1774 735 939 2650 382

1R5F Filler K 1 243 <LOD 1287 1703 554 1304 2090 391

1R5F Filler K 2 246 <LOD 1391 1689 578 1310 2112 369

1R5F Filler K 3 260 <LOD 1450 1811 593 1321 2222 426

1R5F Filler L 1 320 <LOD 1400 1700 660 1300 2300 83

1R5F Filler L 2 300 <LOD 1300 1800 630 1400 2200 81

1R5F Filler L 3 290 <LOD 1200 1600 560 1300 2000 71

1R5F Filler M 1 364.2 19.08 1550 2250 839.4 NA 2689 201.1

1R5F Filler M 2 338.1 20.73 1512 2027 821.8 NA 2632 197.9

1R5F Filler M 3 357.6 19.07 1546 2074 811.5 NA 2639 187.2

1R5F Filler N 1 <LOD 23.65 1416 1710 614.1 1196 2785 1416a

1R5F Filler N 2 435.6a 22.8 1406 1661 613.2 1255 2850 1512

a

1R5F Filler N 3 489a 22.45 1406 1703 606 1566 2720 1423

a




Cd

Cr

Co

Pb Ni Se

1R5F Filler O 1 231.1 25.8a 1421 1747 680 1373 2520 58.26

a

1R5F Filler O 2 238.7 22.33a 1407 2218 692.9 1299 2695 62.03

a

1R5F Filler O 3 262.1 25.71a 1425 1866 680.5 1343 2295 62.46

a

1R5F Filler P 1 323.8 29.08 1334.5 2289 669.2 1079 2183 213.7

1R5F Filler P 2 294.4 10.11a 1376.1 1973 665.8 1109 2222 136.3

1R5F Filler P 3 292.7 27.88 1360.1 2009 719.6 1272 2334 216.7

CRP1.1 A 1 50.35 6.177 190.6 426.3 377.5 110.7 894.3 35.04

CRP1.1 A 2 50.93 7.385 201.9 478.1 363.4 118.9 884.2 37.15

CRP1.1 A 3 44.69 6.332 190.8 436.2 350 107.9 810.1 43.78

CRP1.1 B 1 51.2 6.841 248.7 360.2 NA 121.6 776.6 51.89

CRP1.1 B 2 47.78 7.467 218.8 361.8 NA 115.6 739.5 53.96

CRP1.1 B 3 42.96 7.073 237.2 335.3 NA 127.4 773.3 54.92

CRP1.1 C 1 51.16a <LOD 260.2 431.4 370.6 125.5

a 1019 49.4

a

CRP1.1 C 2 52.95a <LOD 260.9 540.3 372.5 126.8

a 1019 44.97

a

CRP1.1 C 3 54.82a <LOD 264.9 478.6 386.9 128.2

a 1027 48.57

a

CRP1.1 D 1 NA NA NA NA NA NA NA NA



CRP1.1 E 1 66.29 <LOD 229.2 413 373.6 139.9 850.8 115.3

CRP1.1 E 2 79.25 <LOD 241.8 495.7 454.1 160.6 1021 127.9

CRP1.1 E 3 70.46 <LOD 225.8 428.3 430.4 133.9 1009 135.4

CRP1.1 F 1 50.81 8.654 252.6 390.8 359.6 128.4 828.2 45.27

CRP1.1 F 2 51.39 7.377 250.9 383 371.1 118.7 882.8 49.66




Cd

Cr

Co

Pb Ni Se

CRP1.1 F 3 59.83 8.461 251.3 400.9 390 121 914.9 49.02

CRP1.1 G 1 64.68 7.45 220.6 295.5 442.4 197.1 941.4 <LOD

CRP1.1 G 2 58.38 7.626 224.5 432.1 459.8 147.3 1071 <LOD

CRP1.1 G 3 69.9 8.258 217.5 331.2 449.9 148.2 971.8 <LOD

CRP1.1 H 1 85.9 14.21 484.1 604.8 577.6 221.5 1442.3 76.55

CRP1.1 H 2 93 14.39 467.6 586.2 550.2 223.9 1322 75.53

CRP1.1 H 3 85.5 16.7 460.2 772.3 597.9 233.2 1579.4 83.71

CRP1.1 I 1 58a 10.83

a 250.4 336.9 366.2 124.8 829 47.03

a

CRP1.1 I 2 57.05a 8.052

a 252.4 358.2 368.7 120.8 819.6 48.68

a

CRP1.1 I 3 56.87a 10.23

a 255.5 350.1 379.8 117.8 846.6 46.31

a

CRP1.1 J 1 129 NA 250 564 393 161 1308 214

CRP1.1 J 2 101 NA 200 549 321 120 1211 350

