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pdfINTERLABORATORY COMPARISON PROGRAM
FOR METALS IN BIOLOGICAL MATRICES
(PCI)
REPORT FOR ROUND:
2014-02
PTMS SHIPPING DATE:
2014-03-10
DATE OF PUBLICATION:
2014-05-09
Scope of accreditation: The concentration of Selenium in materials PC-S-E1406 and PC-U-N1406
as well as Iodide in material PC-U-I1404 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
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 2014-02.
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
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 #2014-02
Participant
PC-B-C1404
z’-score
PC-B-C1405
z’-score
PC-B-C1406
z’-score
Method
176
18.7
-0.05
121
-0.49
48.9
-0.99
ICP-MS
194
22.5
1.52
128
0.19
55.2
0.26
ND
217
19.0
0.06
116
-0.94
50.8
-0.62
ICP-MS
747
18.6
-0.08
126
0.00
53.5
-0.08
ICP-MS
1095
20.0
0.49
136
0.97
58.6
0.93
ICP-MS (C/R)
1188
20.1
0.54
126
0.00
53.4
-0.10
ICP-MS (C/R)
1418
18.1
-0.27
130
0.38
56.7
0.55
ICP-MS (C/R)
1865
19.1
0.13
129
0.29
56.8
0.57
ICP-MS (C/R)
2305
15.8
-1.25
111
-1.51
51.4
-0.50
ND
2991
21.9
1.27
130
0.42
59.9
1.19
ND
3187
18.4
-0.16
123
-0.29
51.9
-0.40
ICP-MS
3211
18.5
-0.12
120
-0.59
52.5
-0.28
GFAAS
3248
15.5
-1.37
109
-1.63
45.9
-1.59
GFAAS
3853
19.3
0.19
136
1.00
57.1
0.64
ICP-MS
4708
19.1
0.12
128
0.19
54.7
0.16
ICP-MS
4953
20.3
0.61
132
0.55
56.3
0.48
ICP-MS
5591
17.2
-0.66
117
-0.92
49.0
-0.97
ICP-MS
5654
18.8
-0.01
111
-1.49
48.0
-1.16
ICP-MS (C/R)
5691
18.0
-0.33
116
-0.97
53.0
-0.18
ICP-MS
6511
18.7
-0.05
130
0.38
57.8
0.78
ND
6545
18.0
-0.33
120
-0.58
51.9
-0.40
ICP-MS
6689
13.6
-2.14
131
0.44
48.7
-1.04
GFAAS
6794
26.0
2.96
140
1.36
58.1
0.83
GFAAS
6858
14.8
-1.64
129
0.32
52.5
-0.27
ICP-MS
7760
19.2
0.18
132
0.63
56.3
0.48
ICP-MS
9777
22.2
1.42
132
0.58
62.6
1.72
GFAAS
Assigned value
Standard
uncertainty
σ pt
Acceptable range
PC-B-C1404
18.8
0.312
2.41
PC-B-C1405
126
1.83
10.1
PC-B-C1406
53.9
1.04
4.92
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
K-S (Lilliefors)
Species
13.9 - 23.7
Rejected
---
105 - 147
Accepted
---
43.8 - 64.0
Accepted
---
2
Statistics
Blood Cadmium (nmol/L)
All methods
PC-B-C1404
PC-B-C1405
26
26
26
Robust mean Algo A
18.8
126
53.9
Robust STDev
1.27
7.47
4.25
Median
18.7
128
53.5
STDev from MAD
1.08
7.01
4.51
Arithmetic mean
18.9
125
53.9
STDev
2.53
8.33
4.05
CV or Variability
6.8%
5.9%
7.9%
PC-B-C1404
PC-B-C1405
PC-B-C1406
5
5
5
Robust mean Algo A
19.2
126
53.5
Robust STDev
5.69
13.4
7.72
Median
18.5
131
52.5
STDev from MAD
5.55
14.0
8.29
Arithmetic mean
19.2
126
53.5
STDev
5.02
11.9
6.81
CV or Variability
29.7%
10.6%
14.4%
PC-B-C1404
PC-B-C1405
PC-B-C1406
N
Graphite furnace-AAS
N
ICP-MS
N
PC-B-C1406
12
12
12
Robust mean Algo A
18.6
125
53.0
Robust STDev
0.918
7.84
3.09
Median
18.6
125
52.8
STDev from MAD
0.898
8.87
2.89
Arithmetic mean
18.4
125
53.0
STDev
1.37
6.91
2.73
CV or Variability
4.9%
6.3%
5.8%
PC-B-C1404
PC-B-C1405
PC-B-C1406
ICP-MS (collision/reaction cell)
N
5
5
5
Robust mean Algo A
19.2
129
55.6
Robust STDev
0.939
5.60
2.93
Median
19.1
129
56.7
STDev from MAD
1.30
4.44
2.87
Arithmetic mean
19.2
126
54.7
STDev
0.828
9.43
4.16
CV or Variability
4.9%
4.4%
5.3%
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
3
Distribution
Blood Cadmium (nmol/L)
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
4
Individual results
Blood Lead (µmol/L)
Round #2014-02
Participant
PC-B-L1404
z’-score
PC-B-L1405
z’-score
PC-B-L1406
z’-score
194
0.0820
-0.29
0.980
-2.17
