Interlaboratory Comparison Program for Metals in Biological Matrices 3

Att9d PCI 2014-03 Anglais.pdf

Biomonitoring of Great Lakes Populations Program II

Interlaboratory Comparison Program for Metals in Biological Matrices 3

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INTERLABORATORY COMPARISON PROGRAM
FOR METALS IN BIOLOGICAL MATRICES
(PCI)

REPORT FOR ROUND:

2014-03

PTMS SHIPPING DATE:

2014-04-22

DATE OF PUBLICATION:

2014-06-20

Scope of accreditation: The concentration of arsenic in material PC-U-S1407 exceed the level of
our scope of accreditation.

Centre de toxicologie/INSPQ

945, Ave Wolfe
Quebec, QC
Canada, G1V 5B3

Phone: (418) 650-5115 Ext. 5254
Fax : (418) 654-2148
E-mail : [email protected]
http://www.inspq.qc.a/ctq

Interlaboratory Comparison Program for Metals in
Biological Matrices (PCI)

TABLE OF CONTENTS
INTRODUCTION

1

BLOOD
Cadmium

2

Lead

5

Mercury

9

SERUM
Aluminium

12

Copper

15

Manganese

18

Selenium

21

Zinc

24

URINE
Cadmium

27

Chromium

30

Copper

33

Fluoride

36

Inorganic arsenic

39

Iodide

42

Lead

45

Mercury

48

Selenium

51

Total arsenic

54

Zinc

57

ASSIGNED VALUES

60

GROUPING OF ANALYTICAL METHODS FOR STATISTICS

61

END OF REPORT

62

Centre de toxicologie/INSPQ

945, Ave Wolfe
Quebec, QC
Canada, G1V 5B3

Phone: (418) 650-5115 Ext. 5254
Fax : (418) 654-2148
E-mail : [email protected]
http://www.inspq.qc.a/ctq

Interlaboratory Comparison Program for Metals in
Biological Matrices (PCI)

INTRODUCTION
Dear PCI participants:
This report includes the results and performance evaluations of round 2014-03.
Participating laboratories are identified only by their unique subscription number.
Identity of participants will be kept strictly confidential by the PCI organizer.
For this PT exercise, all analytes meet the homogeneity criteria as per ISO/CEI
17043 and 13528 guidelines with the exception of mercury in material PC-U-H1407.
A note concerning the homogeneity of PC-U-H1407 has been included in the
corresponding section.
A study had been previously performed to demonstrate that all the analytes are
stable for the duration of the PT exercise and meet the stability criteria according
to ISO/CEI 17043 and 13528 guidelines.
Please note that the appendices containing statistical approaches are no longer
included in the reports. You will find them within the “Participant’s Guide”.
We are available to assist you at any time. If you have any questions or concerns
regarding our program, do not hesitate to contact us. Your comments help us
enhance the quality of our schemes.
Best regards,

David Bisson, M.Sc. Chemist
Programs Coordinator
External Quality Assessment Schemes and Reference Materials
Centre de toxicologie du Québec / INSPQ
Tel.: (418) 650-5115, extension 4649
E-mail: [email protected]
Web Site: www.inspq.qc.ca/CTQ/paqe

Centre de toxicologie/INSPQ

945, Ave Wolfe
Quebec, QC
Canada, G1V 5B3

Phone: (418) 650-5115 Ext. 5254
Fax : (418) 654-2148
E-mail : [email protected]
http://www.inspq.qc.a/ctq
1

Individual results
Blood Cadmium (nmol/L)
Round #2014-03

Participant

PC-B-C1407

z’-score

PC-B-C1408

z’-score

PC-B-C1409

z’-score

Method

176

81.8

-0.35

13.3

-0.94

30.2

-0.62

ICP-MS

194

72.6

-1.63

15.1

-0.14

28.2

-1.22

ND

217

79.7

-0.65

17.5

0.96

36.2

1.10

ICP-MS

323

78.0

-0.89

15.0

-0.18

33.0

0.17

GFAAS

747

84.7

0.04

15.1

-0.14

29.9

-0.72

ICP-MS

1095

95.5

1.54

16.6

0.55

34.5

0.61

ICP-MS (C/R)

1109

88.1

0.51

18.7

1.51

35.1

0.79

ND

1188

89.0

0.63

15.0

-0.17

30.8

-0.46

ICP-MS (C/R)

1418

82.6

-0.24

15.2

-0.09

35.1

0.77

ICP-MS (C/R)

1865

85.4

0.14

17.1

0.77

37.1

1.36

ICP-MS (C/R)

2305

92.8

1.17

14.9

-0.22

31.6

-0.22

ND

2991

104

2.76

20.0

2.12

39.3

2.01

ND

3187

83.2

-0.17

15.0

-0.18

30.5

-0.55

ICP-MS

3211

82.3

-0.29

15.7

0.14

32.3

-0.03

GFAAS

3248

70.6

-1.90

12.9

-1.15

27.3

-1.48

GFAAS

3853

88.4

0.55

20.5

2.34

42.9

3.04

ICP-MS

4708

84.1

-0.04

15.3

-0.05

31.1

-0.38

ICP-MS

4953

88.1

0.51

15.1

-0.13

32.9

0.15

ICP-MS

5591

78.9

-0.76

14.8

-0.28

31.3

-0.32

ICP-MS

5654

93.1

1.20

16.7

0.61

35.0

0.74

ICP-MS (C/R)

5691

84.0

-0.06

15.0

-0.18

32.0

-0.12

ICP-MS

6511

82.7

-0.23

15.1

-0.13

32.0

-0.11

ND

6545

81.4

-0.42

---

---

---

---

ICP-MS

6689

84.0

-0.06

16.9

0.69

32.6

0.05

GFAAS

6794

83.7

-0.10

16.5

0.53

30.4

-0.57

GFAAS

6858

84.8

0.06

12.8

-1.20

30.3

-0.60

ICP-MS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-B-C1407

84.4

1.24

7.11

70.0 - 98.8

Accepted

---

PC-B-C1408

15.4

0.233

2.17

11.0 - 19.8

Rejected1

---

PC-B-C1409

32.4

0.665

3.39

25.5 - 39.3

Accepted

---

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

2

Statistics
Blood Cadmium (nmol/L)
All methods

PC-B-C1407

PC-B-C1408

26

25

25

Robust mean Algo A

84.4

15.4

32.4

Robust STDev

5.07

0.932

2.66

Median

84.0

15.1

32.0

STDev from MAD

4.95

0.856

2.49

Arithmetic mean

84.8

15.8

32.9

STDev

6.87

1.90

3.46

CV or Variability

6.0%

6.0%

8.2%

PC-B-C1407

PC-B-C1408

PC-B-C1409

5

5

5

Robust mean Algo A

81.4

15.6

31.9

Robust STDev

3.04

1.40

1.20

Median

82.3

15.7

32.3

STDev from MAD

2.49

1.26

1.04

Arithmetic mean

79.7

15.4

31.1

STDev

5.62

1.59

2.35

CV or Variability

3.7%

9.0%

3.8%

PC-B-C1407

PC-B-C1408

PC-B-C1409

N

Graphite furnace-AAS
N

ICP-MS
N

PC-B-C1409

11

10

10

Robust mean Algo A

83.6

15.1

31.5

Robust STDev

3.38

0.443

1.45

Median

84.0

15.1

31.2

STDev from MAD

3.20

0.371

1.34

Arithmetic mean

83.6

15.4

32.7

STDev

3.02

2.17

4.02

CV or Variability

4.0%

2.9%

4.6%

PC-B-C1407

PC-B-C1408

PC-B-C1409

ICP-MS (collision/reaction cell)
N

5

5

5

Robust mean Algo A

89.1

16.3

34.9

Robust STDev

6.00

0.814

0.859

Median

89.0

16.6

35.0

STDev from MAD

6.07

0.712

0.684

Arithmetic mean

89.1

16.1

34.5

STDev

5.29

0.939

2.29

CV or Variability

6.7%

5.0%

2.5%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

3

Distribution
Blood Cadmium (nmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

4

Individual results
Blood Lead (µmol/L)
Round #2014-03

Participant

PC-B-L1407

z’-score

PC-B-L1408

z’-score

PC-B-L1409

z’-score

Method

194

0.144

-0.53

0.392

-1.17

1.50

-1.97

ND

217

0.160

0.32

0.440

0.20

1.78

0.24

ICP-MS

226

0.150

-0.23

0.410

-0.65

1.70

-0.36

ICP-MS

317

0.164

0.53

0.463

0.85

1.80

0.39

GFAAS

323

0.151

-0.16

0.485

1.48

2.02

2.10

GFAAS

387

0.181

1.43

0.428

-0.14

1.80

0.41

GFAAS

636

0.167

0.69

0.453

0.57

1.85

0.76

ICP-MS

744

0.145

-0.47

0.452

0.53

1.82

0.53

ND

747

0.159

0.26

0.431

-0.06

1.79

0.31

ICP-MS

1095

0.150

-0.21

0.420

-0.37

1.79

0.31

GFAAS

1109

0.151

-0.18

0.455

0.62

1.81

0.45

ND

1188

0.163

0.48

0.488

1.57

1.81

0.47

ICP-MS (C/R)

