Interlaboratory Comparison Program for Metals in Biological Matrices

Att9d PCI 2014-01 Anglais.pdf

Biomonitoring of Great Lakes Populations Program II

Interlaboratory Comparison Program for Metals in Biological Matrices

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INTERLABORATORY COMPARISON PROGRAM
FOR METALS IN BIOLOGICAL MATRICES
(PCI)

Centre de toxicologie/INSPQ

REPORT FOR ROUND:

2014-01

PTMS SHIPPING DATE:

2014-01-20

DATE OF PUBLICATION:

2014-03-19

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

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 2014-01.
Participating laboratories are identified only by their unique subscription number.
Identity of participants will be kept strictly confidential by the PCI organizer.
All analytes meet the homogeneity criteria as per ISO/CEI 17043 and 13528
guidelines.
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
Program Coordinators
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 #2014-01

Participant

PC-B-C1401

z’-score

PC-B-C1402

z’-score

PC-B-C1403

z’-score

Method

176

7.12

-1.01

98.7

-0.60

22.2

-0.35

ICP-MS

194

10.1

0.70

113

1.03

29.9

2.43

ND

217

8.27

-0.35

103

-0.14

21.4

-0.64

ICP-MS

323

11.0

1.22

88.0

-1.83

22.0

-0.43

GFAAS

744

11.0

1.23

93.9

-1.15

25.1

0.69

ND

747

8.25

-0.36

101

-0.34

22.0

-0.43

ICP-MS

1095

9.00

0.07

114

1.14

24.0

0.29

ICP-MS (C/R)

1109

10.7

1.03

117

1.43

27.6

1.59

ND

1188

9.87

0.57

103

-0.11

24.1

0.33

ICP-MS (C/R)

1418

8.63

-0.14

107

0.31

23.8

0.20

ICP-MS (C/R)

1865

8.45

-0.25

108

0.42

22.9

-0.12

ICP-MS (C/R)

2305

98.6

51.61

2.19

-11.64

6.67

-5.99

ND

2991

8.27

-0.35

113

1.08

27.2

1.46

ND

3187

8.01

-0.50

103

-0.11

21.9

-0.47

ICP-MS

3211

6.10

-1.60

98.7

-0.61

19.9

-1.20

GFAAS

3215

7.10

-1.02

104

0.00

26.8

1.30

GFAAS

3248

9.70

0.47

74.5

-3.37

35.3

4.39

GFAAS

3853

11.5

1.51

105

0.15

25.1

0.70

ICP-MS

4708

8.30

-0.33

106

0.23

22.6

-0.22

ICP-MS

4953

8.10

-0.45

107

0.31

22.2

-0.38

ICP-MS

5591

7.80

-0.62

97.8

-0.71

22.3

-0.33

ICP-MS

5654

9.43

0.32

92.0

-1.37

23.0

-0.06

ICP-MS (C/R)

5691

9.00

0.07

112

0.91

24.0

0.29

ICP-MS

6511

8.90

0.01

104

0.01

22.2

-0.35

ND

6545

4.14

-2.73

71.5

-3.71

20.8

-0.87

ICP-MS

6689

12.4

2.00

113

1.00

26.2

1.07

ND

6794

9.70

0.47

95.0

-1.03

23.5

0.10

GFAAS

6858

4.55

-2.49

105

0.13

18.4

-1.74

ICP-MS

7760

8.60

-0.16

108

0.48

25.2

0.73

ICP-MS

9777

11.1

1.29

115

1.30

21.9

-0.45

GFAAS

PC-B-C1401

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

8.88

0.382

1.70

5.40 - 12.4

Accepted

---

PC-B-C1402

104

1.98

8.51

86.5 - 121

Accepted

---

PC-B-C1403

23.2

0.440

2.72

17.7 - 28.7

Accepted

---

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

2

Statistics
Blood Cadmium (nmol/L)
All methods

PC-B-C1401

PC-B-C1402

29

29

30

Robust mean Algo A

8.88

104

23.2

Robust STDev

1.64

8.55

1.93

Median

8.63

104

23.0

STDev from MAD

1.58

7.98

1.63

Arithmetic mean

8.80

102

23.3

STDev

1.89

10.9

4.51

CV or Variability

18.5%

8.2%

8.3%

PC-B-C1401

PC-B-C1402

PC-B-C1403

6

6

6

Robust mean Algo A

9.21

96.6

23.5

Robust STDev

2.17

14.1

3.18

Median

9.70

96.9

22.7

STDev from MAD

2.02

11.9

2.70

Arithmetic mean

9.12

95.9

24.9

STDev

2.07

14.0

5.59

CV or Variability

23.5%

14.6%

13.5%

PC-B-C1401

PC-B-C1402

PC-B-C1403

N

Graphite furnace-AAS
N

ICP-MS
N

PC-B-C1403

12

12

12

Robust mean Algo A

8.10

104

22.2

Robust STDev

0.701

4.70

1.04

Median

8.17

104

22.2

STDev from MAD

0.595

4.26

0.860

Arithmetic mean

7.80

102

22.3

STDev

1.93

10.3

1.86

CV or Variability

8.6%

4.5%

4.7%

PC-B-C1401

PC-B-C1402

PC-B-C1403

ICP-MS (collision/reaction cell)
N

5

5

5

Robust mean Algo A

9.08

106

23.6

Robust STDev

0.659

6.56

0.603

Median

9.00

107

23.8

STDev from MAD

0.637

5.56

0.516

Arithmetic mean

9.08

105

23.6

STDev

0.581

8.12

0.565

CV or Variability

7.3%

6.2%

2.6%

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

3

Distribution
Blood Cadmium (nmol/L)

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

4

Individual results
Blood Lead (µmol/L)
Round #2014-01

Participant

PC-B-L1401

z’-score

PC-B-L1402

z’-score

PC-B-L1403

z’-score

Method

194

1.06

-2.74

0.307

0.44

2.89

-3.42

ND

217

1.39

0.74

0.300

0.18

4.20

1.15

ICP-MS

226

1.28

-0.43

0.285

-0.38

3.72

-0.54

ICP-MS

317

1.37

0.53

0.299

0.15

3.75

-0.42

GFAAS

323

1.35

0.36

0.392

3.58

3.21

-2.30

GFAAS

387

1.31

-0.06

0.275

-0.74

3.71

-0.57

GFAAS

636

5.56

44.61

0.330

1.29

4.15

0.98

ICP-MS

744

1.57

2.64

0.316

0.78

3.96

0.32

ND

747

1.32

0.00

0.299

0.15

3.88

0.03

ICP-MS

1095

1.38

0.63

0.300

0.18

4.33

1.60

GFAAS

1109

0.138

-12.44

0.0304

-9.76

0.411

-12.07

ND

1188

1.26

-0.63

0.280

-0.56

3.61

-0.91

ICP-MS (C/R)

1418

1.31

-0.10

0.300

0.19

4.10

0.82

ND

1761

1.33

0.09

0.268

-0.98

3.78

-0.30

GFAAS

1855

1.29

-0.28

0.290

-0.20

4.03

0.54

ICP-MS

1865

1.31

-0.08

0.304

0.33

3.85

-0.08

ICP-MS (C/R)

2305

4.43

32.72

1.55

46.29

0.0500

-13.32

ND

2397

1.29

-0.34

0.275

-0.74

3.73

-0.51

GFAAS

2516

1.55

2.40

0.368

2.69

4.70

2.88

GFAAS

2580

1.31

-0.11

0.220

-2.77

3.72

-0.52

GFAAS

2629

1.45

1.37

0.330

1.29

4.36

1.71

ICP-MS (C/R)

2635

1.42

1.05

0.300

0.18

4.25

1.33

ND

2907

1.12

-2.11

0.248

-1.75

3.29

-2.03

ICP-MS

2937

1.36

0.42

0.319

0.89

---

---

GFAAS

2982

1.10

-2.36

0.236

-2.18

2.79

-3.76

GFAAS

2991

1.23

-0.93

0.311

0.58

3.23

-2.22

ND

3150

1.38

0.63

0.300

0.18

4.13

0.91

GFAAS

3167

1.37

0.53

0.340

1.66

4.26

1.36

GFAAS

3187

1.35

0.32

0.300

0.18

4.02

0.52

ICP-MS

3211

1.38

0.63

0.290

-0.18

3.85

-0.07

GFAAS

3215

1.30

-0.21

0.280

-0.55

>LL

---

GFAAS

3248

1.25

-0.74

0.290

-0.18

3.96

0.31

GFAAS

3423

1.16

-1.73

0.294

-0.05

3.62

-0.86

GFAAS

3513

1.38

0.63

0.330

1.29

3.94

0.24

ICP-MS

3853

1.36

0.42

0.320

0.92

4.21

1.19

ICP-MS

3970

1.50

1.85

0.280

-0.56

4.39

1.80

GFAAS

4082

1.38

0.63

0.287

-0.30

4.04

0.59

ICP-MS

4090

1.25

-0.74

0.270

-0.92

3.84

-0.10

ICP-MS (C/R)

4708

1.32

0.00

0.297

0.07

3.93

0.21

ICP-MS

4953

1.40

0.84

0.275

-0.73

4.09

0.78

GFAAS

5291

1.18

-1.47

0.230

-2.40

3.85

-0.07

ND

5432

1.31

-0.13

0.372

2.83

4.62

2.63

GFAAS

5491

1.35

0.34

0.289

-0.22

3.76

-0.37

GFAAS

5556

1.35

0.33

0.345

1.83

3.85

-0.08

GFAAS

5591

1.22

-1.05

0.280

-0.55

3.64

-0.80

ICP-MS

5654

1.26

-0.58

0.301

0.23

3.71

-0.55

ICP-MS (C/R)