CRP1.1 J 3 180 NA 175 419 346 110 1018 360

CRP1.1 K 1 79 <LOD 194 474 303 95 849 199a

CRP1.1 K 2 112 <LOD 188 493 295 93 822 193a

CRP1.1 K 3 108 <LOD 179 511 299 94 829 212a

CRP1.1 L 1 65 <LOD 230 390 325 160 850 49.5

CRP1.1 L 2 65 <LOD 215 370 310 150 850 45.5

CRP1.1 L 3 55 <LOD 190 315 275 145 700 40

CRP1.1 M 1 67.02 5.108a 249.1 444.5 418 NA 1071 52.12

a

CRP1.1 M 2 62.84 <LOD 241.4 577.8 402.5 NA 1332 58.56a

CRP1.1 M 3 59.12 <LOD 232.4 434.4 386.8 NA 1005 70.56

CRP1.1 N 1 <LOD 15 268 444.3 380.9 <LOD 1087 830a




Cd

Cr

Co

Pb Ni Se

CRP1.1 N 2 <LOD 15.8 273.6 447.6 395.7 <LOD 1112 1042a

CRP1.1 N 3 <LOD 14.45 250.5 418.4 378 <LOD 1052 748.2a

CRP1.1 O 1 33.79a 6.216

a 230.6 369.7 343.7 137.2 834.4 44.25

a

CRP1.1 O 2 33.65a 7.37

a 227.4 385.3 347.4 137.8 974.5 44.39

a

CRP1.1 O 3 39.67a 7.381

a 231.5 368.3 332.2 138.5 809.3 47.27

a

CRP1.1 P 1 42.92 7.8a 212.6 391.3 364.1 100.5 778.1 101.5

CRP1.1 P 2 40.11 9.58 217.4 401.8 370.2 104.4 822.5 61.61

CRP1.1 P 3 34.66 10.84 240.4 417.4 383.1 103.3 831.9 83.3

CRP2.1 A 1 59.71 8.552 559.4 424.9 481.6 166.5 722.7 49.49

CRP2.1 A 2 62.53 9.442 593.1 397.2 504.1 184.6 730.9 54.74

CRP2.1 A 3 67.03 9.642 630 526.4 571.4 196.8 950.2 57.93

CRP2.1 B 1 91.28 11.61 713 489.4 NA 205.7 685.3 50.08

CRP2.1 B 2 74.51 10.66 721.9 393.7 NA 193.1 702 45.15

CRP2.1 B 3 74.22 10.01 709 425.9 NA 183.2 685.9 52.38

CRP2.1 C 1 79.32a <LOD 756.9 511.1 519.6 198.7

a 920.4 41.86

a

CRP2.1 C 2 76.81a <LOD 766.6 468.7 500.1 207.2

a 886.8 38.46

a

CRP2.1 C 3 79.64a <LOD 775.4 464.5 520.4 205.5

a 902.9 39.12

a




CRP2.1 E 1 105.1 <LOD 636.7 781.9 617.5 234.1 980.1 142.9

CRP2.1 E 2 101.9 <LOD 662.9 892.3 626.6 219.6 932.2 158.6

CRP2.1 E 3 113.1 <LOD 667.3 805.9 635.7 206.5 946.8 165.5




Cd

Cr

Co

Pb Ni Se

CRP2.1 F 1 85.55 11.01 723.1 450.2 485.3 187.8 764.9 41.93a

CRP2.1 F 2 87.6 12.13 731.5 490.7 519.9 203.7 770.1 39.98a

CRP2.1 F 3 77.63 10.8 717.5 441 506.4 181.7 765 41.87a

CRP2.1 G 1 79.05 11.29 642.7 508.1 637.4 218.6 904 <LOD

CRP2.1 G 2 80.62 12.01 641.8 499.3 628 304.3 1043 <LOD

CRP2.1 G 3 81.58 11.94 653.2 462 636.6 271 914.7 <LOD

CRP2.1 H 1 121.2 19.9 1396.6 882.5 868.6 320.7 1364.8 72.59

CRP2.1 H 2 126.7 19.86 1359.8 746.9 816.8 323.7 1305.2 59.69

CRP2.1 H 3 111.4 19.67 1330.2 701.3 787.9 308.6 1232.1 66.08

CRP2.1 I 1 75.75 11.02a 717 489.1 517 187.8 725.6 44.39

a

CRP2.1 I 2 80.84 12.78a 714.2 423.6 491.7 194.9 717.4 41.66

a

CRP2.1 I 3 80.91 10.62a 714.9 447.8 511.9 193.3 724.5 41.97

a

CRP2.1 J 1 203 NA 722 777 632 202 1452 1025

CRP2.1 J 2 188 NA 667 860 607 177 1722 1403

CRP2.1 J 3 183 NA 623 792 600 189 1700 1208