1418

0.146

-0.43

0.420

-0.36

1.69

-0.49

ND

1761

LL

---

>LL

---

>LL

---

9674

166

-0.23

LL

---

0.852

-0.98

ICP-MS

1865

2.16

0.37

8.35

-0.03

1.02

0.10

GFAAS

2305

2.26

0.74

8.64

0.26

1.11

0.73

ND

2516

1.28

-2.89

5.98

-2.37

0.493

-3.36

GFAAS

2580

2.01

-0.20

>LL

---

1.20

1.29

GFAAS

2629

2.09

0.11

6.73

-1.63

0.890

-0.73

GFAAS

2763

2.01

-0.18

8.16

-0.22

1.08

0.53

ICP-MS

3150

2.07

0.04

8.83

0.45

1.01

0.07

GFAAS

3167

2.10

0.15

7.86

-0.51

1.00

0.00

GFAAS

3513

2.01

-0.18

9.06

0.67

0.900

-0.66

ICP-MS (C/R)

3853

2.27

0.78

9.43

1.04

0.870

-0.86

ICP-MS

4090

2.16

0.37

8.47

0.09

0.880

-0.79

ICP-MS (C/R)

4953

1.78

-1.04

7.34

-1.03

0.815

-1.22

GFAAS

5556

1.96

-0.35

6.23

-2.13

1.04

0.25

GFAAS

5654

1.99

-0.24

8.50

0.12

1.30

1.96

ICP-MS (C/R)

5691

1.94

-0.44

8.08

-0.30

0.920

-0.53

ICP-MS

5881

2.02

-0.16

9.14

0.75

0.889

-0.73

ICP-MS (C/R)

5955

2.15

0.33

9.20

0.81

1.03

0.20

ND

6511

2.20

0.52

9.11

0.73

1.03

0.20

ND

6702

2.11

0.18

8.59

0.21

0.974

-0.17

GFAAS

7804

2.39

1.22

9.54

1.15

1.26

1.72

ND

8376

2.20

0.52

8.09

-0.29

1.10

0.64

GFAAS

8454

2.05

-0.04

6.20

-2.16

0.980

-0.13

GFAAS

9759

2.04

-0.08

>LL

---

1.03

0.20

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-A1407

2.06

0.0377

0.268

1.52 - 2.60

Accepted

---

PC-S-A1408

8.38

0.238

0.983

6.36 - 10.4

Accepted

---

PC-S-A1409

1.00

0.0305

0.148

0.697 - 1.30

Accepted

---

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

12

Statistics
Serum Aluminium (µmol/L)
All methods

PC-S-A1407

PC-S-A1408

32

29

32

Robust mean Algo A

2.06

8.38

1.00

Robust STDev

0.170

1.02

0.138

Median

2.05

8.47

1.01

STDev from MAD

0.156

0.988

0.141

Arithmetic mean

2.06

8.32

1.01

STDev

0.231

1.15

0.173

CV or Variability

8.3%

12.2%

13.8%

PC-S-A1407

PC-S-A1408

PC-S-A1409

15

13

15

Robust mean Algo A

2.05

7.61

1.00

Robust STDev

0.105

1.24

0.133

Median

2.05

7.65

1.01

0.0890

1.36

0.129

Arithmetic mean

2.00

7.72

1.00

STDev

0.248

1.33

0.208

CV or Variability

5.1%

16.3%

13.2%

PC-S-A1407

PC-S-A1408

PC-S-A1409

N

Graphite furnace-AAS
N

STDev from MAD

ICP-MS
N

PC-S-A1409

7

6

7

Robust mean Algo A

2.02

8.63

0.986

Robust STDev

0.128

0.604

0.136

Median

2.01

8.48

0.978

STDev from MAD

0.104

0.534

0.151

Arithmetic mean

2.07

8.79

0.986

STDev

0.253

0.811

0.120

CV or Variability

6.3%

7.0%

13.8%

PC-S-A1407

PC-S-A1408

PC-S-A1409

ICP-MS (collision/reaction cell)
N

5

5

5

2.03

8.90

0.912

0.0378

0.450

0.0349

Robust mean Algo A
Robust STDev
Median

2.02

9.06

0.900

STDev from MAD

0.0330

0.431

0.0297

Arithmetic mean

2.10

8.90

1.00

STDev

0.141

0.397

0.178

CV or Variability

1.9%

5.1%

3.8%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

13

Distribution
Serum Aluminium (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

14

Individual results
Serum Copper (µmol/L)
Round #2014-03

Participant

PC-S-E1407

z’-score

PC-S-E1408

z’-score

PC-S-E1409

z’-score

217

9.30

-0.07

13.2

-0.10

27.7

0.00

FAAS

226

9.65

0.35

13.2

-0.07

29.2

0.89

ICP-MS (C/R)

387

9.92

0.69

20.0

6.72

29.3

1.00

GFAAS

428

9.93

0.70

14.3

0.96

28.0

0.19

ICP-MS (C/R)

636

9.05

-0.39

12.9

-0.44

28.0

0.21

ICP-MS

744

8.07

-1.59

11.7

-1.58

24.2

-2.12

ND

747

9.16

-0.25

12.9

-0.40

26.7

-0.61

ICP-MS

1095

9.90

0.67

14.1

0.80

29.7

1.22

FAAS

1109

10.3

1.11

14.2

0.89

29.0

0.80

ND

1188

9.27

-0.11

13.1

-0.20

26.7

-0.61

ICP-MS (C/R)

1300

9.60

0.30

13.1

-0.24

28.0

0.19

FAAS

1855

11.7

2.94

11.6

-1.71

29.7

1.21

ICP-MS

2305

7.92

-1.78

11.5

-1.79

24.2

-2.16

ND

2516

6.37

-3.70

9.11

-4.21

23.0

-2.87

GFAAS

2580

8.70

-0.82

12.4

-0.91

27.6

-0.06

FAAS

2763

9.00

-0.45

12.9

-0.40

27.5

-0.12

ICP-MS (C/R)

2907

9.73

0.45

14.0

0.73

28.0

0.18

ICP-MS

2982

10.3

1.18

14.3

0.98

28.0

0.16

FAAS

3150

9.30

-0.07

13.4

0.10

26.3

-0.86

FAAS

3211

10.1

0.91

15.2

1.91

29.3

0.98

FAAS

3423

10.8

1.77

14.6

1.33

29.7

1.23

FAAS

3513

9.60

0.30

13.7

0.40

28.6

0.55

ICP-MS

3773

9.30

-0.07

13.6

0.29

28.5

0.49

ICP-MS (C/R)

3853

9.26

-0.12

13.4

0.11

29.7

1.23

ICP-MS

4082

8.98

-0.47

12.9

-0.40

2.68

-15.32

ICP-MS

4090

8.89

-0.58

12.4

-0.89

26.6

-0.69

ICP-MS (C/R)

4953

9.36

0.00

13.5

0.19

28.1

0.23

ICP-MS

5556

9.76

0.49

14.0

0.71

27.9

0.09

FAAS

5591

9.00

-0.45

15.5

2.21

29.6

1.16

GFAAS

5596

8.31

-1.30

12.1

-1.22

24.9

-1.73

ICP-MS (C/R)

5654

9.04

-0.40

12.9

-0.43

27.5

-0.15

ICP-MS (C/R)

5691

9.60

0.30

14.1

0.80

29.2

0.92

ICP-MS

5881

8.87

-0.61

12.7

-0.63

25.8

-1.18

ICP-MS (C/R)

5955

9.05

-0.38

13.0

-0.30

26.3

-0.86

ND

6511

8.99

-0.46

12.8

-0.49

27.2

-0.28

ND

6711

9.42

0.07

13.3

0.05

27.5

-0.14

FAAS

7311

9.79

0.53

13.8

0.54

28.3

0.39

ICP-MS

7804

9.45

0.11

12.2

-1.16

30.2

1.51

ND

8376

11.2

2.27

15.5

2.21

27.5

-0.12

FAAS

8454

9.96

0.74

13.6

0.30

27.2

-0.31

FAAS

8981

9.28

-0.10

14.2

0.91

25.5

-1.35

ND

9759

8.12

-1.53

11.9

-1.43

24.6

-1.91

FAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

PC-S-E1407

9.36

0.116

0.801

PC-S-E1408

13.3

0.207

0.973

PC-S-E1409

27.7

0.323

1.60

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

Method

K-S (Lilliefors)