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

5

Individual results
Blood Lead (µmol/L)
Round #2014-01

Participant

PC-B-L1401

z’-score

PC-B-L1402

z’-score

PC-B-L1403

z’-score

Method

5691

1.32

0.00

0.290

-0.18

3.85

-0.07

ICP-MS

6200

1.31

-0.07

0.294

-0.03

3.93

0.21

ICP-MS

6276

1.28

-0.38

0.280

-0.56

3.64

-0.81

ICP-MS

6511

1.29

-0.33

0.295

0.01

4.00

0.44

ND

6545

1.28

-0.42

0.280

-0.55

3.62

-0.87

ICP-MS

6794

1.39

0.77

0.302

0.24

4.46

2.06

GFAAS

7111

1.30

-0.17

0.289

-0.22

3.82

-0.18

ICP-MS

7269

1.33

0.11

0.330

1.29

3.76

-0.38

GFAAS

7311

1.33

0.11

0.300

0.18

3.88

0.03

ICP-MS

7760

1.24

-0.82

0.274

-0.79

4.09

0.76

ICP-MS

7804

0.813

-5.33

0.231

-2.35

3.85

-0.06

ND

7932

1.25

-0.74

0.315

0.74

3.14

-2.56

GFAAS

8701

1.22

-1.05

0.270

-0.92

3.55

-1.12

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-B-L1401

1.32

0.0137

0.0937

1.13 - 1.51

Rejected

---

PC-B-L1402

0.295

0.00399

0.0268

0.241 - 0.349

Rejected

---

PC-B-L1403

3.87

0.0518

0.282

3.30 - 4.44

Accepted

---

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

6

Statistics
Blood Lead (µmol/L)
All methods

PC-B-L1401

PC-B-L1402

60

59

56

1.32

0.295

3.87

0.0848

0.0245

0.310

1.31

0.295

3.85

0.0838

0.0229

0.297

Arithmetic mean

1.41

0.313

3.80

STDev

0.705

0.170

0.594

CV or Variability

6.4%

8.3%

8.0%

PC-B-L1401

PC-B-L1402

PC-B-L1403

24

24

22

1.34

0.300

3.89

0.0583

0.0333

0.393

1.35

0.296

3.82

0.0585

0.0316

0.348

N
Robust mean Algo A
Robust STDev
Median
STDev from MAD

Graphite furnace-AAS
N
Robust mean Algo A
Robust STDev
Median
STDev from MAD
Arithmetic mean
STDev

1.34

0.302

3.89

0.0928

0.0405

0.471

4.3%

11.1%

10.1%

PC-B-L1401

PC-B-L1402

PC-B-L1403

CV or Variability
ICP-MS
N

19

19

19

1.32

0.292

3.91

0.0594

0.0143

0.196

Robust mean Algo A
Robust STDev

PC-B-L1403

Median

1.32

0.290

3.93

STDev from MAD

0.0593

0.0148

0.166

Arithmetic mean

1.53

0.293

3.89

STDev

0.978

0.0194

0.232

CV or Variability

4.5%

4.9%

5.0%

PC-B-L1401

PC-B-L1402

PC-B-L1403

ICP-MS (collision/reaction cell)
N

6

5

5

1.27

0.297

3.83

0.0163

0.0265

0.220

Robust mean Algo A
Robust STDev
Median

1.26

0.301

3.84

STDev from MAD

0.0141

0.0315

0.191

Arithmetic mean

1.30

0.297

3.87

0.0765

0.0233

0.289

1.3%

8.9%

5.7%

STDev
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

7

Distribution
Blood Lead (µmol/L)

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

8

Individual results
Blood Mercury (nmol/L)
Round #2014-01

Participant

PC-B-M1401

z’-score

PC-B-M1402

z’-score

PC-B-M1403

z’-score

Method

176

19.9

-0.32

<19,9

---

419

1.22

ICP-MS

217

14.0

-2.51

12.0

2.33

451

1.92

ICP-MS

323

21.0

0.07

8.00

-0.87

328

-0.76

CV

428

22.9

0.79

9.77

0.55

318

-0.99

ICP-MS

744

19.7

-0.42

8.59

-0.40

388

0.55

ND
ICP-MS

747

20.6

-0.07

8.73

-0.29

353

-0.22

1095

19.0

-0.67

8.00

-0.87

354

-0.20

CV

1109

79.9

21.84

123

90.90

357

-0.13

ND

1156

39.9

7.07

7.26

-1.47

384

0.45

ND

1188

20.3

-0.18

8.38

-0.57

361

-0.04

ICP-MS (C/R)

1418

18.9

-0.70

8.48

-0.49

306

-1.25

ND

1865

22.7

0.71

9.87

0.63

384

0.47

CV
ICP-MS

2907

LL

---

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-A1401

1.46

0.0425

0.200

1.05 - 1.87

Accepted

---

PC-S-A1402

0.643

0.0279

0.107

0.421 - 0.865

Accepted

---

PC-S-A1403

6.27

0.180

0.744

4.74 - 7.80

Accepted

---

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

12

Statistics
Serum Aluminium (µmol/L)
All methods

PC-S-A1401

PC-S-A1402

31

31

31

Robust mean Algo A

1.46

0.643

6.27

Robust STDev

0.189

0.124

0.803

Median

1.45

0.660

6.31

STDev from MAD

0.200

0.118

0.838

Arithmetic mean

1.47

0.629

6.16

STDev

0.212

0.142

1.16

CV or Variability

13.0%

19.3%

12.8%

PC-S-A1401

PC-S-A1402

PC-S-A1403

14

14

13

Robust mean Algo A

1.49

0.640

6.43

Robust STDev

0.176

0.142

0.886

Median

1.52

0.660

6.46

STDev from MAD

0.162

0.153

0.863

Arithmetic mean

1.47

0.637

6.37

STDev

0.188

0.130

0.905

CV or Variability

11.8%

22.3%

13.8%

PC-S-A1401

PC-S-A1402

PC-S-A1403

N

Graphite furnace-AAS
N

ICP-MS
N

7

7

7

1.43

0.624

6.06

0.0646

0.134

0.536

Robust mean Algo A
Robust STDev

PC-S-A1403

Median

1.45

0.593

6.09

STDev from MAD

0.0525

0.129

0.512

Arithmetic mean

1.43

0.625

6.06

0.0995

0.119

0.473

4.5%

21.4%

8.9%

PC-S-A1401

PC-S-A1402

PC-S-A1403

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

4

4

5

Robust mean Algo A

1.37

0.598

6.26

Robust STDev

0.150

0.0365

0.821

Median

1.35

0.597

6.25

STDev from MAD

0.124

0.0278

0.628

Arithmetic mean

1.52

0.651

5.67

STDev

0.417

0.133

2.46

CV or Variability

10.9%

6.1%

13.1%

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

13

Distribution
Serum Aluminium (µmol/L)

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

14

Individual results
Serum Copper (µmol/L)
Round #2014-01
Participant

PC-S-E1401

z’-score

PC-S-E1402

z’-score

PC-S-E1403

z’-score

217

17.9

1.06

28.0

0.56

10.8

1.37

Method
FAAS

226

17.6

0.80

27.7

0.35

9.47

-0.24

ICP-MS (C/R)

387

18.7

1.76

28.2

0.68

10.0

0.45

GFAAS

428

17.9

1.02

29.3

1.35

10.1

0.49

ICP-MS (C/R)

636

15.5

-1.03

24.7

-1.48

8.61

-1.29

ICP-MS

744

16.4

-0.31

26.9

-0.10

9.89

0.27

ND

747

16.8

0.09

27.4

0.19

9.73

0.07

ICP-MS

1095

17.2

0.44

28.0

0.56

9.70

0.04

FAAS

1109

16.8

0.09

27.9

0.53

9.62

-0.06

ND

1188

17.0

0.25

27.6

0.31

9.73

0.07

ICP-MS (C/R)

1300

16.8

0.12

27.5

0.27

9.60

-0.09

FAAS

1855

15.8

-0.75

25.8

-0.80

9.77

0.12

ICP-MS

2305

15.6

-1.01

9.35

-11.05

25.2

18.81

ND

2516

11.1

-4.92

19.4

-4.79

6.90

-3.37

ND

2580

17.6

0.79

29.0

1.18

10.5

1.01

FAAS

2763

16.7

0.00

27.0

-0.06

9.52

-0.18

ICP-MS (C/R)

2907

16.4

-0.31

26.9

-0.11

9.43

-0.30

ICP-MS

2982

16.8

0.12

26.5

-0.39

9.43

-0.30

FAAS

3150

16.6

-0.09

26.6

-0.31

9.10

-0.69

FAAS

3211

16.1

-0.53

26.4

-0.44

9.30

-0.45

FAAS

3423

16.1

-0.57

27.6

0.33

8.78

-1.09

FAAS

3513

17.3

0.53

28.6

0.93

10.2

0.64

ICP-MS

3773

19.2

2.18

30.3

2.02

11.4

2.13

ICP-MS (C/R)

3853

19.1

2.09

28.9

1.11

10.8

1.36

ICP-MS

4082

16.7

0.00

27.6

0.31

9.50

-0.21

ICP-MS

4090

16.1

-0.52

27.0

-0.08

8.90

-0.94

ICP-MS (C/R)

4953

17.8

0.95

29.1

1.26

10.4

0.87

ICP-MS

5291

17.7

0.88

29.3

1.37

10.5

1.01

ND

5556

17.0

0.26

26.0

-0.71

10.4

0.87

FAAS

5591

17.2

0.44

28.7

1.00

9.80

0.16

GFAAS

5596

14.8

-1.71

24.6

-1.56

8.88

-0.95

ICP-MS (C/R)

5654

15.4

-1.14

25.0

-1.33

8.63

-1.26

ICP-MS (C/R)

5691

15.9

-0.70

24.8

-1.43

9.30

-0.45

ICP-MS

5881

17.0

0.26

27.2

0.06

9.76

0.11

ICP-MS (C/R)