CRP2.1 K 1 142 <LOD 594 921 403 171 751 254

CRP2.1 K 2 150 <LOD 570 896 407 171 744 243a

CRP2.1 K 3 127 <LOD 566 813 393 171 721 265

CRP2.1 L 1 90 <LOD 640 450 450 250 870 38

CRP2.1 L 2 81 <LOD 610 420 420 200 820 35

CRP2.1 L 3 85 <LOD 640 510 430 220 750 38

CRP2.1 M 1 85.96 10.92a 692.1 571.5 522.1 NA 990.4 108

CRP2.1 M 2 88.06 <LOD 643.1 512.3 508.9 NA 754.9 116.7




Cd

Cr

Co

Pb Ni Se

CRP2.1 M 3 79.35 7.582a 646.3 450.9 504.4 NA 665.2 113.4

CRP2.1 N 1 <LOD 11.55a 697.1 456.7 446.9 304.2

a 970.6 988.2

a

CRP2.1 N 2 <LOD 12.5a 712.9 464.9 465.2 371.5

a 988 1149

a

CRP2.1 N 3 <LOD 11.95a 707.2 591.5 446.1 410.8

a 962.4 1179

a

CRP2.1 O 1 62.44a 9.991

a 720 473.5 534.8 233.1 804.2 34.77

a

CRP2.1 O 2 47.03a 8.169

a 709.4 420.1 478.7 232.2 772.4 35.52

a

CRP2.1 O 3 67.7a 8.532

a 694.1 494.9 521.7 234.1 764.2 28.02

a

CRP2.1 P 1 97.4 15.07a 706.3 510.7 550.1 192.4 808.2 196.1

CRP2.1 P 2 85.33 13.87a 755.2 536.6 577.6 181.6 810.8 142.4

CRP2.1 P 3 87.6 10.39a 751.1 509.9 568.5 189.3 836.9 140.1

CRP3.1 A 1 186.2 16.78 1135 2146 824 518 3224 98.91

CRP3.1 A 2 185.1 17.04 1141 2201 817.7 525.7 3215 94.38

CRP3.1 A 3 186.6 18.23 1133 2386 829.1 571.1 3329 96.18

CRP3.1 B 1 219.5 20.58 1473 2109 NA 547.5 3013 124.4

CRP3.1 B 2 220.9 20.48 1403 2104 NA 563.3 3020 118.9

CRP3.1 B 3 225.7 20.9 1492 2201 NA 561.4 3139 121.8

CRP3.1 C 1 208.8 <LOD 1505 2257 807.6 555.3 3333 85.92

CRP3.1 C 2 215.7 <LOD 1504 2326 799.8 541.9 3301 97.96

CRP3.1 C 3 214.7 <LOD 1490 2579 801.9 569.5 3310 92.27




CRP3.1 E 1 251.9 <LOD 1190 2209 917.2 522.6 3410 336.1




Cd

Cr

Co

Pb Ni Se

CRP3.1 E 2 269.1 <LOD 1155 2005 901.1 503.9 3282 375.3

CRP3.1 E 3 285.5 <LOD 1182 2292 995.8 552.8 3607 403.2

CRP3.1 F 1 230.9 21.27 1407 2222 791 516 3083 97.03

CRP3.1 F 2 235.5 21.8 1385 2305 776.5 543.5 3064 97.19

CRP3.1 F 3 244.7 23.22 1373 2371 774.3 536.8 3071 96.28

CRP3.1 G 1 176.9 16.46 1059 1380 861.4 503.1 2967 <LOD

CRP3.1 G 2 210.8 20.71 1205 1717 1039 632.1 3560 <LOD

CRP3.1 G 3 211.4 24.02 1265 1706 1067 620.2 4012 209.7

CRP3.1 H 1 175.6 20.88 1472.5 2144.7 692.5 551.4 2867.8 88.99

CRP3.1 H 2 169.6 20.56 1429.2 2171.1 638.9 506.5 2939.4 80.1

CRP3.1 H 3 177.2 21.92 1409.2 2257.4 663.6 525.5 2999.1 82.01

CRP3.1 I 1 222.9 27.09a 1409 2300 830.3 525.7 3159 102.5

CRP3.1 I 2 219 27.36a 1414 2307 819 544 3149 98.87

CRP3.1 I 3 219.2 26.52a 1423 2507 832.8 560.8 3197 97.68

CRP3.1 J 1 290 NA 1241 2695 996 509 3920 1269

CRP3.1 J 2 286 NA 1272 2941 1025 515 3994 1771

CRP3.1 J 3 286 NA 1263 2871 1004 525 3852 1453

CRP3.1 K 1 181 <LOD 1217 2208 646 552 2710 297

CRP3.1 K 2 184 <LOD 1196 2107 640 566 2679 263

CRP3.1 K 3 186 <LOD 1195 2065 642 567 2708 248a