Species

7.74 - 11.0

Accepted

---

11.3 - 15.3

Rejected1

---

24.4 - 31.0

Accepted

--15

Statistics
Serum Copper (µmol/L)
All methods

PC-S-E1407

PC-S-E1408

42

42

41

Robust mean Algo A

9.36

13.3

27.7

Robust STDev

0.601

1.07

1.65

Median

9.30

13.3

27.9

STDev from MAD

0.561

1.07

1.71

Arithmetic mean

9.36

13.4

27.6

STDev

0.890

1.56

1.73

CV or Variability

6.4%

8.1%

6.0%

PC-S-E1407

PC-S-E1408

PC-S-E1409

13

13

13

Robust mean Algo A

9.74

13.7

27.7

Robust STDev

0.744

0.932

0.560

Median

9.76

13.6

27.7

STDev from MAD

0.677

0.799

0.462

Arithmetic mean

9.73

13.7

27.8

STDev

0.815

1.03

1.38

CV or Variability

7.6%

6.8%

2.0%

PC-S-E1407

PC-S-E1408

PC-S-E1409

N

Flame-AAS
N

Graphite furnace-AAS
N

PC-S-E1409

3

3

3

Robust mean Algo A

8.62

14.9

29.2

Robust STDev

1.72

6.19

0.505

Median

9.00

15.5

29.3

STDev from MAD

1.36

6.64

0.400

Arithmetic mean

8.43

14.9

27.3

STDev

1.84

5.46

3.72

CV or Variability

20.0%

41.7%

1.7%

PC-S-E1407

PC-S-E1408

PC-S-E1409

ICP-MS
N

10

10

9

Robust mean Algo A

9.46

13.4

28.4

Robust STDev

0.403

0.667

0.628

Median

9.48

13.4

28.3

STDev from MAD

0.409

0.813

0.496

Arithmetic mean

9.63

13.3

28.5

STDev

0.794

0.750

0.953

CV or Variability

4.3%

5.0%

2.2%

PC-S-E1407

PC-S-E1408

PC-S-E1409

9

9

9

ICP-MS (collision/reaction cell)
N
Robust mean Algo A

9.11

13.0

27.2

Robust STDev

0.382

0.565

1.38

Median

9.04

12.9

27.5

STDev from MAD

0.342

0.496

1.31

Arithmetic mean

9.14

13.0

27.2

STDev

0.472

0.641

1.34

CV or Variability

4.2%

4.4%

5.1%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

16

Distribution
Serum Copper (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

17

Individual results
Serum Manganese (nmol/L)
Round #2014-03

Participant

PC-S-G1407

z’-score

PC-S-G1408

z’-score

PC-S-G1409

z’-score

Method

217

56.0

3.11

73.0

1.50

102

1.22

ICP-MS

323

32.0

-1.23

45.0

-1.75

65.0

-1.81

GFAAS
ICP-MS

747

39.1

0.05

62.5

0.28

93.6

0.53

1109

53.7

2.70

75.5

1.79

107

1.67

ND

1188

42.6

0.69

68.4

0.96

98.3

0.92

ICP-MS (C/R)

2629

39.7

0.16

51.7

-0.98

78.8

-0.68

GFAAS

2763

32.7

-1.10

51.2

-1.03

74.7

-1.02

ICP-MS (C/R)

4090

28.9

-1.78

53.8

-0.73

77.1

-0.82

ND

6511

38.4

-0.07

64.4

0.50

96.5

0.77

ND

8376

40.6

0.32

60.4

0.04

86.8

-0.02

GFAAS

9759

36.4

-0.43

54.6

-0.64

78.3

-0.72

ICP-MS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-G1407

38.8

2.32

5.01

27.8 - 49.8

Accepted

---

PC-S-G1408

60.1

4.16

7.55

42.9 - 77.3

Accepted

---

PC-S-G1409

87.1

5.69

10.8

62.7 - 111

Accepted

---

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

18

Statistics
Serum Manganese (nmol/L)
All methods

PC-S-G1407

PC-S-G1408

11

11

11

Robust mean Algo A

38.8

60.1

87.1

Robust STDev

6.16

11.0

15.1

Median

39.1

60.4

86.8

STDev from MAD

5.19

11.8

14.5

Arithmetic mean

40.0

60.1

87.1

STDev

8.41

9.73

13.3

CV or Variability

15.9%

18.4%

17.3%

PC-S-G1407

PC-S-G1408

PC-S-G1409

3

3

3

Robust mean Algo A

39.3

52.4

76.9

Robust STDev

1.71

8.78

12.5

Median

39.7

51.7

78.8

STDev from MAD

1.35

9.92

11.9

Arithmetic mean

37.4

52.4

76.9

STDev

4.72

7.74

11.0

CV or Variability

4.3%

16.8%

16.3%

PC-S-G1407

PC-S-G1408

PC-S-G1409

N

Graphite furnace-AAS
N

ICP-MS
N

PC-S-G1409

3

3

3

Robust mean Algo A

40.2

63.4

91.3

Robust STDev

5.04

10.5

13.6

Median

39.1

62.5

93.6

STDev from MAD

4.00

11.7

12.5

Arithmetic mean

43.8

63.4

91.3

STDev

10.6

9.23

12.0

CV or Variability

12.5%

16.5%

14.9%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

19

Distribution
Serum Manganese (nmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

20

Individual results
Serum Selenium (µmol/L)
Round #2014-03

Participant

PC-S-E1407

z’-score

PC-S-E1408

z’-score

PC-S-E1409

z’-score

217

0.930

0.09

1.78

0.99

2.77

0.30

Method
ICP-MS

226

0.903

-0.18

1.56

-0.46

2.77

0.32

ICP-MS (C/R)

428

0.833

-0.89

1.60

-0.23

2.58

-0.49

ICP-MS (C/R)

636

0.916

-0.05

1.63

0.03

2.72

0.10

ICP-MS

747

0.873

-0.49

1.55

-0.53

2.59

-0.47

ICP-MS

1095

1.06

1.42

1.59

-0.26

2.52

-0.76

GFAAS

1109

0.941

0.20

1.69

0.41

2.75

0.21

ND

1188

1.02

1.01

1.83

1.31

3.13

1.82

ICP-MS (C/R)

1300

1.00

0.81

1.73

0.64

3.04

1.43

HG-AAS

2305

1.06

1.42

1.65

0.13

2.66

-0.17

ND

2516

0.960

0.40

1.37

-1.71

2.32

-1.61

GFAAS

2763

0.860

-0.62

1.59

-0.26

2.74

0.17

ICP-MS (C/R)

3150

0.980

0.60

1.56

-0.46

2.57

-0.55

GFAAS

3513

0.860

-0.62

1.65

0.13

2.20

-2.12

ICP-MS (C/R)

3773

0.865

-0.57

1.61

-0.16

2.76

0.27

ICP-MS (C/R)

3853

0.950

0.30

1.71

0.53

3.09

1.65

ICP-MS (C/R)

4082

0.871

-0.51

1.63

0.00

2.68

-0.08

ICP-MS

4590

0.927

0.06

1.59

-0.26

2.76

0.25

GFAAS

4953

0.899

-0.22

1.62

-0.06

2.71

0.04

ICP-MS (C/R)

5556

0.906

-0.16

1.41

-1.47

2.22

-2.05

GFAAS

5596

0.852

-0.71

1.54

-0.62

2.53

-0.73

ICP-MS (C/R)

5654

0.913

-0.08

1.87

1.55

3.00

1.27

ICP-MS (C/R)

5691

0.750

-1.74

1.57

-0.39

2.64

-0.25

ICP-MS

5881

0.864

-0.58

1.57

-0.38

2.63

-0.28

ICP-MS (C/R)

5955

0.886

-0.36

1.63

0.00

2.72

0.08

ND

6511

0.973

0.53

1.68

0.30

2.72

0.07

ND

6545

1.00

0.80

1.78

0.99

2.78

0.34

ICP-MS

6711

0.610

-3.17

1.92

1.91

3.22

2.20

ICP-MS

7311

1.02

1.01

1.87

1.58

2.94

1.02

ICP-MS

7804

1.05

1.31

0.970

-4.34

1.54

-4.91

ND

8376

62.1

623.06

104

674.58

182

756.98

GFAAS

8454

0.610

-3.17

1.61

-0.13

2.72

0.08

GFAAS

9759

0.980

0.60

1.58

-0.36

2.56

-0.60

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-E1407

0.921

0.0182

0.0965

0.725 - 1.12

Accepted

---

PC-S-E1408

1.63

0.0197

0.151

1.33 - 1.93

Accepted

---

2.23 - 3.17

1

---

PC-S-E1409

2.70

0.0386

0.233

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

Rejected

21

Statistics
Serum Selenium (µmol/L)
All methods

PC-S-E1407

PC-S-E1408

32

32

32

Robust mean Algo A

0.921

1.63

2.70

Robust STDev

0.0824

0.0892

0.175

Median

0.915

1.62

2.72

STDev from MAD

0.0810

0.0822

0.157

Arithmetic mean

0.910

1.62

2.67

STDev

0.107

0.170

0.310

CV or Variability

8.9%

5.5%

6.5%

PC-S-E1407

PC-S-E1408

PC-S-E1409

7

7

7

Robust mean Algo A

0.953

1.57

2.52

Robust STDev

0.0573

0.0298

0.223

Median

0.960

1.58

2.56

STDev from MAD

0.0489

0.0230

0.240

Arithmetic mean

0.918

1.53

2.52

STDev

0.144

0.0980

0.197

CV or Variability

6.0%

1.9%

8.9%

PC-S-E1407

PC-S-E1408

PC-S-E1409

N

Graphite furnace-AAS
N

ICP-MS
N

PC-S-E1409

8

8

8

Robust mean Algo A

0.887

1.72

2.76

Robust STDev

0.117

0.158

0.146

Median

0.895

1.71

2.75

STDev from MAD

0.105

0.159

0.128

Arithmetic mean

0.871

1.72

2.79

STDev

0.135

0.140

0.202

CV or Variability

13.2%

9.2%

5.3%

PC-S-E1407

PC-S-E1408

PC-S-E1409

ICP-MS (collision/reaction cell)
N

11

11

11

Robust mean Algo A

0.884

1.62

2.75

Robust STDev

0.0397

0.0686

0.256

Median

0.865

1.61

2.74

STDev from MAD

0.0470

0.0654

0.232

Arithmetic mean

0.893

1.65

2.74

STDev

0.0539

0.109

0.268

4.5%

4.2%

9.3%

CV or Variability

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

22

Distribution
Serum Selenium (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