0.598
-1.73
ND
217
0.0900
0.24
1.25
1.09
0.730
0.93
ICP-MS
226
0.0917
0.35
1.12
-0.49
0.709
0.51
ICP-MS
317
LL
---
>LL
---
ICP-MS
9674
LL
---
1.67
0.48
0.393
-0.14
ICP-MS (C/R)
2305
4.17
-0.47
1.72
0.80
0.610
3.59
ND
2516
4.15
-0.52
1.52
-0.53
0.420
0.33
GFAAS
2763
4.57
0.63
1.73
0.86
0.390
-0.19
ICP-MS (C/R)
3150
5.36
2.81
1.61
0.07
0.570
2.90
GFAAS
3513
4.16
-0.50
1.52
-0.53
0.350
-0.88
ICP-MS (C/R)
3773
4.36
0.06
1.53
-0.49
0.334
-1.14
ICP-MS (C/R)
3853
4.27
-0.19
1.59
-0.07
0.390
-0.19
ICP-MS (C/R)
4082
4.38
0.11
1.66
0.40
0.398
-0.05
ICP-MS (C/R)
4590
4.57
0.63
1.46
-0.93
0.266
-2.32
GFAAS
4953
4.22
-0.34
1.58
-0.11
0.394
-0.12
ICP-MS (C/R)
5291
4.28
-0.17
1.31
-1.93
0.300
-1.73
ND
5556
4.72
1.06
1.56
-0.28
0.448
0.81
GFAAS
5596
4.42
0.23
1.60
0.00
0.350
-0.88
ICP-MS (C/R)
5654
5.21
2.41
1.96
2.40
0.405
0.07
ICP-MS (C/R)
5691
3.90
-1.21
1.41
-1.26
0.260
-2.42
ICP-MS
5881
4.44
0.28
1.67
0.47
0.410
0.16
ICP-MS (C/R)
5955
4.34
0.00
1.58
-0.13
0.404
0.05
ND
6511
4.18
-0.44
1.64
0.28
0.450
0.83
ND
6545
4.43
0.25
1.73
0.86
0.450
0.84
ICP-MS
6711
4.33
-0.03
1.55
-0.33
0.400
-0.02
ICP-MS
7311
4.27
-0.19
1.62
0.13
0.370
-0.53
ICP-MS
7804
3.58
-2.09
1.47
-0.86
0.990
10.12
ND
8376
3.90
-1.22
1.38
-1.43
0.389
-0.21
GFAAS
8454
3.74
-1.65
1.52
-0.53
0.250
-2.59
GFAAS
9759
4.34
0.01
1.58
-0.15
0.248
-2.62
GFAAS
Assigned value
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
PC-S-E1404
4.34
0.0548
0.359
3.61 - 5.07
Accepted
---
PC-S-E1405
1.60
0.0241
0.149
1.30 - 1.90
Accepted
---
PC-S-E1406
0.401*
0.0138
0.0566
0.284 - 0.518
Rejected
---
The assigned value is outside the concentration range of our scope of accreditation.
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
21
Statistics
Serum Selenium (µmol/L)
All methods
PC-S-E1404
PC-S-E1405
33
34
34
Robust mean Algo A
4.34
1.60
0.401
Robust STDev
0.252
0.112
0.0644
Median
4.34
1.59
0.399
STDev from MAD
0.242
0.104
0.0608
0.419
N
PC-S-E1406
Arithmetic mean
4.36
1.60
STDev
0.354
0.130
0.132
CV or Variability
5.8%
7.0%
16.1%
PC-S-E1404
PC-S-E1405
PC-S-E1406
8
8
8
Robust mean Algo A
4.35
1.53
0.390
Robust STDev
0.479
0.0696
0.143
Median
4.35
1.54
0.404
STDev from MAD
0.445
0.0669
0.196
0.390
Graphite furnace-AAS
N
Arithmetic mean
4.39
1.53
STDev
0.509
0.0750
0.126
CV or Variability
11.0%
4.5%
36.7%
PC-S-E1404
PC-S-E1405
PC-S-E1406
ICP-MS
N
7
7
7
Robust mean Algo A
4.33
1.62
0.400
Robust STDev
0.107
0.117
0.0478
Median
4.33
1.62
0.400
STDev from MAD
0.0890
0.104
0.0445
Arithmetic mean
4.34
1.62
0.390
STDev
0.269
0.118
0.0646
CV or Variability
2.5%
7.2%
11.9%
PC-S-E1404
PC-S-E1405
PC-S-E1406
ICP-MS (collision/reaction cell)
N
12
13
13
Robust mean Algo A
4.39
1.64
0.393
Robust STDev
0.219
0.111
0.0213
Median
4.40
1.66
0.393
STDev from MAD
0.222
0.104
0.0182
Arithmetic mean
4.43
1.65
0.390
STDev
0.298
0.129
0.0292
CV or Variability
5.0%
6.8%
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
22
Distribution
Serum Selenium (µmol/L)
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
23
Individual results
Serum Zinc (µmol/L)
Round #2014-02
Participant
PC-S-E1404
z’-score
PC-S-E1405
z’-score
PC-S-E1406
z’-score
217
39.2
0.27
17.3
0.35
4.58
2.56
Method
FAAS
226
38.1
-0.03
16.3
-0.24
3.64
0.02
ICP-MS (C/R)
428
35.3
-0.76
15.1
-0.96
3.21
-1.13
ICP-MS (C/R)
636
39.1
0.23
17.0
0.17
3.72
0.23
ICP-MS
747
39.1
0.24
17.3
0.36
3.32
-0.84
ICP-MS
1095
36.7
-0.39
16.4
-0.18
3.90
0.73
FAAS
1188
38.5
0.08
17.0
0.16
3.69
0.16
ICP-MS (C/R)
1300