CRP3.1 L 1 210 <LOD 1100 1800 630 480 2700 82

CRP3.1 L 2 220 <LOD 1200 1900 660 500 2800 86

CRP3.1 L 3 220 <LOD 1200 1800 660 540 2700 89




Cd

Cr

Co

Pb Ni Se

CRP3.1 M 1 216.7 9.942a 1255 2511 801.2 NA 3097 191.6

CRP3.1 M 2 213.8 7.486a 1202 2190 761.6 NA 3040 215

CRP3.1 M 3 206.5 16.52 1214 2083 759 NA 2887 184.1

CRP3.1 N 1 <LOD 21.25 1352 2245 721.5 583.3a 3516 1223

a

CRP3.1 N 2 <LOD 22.3 1323 2207 709 512.8a 3442 1171

a

CRP3.1 N 3 <LOD 22.6 1326 2205 726.8 514.8a 3368 1134

a

CRP3.1 O 1 166.2a 20.51

a 1377 2263 805.3 596.8 3287 83.71

a

CRP3.1 O 2 NA NA NA NA NA NA NA NA

CRP3.1 O 3 NA NA NA NA NA NA NA NA

CRP3.1 P 1 234.4 17.34a 1404.5 2854 924.6 524.9 3544 184.7

CRP3.1 P 2 216.3 15.4a 1506.1 2826 930.6 531 3594 236.8

CRP3.1 P 3 223.1 30.18 1482.5 2834 939.7 519.5 3576 302.4

CRP4.1 A 1 71.95 5.229 293.4 763.5 195.3 484 780.1 29.55

CRP4.1 A 2 69.15 4.688 298.3 730.2 196.6 487.1 753.3 25.15

CRP4.1 A 3 83.74 5.813 302.8 861.8 222.1 532.4 869.9 25.28

CRP4.1 B 1 87.26 7.198 349.7 641.5 NA 478.8 715.7 37.24

CRP4.1 B 2 89.82 7.343 350 641.8 NA 477.4 796.4 41.01

CRP4.1 B 3 76.77 7.485 337.8 574.6 NA 495 686.2 54.03

CRP4.1 C 1 83.41a <LOD 352.6 986.9 206.4 477.7 1093 27.2

a

CRP4.1 C 2 89.47a <LOD 373.1 1005 201.7 494.7 1077 <LOD

CRP4.1 C 3 89.77a <LOD 394.1 820.4 215.4 502.1 943.8 <LOD






Cd

Cr

Co

Pb Ni Se


CRP4.1 E 1 118.7a <LOD 301.2 839.8 268.9 458.6 1076 128.3

CRP4.1 E 2 122a <LOD 332.3 802.7 257.1 473.5 1004 147.1

CRP4.1 E 3 129a <LOD 298.1 863.9 245.4 446.1 894.3 147.7

CRP4.1 F 1 89.18 10.25 321.2 1126 200.9 448.4 993.1 27.71a

CRP4.1 F 2 87.02 9.992 334.6 1107 214.9 474.3 943.2 26.08a

CRP4.1 F 3 93.69 9.183 347.9 1055 209.9 464.7 983.6 28.21a

CRP4.1 G 1 91.29 6.221 299.4 645.3 264.9 582.8 940.1 <LOD

CRP4.1 G 2 86.81 5.827 315.6 630.7 265.3 531.7 939.1 <LOD

CRP4.1 G 3 90.35 7.543 307.5 771.9 296 584.8 1111 <LOD

CRP4.1 H 1 91.7 9.91a 409.7 932.1 227.2 529.1 898.2 25.89

CRP4.1 H 2 82.73 10.71a 411 880.4 210 538.5 847.7 27.95

CRP4.1 H 3 90.78 10.88a 401.4 963.5 215.9 553.1 923.8 32.79

CRP4.1 I 1 87.47 10.66a 353.2 1038 267.7 483.5 946.2 27.07

a

CRP4.1 I 2 85.12 10.82a 351.4 822 210.9 462.3 862 23.27

a

CRP4.1 I 3 86.01 11.28a 343.2 932.5 221.1 464.5 887.6 24.74

a

CRP4.1 J 1 104 NA 320 1208 257 416 1698 1423

CRP4.1 J 2 123 NA 319 1152 288 452 1525 1224

CRP4.1 J 3 109 NA 291 1178 269 431 1462 1050

CRP4.1 K 1 72 <LOD 289 1288 186 482 882 <LOD

CRP4.1 K 2 67 <LOD 301 1317 181 469 894 <LOD

CRP4.1 K 3 76 <LOD 299 1108 188 456 895 <LOD

CRP4.1 L 1 95 <LOD 310 590 170 470 870 <LOD




Cd

Cr

Co

Pb Ni Se

CRP4.1 L 2 88 <LOD 290 580 170 400 890 <LOD