23

Individual results
Serum Zinc (µmol/L)
Round #2014-03

Participant

PC-S-E1407

z’-score

PC-S-E1408

z’-score

PC-S-E1409

z’-score

217

11.8

1.02

17.8

0.88

25.4

0.76

Method
FAAS

226

10.7

0.02

16.8

0.25

24.0

0.17

ICP-MS (C/R)

428

11.6

0.87

17.7

0.81

23.8

0.11

ICP-MS (C/R)

636

11.0

0.25

16.6

0.11

24.1

0.20

ICP-MS

744

9.52

-1.10

15.4

-0.58

22.2

-0.60

ND

747

10.0

-0.65

15.5

-0.55

23.1

-0.21

ICP-MS

1095

10.4

-0.28

15.6

-0.49

22.1

-0.64

FAAS

1109

12.2

1.38

19.5

1.90

26.8

1.38

ND

1188

9.96

-0.69

15.4

-0.61

22.4

-0.51

ICP-MS (C/R)

1300

7.03

-3.42

17.1

0.44

23.4

-0.09

FAAS

1855

13.4

2.54

14.3

-1.28

25.4

0.76

ICP-MS

2305

10.7

0.03

15.4

-0.63

22.0

-0.69

ND

2516

10.5

-0.19

16.4

0.00

23.0

-0.26

FAAS

2580

10.4

-0.28

16.4

0.00

23.6

0.00

FAAS

2763

10.3

-0.37

15.9

-0.31

23.1

-0.21

ICP-MS (C/R)

2907

10.2

-0.44

15.3

-0.70

24.4

0.36

ICP-MS

2982

7.12

-3.34

13.2

-1.96

17.7

-2.49

FAAS

3150

10.9

0.19

16.7

0.18

23.5

-0.04

FAAS

3211

11.1

0.37

17.4

0.61

23.7

0.04

FAAS

3423

10.7

0.01

16.4

-0.01

22.9

-0.30

FAAS

3513

11.5

0.75

17.6

0.73

24.5

0.38

ICP-MS

3773

10.5

-0.15

17.2

0.48

24.7

0.46

ICP-MS (C/R)

3853

11.2

0.42

17.2

0.51

25.5

0.82

ICP-MS

4082

10.2

-0.47

16.2

-0.12

22.8

-0.34

ICP-MS

4090

9.57

-1.06

15.4

-0.60

22.3

-0.57

ICP-MS (C/R)

4953

11.0

0.32

17.2

0.50

24.8

0.51

ICP-MS

5556

10.9

0.14

16.8

0.25

23.2

-0.15

FAAS

5591

11.5

0.75

16.8

0.24

23.9

0.13

FAAS

5596

10.1

-0.59

16.1

-0.18

22.3

-0.55

ICP-MS (C/R)

5654

10.6

-0.09

17.5

0.70

24.4

0.35

ICP-MS (C/R)

5691

11.3

0.56

17.9

0.92

25.3

0.72

ICP-MS

5881

9.95

-0.70

15.7

-0.42

22.1

-0.65

ICP-MS (C/R)

5955

9.93

-0.72

15.7

-0.43

22.2

-0.60

ND

6511

10.7

-0.04

16.4

-0.02

23.2

-0.19

ND

6711

12.0

1.19

17.1

0.45

25.8

0.92

ICP-MS

7311

11.2

0.45

17.2

0.47

24.4

0.33

ICP-MS

7804

LL

---

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-R1407

0.176

0.00828

0.0187

0.135 - 0.217

Rejected1

---

PC-U-R1408

0.684

0.0241

0.0578

0.559 - 0.809

Rejected1

---

PC-U-R1409

11.3

0.198

0.877

9.50 - 13.1

Accepted

---

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

33

Statistics
Urine Copper (µmol/L)
All methods

PC-U-R1407

PC-U-R1408

25

27

26

Robust mean Algo A

0.176

0.684

11.3

Robust STDev

0.0331

0.100

0.809

Median

0.173

0.680

11.2

STDev from MAD

0.0301

0.0983

0.714

Arithmetic mean

0.220

0.708

11.5

STDev

0.185

0.154

1.05

CV or Variability

18.8%

14.6%

7.2%

PC-U-R1407

PC-U-R1408

PC-U-R1409

4

4

3

Robust mean Algo A

0.159

0.641

11.4

Robust STDev

0.0326

0.0948

0.859

Median

0.161

0.655

11.6

STDev from MAD

0.0257

0.0820

0.680

N

Graphite furnace-AAS
N

PC-U-R1409

Arithmetic mean

0.156

0.641

11.3

STDev

0.0341

0.0836

0.974

CV or Variability

20.5%

14.8%

7.5%

PC-U-R1407

PC-U-R1408

PC-U-R1409

ICP-MS
N

10

10

10

Robust mean Algo A

0.202

0.708

11.3

Robust STDev

0.0304

0.0552

0.633

Median

0.199

0.699

11.3

STDev from MAD

0.0274

0.0465

0.738

Arithmetic mean

0.278

0.718

11.4

STDev

0.247

0.0681

0.668

CV or Variability

15.1%

7.8%

5.6%

PC-U-R1407

PC-U-R1408

PC-U-R1409

ICP-MS (collision/reaction cell)
N

7

7

6

Robust mean Algo A

0.160

0.655

10.8

Robust STDev

0.0232

0.0869

0.355

Median

0.168

0.658

10.9

STDev from MAD

0.0225

0.0797

0.297

Arithmetic mean

0.143

0.652

10.8

STDev

0.0541

0.0928

0.466

CV or Variability

14.5%

13.3%

3.3%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

34

Distribution
Urine Copper (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

35

Individual results
Urine Fluoride (µmol/L)
Round #2014-03

Participant

PC-U-F1407

z’-score

PC-U-F1408

z’-score

PC-U-F1409

z’-score

Method

176

208

-0.01

90.5

-0.17

1160

-0.34

FSE

1095

187

-1.63

78.0

-1.99

1180

0.00

FSE

1418

199

-0.66

89.0

-0.40

1210

0.39

FSE

1476

195

-1.01

84.0

-1.12

1080

-1.48

FSE

2629

189

-1.43

89.5

-0.32

1160

-0.34

FSE

4604

211

0.24

92.3

0.09

1190

0.14

FSE

5132

206

-0.16

90.7

-0.14

1130

-0.69

ND

5881

208

0.03

87.0

-0.68

1330

2.25

FSE

6200

212

0.28

93.7

0.29

1240

0.88

FSE

6234

213

0.39

95.2

0.51

1220

0.62

FSE

6545

209

0.09

95.1

0.49

1210

0.46

FSE

6702

214

0.46

91.7

0.00

1140

-0.60

FSE

7269

208

0.00

93.0

0.19

1220

0.59

FSE

8701

218

0.79

95.5

0.54

1240

0.91

ND

9759

208

-0.01

100

1.21

1050

-1.96

FSE

9908

214

0.44

95.3

0.52

1170

-0.08

FSE

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

208

2.08

12.7

182 - 234

Accepted

---

PC-U-F1408

91.7

1.36

6.75

77.9 - 105

Accepted

---

PC-U-F1409

1180

16.6

63.0

1050 - 1310

Accepted

---

PC-U-F1407

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

36

Statistics
Urine Fluoride (µmol/L)
All methods

PC-U-F1407

PC-U-F1408

N

16

16

16

Robust mean Algo A

208

91.7

1180

Robust STDev

6.65

4.36

53.0

Median

208

92.0

1180

STDev from MAD

6.05

4.56

51.2

Arithmetic mean

206

91.3

1180

STDev

8.95

5.21

64.6

CV or Variability

3.2%

4.8%

4.5%
PC-U-F1409

Fluoride specific electrode

PC-U-F1409

PC-U-F1407

PC-U-F1408

N

14

14

14

Robust mean Algo A

207

91.5

1180

Robust STDev

6.43

4.54

47.7

Median

208

92.0

1180

STDev from MAD

6.05

4.56

44.5

Arithmetic mean

205

91.0

1180

STDev

8.98

5.46

66.3

CV or Variability

3.1%

5.0%

4.0%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

37

Distribution
Urine Fluoride (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

38

Individual results
Urine Inorganic arsenic (µmol/L)
Round #2014-03

*

Participant

PC-U-S1407

z’-score

PC-U-S1408

z’-score

PC-U-S1409

z’-score

Method

217

0.380

2.28

1.34

0.00

6.31

0.07

GFAAS

317

0.280

0.00

1.24

-0.71

6.65

0.62

GFAAS

428

0.259

-0.48

1.40

0.44

5.77

-0.82

ICP-MS (C/R)

730

0.302

0.49

1.39

0.34

6.91

1.05

ICP-MS (C/R)

747

0.293

0.30

1.39

0.35

6.48

0.34

ICP-MS (C/R)