5955

16.9

0.18

27.7

0.37

9.69

0.02

ND

6511

16.4

-0.31

27.0

-0.04

9.13

-0.66

ND

6711

16.2

-0.47

26.1

-0.65

9.73

0.08

ND

7311

16.4

-0.24

27.2

0.08

9.79

0.15

ICP-MS

7804

24.4

6.73

19.0

-5.05

6.35

-4.03

ND

8376

18.8

1.84

31.8

2.92

11.3

1.98

FAAS

8454

16.4

-0.26

26.1

-0.62

9.71

0.05

FAAS

8981

15.9

-0.70

24.9

-1.37

9.43

-0.29

ND

9677

14.6

-1.86

23.8

-2.06

8.34

-1.61

ICP-OES

9759

15.9

-0.71

27.0

-0.07

9.65

-0.03

FAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-E1401

16.7

0.193

1.12

14.4 - 19.0

Rejected

---

PC-S-E1402

27.1

0.315

1.57

23.9 - 30.3

Rejected

---

PC-S-E1403

9.67

0.120

0.814

8.02 - 11.3

Rejected

---

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

15

Statistics
Serum Copper (µmol/L)
All methods

PC-S-E1401

PC-S-E1402

44

44

44

Robust mean Algo A

16.7

27.1

9.67

Robust STDev

1.02

1.67

0.636

Median

16.8

27.1

9.70

STDev from MAD

1.00

1.53

0.572

Arithmetic mean

16.8

26.5

9.93

STDev

1.77

3.51

2.52

CV or Variability

6.1%

6.2%

6.6%

PC-S-E1401

PC-S-E1402

PC-S-E1403

12

12

12

Robust mean Algo A

16.9

27.3

9.80

Robust STDev

0.823

1.19

0.730

Median

16.8

27.3

9.67

STDev from MAD

0.872

1.14

0.702

Arithmetic mean

16.9

27.5

9.85

STDev

0.847

1.62

0.742

CV or Variability

4.9%

4.3%

7.4%

PC-S-E1401

PC-S-E1402

PC-S-E1403

N

Flame-AAS
N

ICP-MS
N

PC-S-E1403

10

10

10

Robust mean Algo A

16.7

27.1

9.76

Robust STDev

0.959

1.79

0.593

Median

16.6

27.3

9.75

STDev from MAD

1.03

2.07

0.574

Arithmetic mean

16.8

27.1

9.75

STDev

1.06

1.58

0.611

CV or Variability

5.8%

6.6%

6.1%

PC-S-E1401

PC-S-E1402

PC-S-E1403

ICP-MS (collision/reaction cell)
N

9

9

9

Robust mean Algo A

16.8

27.2

9.51

Robust STDev

1.38

0.884

0.724

Median

17.0

27.2

9.52

STDev from MAD

1.29

0.700

0.818

Arithmetic mean

16.8

27.3

9.60

STDev

1.33

1.82

0.833

CV or Variability

8.2%

3.2%

7.6%

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

16

Distribution
Serum Copper (µmol/L)

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

17

Individual results
Serum Manganese (nmol/L)
Round #2014-01

Participant

PC-S-G1401

z’-score

PC-S-G1402

z’-score

PC-S-G1403

z’-score

Method

217

36.0

1.49

17.0

2.78

58.0

0.59

ICP-MS

323

28.0

-0.46

8.00

-1.77

49.0

-0.62

GFAAS
ICP-MS

747

29.3

-0.15

13.0

0.76

54.6

0.13

1109

34.6

1.14

17.3

2.92

71.0

2.34

ND

1188

31.1

0.29

11.5

0.00

55.5

0.26

ICP-MS (C/R)

2629

19.7

-2.50

10.9

-0.29

31.3

-3.00

GFAAS

2763

26.7

-0.78

9.94

-0.79

46.1

-1.01

ICP-MS (C/R)

2978

32.2

0.57

11.7

0.09

62.3

1.17

ICP-MS (C/R)

6511

29.7

-0.06

11.5

-0.02

52.4

-0.16

ND

8376

28.0

-0.46

9.10

-1.21

47.3

-0.85

GFAAS

9759

30.9

0.25

10.9

-0.29

56.4

0.38

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-G1401

29.9

1.09

3.95

21.7 - 38.1

Accepted

---

PC-S-G1402

11.5

0.912

1.76

7.54 - 15.5

Rejected

---

PC-S-G1403

53.6

3.03

6.78

38.8 - 68.4

Accepted

---

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

18

Statistics
Serum Manganese (nmol/L)
All methods

PC-S-G1401

PC-S-G1402

11

11

11

Robust mean Algo A

29.9

11.5

53.6

Robust STDev

2.90

2.42

8.03

Median

29.7

11.5

54.6

STDev from MAD

2.48

2.27

8.30

Arithmetic mean

29.7

11.9

53.1

STDev

4.35

2.92

10.1

CV or Variability

9.7%

21.1%

15.0%

PC-S-G1401

PC-S-G1402

PC-S-G1403

4

4

4

Robust mean Algo A

27.9

9.74

47.7

Robust STDev

2.87

1.63

8.57

Median

28.0

10.0

48.2

STDev from MAD

2.18

1.35

6.75

Arithmetic mean

26.7

9.74

46.0

STDev

4.87

1.44

10.6

CV or Variability

10.3%

16.8%

18.0%

PC-S-G1401

PC-S-G1402

PC-S-G1403

N

Graphite furnace-AAS
N

ICP-MS (collision/reaction cell)
N

PC-S-G1403

3

3

3

Robust mean Algo A

30.6

11.4

54.6

Robust STDev

2.09

0.348

9.20

Median

31.1

11.5

55.5

STDev from MAD

1.66

0.276

10.0

Arithmetic mean

30.0

11.0

54.6

STDev

2.92

0.959

8.11

CV or Variability

6.8%

3.0%

16.8%

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

19

Distribution
Serum Manganese (nmol/L)

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

20

Individual results
Serum Selenium (µmol/L)
Round #2014-01

Participant

PC-S-E1401

z’-score

PC-S-E1402

z’-score

PC-S-E1403

z’-score

217

1.95

1.71

2.39

0.96

1.50

1.23

Method
ICP-MS

226

1.77

0.55

2.27

0.34

1.34

0.02

ICP-MS (C/R)

428

1.65

-0.21

2.20

0.02

1.32

-0.18

ICP-MS (C/R)

636

1.61

-0.44

2.17

-0.15

1.30

-0.31

ICP-MS

747

1.56

-0.76

2.14

-0.30

1.28

-0.46

ICP-MS

1095

1.58

-0.63

2.09

-0.55

1.40

0.46

GFAAS

1109

1.82

0.88

2.27

0.34

1.61

2.04

ND

1188

1.84

1.01

2.43

1.16

1.47

1.00

ICP-MS (C/R)

1300

1.89

1.31

2.20

0.02

1.29

-0.37

HG-AAS

1855

1.62

-0.37

2.28

0.40

1.47

0.99

ICP-MS (C/R)

2305

1.75

0.44

1.90

-1.51

1.33

-0.08

ND

2516

1.87

1.20

2.50

1.51

1.59

1.92

ND

2763

1.59

-0.57

2.08

-0.61

1.23

-0.84

ICP-MS (C/R)

3150

1.58

-0.63

2.11

-0.45

1.40

0.46

GFAAS

3513

1.50

-1.14

1.92

-1.41

1.25

-0.69

ICP-MS (C/R)

3773

1.74

0.36

2.34

0.71

1.35

0.11

ICP-MS (C/R)

3853

1.83

0.95

2.28

0.40

1.41

0.54

ICP-MS (C/R)

4082

1.70

0.13

2.33

0.66

1.33

-0.08

ICP-MS

4590

1.40

-1.79

1.99

-1.06

1.11

-1.78

GFAAS

4953

1.60

-0.53

2.10

-0.49

1.24

-0.80

ICP-MS (C/R)

5291

1.53

-0.95

2.18

-0.10

1.35

0.08

ND

5556

1.38

-1.89

2.05

-0.75

1.24

-0.78

GFAAS

5596

1.75

0.42

2.37

0.84

1.38

0.27

ICP-MS (C/R)

5654

1.86

1.14

2.39

0.98

1.38

0.31

ICP-MS (C/R)

5691

1.53

-0.95

1.92

-1.41

1.18

-1.23

ICP-MS

5881

1.68

0.00

2.22

0.10

1.32

-0.15

ICP-MS (C/R)

5955

1.63

-0.32

2.19

-0.05

1.30

-0.31

ND

6511

1.75

0.43

2.29

0.44

1.32

-0.16

ND

6545

1.74

0.38

2.27

0.35

1.37

0.23

ICP-MS

7311

1.86

1.14

2.43

1.16

1.43

0.69

ICP-MS

7804

1.40

-1.77

1.80

-2.02

1.23

-0.84

ND

8376

1.63

-0.33

2.16

-0.22

1.38

0.30

GFAAS

8454

1.59

-0.57

2.05

-0.76

1.32

-0.15

GFAAS

9759

1.84

1.02

2.40

1.01

1.56

1.67

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-E1401

1.68

0.0329

0.155

1.36 - 2.00

Accepted

---

PC-S-E1402

2.20

0.0379

0.195

1.80 - 2.60

Accepted

---

PC-S-E1403

1.34

0.0202

0.129

1.08 - 1.60

Accepted

---

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

21

Statistics
Serum Selenium (µmol/L)
All methods

PC-S-E1401

PC-S-E1402

34

34

34

Robust mean Algo A

1.68

2.20

1.34

Robust STDev

0.153

0.177

0.0942

Median

1.66

2.20

1.34

STDev from MAD

0.141

0.176

0.0890

N

PC-S-E1403

Arithmetic mean

1.68

2.20

1.35

STDev

0.149

0.170

0.111

CV or Variability

9.1%

8.0%

7.0%

PC-S-E1401

PC-S-E1402

PC-S-E1403

7

7

7

1.57

2.09

1.36

0.0871

0.0714

0.107

1.58

2.09

1.38

0.0703

0.0593

0.0878

Graphite furnace-AAS
N
Robust mean Algo A
Robust STDev
Median
STDev from MAD
Arithmetic mean