CRP4.1 L 3 88 <LOD 300 610 160 420 970 <LOD

CRP4.1 M 1 84.23 <LOD 289.1 911.7 206.9 NA 950.9 59.12a

CRP4.1 M 2 91.81 <LOD 320.4 819.9 200.1 NA 824.7 39.77a

CRP4.1 M 3 87.96 <LOD 320.3 1051 223.7 NA 995.4 55.89a

CRP4.1 N 1 <LOD 9.75a 342.5 1055 200.6 513.1

a 1314 857.8

a

CRP4.1 N 2 <LOD 9.05a 336.3 1093 201.5 566.8

a 1351 949.9

a

CRP4.1 N 3 <LOD 7.85a 346.8 1059 188 627

a 1296 1011

a

CRP4.1 O 1 33.37a 7.984

a 327.8 1137 213.8 388.5 1512 29.02

a

CRP4.1 O 2 39.02a 7.094

a 347.6 1173 201.1 371.5 1528 22.74

a

CRP4.1 O 3 48.16a 9.921

a 322.8 1313 208.1 441.2 1580 39.31

a

CRP4.1 P 1 109.3 7.02a 374.3 871.2 268.3 501 887.5 216.5

CRP4.1 P 2 71.32 11.44a 391.7 840.7 242.4 458.8 878.6 171.3

CRP4.1 P 3 77.02 19.05a 359.6 843.6 244 453.3 985.5 102.9

Flue-Cured #1 A 1 158.3 7.602 867 601.9 285.6 374.4 471 82.55

Flue-Cured #1 A 2 162.5 6.932 856 590.2 297 359.8 476 95.59

Flue-Cured #1 A 3 164 7.555 854.7 724.7 299.8 363.6 550.6 83.71

Flue-Cured #1 B 1 182.1 8.006 1019 465 NA 382.7 407.3 128.1

Flue-Cured #1 B 2 187.9 8.54 1046 518.8 NA 384.8 423.1 134.4

Flue-Cured #1 B 3 192.9 8.322 1045 517.3 NA 366.9 429 120.1

Flue-Cured #1 C 1 171.9 <LOD 1032 523.2 281.5 353 564.2 86.8

Flue-Cured #1 C 2 180 <LOD 1079 681.6 286.5 374 599.5 84.17

Flue-Cured #1 C 3 166 <LOD 1078 538 279.5 361 540.4 89.17




Cd

Cr

Co

Pb Ni Se

Flue-Cured #1 D 1 174.6 NA 1040.6 716.3 NA 357.8 422.3 110.6

Flue-Cured #1 D 2 175.4 NA 1098.4 629.9 NA 369.7 378.5 108.7

Flue-Cured #1 D 3 166.8 NA 1102.6 696.2 NA 374.9 403.4 107.8

Flue-Cured #1 E 1 NA NA NA NA NA NA NA NA



Flue-Cured #1 F 1 204.3 6.993 1019 471.5 267.9 363.1 390.6 91.14

Flue-Cured #1 F 2 199.7 8.218 1033 550.8 267.4 374.8 441.3 89.24

Flue-Cured #1 F 3 204.2 6.904 1021 569.3 266.5 348.3 422.5 94.31

Flue-Cured #1 G 1 187.2 8.208 947.5 375 381.2 497.1 495 <LOD

Flue-Cured #1 G 2 186.3 8.59 984.5 563.3 376.9 443.4 617.7 <LOD

Flue-Cured #1 G 3 178.8 8.541 956.9 557.9 369.9 405.9 563.3 <LOD

Flue-Cured #1 H 1 157.7 8.95a 1160.3 580.5 262.9 378.6 415.2 81.58

Flue-Cured #1 H 2 157 9.69a 1123.6 623 260.1 383.5 452.5 87.28

Flue-Cured #1 H 3 154.1 9.11a 1086.8 517.1 254.8 358.6 423.8 87.96

Flue-Cured #1 I 1 183.2 11.7a 1024 583.9 289.4 352.6 441.8 90.65

Flue-Cured #1 I 2 190.8 10.64a 1033 665.8 292.1 368 433.9 96.52

Flue-Cured #1 I 3 182.1 9.287a 1034 676.9 278.4 355.1 432.9 95.88

Flue-Cured #1 J 1 201 NA 962 705 356 329 1142 1161

Flue-Cured #1 J 2 203 NA 959 668 372 387 1075 907

Flue-Cured #1 J 3 189 NA 896 606 348 330 958 1308

Flue-Cured #1 K 1 131 <LOD 917 705 220 383 524 142a

Flue-Cured #1 K 2 137 <LOD 952 768 223 358 534 158a




Cd

Cr

Co

Pb Ni Se

Flue-Cured #1 K 3 135 <LOD 923 713 225 370 541 148a