1095

0.280

0.00

1.39

0.35

6.78

0.83

GFAAS

1418

0.269

-0.26

1.35

0.10

5.82

-0.74

HG-AAS

1476

0.450

3.87

1.33

-0.07

4.99

-2.09

ICP-MS

1820

0.268

-0.27

1.33

-0.07

7.14

1.42

GFAAS

1827

0.243

-0.84

1.26

-0.57

5.99

-0.46

ICP-MS (C/R)

1865

0.195

-1.94

0.878

-3.27

6.50

0.38

HG-AAS

2580

0.275

-0.11

1.40

0.45

6.86

0.97

GFAAS

2978

0.274

-0.15

1.28

-0.42

5.87

-0.65

ICP-MS

3215

0.330

1.14

1.51

1.20

>LL

---

GFAAS

3423

0.240

-0.91

1.32

-0.13

6.37

0.16

HG-AAS

3853

0.327

1.07

1.37

0.18

6.30

0.04

ICP-MS (C/R)

5375

0.253

-0.61

1.39

0.35

7.22

1.55

ICP-MS

5495

0.315

0.79

1.47

0.89

6.07

-0.32

ICP-MS (C/R)

5691

0.320

0.91

1.17

-1.20

5.89

-0.62

ND

5881

0.237

-0.97

1.17

-1.21

6.10

-0.28

HG-AAS

6511

0.272

-0.18

1.38

0.30

6.27

-0.01

ND

6545

0.290

0.23

1.33

-0.07

5.97

-0.49

ICP-MS (C/R)

7162

0.160

-2.73

1.12

-1.56

5.97

-0.49

GFAAS

8701

0.284

0.09

1.43

0.62

5.96

-0.51

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

PC-U-S1407

0.280*

0.00979

0.0409

0.196 - 0.364

Accepted

MAA added

PC-U-S1408

1.34

0.0206

0.140

1.06 - 1.62

Accepted

Workers Profile

PC-U-S1409

6.27

0.123

0.600

5.05 - 7.49

Accepted

As+3 added

Species

The assigned value is outside the concentration range of our scope of accreditation.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

39

Statistics
Urine Inorganic arsenic (µmol/L)
All methods

PC-U-S1407

PC-U-S1408

24

24

23

Robust mean Algo A

0.280

1.34

6.27

Robust STDev

0.0384

0.0809

0.473

Median

0.278

1.35

6.27

STDev from MAD

0.0361

0.0727

0.451

N

PC-U-S1409

Arithmetic mean

0.283

1.32

6.27

STDev

0.0571

0.132

0.512

CV or Variability

13.7%

6.0%

7.5%

PC-U-S1407

PC-U-S1408

PC-U-S1409

7

7

6

Robust mean Algo A

0.281

1.34

6.64

Robust STDev

0.0222

0.111

0.430

Median

0.280

1.34

6.72

STDev from MAD

0.0178

0.0949

0.409

Graphite furnace-AAS
N

Arithmetic mean

0.282

1.33

6.62

STDev

0.0671

0.125

0.418

7.9%

8.3%

6.5%

PC-U-S1407

PC-U-S1408

PC-U-S1409

CV or Variability
Hydride generation-AAS
N

4

4

4

Robust mean Algo A

0.238

1.22

6.20

Robust STDev

0.0299

0.164

0.343

Median

0.239

1.25

6.23

STDev from MAD

0.0232

0.136

0.298

Arithmetic mean

0.235

1.18

6.20

STDev

0.0304

0.217

0.302

CV or Variability

12.6%

13.4%

5.5%

PC-U-S1407

PC-U-S1408

PC-U-S1409

ICP-MS
N

3

3

3

Robust mean Algo A

0.282

1.33

6.03

Robust STDev

0.0386

0.0617

1.27

Median

0.274

1.33

5.87

STDev from MAD

0.0306

0.0722

1.31

Arithmetic mean

0.326

1.33

6.03

STDev

0.108

0.0544

1.12

CV or Variability

13.7%

4.6%

21.1%

PC-U-S1407

PC-U-S1408

PC-U-S1409

7

7

7

ICP-MS (collision/reaction cell)
N
Robust mean Algo A

0.290

1.38

6.16

Robust STDev

0.0332

0.0400

0.332

Median

0.293

1.39

6.07

STDev from MAD

0.0322

0.0328

0.331

Arithmetic mean

0.290

1.37

6.21

STDev

0.0297

0.0640

0.387

CV or Variability

11.5%

2.9%

5.4%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

40

Distribution
Urine Inorganic arsenic (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

41

Individual results
Urine Iodide (µmol/L)
Round #2014-03

Participant

PC-U-I1407

z’-score

PC-U-I1408

z’-score

PC-U-I1409

z’-score

217

1.53

0.46

0.900

0.20

2.73

0.36

Method
ICP-MS

428

1.47

0.09

0.898

0.18

2.74

0.41

ICP-MS (C/R)

747

1.39

-0.46

0.841

-0.45

2.54

-0.33

ICP-MS

1095

1.75

1.90

0.923

0.45

3.07

1.60

ICP-MS (C/R)

1855

1.65

1.28

0.953

0.79

3.01

1.38

ICP-MS

2629

1340

8783.51

788

8733.80

2530

9206.59

ND

2763

1.45

-0.07

0.875

-0.08

2.59

-0.15

ICP-MS

2951

1.38

-0.53

0.900

0.20

2.38

-0.91

COLOR

3187

1.36

-0.66

0.809

-0.81

2.56

-0.26

ICP-MS

3513

1.27

-1.25

0.770

-1.24

2.29

-1.24

ICP-MS

4708

1.49

0.20

0.895

0.14

2.73

0.36

ICP-MS

5881

1.84

2.53

1.05

1.87

3.28

2.36

ICP-MS (C/R)

6200

1.51

0.35

0.932

0.55

2.75

0.43

ICP-MS

6511

1.36

-0.64

0.872

-0.11

2.58

-0.19

ND

6545

1.46

0.00

0.840

-0.47

2.58

-0.18

ICP-MS

8981

1.24

-1.44

0.760

-1.35

2.25

-1.38

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-I1407

1.46

0.0435

0.146

1.16 - 1.76

Accepted

---

PC-U-I1408

0.882

0.0185

0.0882

0.702 - 1.06

Accepted

---

PC-U-I1409

2.63

0.0785

0.263

2.08 - 3.18

Accepted

---

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

42

Statistics
Urine Iodide (µmol/L)
All methods

PC-U-I1407

PC-U-I1408

15

15

15

Robust mean Algo A

1.46

0.882

2.63

Robust STDev

0.135

0.0574

0.243

Median

1.46

0.895

2.59

STDev from MAD

0.119

0.0549

0.226

N

PC-U-I1409

Arithmetic mean

1.48

0.881

2.67

STDev

0.167

0.0732

0.283

CV or Variability

9.2%

6.5%

9.2%

PC-U-I1407

PC-U-I1408

PC-U-I1409

9

9

9

Robust mean Algo A

1.46

0.871

2.63

Robust STDev

0.108

0.0608

0.184

Median

1.46

0.875

2.59

STDev from MAD

0.104

0.0519

0.208

ICP-MS
N

Arithmetic mean

1.46

0.868

2.64

STDev

0.110

0.0589

0.197

CV or Variability

7.4%

7.0%

7.0%

PC-U-I1407

PC-U-I1408

PC-U-I1409

ICP-MS (collision/reaction cell)
N

3

3

3

Robust mean Algo A

1.71

0.933

3.03

Robust STDev

0.177

0.0462

0.306

Median

1.75

0.923

3.07

STDev from MAD

0.140

0.0366

0.306

Arithmetic mean

1.69

0.957

3.03

STDev

0.193

0.0816

0.269

CV or Variability

10.4%

5.0%

10.1%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

43

Distribution
Urine Iodide (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

44

Individual results
Urine Lead (µmol/L)
Round #2014-03

Participant

PC-U-P1407

z’-score

PC-U-P1408

z’-score

PC-U-P1409

z’-score

Method

176

0.555

0.21

0.285

1.14

4.68

1.13

ICP-MS

194

0.472

-1.69

0.234

-1.20

3.74

-1.61

ND

217

0.560

0.32

0.260

0.00

4.58

0.85

ICP-MS

747

0.547

0.02

0.258

-0.09

4.08

-0.62

ICP-MS

1095

0.620

1.69

0.270

0.46

4.21

-0.23

ICP-MS (C/R)

1109

0.533

-0.30

0.252

-0.35

4.13

-0.48

ND

1855

0.545

-0.01

0.256

-0.19

4.36

0.21

ICP-MS

2182

4.34

86.78

0.271

0.50

0.598

-10.83

GFAAS

3167

0.540

-0.14

0.260

0.00

4.54

0.73

GFAAS

3187

0.543

-0.07

0.260

0.00

4.24

-0.15

ICP-MS

3211

0.557

0.25

0.270

0.46

4.17

-0.36

GFAAS

3423

0.550

0.10

0.256

-0.17

4.51

0.65

GFAAS

3776

3.52

67.91

2.94

123.59

7.53

9.51

ND

3853

0.532

-0.32

0.254

-0.28

4.15

-0.42

ICP-MS

3970

0.512

-0.79

0.232

-1.31

6.15

5.45

GFAAS

4090

0.550

0.09

0.243

-0.79

4.36

0.21

ICP-MS (C/R)