38.2
0.01
17.3
0.35
3.52
-0.31
FAAS
1855
37.1
-0.28
15.9
-0.45
3.12
-1.38
ICP-MS
2305
35.3
-0.77
4.45
-7.35
16.0
33.50
ND
2516
37.4
-0.21
16.3
-0.24
3.70
0.19
FAAS
2580
38.2
0.00
16.7
0.00
2.30
-3.59
FAAS
2763
37.6
-0.16
16.6
-0.06
3.53
-0.27
ICP-MS (C/R)
2907
43.8
1.46
19.0
1.39
LL
---
0.320
-1.41
>LL
---
GFAAS
3423
2.90
0.58
0.404
0.19
4.07
-0.30
HG-AAS
3853
2.78
0.15
0.406
0.23
4.37
0.39
ICP-MS (C/R)
5375
2.69
-0.18
0.425
0.59
4.12
-0.19
ICP-MS
5495
2.83
0.34
0.282
-2.13
4.14
-0.14
ICP-MS (C/R)
5691
2.63
-0.40
0.400
0.11
3.72
-1.14
ND
5881
2.17
-2.07
0.361
-0.63
3.28
-2.17
HG-AAS
6511
2.84
0.35
0.364
-0.56
4.03
-0.40
ND
6545
3.05
1.12
0.360
-0.65
4.14
-0.14
ND
7162
2.59
-0.54
0.414
0.38
4.51
0.72
ND
8701
2.86
0.43
0.380
-0.27
4.35
0.35
ND
Assigned value
Standard
uncertainty
PC-U-S1404
2.74
0.0595
PC-U-S1405
0.394
0.0100
PC-U-S1406
4.20
0.117
0.406
σ pt
Acceptable range
K-S (Lilliefors)
Species
0.270
2.19 - 3.29
Accepted
Workers Profile
0.0515
0.289 - 0.499
Accepted
As+3 added
3.35 - 5.05
Accepted
As+5 added
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
39
Statistics
Urine Inorganic arsenic (µmol/L)
All methods
PC-U-S1404
PC-U-S1405
21
22
21
Robust mean Algo A
2.74
0.394
4.20
Robust STDev
0.218
0.0375
0.429
Median
2.76
0.402
4.14
STDev from MAD
0.210
0.0402
0.498
N
PC-U-S1406
Arithmetic mean
2.69
0.391
4.18
STDev
0.282
0.0425
0.467
CV or Variability
8.0%
9.5%
10.2%
PC-U-S1404
PC-U-S1405
PC-U-S1406
5
6
5
Robust mean Algo A
2.84
0.410
4.37
Robust STDev
0.155
0.0214
0.379
Median
2.89
0.412
4.51
STDev from MAD
0.142
0.0215
0.399
Graphite furnace-AAS
N
Arithmetic mean
2.79
0.400
4.37
STDev
0.240
0.0409
0.334
CV or Variability
5.5%
5.2%
8.7%
PC-U-S1404
PC-U-S1405
PC-U-S1406
Hydride generation-AAS
N
4
4
4
Robust mean Algo A
2.43
0.409
3.80
Robust STDev
0.542
0.0463
0.813
Median
2.46
0.407
3.68
STDev from MAD
0.544
0.0360
0.675
Arithmetic mean
2.43
0.411
3.91
STDev
0.478
0.0453
0.900
CV or Variability
22.3%
11.3%
21.4%
PC-U-S1404
PC-U-S1405
PC-U-S1406
ICP-MS (collision/reaction cell)
N
5
5
5
Robust mean Algo A
2.76
0.370
4.33
Robust STDev
0.159
0.0688
0.350
Median
2.78
0.368
4.37
STDev from MAD
0.167
0.0564
0.332
Arithmetic mean
2.76
0.370
4.33
STDev
0.140
0.0611
0.309
CV or Variability
5.8%
18.6%
8.1%
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
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 #2014-02
Participant
PC-U-I1404
z’-score
PC-U-I1405
z’-score
PC-U-I1406
z’-score
217
3.49
0.53
0.460
1.68
2.59
0.55
ICP-MS
428
3.33
0.04
0.383
-0.25
2.38
-0.28
ICP-MS (C/R)
747
3.35
0.12
0.387
-0.15
2.45
0.00
ICP-MS
1095
3.50
0.56
0.510
2.93
2.55
0.39
ICP-MS (C/R)
1855
3.50
0.55
0.426
0.81
2.49
0.16
ICP-MS
2629
4.57
3.69
0.500
2.68
3.01
2.21
ND
2763
3.15
-0.47
0.381
-0.30
2.26
-0.75
ICP-MS
3187
3.30
-0.03
0.383
-0.25
2.45
0.00
ICP-MS
3513
2.94
-1.08
0.320
-1.83
2.04
-1.62
ICP-MS
4708
3.23
-0.23
0.383
-0.25
2.39
-0.24
ICP-MS
5881
3.46
0.43
0.394
0.02
2.90
1.77
ICP-MS (C/R)
6200
3.54
0.66
0.439
1.15
2.62
0.69
ICP-MS
6511
2.98
-0.97
0.382
-0.27
2.23
-0.89
ND
6545
3.17
-0.41
0.400
0.18
2.32
-0.51
ICP-MS
8981
3.01
-0.88
0.260
-3.33
2.33
-0.47
ND
Assigned value
*
Method
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
PC-U-I1404
3.31*
0.0827
0.331
2.63 - 3.99
Rejected
---
PC-U-I1405
0.393
0.00739
0.0393
0.313 - 0.473
Accepted
---
PC-U-I1406
2.45
0.0648
0.245
1.94 - 2.96
Accepted
---
The assigned value is outside the concentration range of our scope of accreditation.