1.57

2.12

1.34

STDev

0.155

0.134

0.142

CV or Variability

5.5%

3.4%

7.9%

PC-S-E1401

PC-S-E1402

PC-S-E1403

ICP-MS
N

7

7

7

Robust mean Algo A

1.71

2.25

1.34

Robust STDev

0.177

0.172

0.0917

Median

1.70

2.27

1.33

STDev from MAD

0.208

0.178

0.0742

Arithmetic mean

1.71

2.24

1.34

STDev

0.156

0.175

0.104

CV or Variability

10.4%

7.7%

6.9%

PC-S-E1401

PC-S-E1402

PC-S-E1403

ICP-MS (collision/reaction cell)
N

12

12

12

Robust mean Algo A

1.70

2.26

1.35

Robust STDev

0.128

0.132

0.0845

Median

1.71

2.27

1.35

STDev from MAD

0.148

0.120

0.0701

Arithmetic mean

1.70

2.24

1.35

STDev

0.114

0.147

0.0815

CV or Variability

7.5%

5.9%

6.3%

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

22

Distribution
Serum Selenium (µmol/L)

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

23

Individual results
Serum Zinc (µmol/L)
Round #2014-01

Participant

PC-S-E1401

z’-score

PC-S-E1402

z’-score

PC-S-E1403

z’-score

217

21.2

1.14

29.3

0.89

14.4

1.62

Method
FAAS

226

19.7

0.38

25.2

-0.62

13.0

0.48

ICP-MS (C/R)

428

19.6

0.30

28.4

0.54

12.9

0.43

ICP-MS (C/R)

636

17.3

-0.89

26.5

-0.15

12.0

-0.30

ICP-MS

744

17.5

-0.77

26.9

-0.01

11.4

-0.77

ND

747

19.0

0.00

27.1

0.07

12.3

-0.08

ICP-MS

1095

16.8

-1.15

24.2

-1.00

10.9

-1.21

FAAS

1109

21.4

1.26

29.0

0.80

14.1

1.38

ND

1188

19.0

-0.03

26.6

-0.11

12.5

0.08

ICP-MS (C/R)

1300

20.3

0.70

28.1

0.46

13.0

0.48

FAAS

1855

16.9

-1.11

24.1

-1.05

12.6

0.17

ICP-MS

2305

17.4

-0.86

24.8

-0.77

11.8

-0.52

ND

2516

19.6

0.31

28.6

0.63

13.2

0.64

ND

2580

19.2

0.10

27.3

0.15

12.6

0.16

FAAS

2763

18.3

-0.37

25.8

-0.41

11.8

-0.48

ICP-MS (C/R)

2907

20.4

0.73

26.9

-0.01

12.7

0.23

ICP-MS

2982

15.8

-1.66

23.3

-1.35

9.88

-2.03

FAAS

3150

18.9

-0.05

26.6

-0.11

12.1

-0.24

FAAS

3211

19.5

0.26

28.0

0.41

12.6

0.16

FAAS

3423

18.1

-0.45

27.0

0.05

11.9

-0.39

FAAS

3513

18.8

-0.10

27.7

0.30

12.2

-0.16

ICP-MS

3773

21.4

1.27

29.6

1.00

14.5

1.72

ICP-MS (C/R)

3853

21.4

1.28

28.5

0.61

13.7

1.01

ICP-MS

4082

19.2

0.10

27.9

0.37

12.3

-0.08

ICP-MS (C/R)

4090

18.0

-0.51

25.5

-0.54

11.1

-1.05

ICP-MS (C/R)

4953

20.5

0.77

28.8

0.71

13.5

0.89

ICP-MS

5291

22.9

2.04

32.2

1.97

15.0

2.10

ND

5556

18.8

-0.10

25.4

-0.57

11.9

-0.38

FAAS

5591

18.8

-0.10

25.8

-0.41

12.7

0.24

FAAS

5596

18.0

-0.51

25.7

-0.44

12.2

-0.19

ICP-MS (C/R)

5654

17.5

-0.78

25.3

-0.60

11.3

-0.88

ICP-MS (C/R)

5691

17.8

-0.63

24.6

-0.85

11.9

-0.40

ICP-MS

5881

19.2

0.12

27.4

0.19

12.4

0.02

ICP-MS (C/R)

5955

18.6

-0.21

26.7

-0.07

12.2

-0.16

ND

6511

19.2

0.09

27.1

0.07

12.1

-0.25

ND

7311

19.8

0.41

28.1

0.45

12.9

0.42

ICP-MS

7804

16.5

-1.31

21.1

-2.16

6.90

-4.43

ND

8376

20.0

0.54

28.5

0.61

13.4

0.82

FAAS

8454

17.4

-0.84

25.5

-0.52

12.0

-0.32

FAAS

8981

20.5

0.79

28.1

0.45

13.3

0.73

ND

9677

16.9

-1.10

24.2

-1.02

10.7

-1.40

ICP-OES

9759

21.1

1.07

29.8

1.08

14.3

1.51

FAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-S-E1401

19.0

0.320

1.88

15.2 - 22.8

Accepted

---

PC-S-E1402

26.9

0.379

2.66

21.5 - 32.3

Accepted

---

PC-S-E1403

12.4

0.177

1.23

9.91 - 14.9

Accepted

---

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

24

Statistics
Serum Zinc (µmol/L)
All methods

PC-S-E1401

PC-S-E1402

42

42

42

Robust mean Algo A

19.0

26.9

12.4

Robust STDev

1.66

1.96

0.918

Median

19.0

27.0

12.4

STDev from MAD

1.65

2.12

0.841

Arithmetic mean

19.0

26.8

12.4

STDev

1.57

2.04

1.37

CV or Variability

8.7%

7.3%

7.4%

PC-S-E1401

PC-S-E1402

PC-S-E1403

13

13

13

Robust mean Algo A

19.0

26.9

12.5

Robust STDev

1.70

2.14

1.10

Median

18.9

27.0

12.6

STDev from MAD

1.67

2.21

1.00

Arithmetic mean

18.9

26.8

12.4

STDev

1.59

1.95

1.24

CV or Variability

9.0%

7.9%

8.8%

PC-S-E1401

PC-S-E1402

PC-S-E1403

N

Flame-AAS
N

ICP-MS
N

PC-S-E1403

9

9

9

Robust mean Algo A

19.1

27.0

12.6

Robust STDev

1.77

1.64

0.676

Median

19.0

27.1

12.6

STDev from MAD

2.07

1.50

0.612

Arithmetic mean

19.1

26.9

12.6

STDev

1.56

1.66

0.619

CV or Variability

9.3%

6.1%

5.4%

PC-S-E1401

PC-S-E1402

PC-S-E1403

ICP-MS (collision/reaction cell)
N

10

10

10

Robust mean Algo A

18.9

26.6

12.3

Robust STDev

1.06

1.43

0.875

Median

19.1

26.2

12.4

STDev from MAD

1.05

1.39

0.841

Arithmetic mean

19.0

26.7

12.4

STDev

1.13

1.51

0.971

CV or Variability

5.6%

5.4%

7.1%

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

25

Distribution
Serum Zinc (µmol/L)

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

26

Individual results
Urine Cadmium (nmol/L)
Round #2014-01

Participant

PC-U-D1401

z’-score

PC-U-D1402

z’-score

PC-U-D1403

z’-score

Method

217

91.6

-0.20

18.7

-0.30

64.1

2.42

ICP-MS

744

89.4

-0.51

16.0

-1.55

49.0

-0.84

ND

747

89.1

-0.55

19.3

0.00

46.8

-1.32

ICP-MS

1095

107

1.91

23.0

1.76

60.0

1.54

ICP-MS (C/R)

1109

99.2

0.84

20.1

0.38

60.8

1.70

ND

1418

93.9

0.12

19.7

0.21

53.6

0.16

ICP-MS (C/R)

1865

93.4

0.04

18.9

-0.21

61.3

1.82

ICP-MS (C/R)

2937

73.1

-2.75

13.2

-2.91

53.6

0.15

ICP-MS

2991

91.2

-0.26

21.5

1.06

50.2

-0.59

ND

3187

92.2

-0.12

18.6

-0.33

46.0

-1.50

ICP-MS

3211

94.6

0.21

17.5

-0.86

50.3

-0.56

GFAAS

3215

>LL

---

19.6

0.14

56.4

0.76

GFAAS

3423

87.9

-0.72

20.0

0.34

51.4

-0.32

GFAAS

3853

91.0

-0.29

16.0

-1.57

44.0

-1.93

ICP-MS

4466

84.9

-1.13

11.4

-3.78

41.2

-2.55

GFAAS

4708

93.4

0.04

19.3

0.00

52.2

-0.15

ICP-MS

4953

97.9

0.65

19.4

0.04

56.2

0.72

ICP-MS

5591

94.1

0.14

19.2

-0.05

50.4

-0.54

ICP-MS

5654

94.5

0.19

19.9

0.30

60.8

1.70

ICP-MS (C/R)

5691

93.0

-0.01

19.0

-0.14

54.0

0.24

ICP-MS

5881

93.4

0.04

19.7

0.21

53.2

0.06

ICP-MS (C/R)