Flue-Cured #1 L 1 NA NA NA NA NA NA NA NA



Flue-Cured #1 M 1 185.7 8.465 898 451.2 267.6 NA 450.1 272.5

Flue-Cured #1 M 2 193.6 <LOD 922 522.8 282.9 NA 463.9 246.4

Flue-Cured #1 M 3 186.3 <LOD 935.6 557.8 297.6 NA 483.8 236.7

Flue-Cured #1 N 1 NA NA NA NA NA NA NA NA



Flue-Cured #1 O 1 39.8a 5.786

a 852.7 187.8

a 217.6 246.9 803.9 32.33

a

Flue-Cured #1 O 2 44.84a 7.925

a 907.2 179.2

a 224.1 248.4 799.9 33.57

a

Flue-Cured #1 O 3 62.17a 9.884

a 886.2 223.7 227.8 271.5 977.2 30.83

a

Flue-Cured #1 P 1 183.5 8.6a 1083.7 660.2 348.3 332.1 531.6 216

Flue-Cured #1 P 2 217 6.99a 1132.6 723.4 352.3 350 545.5 294.2

Flue-Cured #1 P 3 184.9 <LOD 1112.3 727.5 332.7 359.3 513.9 311.7

Cigar Filler #1 A 1 121.2 17.71 687.1 1583 901 408.7 2075 41.32

Cigar Filler #1 A 2 121.6 17.22 676.8 1663 934.8 389.9 2023 29.87

Cigar Filler #1 A 3 120.6 18.17 696.9 1701 921.2 416.1 2129 31.25

Cigar Filler #1 B 1 142.4 22.4 859.3 1451 NA 428.6 1928 78.98

Cigar Filler #1 B 2 142.3 21.17 828.5 1384 NA 421.3 1842 78.48

Cigar Filler #1 B 3 136.4 20.55 833.1 1393 NA 421.8 1857 85.49

Cigar Filler #1 C 1 148.9 <LOD 888.5 1624 1341 410.3 2139 52.64a




Cd

Cr

Co

Pb Ni Se

Cigar Filler #1 C 2 139.5 <LOD 896.7 1583 1169 447.9 2152 49.28a

Cigar Filler #1 C 3 135.1 <LOD 874.4 1542 901.5 393.9 2113 47.2a

Cigar Filler #1 D 1 127.4 NA 931.1 1509.1 NA 384.2 1899.6 61.1a

Cigar Filler #1 D 2 119.3 NA 932.9 1568.2 NA 368.6 1880.5 61.2a

Cigar Filler #1 D 3 129.3 NA 945.7 1486 NA 358.9 1830.8 59.8a

Cigar Filler #1 E 1 NA NA NA NA NA NA NA NA



Cigar Filler #1 F 1 170.5 20.53 836.5 1682 868.4 394.9 1978 57.28

Cigar Filler #1 F 2 170.3 20.79 851.5 1702 873.3 384.2 2015 57.57

Cigar Filler #1 F 3 162.3 19.32 849.8 1498 869 393.8 1916 54.81

Cigar Filler #1 G 1 145 23.14 782.5 1666 1194 476.1 2521 <LOD

Cigar Filler #1 G 2 146 21.33 751.4 1255 1163 406.9 2313 <LOD

Cigar Filler #1 G 3 141.9 22.54 783.9 1654 1176 492.6 2489 <LOD

Cigar Filler #1 H 1 109 22 924.8 1290.2 786.3 401.4 1759.1 46.85

Cigar Filler #1 H 2 111.5 23.06 932.9 1302.5 720.4 438.7 1694.3 46.8

Cigar Filler #1 H 3 111.5 23.32 925.2 1321.1 758.6 402.8 1729.2 41.2

Cigar Filler #1 I 1 142.3 27.3a 874.2 1543 918.8 405.2 1976 53.61

a

Cigar Filler #1 I 2 150.9 24.69a 882.7 1632 930.5 359.3 2025 58.29

a

Cigar Filler #1 I 3 142.1 24.94a 860.8 1557 919.7 540.1 1980 54.42

a

Cigar Filler #1 J 1 174 NA 811 1823 1121 385 2786 1097

Cigar Filler #1 J 2 187 NA 868 1853 1165 339 2468 1054

Cigar Filler #1 J 3 164 NA 766 1674 1111 376 2506 812




Cd

Cr

Co

Pb Ni Se

Cigar Filler #1 K 1 97 <LOD 741 1570 699 383 1700 103a



Cigar Filler #1 L 1 170 <LOD 810 1500 830 400 2000 58