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
42
Statistics
Urine Iodide (µmol/L)
All methods
PC-U-I1404
PC-U-I1405
15
15
15
Robust mean Algo A
3.31
0.393
2.45
Robust STDev
0.256
0.0229
0.201
Median
3.33
0.387
2.45
STDev from MAD
0.257
0.0193
0.193
N
PC-U-I1406
Arithmetic mean
3.37
0.401
2.47
STDev
0.388
0.0630
0.249
CV or Variability
7.7%
5.8%
8.2%
PC-U-I1404
PC-U-I1405
PC-U-I1406
9
9
9
Robust mean Algo A
3.30
0.393
2.41
Robust STDev
0.213
0.0225
0.170
Median
3.30
0.387
2.45
STDev from MAD
0.222
0.0193
0.193
ICP-MS
N
Arithmetic mean
3.30
0.398
2.40
STDev
0.196
0.0407
0.179
CV or Variability
6.5%
5.7%
7.1%
PC-U-I1404
PC-U-I1405
PC-U-I1406
ICP-MS (collision/reaction cell)
N
3
3
3
3.44
0.399
2.61
0.0791
0.0206
0.301
Robust mean Algo A
Robust STDev
Median
3.46
0.394
2.55
STDev from MAD
0.0627
0.0164
0.252
Arithmetic mean
3.43
0.429
2.61
0.0911
0.0704
0.265
2.3%
5.2%
11.5%
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
43
Distribution
Urine Iodide (µmol/L)
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
44
Individual results
Urine Lead (µmol/L)
Round #2014-02
Participant
PC-U-P1404
z’-score
PC-U-P1405
z’-score
PC-U-P1406
z’-score
Method
176
0.801
0.00
0.179
-0.16
0.0869
-0.33
ICP-MS
194
0.502
-4.63
0.132
-3.14
0.0730
-1.99
ND
217
0.850
0.76
0.230
3.14
0.100
1.25
ICP-MS
747
0.777
-0.37
0.178
-0.19
0.0878
-0.22
ICP-MS
1095
0.830
0.45
0.190
0.58
0.100
1.25
ICP-MS (C/R)
1109
0.851
0.78
0.194
0.81
0.0963
0.81
ND
1855
0.792
-0.15
0.179
-0.16
0.0869
-0.33
ICP-MS
2182
0.864
0.97
0.198
1.08
0.114
2.91
GFAAS
3167
0.830
0.45
0.230
3.14
0.130
4.85
GFAAS
3187
0.801
0.00
0.177
-0.26
0.0897
0.01
ICP-MS
3211
0.908
1.66
0.189
0.51
0.0900
0.05
GFAAS
3423
0.869
1.05
0.192
0.68
0.0917
0.25
GFAAS
3853
0.753
-0.74
0.173
-0.51
0.0850
-0.55
ICP-MS
3970
0.845
0.67
0.183
0.15
0.0820
-0.91
GFAAS
4708
0.770
-0.48
0.173
-0.51
0.0871
-0.30
ICP-MS
4953
0.796
-0.07
0.178
-0.19
0.0898
0.02
ICP-MS
5591
0.780
-0.33
0.180
-0.06
0.0900
0.05
ICP-MS
5654
0.739
-0.96
0.160
-1.33
0.0808
-1.06
ICP-MS (C/R)
5691
0.690
-1.72
0.150
-1.99
0.0800
-1.15
ICP-MS
5881
0.756
-0.69
0.169
-0.75
0.0847
-0.58
ICP-MS (C/R)
6511
0.798
-0.04
0.181
0.00
0.0898
0.02
ND
6545
0.790
-0.17
0.170
-0.70
0.0900
0.05
ICP-MS
7111
0.791
-0.15
0.175
-0.38
0.0870
-0.31
ICP-MS
9674
0.806
0.08
0.243
3.99
0.132
5.11
GFAAS
9759
>LL
---
0.192
0.71
0.0840
-0.67
GFAAS
Assigned value
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
PC-U-P1404
0.801
0.0126
0.0633
0.672 - 0.930
Accepted
---
PC-U-P1405
0.181
0.00348
0.0152
0.150 - 0.212
Rejected
---
PC-U-P1406
0.0896
0.00187
0.00812
0.0729 - 0.106
Rejected
---
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
45
Statistics
Urine Lead (µmol/L)
All methods
PC-U-P1404
PC-U-P1405
24
25
25
Robust mean Algo A
0.801
0.181
0.0896
Robust STDev
0.0492
0.0139
0.00747
Median
0.797
0.179
0.0897
STDev from MAD
0.0485
0.0138
0.00697
N
PC-U-P1406
Arithmetic mean
0.791
0.184
0.0923
STDev
0.0776
0.0238
0.0140
6.2%
7.7%
8.3%
PC-U-P1404
PC-U-P1405
PC-U-P1406
6
7
7
Robust mean Algo A
0.853
0.195
0.0982
Robust STDev
0.0347
0.00923
0.0163
Median
0.854
0.192
0.0917