6511

93.4

0.04

19.1

-0.08

56.9

0.87

ND

6545

50.0

-5.93

20.3

0.48

42.1

-2.34

ICP-MS

6689

96.2

0.42

19.7

0.17

49.4

-0.77

ND

6794

93.9

0.12

18.7

-0.29

54.0

0.24

GFAAS

6858

86.1

-0.96

17.4

-0.92

48.4

-0.98

ICP-MS

6920

99.0

0.81

21.4

1.00

53.5

0.13

ND

7760

101

1.14

20.5

0.57

61.2

1.80

ICP-MS

8701

101

1.02

19.4

0.06

52.5

-0.08

ND

9759

89.0

-0.57

22.2

1.40

48.9

-0.86

GFAAS

9777

638

74.95

4220

2002.08

845

171.79

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-D1401

93.1

1.06

7.18

78.6 - 108

Accepted

---

PC-U-D1402

19.3

0.254

2.09

15.1 - 23.5

Accepted

---

PC-U-D1403

52.9

1.35

4.40

43.7 - 62.1

Accepted

---

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

27

Statistics
Urine Cadmium (nmol/L)
All methods

PC-U-D1401

PC-U-D1402

29

30

30

Robust mean Algo A

93.1

19.3

52.9

Robust STDev

4.58

1.11

5.93

Median

93.4

19.3

52.9

STDev from MAD

4.09

0.991

5.47

Arithmetic mean

91.5

19.0

52.7

STDev

10.0

2.37

5.83

CV or Variability

4.9%

5.8%

11.2%

PC-U-D1401

PC-U-D1402

PC-U-D1403

5

6

6

Robust mean Algo A

90.1

19.0

51.0

Robust STDev

4.68

2.24

4.44

Median

89.0

19.1

50.9

STDev from MAD

5.99

1.87

3.76

Arithmetic mean

90.1

18.2

50.4

STDev

4.12

3.72

5.25

CV or Variability

5.2%

11.8%

8.7%

PC-U-D1401

PC-U-D1402

PC-U-D1403

N

Graphite furnace-AAS
N

ICP-MS
N

PC-U-D1403

12

12

12

Robust mean Algo A

91.5

19.0

51.4

Robust STDev

4.46

0.818

7.18

Median

91.9

19.1

51.3

STDev from MAD

3.71

0.682

6.99

Arithmetic mean

87.7

18.4

51.6

STDev

13.7

2.04

6.69

CV or Variability

4.9%

4.3%

14.0%

PC-U-D1401

PC-U-D1402

PC-U-D1403

ICP-MS (collision/reaction cell)
N

5

5

5

Robust mean Algo A

94.1

19.8

59.3

Robust STDev

0.837

0.330

2.27

Median

93.9

19.7

60.0

STDev from MAD

0.792

0.264

1.92

Arithmetic mean

96.4

20.3

57.8

STDev

5.92

1.59

4.01

CV or Variability

0.9%

1.7%

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

28

Distribution
Urine Cadmium (nmol/L)

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

29

Individual results
Urine Chromium (nmol/L)
Round #2014-01

Participant

PC-U-B1401

z’-score

PC-U-B1402

z’-score

PC-U-B1403

z’-score

Method

176

23.1

0.17

235

-0.25

30.8

-0.51

ICP-MS (C/R)

744

17.1

-0.85

247

0.34

38.1

0.58

ND

747

21.7

-0.07

242

0.09

36.7

0.38

ICP-MS (C/R)

1095

28.0

1.01

245

0.23

36.0

0.27

GFAAS

1109

23.5

0.23

255

0.67

38.7

0.67

ND

1418

19.0

-0.52

223

-0.78

31.2

-0.46

ICP-MS (C/R)

1865

31.2

1.55

256

0.73

48.5

2.14

ICP-MS (C/R)

2982

LL

---

2.13

-0.04

>LL

---

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-R1401

4.01

0.0757

0.314

3.36 - 4.66

Accepted

---

PC-U-R1402

2.14

0.0320

0.170

1.79 - 2.49

Accepted

---

PC-U-R1403

14.6

0.205

1.13

12.3 - 16.9

Accepted

---

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

33

Statistics
Urine Copper (µmol/L)
All methods

PC-U-R1401

PC-U-R1402

27

28

27

Robust mean Algo A

4.01

2.14

14.6

Robust STDev

0.315

0.135

0.851

Median

4.01

2.15

14.7

STDev from MAD

0.280

0.141

0.742
14.7

N

PC-U-R1403

Arithmetic mean

4.02

2.11

STDev

0.440

0.193

1.25

CV or Variability

7.9%

6.3%

5.8%

PC-U-R1401

PC-U-R1402

PC-U-R1403

3

4

3

Robust mean Algo A

3.84

2.17

16.5

Robust STDev

0.909

0.199

0.959

Median

4.01

2.19

16.7

STDev from MAD

0.784

0.165

0.760
15.7

Graphite furnace-AAS
N

Arithmetic mean

3.84

2.03

STDev

0.802

0.438

2.29

CV or Variability

23.7%

9.2%

5.8%

PC-U-R1401

PC-U-R1402

PC-U-R1403

ICP-MS
N

10

10

10

Robust mean Algo A

3.97

2.20

14.4

Robust STDev

0.168

0.0768

0.392

Median

3.98

2.20

14.4

STDev from MAD

0.174

0.0701

0.371

Arithmetic mean

3.96

2.18

14.4

STDev

0.162

0.108

0.345

CV or Variability

4.2%

3.5%

2.7%

PC-U-R1401

PC-U-R1402

PC-U-R1403

ICP-MS (collision/reaction cell)
N

7

7

7

Robust mean Algo A

3.96

2.15

14.7

Robust STDev

0.333

0.122

0.457

Median

3.98

2.16

14.7

STDev from MAD

0.282

0.133

0.438

Arithmetic mean

3.98

2.15

14.6

STDev

0.345

0.108

0.588

CV or Variability

8.4%

5.7%

3.1%

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

34

Distribution
Urine Copper (µmol/L)

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

35

Individual results
Urine Fluoride (µmol/L)
Round #2014-01

Participant

PC-U-F1401

z’-score

PC-U-F1402

z’-score

PC-U-F1403

z’-score

Method

176

26.9

-0.23

57.4

0.01

253

-0.18

FSE

1095

28.0

0.09

58.0

0.14

259

0.19

FSE

1418

28.4

0.21

57.4

0.01

257

0.06

ND

1476

26.0

-0.49

58.0

0.14

258

0.13

FSE

2629

27.1

-0.18

54.1

-0.64

226

-1.95

FSE

4604

30.4

0.77

57.1

-0.04

244

-0.76

ND

5132

28.1

0.10

57.3

-0.01

249

-0.45

ND

5881

27.4

-0.09

58.4

0.22

274

1.19

FSE

6200

27.4

-0.09

56.3

-0.19

243

-0.83

FSE

6234

26.4

-0.37

55.3

-0.40

254

-0.16

ND

6545

30.6

0.83

59.5

0.44

261

0.31

FSE

6702

29.4

0.49

60.1

0.56

270

0.90

FSE

7269

28.0

0.09

60.0

0.54

259

0.19

FSE

8701

15.4

-3.53

13.2

-8.75

16.3

-15.49

ND

9759

5.26

-6.42

10.0

-9.39

44.7

-13.65

FSE

9908

30.3

0.75

60.5

0.64

263

0.46

FSE

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-F1401

27.7

0.550

3.45

20.7 - 34.7

Rejected

---

PC-U-F1402

57.3

0.773

4.98

47.2 - 67.4

Rejected

---

PC-U-F1403

256

2.89

15.2

225 - 287

Accepted

---

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

36

Statistics
Urine Fluoride (µmol/L)
All methods

PC-U-F1401

PC-U-F1402

16

16

14

Robust mean Algo A

27.7

57.3

256

Robust STDev

1.76

2.47

8.65

Median

27.7

57.4

257

STDev from MAD

1.54

2.32

7.42

Arithmetic mean

25.9

52.0

255

STDev

6.52

15.9

12.1

CV or Variability

6.3%

4.3%

3.4%

PC-U-F1401

PC-U-F1402

PC-U-F1403

11

11

10

Robust mean Algo A

27.5

57.9

259

Robust STDev

1.16

2.49

8.85

Median

27.4

58.0

259

STDev from MAD

0.933

2.49

7.42

Arithmetic mean

26.0

53.8

257

STDev

7.04

14.7

13.8

CV or Variability

4.2%

4.3%

3.4%

N

Fluoride specific electrode
N

PC-U-F1403

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 #2014-01

Participant

PC-U-S1401

z’-score

PC-U-S1402

z’-score

PC-U-S1403

z’-score

Method

217

0.540

1.25

1.31

-0.86

0.620

-0.44

GFAAS

317

0.427

-0.63

1.35

-0.60

0.668

0.18

GFAAS

428

0.483

0.30

1.36

-0.52

0.625

-0.38

ICP-MS (C/R)

747

0.451

-0.23

1.48

0.26

0.692

0.50

ICP-MS (C/R)

1095

0.450

-0.25

1.44

0.00

0.660

0.08

GFAAS

1418

0.426

-0.65

1.47

0.19

0.780

1.64

HG-AAS

1476

0.410

-0.92

1.01

-2.85

0.520

-1.75

ICP-MS

1820

0.474

0.15

1.39

-0.33

0.679

0.33

GFAAS

1827

0.536

1.18

1.55

0.73

0.670

0.21

ICP-MS (C/R)

1865

0.416

-0.81

1.57

0.86

0.727

0.96

HG-AAS

2580

0.398

-1.12

1.45

0.07

0.716

0.81

GFAAS

2978

0.490

0.41

1.47

0.19

0.654

0.00

ICP-MS

3215

0.450

-0.25

1.48

0.26

0.670

0.21

GFAAS

3423

0.414

-0.85

1.28

-1.05

0.601

-0.70

HG-AAS

3853

0.505

0.67

1.49

0.33

0.650

-0.05

ICP-MS (C/R)

4953

0.522

0.95

1.95

3.37

0.715

0.80

ICP-MS (C/R)

5375

0.491

0.43

1.47

0.20

0.671

0.22

ICP-MS

5495

0.574

1.81

1.43

-0.10

0.576

-1.01

ICP-MS (C/R)