Cigar Filler #1 M 1 141.2 14.12 745.7 1388 857.4 NA 1875 191.5

Cigar Filler #1 M 2 149.8 11.65a 751.1 1442 862 NA 1825 120.9

Cigar Filler #1 M 3 148.1 14.95 720.7 1672 879.4 NA 2004 164.7

Cigar Filler #1 N 1 <LOD 20.65 767.9 1517 787.4 <LOD 2334 849.6a

Cigar Filler #1 N 2 <LOD 20.5 803.4 1505 798.4 <LOD 2474 1059a

Cigar Filler #1 N 3 <LOD 19.95 839.7 1544 811.5 369a 2552 1280

a

Cigar Filler #1 O 1 84.38a 22.94

a 230.6 1495 912.2 137.2

a 2572 42.88

a


a 227.4 1495 886.5 137.8

a 2466 46.33

a


a 231.5 1595 900.5 138.5

a 2526 66.97

a

Cigar Filler #1 P 1 166.8 24.48 925 1948 1038 357.9 2246 293.2

Cigar Filler #1 P 2 178.7 24.52 891.6 1763 1031 372.5 2215 314

Cigar Filler #1 P 3 204.6 12.1a 916.8 1807 1050 359.1 2236 221.6

Cigar M16 A 1 217 25.63 556.5 3070 714.3 583.6 2366 162

Cigar M16 A 2 237.6 23.12 556.2 2903 749.8 619 2422 154.6

Cigar M16 A 3 226.5 24.64 563.2 3082 749 598.4 2446 154.7

Cigar M16 B 1 241.9 28.23 676.2 2968 NA 644.6 2208 245.7

Cigar M16 B 2 244.9 34.03 689.7 2998 NA 804.2 2220 240




Cd

Cr

Co

Pb Ni Se

Cigar M16 B 3 236.4 27.17 666.4 2891 NA 585.1 2149 238.4

Cigar M16 C 1 251.4 32.95a 726.9 3561 716.6 614 2588 196.5

Cigar M16 C 2 246.7 32.66a 724.6 3238 727.5 658.2 2492 202.8

Cigar M16 C 3 246.3 33.27a 714.9 3218 732.3 646.3 2489 194.9

Cigar M16 D 1 223.8 NA 753.6 3085.2 NA 600.8 2176.7 208.3

Cigar M16 D 2 220.5 NA 741.4 3170.3 NA 607.9 2124.9 208.7

Cigar M16 D 3 228.2 NA 732.3 3172 NA 650.8 2299.5 217.9

Cigar M16 E 1 NA NA NA NA NA NA NA NA



Cigar M16 F 1 270.4 32.54 691.3 3786 727.3 607.4 2352 223.8

Cigar M16 F 2 279.7 32.92 689.2 3208 731.3 634.6 2357 226.2

Cigar M16 F 3 272.2 30.2 695.1 3257 713 607.3 2304 224.8

Cigar M16 G 1 259.5 26.29 614.8 2474 921.4 681.1 2708 306.5

Cigar M16 G 2 250.5 26.24 613.4 2500 916.8 807.3 2674 255.6

Cigar M16 G 3 245 25.65 606.4 2440 902.8 729.1 2685 285

Cigar M16 H 1 195.2 34.02 738.7 2547.3 574.7 620.4 1816.7 155

Cigar M16 H 2 186.5 33.67 750 2590.1 561.1 607 1915.8 166

Cigar M16 H 3 194.7 34.36 745.4 2470.8 585 624.1 1834.5 165.9

Cigar M16 I 1 242.2 35.37a 690.9 3659 747.2 573.8 2340 206.5

Cigar M16 I 2 242.8 32.32a 686 3418 771.2 604.5 2329 198.6

Cigar M16 I 3 250.3 37.88a 701.5 3501 765 648.6 2345 203.6

Cigar M16 J 1 304 NA 631 3828 916 587 3138 961




Cd

Cr

Co

Pb Ni Se

Cigar M16 J 2 308 NA 623 3665 933 563 3094 1081

Cigar M16 J 3 282 NA 656 3559 966 590 3325 1100

Cigar M16 K 1 201 <LOD 600 2755 584 689 2162 326

Cigar M16 K 2 202 <LOD 638 2898 579 676 2102 358

Cigar M16 K 3 194 <LOD 613 2836 581 621 2134 316

Cigar M16 L 1 280 <LOD 670 2900 680 680 2300 220

Cigar M16 L 2 250 <LOD 600 2700 610 550 2200 180