4708

0.572

0.59

0.270

0.46

4.47

0.53

ICP-MS

4953

0.555

0.21

0.263

0.12

4.41

0.36

ICP-MS

5591

0.580

0.78

0.280

0.92

4.47

0.53

ICP-MS

5654

0.481

-1.50

0.246

-0.66

4.38

0.28

ICP-MS (C/R)

5691

0.540

-0.14

0.260

0.00

4.32

0.09

ICP-MS

5881

0.529

-0.38

0.250

-0.45

4.02

-0.80

ICP-MS (C/R)

6511

0.547

0.03

0.265

0.23

4.14

-0.43

ND

6545

0.540

-0.14

0.260

0.00

4.21

-0.23

ICP-MS

7111

0.547

0.02

0.266

0.28

4.30

0.02

ICP-MS

7804

0.648

2.33

0.0541

-9.51

3.35

-2.75

ND

9674

0.516

-0.68

0.247

-0.62

3.71

-1.71

GFAAS

9759

>LL

---

0.385

5.78

>LL

---

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-P1407

0.546

0.00419

0.0436

0.458 - 0.634

Rejected1

---

PC-U-P1408

0.260

0.00353

0.0213

0.217 - 0.303

Rejected1

---

1

---

PC-U-P1409

4.29

0.0662

0.334

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

3.61 - 4.97

Rejected

45

Statistics
Urine Lead (µmol/L)
All methods

PC-U-P1407

PC-U-P1408

25

28

27

Robust mean Algo A

0.546

0.260

4.29

Robust STDev

0.0168

0.0150

0.275

Median

0.547

0.260

4.30

STDev from MAD

0.0148

0.0147

0.255

Arithmetic mean

0.547

0.351

4.29

STDev

0.0358

0.509

1.07

3.1%

5.8%

6.4%

PC-U-P1407

PC-U-P1408

PC-U-P1409

5

7

6

Robust mean Algo A

0.535

0.261

4.27

Robust STDev

0.0229

0.0182

0.750

Median

0.540

0.260

4.34

STDev from MAD

0.0252

0.0159

0.618
3.95

N

CV or Variability
Graphite furnace-AAS
N

PC-U-P1409

Arithmetic mean

0.535

0.274

STDev

0.0202

0.0507

1.84

4.3%

7.0%

17.6%

PC-U-P1407

PC-U-P1408

PC-U-P1409

CV or Variability
ICP-MS
N

12

12

12

Robust mean Algo A

0.549

0.262

4.35

Robust STDev

0.0115

0.00530

0.191

Median

0.547

0.260

4.34

STDev from MAD

0.0111

0.00501

0.191

Arithmetic mean

0.551

0.264

4.36

STDev

0.0139

0.00951

0.176

2.1%

2.0%

4.4%

PC-U-P1407

PC-U-P1408

PC-U-P1409

CV or Variability
ICP-MS (collision/reaction cell)
N

4

4

4

Robust mean Algo A

0.544

0.249

4.26

Robust STDev

0.0641

0.00642

0.156

Median

0.540

0.248

4.29

STDev from MAD

0.0515

0.00533

0.130

Arithmetic mean

0.545

0.252

4.24

STDev

0.0579

0.0122

0.170

CV or Variability

11.8%

2.6%

3.7%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

46

Distribution
Urine Lead (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

47

Individual results
Urine Mercury (nmol/L)
Round #2014-03
Participant

PC-U-H1407

z’-score

PC-U-H1408

z’-score

PC-U-H1409

z’-score

Method

176

74.8

0.67

414

0.52

1380

0.82

ICP-MS

217

65.0

-0.18

347

-0.88

1340

0.53

ICP-MS

428

85.2

1.58

488

2.07

1510

1.70

ICP-MS (C/R)

720

34.9

-2.81

309

-1.67

1220

-0.30

CV

744

79.1

1.05

465

1.60

1650

2.61

ND

1095

69.0

0.17

396

0.15

1250

-0.09

CV

1109

65.8

-0.11

401

0.26

1260

-0.02

ND

1156

24.4

-3.73

202

-3.91

646

-4.16

ND

1418

61.9

-0.45

343

-0.95

1090

-1.16

ND

1865

74.3

0.63

419

0.62

1290

0.21

CV

2629

58.3

-0.77

367

-0.46

1260

0.01

ICP-MS (C/R)

2982

61.0

-0.53

410

0.44

1040

-1.51

CV

3187

60.7

-0.56

366

-0.48

1140

-0.81

ICP-MS

3468

80.7

1.18

401

0.24

1520

1.75

GA-AAS

3513

66.0

-0.10

358

-0.65

1160

-0.68

ICP-MS

3853

69.2

0.18

404

0.31

1320

0.44

ICP-MS

4604

65.0

-0.18

25.4

-7.60

136

-7.63

CV

4708

68.9

0.16

409

0.42

1330

0.44

ICP-MS

4953

71.3

0.37

408

0.40

1370

0.75

ICP-MS

5029

50.5

-1.45

231

-3.31

718

-3.68

ND

5491

60.0

-0.62

428

0.82

1420

1.07

CV

5591

65.3

-0.16

369

-0.43

1250

-0.10

ICP-MS

5654

94.2

2.37

467

1.62

1490

1.54

ICP-MS (C/R)

5691

69.0

0.17

361

-0.59

1380

0.79

ICP-MS

5881

64.8

-0.20

376

-0.26

1230

-0.23

ICP-MS (C/R)

6200

61.6

-0.48

356

-0.70

1220

-0.29

ICP-MS

6210

66.3

-0.07

361

-0.59

1200

-0.42

ND

6511

106

3.41

430

0.86

1480

1.52

ND

6545

70.0

0.25

489

2.08

1670

2.78

ICP-MS

6702

70.5

0.30

398

0.19

1380

0.79

CV

6794

73.8

0.58

393

0.08

1290

0.18

GA-AAS

6892

65.5

-0.14

360

-0.61

1200

-0.43

ND

6920

56.8

-0.90

927

11.24

323

-6.36

ND

7184

70.4

0.29

422

0.69

1350

0.63

CV

7190

62.8

-0.37

388

-0.01

>LL

---

ICP-MS (C/R)

7269

68.0

0.08

397

0.17

1210

-0.35

CV

7864

69.0

0.17

333

-1.17

1150

-0.76

ND

8701

61.2

-0.51

345

-0.92

1150

-0.72

ND

9674

66.8

-0.03

370

-0.40

962

-2.02

CV

9759

84.8

1.54

439

1.04

>LL

---

GA-AAS

9777

68.7

0.14

383

-0.12

1270

0.09

GA-AAS

PC-U-H1407

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

67.1

1.38

11.4

44.2 - 90.0

Rejected1

---

1

PC-U-H1408

389

9.12

46.9

293 - 485

Rejected

---

PC-U-H1409

1260

34.7

143

965 - 1550

Accepted

---

Criteria of homogeneity: according to ISO/CEI 17043 criteria, mercury in material PC-U-H1407 doesn’t respect acceptable heterogeneity. The
statistical data are produced as an indication only.
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

48

Statistics
Urine Mercury (nmol/L)
All methods

PC-U-H1407

PC-U-H1408

41

41

39

Robust mean Algo A

67.1

389

1260

Robust STDev

7.06

46.7

173

Median

66.8

393

1260

STDev from MAD

6.65

46.9

163

Arithmetic mean

67.4

389

1210

STDev

13.3

117

308

CV or Variability

10.5%

12.0%

13.7%

PC-U-H1407

PC-U-H1408

PC-U-H1409

10

10

10

Robust mean Algo A

66.6

393

1200

Robust STDev

5.35

33.6

195

Median

67.4

398

1230

STDev from MAD

4.52

33.9

197

Arithmetic mean

64.0

357

1120

STDev

11.1

122

376

CV or Variability

8.0%

8.5%

16.2%

PC-U-H1407

PC-U-H1408

PC-U-H1409

N

Cold vapor
N

Gold amalgamation-AAS
N

PC-U-H1409

4

4

3

Robust mean Algo A

77.0

398

1290

Robust STDev

8.11

15.5

23.0

Median

77.2

397

1290

STDev from MAD

8.13

12.7

18.2

Arithmetic mean

77.0

404

1360

STDev

7.15

24.3

138

CV or Variability

10.5%

3.9%

1.8%

PC-U-H1407

PC-U-H1408

PC-U-H1409

ICP-MS
N

11

11

11

Robust mean Algo A

67.6

382

1310

Robust STDev

4.18

31.0

95.2

Median

68.9

369

1330

STDev from MAD

4.30

31.9

82.9

Arithmetic mean

67.4

389

1320

STDev

4.18

41.4

143

CV or Variability

6.2%

8.1%

7.3%

PC-U-H1407

PC-U-H1408

PC-U-H1409

5

5

4
1370

ICP-MS (collision/reaction cell)
N
Robust mean Algo A

68.9

401

Robust STDev

11.0

37.5

168

Median

64.8

388

1370

STDev from MAD

9.61

31.8

185

Arithmetic mean

73.1

417

1370

STDev

15.7

55.9

148

CV or Variability

16.0%

9.4%

12.3%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

49

Distribution
Urine Mercury (nmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