STDev from MAD
0.0287
0.00859
0.0143
CV or Variability
Graphite furnace-AAS
N
Arithmetic mean
0.854
0.204
0.103
STDev
0.0352
0.0231
0.0216
4.1%
4.7%
16.6%
PC-U-P1404
PC-U-P1405
PC-U-P1406
CV or Variability
ICP-MS
N
12
12
12
Robust mean Algo A
0.787
0.176
0.0880
Robust STDev
0.0169
0.00391
0.00285
Median
0.791
0.178
0.0875
STDev from MAD
0.0157
0.00371
0.00339
Arithmetic mean
0.783
0.178
0.0883
STDev
0.0373
0.0181
0.00461
2.1%
2.2%
3.2%
PC-U-P1404
PC-U-P1405
PC-U-P1406
CV or Variability
ICP-MS (collision/reaction cell)
N
3
3
3
Robust mean Algo A
0.763
0.173
0.0864
Robust STDev
0.0324
0.0170
0.00741
Median
0.756
0.169
0.0847
STDev from MAD
0.0257
0.0135
0.00587
Arithmetic mean
0.775
0.173
0.0885
STDev
0.0483
0.0153
0.0101
4.2%
9.8%
8.6%
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
46
Distribution
Urine Lead (µmol/L)
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
47
Individual results
Urine Mercury (nmol/L)
Round #2014-02
Participant
PC-U-H1404
z’-score
PC-U-H1405
z’-score
PC-U-H1406
z’-score
Method
176
588
0.44
140
0.46
214
0.27
ICP-MS
217
477
-1.23
119
-0.65
177
-1.11
ICP-MS
428
588
0.44
150
1.00
205
-0.06
ICP-MS (C/R)
720
454
-1.58
125
-0.34
145
-2.30
CV
1095
578
0.28
130
-0.05
205
-0.07
CV
1156
577
0.27
123
-0.42
261
1.98
ND
1418
498
-0.92
130
-0.05
210
0.11
ND
1865
565
0.09
142
0.57
222
0.57
CV
2629
593
0.51
137
0.33
188
-0.70
ICP-MS (C/R)
2982
529
-0.44
127
-0.20
211
0.16
CV
3187
538
-0.31
117
-0.75
184
-0.85
ICP-MS
3468
405
-2.31
128
-0.16
213
0.22
GA-AAS
3513
636
1.15
151
1.08
214
0.26
ICP-MS
3853
615
0.84
139
0.43
222
0.55
ICP-MS
4604
574
0.22
134
0.16
220
0.48
ND
4708
568
0.13
129
-0.11
212
0.18
ICP-MS
4953
633
1.11
145
0.76
224
0.64
ICP-MS
5491
627
1.02
159
1.51
239
1.18
CV
5591
555
-0.07
127
-0.20
197
-0.36
ICP-MS
5654
644
1.28
147
0.85
203
-0.15
ICP-MS (C/R)
5691
435
-1.86
107
-1.29
143
-2.36
ICP-MS
5881
597
0.57
131
-0.02
213
0.22
ICP-MS (C/R)
6200
558
-0.01
123
-0.43
198
-0.34
ICP-MS
6210
560
0.02
127
-0.24
202
-0.19
ND
6511
607
0.71
136
0.27
182
-0.91
ND
6545
341
-3.26
78.3
-2.84
95.9
-4.10
ICP-MS
6702
558
-0.01
133
0.11
219
0.44
CV
6794
602
0.64
143
0.66
229
0.81
GA-AAS
6892
559
0.00
127
-0.22
202
-0.18
ND
6920
495
-0.96
124
-0.36
188
-0.70
ND
7184
614
0.82
135
0.22
217
0.37
CV
7190
>LL
---
120
-0.61
197
-0.35
ND
7269
566
0.10
131
0.00
207
0.00
CV
7864
534
-0.37
113
-0.97
221
0.52
ND
8701
524
-0.52
124
-0.40
207
0.01
ND
9674
155
-6.05
236
5.65
633
15.73
CV
9759
587
0.42
136
0.25
225
0.68
GA-AAS
9777
280
-4.18
128
-0.16
135
-2.64
GA-AAS
Assigned value
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
PC-U-H1404
559
11.5
65.7
426 - 692
Accepted
---
PC-U-H1405
131
2.15
18.4
93.9 - 168
Rejected
---
PC-U-H1406
207
3.69
26.9
153 - 261
Rejected
---
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
48
Statistics
Urine Mercury (nmol/L)
All methods
PC-U-H1404
PC-U-H1405
N
37
38
38
Robust mean Algo A
559
131
207
Robust STDev
56.0
10.6
18.2
Median
565
130
209
STDev from MAD
52.5
9.89
16.8
Arithmetic mean
536
133
213
STDev
102
22.0
76.3
10.0%
8.1%
8.8%
PC-U-H1404
PC-U-H1405
PC-U-H1406
9
9
9
Robust mean Algo A