Cigar M16 L 3 260 <LOD 600 2500 610 610 2300 190

Cigar M16 M 1 235.6 23.21 596.3 3305 707.6 NA 2479 285.6

Cigar M16 M 2 237 16.6 587.6 2993 663.4 NA 2119 269.5

Cigar M16 M 3 238.9 15.77 606.7 3272 714.4 NA 2234 303.8

Cigar M16 N 1 579.1a 58.9 662.9 3166 675 505.6

a 2850 1457

a

Cigar M16 N 2 560.2a 65 662.8 3191 676 551.4

a 2935 1677

a

Cigar M16 N 3 481.5a 63.2 666.9 3147 681.9 486.5

a 2923 1573

a

Cigar M16 O 1 201.1 29.82a 845.8 473.5 534.8 233.1 804.2 214.2

Cigar M16 O 2 223.1 27.79a 709.4 420.1 478.7 232.2 772.4 200.3

Cigar M16 O 3 193.7a 32.6

a 694.1 494.9 521.7 234.1 764.2 219

Cigar M16 P 1 253.3 9a 654.4 3618 817.7 612.1 2552 185

Cigar M16 P 2 289.6 25.08 684 3810 844.2 587 2536 282

Cigar M16 P 3 323.2 29.96 724.7 3801 799.4 562.9 2610 208.8

1. “NA” signifies the laboratory did not submit data for this sample/ element. 2. The superscript “a” signifies the reported value was between the limit of detection and the limit of quantitation. 3. “<LOD” signifies the data were below the limit of detection.


Appendix C: Isotopes

Lab Identification Code

Element A B C D E F G H I J K L M Nb

O P

As 75 75 75 75 75 75 75 75 75 75 75 75 75 b 75 75

Be 9 9 9 NA 9 9 9 9 9 NA 9 9 9 b 9 9

Cd 111 111 111 114 111 111 114 114 114 111 111 111 111 b 111 111

Cr 52 52 52 52 52 52 52 52 52 53 52 52 52 b 52 52

Co 59 NA 59 NA 59 59 59 59 59 59 59 59 59 b 59 59

Pb 208 ∑ 206,207,208 208 ∑ 206,207,208 208 ∑ 206,207,208 208 208 208 206 208 ∑ 206,207,208 208 b 208 208

Ni 60 60 60 60 60 60 60 60 60 62 60 60 60 b 60 60

Se 78 78 78 78,80 78 78 78 78 78 78 82 78 78 b 78 78

1. The letter “b” indicates the lab used Inductively Coupled Plasma Optical Emission Spectroscopy instead of ICP-MS. 2. “NA” signifies lab did not determine the element.


Appendix D: Reaction and Collision Cell Gases

Lab Identification Code

Element A B C D E F G H I J K L M Nb

O P

As He He He H2/He He He He H2/He H2/He He NG He He b He He

Be NG NG NG NA He NG NG NG H2/He NA NG He He b NG NG

Cd NG He He H2/He He NG NG H2/He NG NG NG He He b NG He

Cr He He He H2/He He He NH3 H2/He H2/He NG NG He He b He He

Co He NA He NA He He He H2/He H2/He NG NG He He b He He

Pb NG NG He NG He NG NG H2/He NG NG NG He He b NG NG

Ni He He He H2/He He He He H2/He H2/He NG NG He He b He He

Se NH3 He H2 H2/He He H2 He H2/He H2/He He NG H2 He b H2 He

1. The letter “b” indicates the lab used Inductively Coupled Plasma Optical Emission Spectroscopy instead of ICP-MS. 2. “NA” indicates the lab did not determine the element. 3. “NG” indicates the lab did not use a collision or reaction gas for the analysis of that element.

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