50

Individual results
Urine Selenium (µmol/L)
Round #2014-03

Participant

PC-U-N1407

z’-score

PC-U-N1408

z’-score

PC-U-N1409

z’-score

Method

747

2.95

-0.10

1.23

0.16

1.78

0.00

ICP-MS

3187

2.89

-0.24

1.14

-0.21

1.70

-0.27

ICP-MS

3423

2.37

-1.50

1.03

-0.66

1.81

0.11

HG-AAS

3853

3.34

0.85

1.30

0.45

1.92

0.48

ICP-MS (C/R)

4090

2.99

0.00

1.20

0.04

1.73

-0.17

ICP-MS (C/R)

5691

2.72

-0.65

1.11

-0.33

1.51

-0.93

ICP-MS

5881

3.11

0.28

1.17

-0.10

1.76

-0.05

ICP-MS (C/R)

6511

3.77

1.88

1.58

1.62

2.31

1.83

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-N1407

2.99

0.145

0.388

2.16 - 3.82

Accepted

Workers Profile

PC-U-N1408

1.19

0.0460

0.239

0.703 - 1.68

Accepted

Se+4 added

PC-U-N1409

1.78

0.0451

0.288

1.20 - 2.36

Accepted

Workers Profile

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

51

Statistics
Urine Selenium (µmol/L)
All methods

PC-U-N1407

PC-U-N1408

8

8

8

Robust mean Algo A

2.99

1.19

1.78

Robust STDev

0.329

0.104

0.102

Median

2.97

1.18

1.77

STDev from MAD

0.286

0.0890

0.0847

N

PC-U-N1409

Arithmetic mean

3.02

1.22

1.82

STDev

0.415

0.168

0.232

CV or Variability

11.0%

8.8%

5.7%

PC-U-N1407

PC-U-N1408

PC-U-N1409

3

3

3

Robust mean Algo A

2.87

1.15

1.67

Robust STDev

0.112

0.0562

0.150

Median

2.89

1.14

1.70

0.0890

0.0445

0.119

ICP-MS
N

STDev from MAD
Arithmetic mean

2.85

1.16

1.66

STDev

0.119

0.0625

0.139

CV or Variability

3.9%

4.9%

9.0%

PC-U-N1407

PC-U-N1408

PC-U-N1409

ICP-MS (collision/reaction cell)
N

3

3

3

Robust mean Algo A

3.15

1.21

1.78

Robust STDev

0.202

0.0645

0.0640

Median

3.11

1.20

1.76

STDev from MAD

0.171

0.0511

0.0507

Arithmetic mean

3.15

1.22

1.80

STDev

0.178

0.0698

0.101

CV or Variability

6.4%

5.3%

3.6%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

52

Distribution
Urine Selenium (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

53

Individual results
Urine Total arsenic (µmol/L)
Round #2014-03

Participant

PC-U-S1407

z’-score

PC-U-S1408

z’-score

PC-U-S1409

z’-score

176

0.387

0.36

1.55

0.89

6.67

0.32

Method
ICP-MS

730

0.387

0.36

1.39

-0.42

6.93

0.81

ICP-MS (C/R)
ICP-MS

747

0.338

-0.82

1.34

-0.82

5.80

-1.38

1109

0.448

1.83

1.71

2.17

7.41

1.75

ND

1476

0.360

-0.29

1.39

-0.41

5.49

-1.98

ICP-MS

1827

0.329

-1.03

1.32

-0.98

5.98

-1.03

ICP-MS (C/R)

1865

0.386

0.33

1.53

0.72

6.89

0.73

ICP-MS (C/R)

2182

0.423

1.23

1.52

0.67

6.81

0.58

GFAAS

2937

0.493

2.90

1.60

1.33

7.10

1.15

ICP-MS

2978

0.367

-0.12

1.41

-0.21

6.19

-0.62

ICP-MS

3187

0.377

0.12

1.43

-0.08

6.22

-0.56

ICP-MS

3423

0.347

-0.60

1.41

-0.21

6.30

-0.41

HG-AAS

3513

0.360

-0.29

1.47

0.25

6.36

-0.29

ICP-MS

3853

0.372

0.00

1.52

0.62

6.74

0.44

ICP-MS (C/R)

4708

0.370

-0.05

1.41

-0.25

6.58

0.14

ICP-MS

4953

0.342

-0.73

1.44

0.01

6.63

0.24

ICP-MS (C/R)

5375

0.343

-0.70

1.40

-0.33

7.24

1.42

ICP-MS

5495

0.400

0.67

1.48

0.34

6.13

-0.74

ICP-MS (C/R)

5591

0.403

0.74

1.61

1.39

7.48

1.89

ICP-MS

5654

0.349

-0.55

1.29

-1.19

5.25

-2.45

ICP-MS (C/R)

5691

0.380

0.19

1.45

0.08

6.22

-0.56

ND

5881

0.383

0.27

1.51

0.59

6.68

0.33

ICP-MS (C/R)

6511

0.382

0.23

1.43

-0.04

6.59

0.16

ND

6545

0.370

-0.05

1.43

-0.08

6.31

-0.39

ICP-MS (C/R)

6892

0.400

0.67

1.34

-0.82

5.45

-2.06

ND

7864

0.334

-0.91

1.40

-0.33

6.45

-0.12

ND

9674

0.266

-2.55

1.31

-1.08

6.90

0.76

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

PC-U-S1407

0.372

0.00764

0.0410

0.289 - 0.455

Accepted

MAA added

PC-U-S1408

1.44

0.0205

0.120

1.20 - 1.68

Accepted

Workers Profile

PC-U-S1409

6.51

0.127

0.498

5.48 - 7.54

Accepted

As+3 added

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

Species

54

Statistics
Urine Total arsenic (µmol/L)
All methods

PC-U-S1407

PC-U-S1408

27

27

27

Robust mean Algo A

0.372

1.44

6.51

Robust STDev

0.0317

0.0851

0.526

Median

0.372

1.43

6.58

STDev from MAD

0.0343

0.0757

0.515

N

PC-U-S1409

Arithmetic mean

0.374

1.45

6.47

STDev

0.0418

0.0977

0.567

8.5%

5.9%

8.1%

PC-U-S1407

PC-U-S1408

PC-U-S1409

10

10

10

Robust mean Algo A

0.370

1.44

6.51

Robust STDev

0.0237

0.0675

0.718

Median

0.369

1.42

6.47

STDev from MAD

0.0201

0.0593

0.673

CV or Variability
ICP-MS
N

Arithmetic mean

0.380

1.46

6.51

STDev

0.0442

0.0938

0.634

6.4%

4.7%

11.0%

PC-U-S1407

PC-U-S1408

PC-U-S1409

CV or Variability
ICP-MS (collision/reaction cell)
N

9

9

9

Robust mean Algo A

0.370

1.43

6.47

Robust STDev

0.0249

0.0972

0.429

Median

0.372

1.44

6.63

STDev from MAD

0.0224

0.105

0.435

Arithmetic mean

0.369

1.43

6.39

STDev

0.0238

0.0857

0.540

6.7%

6.8%

6.6%

CV or Variability

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

55

Distribution
Urine Total arsenic (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

56

Individual results
Urine Zinc (µmol/L)
Round #2014-03

Participant

PC-U-R1407

z’-score

PC-U-R1408

z’-score

PC-U-R1409

z’-score

Method

176

4.42

0.39

4.91

0.04

24.6

0.24

ICP-MS

747

4.29

0.05

4.99

0.22

25.5

0.67

ICP-MS

1095

4.45

0.47

5.17

0.63

24.9

0.38

FAAS

1109

4.61

0.90

5.40

1.15

26.0

0.90

ND

1188

4.01

-0.68

4.33

-1.25

22.1

-0.95

ICP-MS (C/R)

1418

4.05

-0.57

4.36

-1.19

22.0

-0.99

ICP-MS (C/R)

2629

3.41

-2.26

4.03

-1.92

21.1

-1.45

ICP-OES

2763

4.17

-0.26

4.88

-0.02

24.0

-0.05

ICP-MS (C/R)

3187

3.83

-1.16

4.36

-1.19

23.5

-0.29

ICP-MS

3211

4.60

0.87

5.50

1.37

25.3

0.57

FAAS

3423

5.06

2.07

5.79

2.01

26.6

1.20

FAAS

3513

3.90

-0.97

4.60

-0.65

25.6

0.71

ICP-MS

3853

4.04

-0.60

4.76

-0.29

23.0

-0.51

ICP-MS

4090

3.27

-2.63

3.98

-2.04

23.4

-0.32

ICP-MS (C/R)

4708

4.24

-0.08

4.96

0.16

24.4

0.14

ICP-MS

4953

4.11

-0.41

4.82

-0.17

23.2

-0.42

ICP-MS

5591

4.00

-0.71

4.90

0.02

23.4

-0.33

FAAS

5691

4.30

0.08

4.80

-0.20

24.4

0.14

ICP-MS

5881

3.68

-1.54

4.37

-1.16

21.9

-1.03

ICP-MS (C/R)