557
135
217
Robust STDev
56.1
8.89
16.9
Median
565
133
217
STDev from MAD
52.5
8.56
14.8
Arithmetic mean
516
146
255
STDev
144
35.1
144
10.1%
6.6%
7.8%
PC-U-H1404
PC-U-H1405
PC-U-H1406
CV or Variability
Cold vapor
N
CV or Variability
Gold amalgamation-AAS
N
PC-U-H1406
4
4
4
Robust mean Algo A
468
133
217
Robust STDev
175
6.89
14.2
Median
496
132
219
STDev from MAD
146
5.68
11.8
Arithmetic mean
468
134
201
STDev
CV or Variability
ICP-MS
154
7.32
44.0
37.3%
5.2%
6.5%
PC-U-H1404
PC-U-H1405
PC-U-H1406
N
11
11
11
Robust mean Algo A
549
127
197
Robust STDev
82.6
17.8
26.1
Median
558
127
198
STDev from MAD
84.2
17.4
24.4
Arithmetic mean
540
125
189
STDev
90.4
20.3
39.0
CV or Variability
15.1%
14.0%
13.3%
PC-U-H1404
PC-U-H1405
PC-U-H1406
4
4
4
ICP-MS (collision/reaction cell)
N
Robust mean Algo A
596
141
204
Robust STDev
8.13
9.91
9.32
Median
595
142
204
STDev from MAD
6.65
9.24
7.43
Arithmetic mean
606
141
202
STDev
26.0
8.74
10.4
CV or Variability
1.4%
7.0%
4.6%
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
49
Distribution
Urine Mercury (nmol/L)
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
50
Individual results
Urine Selenium (µmol/L)
Round #2014-02
Participant
PC-U-N1404
z’-score
PC-U-N1405
z’-score
PC-U-N1406
z’-score
Method
747
1.88
0.00
2.25
0.28
5.08
-0.13
ICP-MS
3187
1.84
-0.11
2.22
0.18
4.97
-0.30
ICP-MS
3423
1.37
-1.42
2.17
0.04
5.65
0.78
HG-AAS
3853
4.94
8.60
2.04
-0.37
1.79
-5.39
ICP-MS (C/R)
5691
1.53
-0.98
1.85
-0.95
4.91
-0.40
ICP-MS
5881
1.89
0.02
2.10
-0.19
5.42
0.42
ICP-MS (C/R)
6511
2.15
0.76
2.63
1.43
5.75
0.94
ND
Assigned value
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
1.88
0.197
0.296
1.17 - 2.59
Rejected
Workers Profile
PC-U-N1405
2.16
0.0647
0.319
1.51 - 2.81
Accepted
Se+4 added
PC-U-N1406
5.16*
0.264
0.567
3.91 - 6.41
Accepted
Spiked with TMSe
PC-U-N1404
*
The assigned value is outside the concentration range of our scope of accreditation.
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
51
Statistics
Urine Selenium (µmol/L)
All methods
PC-U-N1404
PC-U-N1405
7
7
7
Robust mean Algo A
1.88
2.16
5.16
Robust STDev
0.417
0.137
0.559
Median
1.88
2.17
5.08
STDev from MAD
0.399
0.113
0.505
Arithmetic mean
2.23
2.18
4.79
STDev
1.22
0.238
1.36
CV or Variability
22.2%
6.3%
10.8%
PC-U-N1404
PC-U-N1405
PC-U-N1406
3
3
3
1.82
2.21
4.99
0.0749
0.0562
0.0978
1.84
2.22
4.97
0.0593
0.0445
0.0890
N
ICP-MS
N
Robust mean Algo A
Robust STDev
Median
STDev from MAD
PC-U-N1406
Arithmetic mean
1.75
2.11
4.99
STDev
0.192
0.223
0.0862
CV or Variability
4.1%
2.5%
2.0%
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
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 #2014-02
Participant
PC-U-S1404
z’-score
PC-U-S1405
z’-score
PC-U-S1406
z’-score
Method
176
3.12
-0.26
0.440
0.16
4.24
-0.47
ICP-MS
747
3.09
-0.39
0.429
-0.09
4.21
-0.57
ICP-MS
1109
3.78
2.31
0.494
1.32
5.05
1.81
ND
1827
3.09
-0.39
0.403
-0.65
4.31
-0.29
ICP-MS (C/R)
1865
3.39
0.79
0.422
-0.24
4.68
0.79
ICP-MS (C/R)
2182
3.11
-0.32
0.454
0.45
4.43
0.06
GFAAS
2937
2.52
-2.66
0.441
0.17
3.55
-2.47
ICP-MS
2978
3.15
-0.16
0.410
-0.50
4.38
-0.09
ICP-MS