5691

0.450

-0.25

1.38

-0.40

0.590

-0.83

ND

5881

0.379

-1.43

1.19

-1.63

0.626

-0.37

HG-AAS

6511

0.529

1.06

1.53

0.63

0.622

-0.42

ND

7162

0.414

-0.85

1.44

-0.01

0.641

-0.17

ND

8701

0.502

0.62

1.45

0.09

0.647

-0.09

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

0.465

0.0146

0.0581

0.345 - 0.585

Accepted

DMAA added

PC-U-S1402

1.44

0.0242

0.149

1.14 - 1.74

Rejected

Workers Profile

PC-U-S1403

0.654

0.0124

0.0757

0.501 - 0.807

Accepted

As+3 added

PC-U-S1401

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

39

Statistics
Urine Inorganic arsenic (µmol/L)
All methods

PC-U-S1401

PC-U-S1402

23

23

23

Robust mean Algo A

0.465

1.44

0.654

Robust STDev

0.0559

0.0928

0.0476

Median

0.451

1.45

0.654

STDev from MAD

0.0576

0.0905

0.0435

N

PC-U-S1403

Arithmetic mean

0.467

1.43

0.653

STDev

0.0525

0.167

0.0551

CV or Variability

12.0%

6.5%

7.3%

PC-U-S1401

PC-U-S1402

PC-U-S1403

6

6

6

Robust mean Algo A

0.450

1.40

0.669

Robust STDev

0.0410

0.0739

0.0166

Median

0.450

1.42

0.669

STDev from MAD

0.0349

0.0749

0.0141

Graphite furnace-AAS
N

Arithmetic mean

0.457

1.40

0.669

STDev

0.0483

0.0652

0.0310

9.1%

5.3%

2.5%

PC-U-S1401

PC-U-S1402

PC-U-S1403

CV or Variability
Hydride generation-AAS
N

4

4

4

Robust mean Algo A

0.414

1.38

0.683

Robust STDev

0.0115

0.194

0.0958

Median

0.415

1.37

0.677

STDev from MAD

0.00911

0.203

0.0940

Arithmetic mean

0.409

1.38

0.683

STDev

0.0205

0.171

0.0845

2.8%

14.1%

14.0%

PC-U-S1401

PC-U-S1402

PC-U-S1403

CV or Variability
ICP-MS
N
Robust mean Algo A
Robust STDev
Median

3

3

3

0.489

1.47

0.647

0.00216

0.00337

0.0318

0.490

1.47

0.654

STDev from MAD

0.00171

0.00267

0.0252

Arithmetic mean

0.464

1.32

0.615

STDev

0.0464

0.265

0.0827

0.4%

0.2%

4.9%

PC-U-S1401

PC-U-S1402

PC-U-S1403

6

6

6

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

0.512

1.49

0.656

Robust STDev

0.0467

0.104

0.0534

Median

0.513

1.49

0.660

STDev from MAD

0.0392

0.0924

0.0499

Arithmetic mean

0.512

1.54

0.655

STDev

0.0426

0.209

0.0497

9.1%

7.0%

8.1%

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

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 #2014-01

Participant

PC-U-I1401

z’-score

PC-U-I1402

z’-score

PC-U-I1403

z’-score

217

0.650

0.68

1.71

0.06

2.20

0.09

Method
ICP-MS

428

0.545

-1.03

1.57

-0.76

2.01

-0.77

ICP-MS (C/R)

747

0.595

-0.21

1.69

-0.06

2.17

-0.05

ICP-MS

1095

0.620

0.19

1.78

0.46

2.32

0.63

ICP-MS (C/R)

1855

0.599

-0.15

1.69

-0.03

2.30

0.55

ICP-MS

2763

0.667

0.96

1.84

0.81

2.28

0.45

ICP-MS

3187

0.597

-0.18

1.59

-0.64

2.13

-0.23

ICP-MS

3513

0.600

-0.13

1.70

0.00

2.15

-0.14

ICP-MS

4708

0.607

-0.02

1.71

0.06

2.20

0.09

ICP-MS

5881

0.655

0.76

1.76

0.37

2.24

0.29

ICP-MS (C/R)

6200

0.655

0.76

1.87

0.97

2.29

0.51

ICP-MS

6511

0.587

-0.34

1.66

-0.23

2.07

-0.50

ND

6545

0.610

0.03

1.69

-0.06

2.15

-0.14

ICP-MS

8981

0.550

-0.94

1.47

-1.33

1.92

-1.17

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-I1401

0.608

0.00971

0.0608

0.485 - 0.731

Accepted

---

PC-U-I1402

1.70

0.0295

0.170

1.36 - 2.04

Accepted

---

PC-U-I1403

2.18

0.0384

0.218

1.74 - 2.62

Accepted

---

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

42

Statistics
Urine Iodide (µmol/L)
All methods

PC-U-I1401

PC-U-I1402

14

14

14

Robust mean Algo A

0.608

1.70

2.18

Robust STDev

0.0291

0.0884

0.115

Median

0.604

1.70

2.19

STDev from MAD

0.0244

0.0777

0.114

N

PC-U-I1403

Arithmetic mean

0.610

1.70

2.17

STDev

0.0372

0.105

0.116

4.8%

5.2%

5.3%

PC-U-I1401

PC-U-I1402

PC-U-I1403

9

9

9

Robust mean Algo A

0.611

1.70

2.21

Robust STDev

0.0167

0.0174

0.0756

Median

0.607

1.70

2.20

STDev from MAD

0.0148

0.0148

0.0742

CV or Variability
ICP-MS
N

Arithmetic mean

0.620

1.72

2.21

STDev

0.0287

0.0836

0.0667

2.7%

1.0%

3.4%

PC-U-I1401

PC-U-I1402

PC-U-I1403

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

3

3

3

Robust mean Algo A

0.606

1.76

2.21

Robust STDev

0.0640

0.0294

0.143

Median

0.620

1.76

2.24

STDev from MAD

0.0516

0.0233

0.114

Arithmetic mean

0.606

1.70

2.19

STDev

0.0564

0.118

0.162

CV or Variability

10.5%

1.7%

6.5%

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

43

Distribution
Urine Iodide (µmol/L)

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

44

Individual results
Urine Lead (µmol/L)
Round #2014-01

Participant

PC-U-P1401

z’-score

PC-U-P1402

z’-score

PC-U-P1403

z’-score

Method

176

0.0483

-1.55

0.767

-0.12

0.420

0.36

ICP-MS

194

0.0630

0.98

0.777

0.03

0.428

0.60

ND

217

0.0700

2.18

0.860

1.37

0.430

0.66

ICP-MS

744

0.0864

4.99

0.760

-0.24

0.395

-0.37

ND

747

0.0563

-0.17

0.783

0.13

0.405

-0.09

ICP-MS

1095

0.0600

0.46

0.860

1.37

0.450

1.26

ICP-MS (C/R)

1109

0.0538

-0.60

0.749

-0.42

0.386

-0.67

ND

1855

0.0579

0.11

0.734

-0.67

0.376

-0.94

ICP-MS

2182

0.111

9.30

0.927

2.44

0.516

3.24

GFAAS

3167

0.0400

-2.97

0.780

0.08

0.420

0.36

GFAAS

3187

0.0587

0.24

0.804

0.47

0.428

0.60

ICP-MS

3211

0.0540

-0.57

0.780

0.08

0.411

0.09

GFAAS

3423

0.0700

2.18

0.796

0.34

0.421

0.40

GFAAS

3853

0.0570

-0.05

0.769

-0.10

0.393

-0.45

ICP-MS

3970

0.0531

-0.72

0.820

0.73

0.401

-0.22

GFAAS

4090

0.837

133.88

0.420

-5.71

0.0530

-10.61

ICP-MS (C/R)

4708

0.0580

0.12

0.791

0.26

0.430

0.66

ICP-MS

4953

0.0550

-0.39

0.806

0.50

0.416

0.23

ICP-MS

5591

0.0500

-1.25

0.730

-0.72

0.390

-0.54

ICP-MS

5654

0.0509

-1.10

0.726

-0.78

0.369

-1.18

ICP-MS (C/R)

5691

0.0600

0.46

0.770

-0.08

0.400

-0.24

ICP-MS

5881

0.0533

-0.69

0.754

-0.34

0.389

-0.58

ICP-MS (C/R)

6511

0.0560

-0.23

0.787

0.19

0.411

0.10

ND

6545

0.0600

0.46

0.760

-0.24

0.410

0.06

ICP-MS

7111

0.0570

-0.05

0.811

0.58

0.407

-0.03

ICP-MS

7804

0.0307

-4.57

0.408

-5.90

0.310

-2.92

ND

9674

0.0864

4.99

0.426

-5.62

0.763

10.60

GFAAS

9759

0.0994

7.23

>LL

---

>LL

---

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-P1401

0.0573

0.00154

0.00561

0.0457 - 0.0689

Rejected

---

PC-U-P1402

0.775

0.0101

0.0613

0.651 - 0.899

Rejected

---

PC-U-P1403

0.408

0.00638

0.0329

0.341 - 0.475

Rejected

---

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

45

Statistics
Urine Lead (µmol/L)
All methods

PC-U-P1401

PC-U-P1402

28

27

27

Robust mean Algo A

0.0573

0.775

0.408

Robust STDev

0.00652

0.0420

0.0265

Median

0.0570

0.777

0.410

STDev from MAD

0.00566

0.0400

0.0267

Arithmetic mean

0.0610

0.746

0.408

STDev

0.0169

0.126

0.104

CV or Variability

11.4%

5.4%

6.5%

PC-U-P1401

PC-U-P1402

PC-U-P1403

7

6

6

Robust mean Algo A

0.0729

0.792

0.427

Robust STDev

0.0290

0.0366

0.0252

Median

0.0700

0.788

0.421

STDev from MAD

0.0251

0.0300

0.0221

Arithmetic mean

0.0735

0.755

0.489

STDev

0.0265

0.170

0.141

CV or Variability

39.8%

4.6%

5.9%

PC-U-P1401

PC-U-P1402

PC-U-P1403

N

Graphite furnace-AAS
N

ICP-MS
N

PC-U-P1403

12

12

12

Robust mean Algo A

0.0574

0.779

0.409

Robust STDev

0.00292

0.0339

0.0185

Median

0.0575

0.777

0.409

STDev from MAD

0.00273

0.0326

0.0199

Arithmetic mean

0.0573

0.782

0.409

STDev

0.00539

0.0358

0.0170

5.1%

4.4%

4.5%

PC-U-P1401

PC-U-P1402

PC-U-P1403

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

4

4

4

Robust mean Algo A

0.0524

0.733

0.374

Robust STDev

0.00217

0.125

0.0758

Median

0.0521

0.740

0.379

STDev from MAD

0.00179

0.0990

0.0603

Arithmetic mean

0.0538

0.690

0.315

STDev

0.00432

0.189

0.178

4.1%

17.1%

20.3%

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

46

Distribution
Urine Lead (µmol/L)