6511

4.62

0.91

5.32

0.96

26.3

1.07

ND

7804

4.79

1.36

1.45

-7.70

6.52

-8.36

ND

8376

4.28

0.02

5.10

0.46

24.5

0.18

FAAS

8454

4.90

1.66

5.37

1.07

24.5

0.19

FAAS

8981

4.28

0.03

6.11

2.73

22.6

-0.71

ND

9759

6.38

5.56

6.69

4.03

26.5

1.13

FAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-R1407

4.27

0.109

0.364

3.51 - 5.03

Accepted

---

PC-U-R1408

4.89

0.159

0.418

4.00 - 5.78

Accepted

---

19.9 - 28.3

1

---

PC-U-R1409

24.1

0.438

2.06

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

Rejected

57

Statistics
Urine Zinc (µmol/L)
All methods

PC-U-R1407

PC-U-R1408

25

25

25

Robust mean Algo A

4.27

4.89

24.1

Robust STDev

0.435

0.637

1.75

Median

4.28

4.90

24.4

STDev from MAD

0.411

0.697

1.77
23.4

N

PC-U-R1409

Arithmetic mean

4.31

4.84

STDev

0.606

0.943

3.84

CV or Variability

10.2%

13.0%

7.3%

PC-U-R1407

PC-U-R1408

PC-U-R1409

7

7

7

Robust mean Algo A

4.66

5.40

25.0

Robust STDev

0.523

0.437

0.803

Median

4.60

5.37

24.9

STDev from MAD

0.478

0.405

0.615
25.1

Flame-AAS
N

Arithmetic mean

4.81

5.50

STDev

0.781

0.598

1.15

CV or Variability

11.2%

8.1%

3.2%

PC-U-R1407

PC-U-R1408

PC-U-R1409

ICP-MS
N

8

8

8

Robust mean Algo A

4.15

4.80

24.3

Robust STDev

0.222

0.186

1.11

Median

4.18

4.81

24.4

STDev from MAD

0.193

0.187

1.48

Arithmetic mean

4.14

4.77

24.3

STDev

0.207

0.208

0.979

CV or Variability

5.3%

3.9%

4.6%

PC-U-R1407

PC-U-R1408

PC-U-R1409

ICP-MS (collision/reaction cell)
N

5

5

5

Robust mean Algo A

3.91

4.35

22.2

Robust STDev

0.263

0.0516

0.280

Median

4.01

4.36

22.1

STDev from MAD

0.237

0.0403

0.239

Arithmetic mean

3.84

4.38

22.7

STDev

0.365

0.321

0.950

CV or Variability

6.7%

1.2%

1.3%

When fewer than 20 results were considered for statistical treatment of all or a sub-sample of
results, the accuracy of statistical data may be questionable.

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

58

Distribution
Urine Zinc (µmol/L)

Centre de toxicologie du Québec/INSPQ - External quality assessment schemes

59

Interlaboratory Comparison Program
for Metals in Biological Matrices

ASSIGNED VALUES
ROUND:
2014-03
SHIPPED ON: 2014-04-22
DEADLINE: 2014-05-30
MATRIX

Blood

Serum

Urine

ANALYTE

UNIT

PTM

ASSIGNED
VALUE

PTM

ASSIGNED
VALUE

PTM

ASSIGNED
VALUE

Cadmium

nmol/L

PC-B-C1407

84.4

PC-B-C1408

15.4

PC-B-C1409

32.4

Lead

µmol/L

PC-B-L1407

0.154

PC-B-L1408

0.433

PC-B-L1409

1.75

Mercury

nmol/L

PC-B-M1407

171

PC-B-M1408

12.2

PC-B-M1409

81.2

Aluminium

µmol/L

PC-S-A1407

2.06

PC-S-A1408

8.38

PC-S-A1409

1.00

Copper

µmol/L

PC-S-E1407

9.36

PC-S-E1408

13.3

PC-S-E1409

27.7

Manganese

nmol/L

PC-S-G1407

38.8

PC-S-G1408

60.1

PC-S-G1409

87.1

Selenium

µmol/L

PC-S-E1407

0.921

PC-S-E1408

1.63

PC-S-E1409

2.70

Zinc

µmol/L

PC-S-E1407

10.7

PC-S-E1408

16.4

PC-S-E1409

23.6

Cadmium

nmol/L

PC-U-D1407

27.5

PC-U-D1408

82.7

PC-U-D1409

10.8

Chromium

nmol/L

PC-U-B1407

307

PC-U-B1408

27.9

PC-U-B1409

147

Copper

µmol/L

PC-U-R1407

0.176

PC-U-R1408

0.684

PC-U-R1409

11.3

Fluoride

µmol/L

PC-U-F1407

208

PC-U-F1408

91.7

PC-U-F1409

1180

Inorganic arsenic

µmol/L

PC-U-S1407

0.280

PC-U-S1408

1.34

PC-U-S1409

6.27

Iodide

µmol/L

PC-U-I1407

1.46

PC-U-I1408

0.882

PC-U-I1409

2.63

Lead

µmol/L

PC-U-P1407

0.546

PC-U-P1408

0.260

PC-U-P1409

4.29

Mercury

nmol/L

PC-U-H1407

67.1

PC-U-H1408

389

PC-U-H1409

1260

Selenium

µmol/L

PC-U-N1407

2.99

PC-U-N1408

1.19

PC-U-N1409

1.78

Total arsenic

µmol/L

PC-U-S1407

0.372

PC-U-S1408

1.44

PC-U-S1409

6.51

Zinc

µmol/L

PC-U-R1407

4.27

PC-U-R1408

4.89

PC-U-R1409

24.1

Centre de toxicologie/INSPQ

945, Ave Wolfe
Quebec, QC
Canada, G1V 5B3

Phone: (418) 650-5115 Ext. 5254
Fax : (418) 654-2148
E-mail : [email protected]
http://www.inspq.qc.a/ctq

60

Interlaboratory Comparison Program for Metals in
Biological Matrices (PCI)

GROUPING OF ANALYTICAL METHODS
FOR STATISTICS
METHODS GROUPING
CODE

METHODS GROUPING

METHODS INCLUDED

METHODS CODE

Atomic fluorescence

AFS

AFS

Atomic fluorescence

Cold vapor-atomic
fluorescence

CV-AFS

COLOR

Colorimetry

Colorimetry

Color

CV

Cold vapor

Cold vapor

CV

Cold vapor-AAS

CV-AAS

ESA

ESA Lead Care TM
system

ESA Lead Care TM
system

ESA Lead

FAAS

Flame-AAS

Flame-AAS

FAAS

FSE

Fluoride specific
electrode

Fluoride specific
electrode

FSE

GA-AAS

Gold amalgamationAAS

Gold amalgamationAAS

AA-Gold A

Deuterium and otherGraphite furnace-AAS

D2-GFAAS

Zeeman-Graphite
furnace-AAS

Z-GFAAS

GFAAS

Graphite furnace-AAS

HG-AAS

Hydride generationAAS

Hydride generationAAS

HG-AAS

HR-ICP-MS

ICP-MS (high
resolution)

ICP-MS (high
resolution)

HR-ICP-MS

ICP-MS

ICP-MS

ICP-MS (isotopic
dilution)

ID-ICP-MS

ICP-MS (laser
ablation/furnace)

ICP-MS (LA)

ICP-MS

ICP-MS

ICP-MS (C/R)

ICP-MS
(collision/reaction
cell)

ICP-MS
(collision/reaction
cell)

ICP-MS(C/R)

ICP-OES

ICP-OES (optical
emission)

ICP-OES (optical
emission)

ICP-OES

POL

Polarography

Polarography

Polaro

Centre de toxicologie/INSPQ

945, Ave Wolfe
Quebec, QC
Canada, G1V 5B3

Phone: (418) 650-5115 Ext. 5254
Fax : (418) 654-2148
E-mail : [email protected]
http://www.inspq.qc.a/ctq
61

Interlaboratory Comparison Program
for Metals in Biological Matrices (PCI)

1. Kolmogorov-Smirnov (Lilliefors) test
The Kolmogorov-Smirnov (Lilliefors) statistical test is a tool used to evaluate the normality
of a distribution of results. The test can be performed with N ≥ 4.
The power of the test increases rapidly with the number of observations. For≥ N30, the
test will be sensitive to account for small deviations from normality even with the presence
of only one outlier.
For a small sample size (N ≤ 10), the hypothesis that the observations follow a normal
distribution will generally be accepted. However, if normality is rejected for N≤ 10, this
indicates that the observations are far from following a normal distribution and that one or
more observations are most likely outliers.
When the normality hypothesis is rejected, the use of robust methods for the determination
of the AV by consensus such as the Algorithm A allows to obtain a better estimation of the
AV. Outliers are retained except if their deviation from the other observations can be
clearly explained as indicated in section 1.1.
The normality hypothesis is rejected when the statistical value is too weak according to the
Kolmogorov-Smirnov (Lilliefors) critical value table. The result of the normality of the
distribution of each set of observations is provided in the report whether the test is
“Accepted” or “Rejected” under the column labeled “KS (Lilliefors)”.

*** END OF REPORT ***

Centre de toxicologie/INSPQ

945, Wolfe Avenue
Quebec, QC
Canada, G1V 5B3

Phone: (418) 650-5115, ext. 5254
Fax: (418) 654-2148
E-mail: [email protected]
http://www.inspq.qc.ca/ctq
62


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AuthorDavid Bisson
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