3187
3.22
0.12
0.424
-0.20
4.37
-0.11
ICP-MS
3423
3.16
-0.12
0.464
0.68
4.33
-0.22
HG-AAS
3513
3.25
0.24
0.450
0.37
4.59
0.51
ICP-MS
3853
3.44
0.99
0.424
-0.20
4.71
0.86
ICP-MS (C/R)
4708
3.25
0.24
0.424
-0.20
4.40
-0.03
ICP-MS
4953
3.46
1.05
0.416
-0.36
4.70
0.82
ICP-MS (C/R)
5375
3.00
-0.75
0.436
0.07
4.16
-0.71
ICP-MS
5495
3.07
-0.47
0.296
-2.99
4.18
-0.65
ICP-MS (C/R)
5591
2.98
-0.85
0.439
0.13
4.25
-0.47
ICP-MS
5654
3.13
-0.23
0.460
0.58
4.16
-0.72
ICP-MS (C/R)
5691
3.11
-0.32
0.410
-0.50
4.22
-0.54
ND
5881
3.50
1.21
0.439
0.12
4.82
1.17
ICP-MS (C/R)
6511
3.22
0.13
0.438
0.10
4.54
0.38
ND
6545
3.68
1.93
0.500
1.45
5.14
2.09
ND
6892
3.28
0.35
0.467
0.74
4.15
-0.74
ND
7864
2.76
-1.68
0.374
-1.28
3.98
-1.24
ND
9674
3.51
1.26
0.246
-4.07
4.70
0.82
GFAAS
Assigned value
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
PC-U-S1404
3.19
0.0393
0.251
2.68 - 3.70
Accepted
Workers Profile
PC-U-S1405
0.433
0.00680
0.0456
0.341 - 0.525
Accepted
As+3 added
PC-U-S1406
4.41
0.0758
0.341
3.71 - 5.11
Accepted
As+5 added
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
54
Statistics
Urine Total arsenic (µmol/L)
All methods
PC-U-S1404
PC-U-S1405
25
25
25
Robust mean Algo A
3.19
0.433
4.41
Robust STDev
0.157
0.0272
0.303
Median
3.16
0.436
4.37
STDev from MAD
0.133
0.0264
0.311
N
PC-U-S1406
Arithmetic mean
3.21
0.424
4.41
STDev
0.269
0.0540
0.343
CV or Variability
4.9%
6.3%
6.9%
PC-U-S1404
PC-U-S1405
PC-U-S1406
9
9
9
Robust mean Algo A
3.10
0.434
4.28
Robust STDev
0.151
0.0112
0.175
Median
3.12
0.436
4.25
STDev from MAD
0.183
0.0104
0.185
ICP-MS
N
Arithmetic mean
3.06
0.433
4.24
STDev
0.229
0.0121
0.290
CV or Variability
4.9%
2.6%
4.1%
PC-U-S1404
PC-U-S1405
PC-U-S1406
ICP-MS (collision/reaction cell)
N
7
7
7
Robust mean Algo A
3.32
0.421
4.58
Robust STDev
0.181
0.0274
0.216
Median
3.39
0.422
4.68
STDev from MAD
0.158
0.0251
0.202
Arithmetic mean
3.30
0.408
4.51
STDev
0.190
0.0530
0.281
CV or Variability
5.5%
6.5%
4.7%
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
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 #2014-02
Participant
PC-U-R1404
z’-score
PC-U-R1405
z’-score
PC-U-R1406
z’-score
Method
176
7.08
0.05
11.8
0.32
16.2
0.26
ICP-MS
747
7.20
0.25
11.9
0.40
16.0
0.15
ICP-MS
1095
7.23
0.30
11.9
0.40
16.6
0.59
FAAS
1188
7.10
0.08
11.5
-0.05
15.6
-0.15
ICP-MS (C/R)
1418
6.43
-1.01
10.9
-0.57
15.3
-0.33
ICP-MS (C/R)
2629
6.28
-1.26
10.3
-1.19
14.1
-1.27
ICP-OES
2763
6.91
-0.23
11.5
0.00
15.7
-0.07
ICP-MS (C/R)
3187
7.29
0.39
11.7
0.20
15.8
0.00
ICP-MS
3211
7.60
0.90
12.4
0.91
16.9
0.81
FAAS
3423
12.0
8.18
13.6
2.09
18.3
1.86
FAAS
3513
7.62
0.93
11.9
0.40
16.5
0.48
ICP-MS
3853
6.38
-1.10
10.7
-0.83
14.3
-1.12
ICP-MS
4708
7.02
-0.05
11.6
0.10
15.9
0.07
ICP-MS
4953
6.93
-0.20
11.3
-0.17
16.1
0.23
ICP-MS
5591
7.10
0.08
11.7
0.20
16.2
0.29
FAAS
5691
6.30
-1.23
10.6
-0.91
15.1
-0.51
ICP-MS
5881
7.10
0.08
11.2
-0.28
15.2
-0.41
ICP-MS (C/R)
6511
7.63
0.95
12.8
1.31
16.9
0.78
ND
7804
3.63
-5.61
5.80
-5.74
9.01
-4.97
ND
8376
7.03
-0.04
11.3
-0.22
15.6
-0.18
FAAS
8454
7.32
0.44
11.6
0.10
15.5
-0.22
FAAS
8981
6.90
-0.25
14.5
3.02
16.3
0.37