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

47

Individual results
Urine Mercury (nmol/L)
Round #2014-01

Participant

PC-U-H1401

z’-score

PC-U-H1402

z’-score

PC-U-H1403

z’-score

Method

176

84.8

0.02

115

0.04

533

0.09

ICP-MS

217

80.0

-0.34

109

-0.30

514

-0.22

ICP-MS

428

97.2

0.95

111

-0.20

553

0.40

ICP-MS (C/R)

720

59.8

-1.84

94.7

-1.15

528

0.01

CV

744

93.0

0.63

133

1.13

609

1.28

ND

1095

90.0

0.41

123

0.54

638

1.74

CV

1109

22.8

-4.60

13.7

-6.00

407

-1.92

ND

1156

82.3

-0.16

97.0

-1.02

550

0.36

ND

1418

79.7

-0.36

108

-0.35

485

-0.68

ND

1865

90.7

0.47

126

0.73

533

0.09

CV

2629

60.3

-1.80

83.3

-1.84

265

-4.15

ICP-MS (C/R)

2982

82.8

-0.13

119

0.28

577

0.78

CV

3468

86.5

0.15

115

0.03

540

0.19

GA-AAS

3513

87.0

0.19

120

0.36

593

1.03

ICP-MS

3853

89.0

0.34

122

0.48

542

0.22

ICP-MS

4708

87.7

0.24

122

0.48

559

0.49

ICP-MS

4953

94.2

0.73

129

0.87

568

0.64

ICP-MS

5029

9.03

-5.63

24.4

-5.36

144

-6.07

ND

5491

80.0

-0.34

104

-0.60

532

0.06

CV

5591

82.8

-0.13

115

0.07

557

0.45

ICP-MS

5654

92.7

0.61

111

-0.21

460

-1.08

ICP-MS (C/R)

5691

48.0

-2.72

52.0

-3.71

205

-5.10

ICP-MS

5881

62.8

-1.62

110

-0.26

494

-0.54

ICP-MS (C/R)

5980

14.9

-5.19

20.8

-5.58

95.6

-6.83

ND

6200

87.5

0.22

113

-0.04

533

0.07

ICP-MS

6210

83.3

-0.09

117

0.16

536

0.13

ND

6511

69.3

-1.13

83.3

-1.84

263

-4.19

ND

6545

85.9

0.10

119

0.28

564

0.57

ICP-MS

6702

83.3

-0.09

112

-0.12

505

-0.36

CV

6794

87.7

0.24

123

0.52

600

1.13

GA-AAS

6892

83.6

-0.07

117

0.18

538

0.16

ND

6920

79.3

-0.39

106

-0.51

421

-1.69

ND

7184

98.3

1.03

135

1.24

597

1.09

CV

7190

78.8

-0.43

108

-0.38

467

-0.96

ND

7269

84.0

-0.04

119

0.30

540

0.19

CV

7804

132

3.55

122

0.48

177

-5.55

ND

7864

98.0

1.01

123

0.54

541

0.21

ND

8701

85.6

0.08

123

0.53

531

0.05

ND

9674

90.7

0.47

124

0.61

568

0.64

CV

9759

111

1.99

152

2.25

649

1.91

GA-AAS

9777

86.1

0.12

114

0.02

516

-0.18

GA-AAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-H1401

84.5

1.68

13.3

57.7 - 111

Rejected

---

PC-U-H1402

114

2.28

16.6

80.6 - 147

Rejected

---

PC-U-H1403

528

11.0

62.3

401 - 655

Rejected

---

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

48

Statistics
Urine Mercury (nmol/L)
All methods

PC-U-H1401

PC-U-H1402

41

41

41

Robust mean Algo A

84.5

114

528

Robust STDev

8.60

11.7

56.5

Median

84.8

115

533

STDev from MAD

7.79

10.9

51.8

Arithmetic mean

80.1

107

489

STDev

22.8

29.5

136

CV or Variability

10.2%

10.2%

10.7%

PC-U-H1401

PC-U-H1402

PC-U-H1403

9

9

9

Robust mean Algo A

85.7

118

554

Robust STDev

8.35

11.7

38.4

Median

84.0

119

540

STDev from MAD

8.90

10.4

42.0

Arithmetic mean

84.4

117

558

STDev

10.8

12.2

41.4

CV or Variability

9.7%

9.9%

6.9%

PC-U-H1401

PC-U-H1402

PC-U-H1403

N

Cold vapor
N

Gold amalgamation-AAS
N

PC-U-H1403

4

4

4

Robust mean Algo A

87.3

120

576

Robust STDev

1.44

7.53

67.7

Median

87.1

119

570

STDev from MAD

1.20

6.21

61.9

Arithmetic mean

92.9

126

576

STDev

12.2

17.6

59.7

CV or Variability

1.6%

6.3%

11.7%

PC-U-H1401

PC-U-H1402

PC-U-H1403

ICP-MS
N

10

10

10

Robust mean Algo A

85.9

117

547

Robust STDev

3.59

6.92

27.0

Median

86.5

117

549

STDev from MAD

3.15

6.44

24.1

Arithmetic mean

82.7

112

517

STDev

12.8

21.6

112

CV or Variability

4.2%

5.9%

4.9%

PC-U-H1401

PC-U-H1402

PC-U-H1403

4

4

4

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

78.3

110

470

Robust STDev

22.0

0.890

85.8

Median

77.7

110

477

STDev from MAD

24.0

0.739

69.6

Arithmetic mean

78.3

104

443

STDev

19.4

13.5

125

CV or Variability

28.1%

0.8%

18.3%

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 #2014-01

Participant

PC-U-N1401

z’-score

PC-U-N1402

z’-score

PC-U-N1403

z’-score

Method

747

0.966

-0.19

2.24

-0.09

1.90

-0.20

ICP-MS

3187

1.06

0.22

2.39

0.35

2.01

0.16

ICP-MS

3423

1.03

0.07

1.79

-1.42

1.96

0.01

HG-AAS

3853

1.06

0.22

2.44

0.50

2.10

0.46

ICP-MS (C/R)

4090

0.980

-0.13

2.25

-0.06

1.93

-0.10

ICP-MS (C/R)

5691

0.910

-0.44

2.12

-0.44

1.82

-0.46

ICP-MS

5881

0.950

-0.26

2.23

-0.11

1.89

-0.23

ICP-MS (C/R)

6511

1.39

1.65

2.81

1.57

2.35

1.29

ND

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

Species

PC-U-N1401

1.01

0.0354

0.224

0.556 - 1.46

Rejected

Spiked with TMSe

PC-U-N1402

2.27

0.0943

0.328

1.59 - 2.95

Accepted

Workers Profile

PC-U-N1403

1.96

0.0463

0.303

1.35 - 2.57

Accepted

Selenomethionine added

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

51

Statistics
Urine Selenium (µmol/L)
All methods

PC-U-N1401

PC-U-N1402

8

8

8

1.01

2.27

1.96

0.0801

0.213

0.105

1.00

2.25

1.95

0.0814

0.200

0.0884

N
Robust mean Algo A
Robust STDev
Median
STDev from MAD

PC-U-N1403

Arithmetic mean

1.04

2.28

2.00

STDev

0.149

0.291

0.167

CV or Variability

7.9%

9.4%

5.3%

PC-U-N1401

PC-U-N1402

PC-U-N1403

3

3

3

Robust mean Algo A

0.979

2.25

1.91

Robust STDev

0.0860

0.153

0.108

Median

0.966

2.24

1.90

STDev from MAD

0.0830

0.178

0.119

ICP-MS
N

Arithmetic mean

0.979

2.25

1.91

STDev

0.0758

0.135

0.0954

8.8%

6.8%

5.7%

PC-U-N1401

PC-U-N1402

PC-U-N1403

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

3

3

3

Robust mean Algo A

0.992

2.26

1.95

Robust STDev

0.0557

0.0346

0.0733

Median

0.980

2.25

1.93

STDev from MAD

0.0442

0.0274

0.0581

Arithmetic mean

0.997

2.31

1.97

STDev

0.0568

0.115

0.111

5.6%

1.5%

3.8%

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

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 #2014-01

Participant

PC-U-S1401

z’-score

PC-U-S1402

z’-score

PC-U-S1403

z’-score

Method

176

0.641

1.07

2.00

0.64

0.787

0.92

ICP-MS

744

0.231

-5.91

0.921

-6.17

0.474

-3.61

ND
ICP-MS

747

0.567

-0.19

1.77

-0.82

0.707

-0.25

1109

0.706

2.18

2.04

0.87

0.793

0.99

ND

1476

0.560

-0.31

1.94

0.25

0.720

-0.06

ICP-MS

1827

0.577

-0.02

1.79

-0.69

0.682

-0.61

ICP-MS (C/R)

1865

0.579

0.02

2.02

0.74

0.727

0.05

ICP-MS (C/R)

2182

0.464

-1.93

1.82

-0.53

0.685

-0.57

GFAAS

2937

0.653

1.28

1.81

-0.57

0.784

0.87

ICP-MS

2978

0.490

-1.50

1.76

-0.87

0.654

-1.01

ICP-MS

3187

0.558

-0.34

1.86

-0.25

0.703

-0.30

ICP-MS

3423

0.534

-0.75

1.92

0.14

0.734

0.15

HG-AAS

3513

0.610

0.55

2.15

1.58

0.870

2.11

ICP-MS

3853

0.634

0.95

2.13

1.44

0.787

0.91

ICP-MS (C/R)

4708

0.567

-0.19

1.93

0.19

0.740

0.23

ICP-MS

5375

0.532

-0.78

1.85

-0.32

0.733

0.13

ICP-MS

5495

0.634

0.95

1.73

-1.10

0.628

-1.38

ICP-MS (C/R)

5591

0.558

-0.34

1.92

0.10

0.726

0.03

ICP-MS

5654

0.688

1.88

1.92

0.10

0.782

0.83

ICP-MS (C/R)

5691

0.530

-0.82

1.77

-0.82

0.680

-0.63

ND

5881

0.590

0.21

1.97

0.42

0.760

0.52

ICP-MS (C/R)

6511

0.571

-0.11

1.90

0.00

0.745

0.30

ND

6892

0.718

2.39

2.09

1.20

0.820

1.38

ND

7864

0.614

0.61

2.02

0.76

0.654

-1.01

ND

9674

0.505

-1.25

1.79

-0.70

0.626

-1.41

GFAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

K-S (Lilliefors)

PC-U-S1401

0.578

0.0164

0.0564

0.461 - 0.695

Accepted

DMAA added

PC-U-S1402

1.90

0.0347

0.155

1.58 - 2.22

Accepted

Workers Profile

PC-U-S1403

0.724

0.0170

0.0672

0.585 - 0.863

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-S1401

PC-U-S1402

25

25

25

Robust mean Algo A

0.578

1.90

0.724

Robust STDev

0.0656

0.139

0.0681

Median

0.571

1.92

0.727

STDev from MAD

0.0612

0.155

0.0703

N

PC-U-S1403

Arithmetic mean

0.572

1.87

0.720

STDev

0.0956

0.231

0.0789

CV or Variability

11.3%

7.3%

9.4%

PC-U-S1401

PC-U-S1402

PC-U-S1403

10

10

10

Robust mean Algo A

0.568

1.89

0.736

Robust STDev

0.0331

0.105

0.0430

Median

0.564

1.89

0.730

STDev from MAD

0.0274

0.0971

0.0363

ICP-MS
N

Arithmetic mean

0.574

1.90

0.742

STDev

0.0490

0.117

0.0592

5.8%

5.6%

5.8%

PC-U-S1401

PC-U-S1402

PC-U-S1403

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

6

6

6

Robust mean Algo A

0.615

1.92

0.732

Robust STDev

0.0436

0.168

0.0620

Median

0.612

1.94

0.744

STDev from MAD

0.0406

0.168

0.0602

Arithmetic mean

0.617

1.92

0.728

STDev

0.0432

0.148

0.0624

7.1%

8.7%

8.5%

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 #2014-01

Participant

PC-U-R1401

z’-score

PC-U-R1402

z’-score

PC-U-R1403

z’-score

Method

176

11.0

0.20

8.44

0.00

14.7

0.07

ICP-MS

747

11.2

0.42

8.32

-0.16

14.8

0.16

ICP-MS

1095

10.3

-0.51

7.83

-0.82

13.6

-0.79

FAAS

1109

12.6

1.86

10.3

2.57

16.3

1.34

ND

1188

14.3

3.64

10.3

2.51

15.4

0.59

ICP-MS (C/R)

1418

9.78

-1.06

7.85

-0.79

14.0

-0.51

ICP-MS (C/R)

2629

9.10

-1.77

7.12

-1.78

12.4

-1.72

ICP-OES

2763

10.4

-0.42

8.29

-0.20

14.2

-0.31

ICP-MS (C/R)

3187

10.2

-0.62

8.11

-0.44

15.0

0.31

ICP-MS

3211

11.0

0.21

9.00

0.75

14.8

0.16

FAAS

3423

13.1

2.36

8.79

0.47

16.4

1.41

FAAS

3513

11.5

0.73

8.90

0.62

15.2

0.47

ICP-MS

3853

9.65

-1.19

7.60

-1.13

12.8

-1.46

ICP-MS

4090

10.5

-0.30

8.10

-0.46

14.4

-0.14

ICP-MS (C/R)

4708

10.7

-0.10

8.55

0.15

14.3

-0.24

ICP-MS

4953

10.6

-0.18

8.30

-0.19

14.2

-0.29

ICP-MS

5591

11.0

0.21

8.40

-0.05

14.1

-0.39

FAAS

5691

10.0

-0.83

7.90

-0.73

13.5

-0.87

ICP-MS

5881

10.7

-0.14

8.18

-0.35

14.2

-0.34

ICP-MS (C/R)

6511

11.7

0.96

9.42

1.32

15.3

0.59

ND

7804

7.61

-3.32

8.25

-0.26

15.8

0.98

ND

8376

11.6

0.79

8.67

0.32

14.6

-0.01

FAAS

8454

8.51

-2.38

6.59

-2.49

12.2

-1.89

FAAS

8981

11.0

0.21

10.1

2.24

16.2

1.26

ND

9759

19.8

9.34

9.65

1.63

14.6

0.03

FAAS

Assigned value

Standard
uncertainty

σ pt

Acceptable range

PC-U-R1401

10.8

0.277

0.919

PC-U-R1402

8.44

0.177

0.721

PC-U-R1403

14.6

0.244

1.24

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

K-S (Lilliefors)

Species

8.88 - 12.7

Rejected

---

6.96 - 9.92

Accepted

---

12.1 - 17.1

Accepted

---

57

Statistics
Urine Zinc (µmol/L)
All methods

PC-U-R1401

PC-U-R1402

25

25

25

Robust mean Algo A

10.8

8.44

14.6

Robust STDev

1.11

0.707

0.975

Median

10.7

8.32

14.6

STDev from MAD

1.04

0.696

0.903

Arithmetic mean

11.1

8.52

14.5

STDev

2.27

0.915

1.10

CV or Variability

10.3%

8.4%

6.7%

PC-U-R1401

PC-U-R1402

PC-U-R1403

7

7

7

Robust mean Algo A

11.2

8.60

14.4

Robust STDev

1.27

0.607

0.859

Median

11.0

8.67

14.6

STDev from MAD

1.02

0.482

0.729

Arithmetic mean

12.2

8.42

14.3

STDev

3.62

0.979

1.27

CV or Variability

11.4%

7.1%

6.0%

PC-U-R1401

PC-U-R1402

PC-U-R1403

N

Flame-AAS
N

ICP-MS
N

PC-U-R1403

8

8

8

Robust mean Algo A

10.6

8.28

14.4

Robust STDev

0.712

0.372

0.686

Median

10.7

8.31

14.5

STDev from MAD

0.742

0.326

0.599

Arithmetic mean

10.6

8.27

14.3

STDev

0.628

0.400

0.824

CV or Variability

6.7%

4.5%

4.8%

PC-U-R1401

PC-U-R1402

PC-U-R1403

ICP-MS (collision/reaction cell)
N

5

5

5

Robust mean Algo A

10.5

8.19

14.3

Robust STDev

0.305

0.207

0.315

Median

10.5

8.18

14.2

STDev from MAD

0.237

0.160

0.326

Arithmetic mean

11.1

8.54

14.4

STDev

1.80

0.995

0.545

CV or Variability

2.9%

2.5%

2.2%

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:
2014-01
SHIPPED ON: 2014-01-20
DEADLINE: 2014-02-28
UNIT

PTM

ASSIGNED
VALUE

PTM

ASSIGNED
VALUE

PTM

ASSIGNED
VALUE

Cadmium

nmol/L

PC-B-C1401

8.88

PC-B-C1402

104

PC-B-C1403

23.2

Lead

µmol/L

PC-B-L1401

1.32

PC-B-L1402

0.295

PC-B-L1403

3.87

Mercury

nmol/L

PC-B-M1401

20.8

PC-B-M1402

9.09

PC-B-M1403

363

Aluminium

µmol/L

PC-S-A1401

1.46

PC-S-A1402

0.643

PC-S-A1403

6.27

Copper

µmol/L

PC-S-E1401

16.7

PC-S-E1402

27.1

PC-S-E1403

9.67

Manganese

nmol/L

PC-S-G1401

29.9

PC-S-G1402

11.5

PC-S-G1403

53.6

Selenium

µmol/L

PC-S-E1401

1.68

PC-S-E1402

2.20

PC-S-E1403

1.34

Zinc

µmol/L

PC-S-E1401

19.0

PC-S-E1402

26.9

PC-S-E1403

12.4

Cadmium

nmol/L

PC-U-D1401

93.1

PC-U-D1402

19.3

PC-U-D1403

52.9

Chromium

nmol/L

PC-U-B1401

22.1

PC-U-B1402

240

PC-U-B1403

34.2

Copper

µmol/L

PC-U-R1401

4.01

PC-U-R1402

2.14

PC-U-R1403

14.6

Fluoride

µmol/L

PC-U-F1401

27.7

PC-U-F1402

57.3

PC-U-F1403

256

Inorganic arsenic

µmol/L

PC-U-S1401

0.465

PC-U-S1402

1.44

PC-U-S1403

0.654

Iodide

µmol/L

PC-U-I1401

0.608

PC-U-I1402

1.70

PC-U-I1403

2.18

Lead

µmol/L

PC-U-P1401

0.0573

PC-U-P1402

0.775

PC-U-P1403

0.408

Mercury

nmol/L

PC-U-H1401

84.5

PC-U-H1402

114

PC-U-H1403

528

Selenium

µmol/L

PC-U-N1401

1.01

PC-U-N1402

2.27

PC-U-N1403

1.96

Total arsenic

µmol/L

PC-U-S1401

0.578

PC-U-S1402

1.90

PC-U-S1403

0.724

Zinc

µmol/L

PC-U-R1401

10.8

PC-U-R1402

8.44

PC-U-R1403

14.6

MATRIX
Blood

Serum

Urine

ANALYTE

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


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