ND
9759
1.79
-8.62
2.42
-9.15
3.58
-8.95
FAAS
Assigned value
Standard
uncertainty
σ pt
Acceptable range
K-S (Lilliefors)
Species
PC-U-R1404
7.05
0.0980
0.601
5.83 - 8.27
Rejected
---
PC-U-R1405
11.5
0.148
0.986
9.51 - 13.5
Rejected
---
PC-U-R1406
15.8
0.214
1.35
13.1 - 18.5
Rejected
---
Centre de toxicologie du Québec/INSPQ - External quality assessment schemes
57
Statistics
Urine Zinc (µmol/L)
All methods
PC-U-R1404
PC-U-R1405
23
23
23
Robust mean Algo A
7.05
11.5
15.8
Robust STDev
0.376
0.568
0.819
Median
7.08
11.6
15.8
STDev from MAD
0.314
0.470
0.742
Arithmetic mean
6.87
11.1
15.1
STDev
1.74
2.44
3.02
CV or Variability
5.3%
4.9%
5.2%
PC-U-R1404
PC-U-R1405
PC-U-R1406
7
7
7
Robust mean Algo A
7.25
11.8
16.2
Robust STDev
0.363
0.719
1.17
Median
7.23
11.7
16.2
STDev from MAD
0.303
0.618
1.04
Arithmetic mean
7.16
10.7
14.7
STDev
2.97
3.73
4.98
CV or Variability
5.0%
6.1%
7.2%
PC-U-R1404
PC-U-R1405
PC-U-R1406
N
Flame-AAS
N
ICP-MS
N
PC-U-R1406
8
8
8
Robust mean Algo A
7.03
11.6
15.9
Robust STDev
0.349
0.385
0.335
Median
7.05
11.7
16.0
STDev from MAD
0.290
0.371
0.277
Arithmetic mean
6.98
11.4
15.7
STDev
0.446
0.528
0.706
CV or Variability
5.0%
3.3%
2.1%
PC-U-R1404
PC-U-R1405
PC-U-R1406
ICP-MS (collision/reaction cell)
N
4
4
4
Robust mean Algo A
6.97
11.3
15.5
Robust STDev
0.168
0.248
0.243
Median
7.00
11.3
15.5
STDev from MAD
0.139
0.206
0.260
Arithmetic mean
6.88
11.3
15.5
STDev
0.312
0.258
0.215
CV or Variability
2.4%
2.2%
1.6%
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
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:
2014-02
SHIPPED ON: 2014-03-10
DEADLINE: 2014-04-18
MATRIX
Blood
Serum
Urine
ANALYTE
UNIT
PTM
ASSIGNED
VALUE
PTM
ASSIGNED
VALUE
PTM
ASSIGNED
VALUE
Cadmium
nmol/L
PC-B-C1404
18.8
PC-B-C1405
126
PC-B-C1406
53.9
Lead
µmol/L
PC-B-L1404
0.0864
PC-B-L1405
1.16
PC-B-L1406
0.684
Mercury
nmol/L
PC-B-M1404
15.0
PC-B-M1405
51.3
PC-B-M1406
94.5
Aluminium
µmol/L
PC-S-A1404
0.482
PC-S-A1405
3.29
PC-S-A1406
1.78
Copper
µmol/L
PC-S-E1404
39.1
PC-S-E1405
16.0
PC-S-E1406
3.34
Manganese
nmol/L
PC-S-G1404
67.4
PC-S-G1405
104
PC-S-G1406
11.3
Selenium
µmol/L
PC-S-E1404
4.34
PC-S-E1405
1.60
PC-S-E1406
0.401
Zinc
µmol/L
PC-S-E1404
38.2
PC-S-E1405
16.7
PC-S-E1406
3.63
Cadmium
nmol/L
PC-U-D1404
8.44
PC-U-D1405
36.4
PC-U-D1406
70.0
Chromium
nmol/L
PC-U-B1404
55.0
PC-U-B1405
414
PC-U-B1406
89.6
Copper
µmol/L
PC-U-R1404
0.342
PC-U-R1405
3.28
PC-U-R1406
1.13
Fluoride
µmol/L
PC-U-F1404
14.6
PC-U-F1405
408
PC-U-F1406
180
Inorganic arsenic
µmol/L
PC-U-S1404
2.74
PC-U-S1405
0.394
PC-U-S1406
4.20
Iodide
µmol/L
PC-U-I1404
3.31
PC-U-I1405
0.393
PC-U-I1406
2.45
Lead
µmol/L
PC-U-P1404
0.801
PC-U-P1405
0.181
PC-U-P1406
0.0896
Mercury
nmol/L
PC-U-H1404
559
PC-U-H1405
131
PC-U-H1406
207
Selenium
µmol/L
PC-U-N1404
1.88
PC-U-N1405
2.16
PC-U-N1406
5.16
Total arsenic
µmol/L
PC-U-S1404
3.19
PC-U-S1405
0.433
PC-U-S1406
4.41
Zinc
µmol/L
PC-U-R1404
7.05
PC-U-R1405
11.5
PC-U-R1406
15.8
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
| File Type | application/pdf |
| Author | David Bisson |
| File Modified | 2014-05-09 |
| File Created | 2014-05-09 |