coal (round 22) proficiency testing programpta.asn.au/phocadownload/reports/2007/531.pdf · 2015....

COAL (ROUND 22)

PROFICIENCY TESTING PROGRAM

JANUARY 2007

REPORT NO. 531

ACKNOWLEDGEMENTS PTA wishes to acknowledge gratefully the technical assistance provided for this program by Mr M Preston of ACIRL Quality Testing Services Ltd, Gladstone QLD and Mr J Kelly of BHP Billiton Mitsubishi Alliance, QLD.

© COPYRIGHT 2007 PROFICIENCY TESTING AUSTRALIA

PO Box 7507, Silverwater, NSW 2128 Australia

CONTENTS Page 1. Foreword 1

2. Features of the program 1

3. Format of appendices 2

4. Statistical design of the program 2

TABLE A: Summary Statistics 3

5. Outlier results 3

TABLE B: Outlier Results 4

6. Technical comments 4

TABLE C: Robust Co-efficient of Variation (%) 5

TABLE D: Outlier Results – Previous Rounds 5

7. Reference 6

APPENDIX A – Summary of Results and Robust Z-Score Charts

Moisture (air-dry basis) A1 – A2 Ash A3 – A4 Volatile Matter A5 – A6 Gross Calorific Value A7 – A8 Total Sulfur A9 – A10 Pyritic Sulfur, Sulphate Sulfur A11 Chlorine A12 – A13 Carbon (total) A14 Hydrogen A15 Nitrogen A16 Carbonate Carbon A17 Phosphorus in Coal A18 – A19 Relative Density A20 – A21 Fluorine, Mercury, Selenium & Arsenic A22

APPENDIX B Sample preparation and homogeneity testing B1 APPENDIX C Instructions to Participants and Results Sheet C1 – C3

1

1. FOREWORD This report summarises the results for round twenty-two of a series of proficiency testing

programs on the chemical analysis of coal.

The exercise was conducted by Proficiency Testing Australia in October 2006. The aim of the program was to assess laboratories' ability to competently perform the tests examined.

2. FEATURES OF THE PROGRAM a) A total of 34 laboratories were sent samples for the program, comprising of:

29 laboratories from Australia; 1 laboratory from Malaysia; 2 laboratories from Hong Kong; 1 laboratory from New Zealand and 1 laboratory from India. 31 of the 34 laboratories returned results in time for inclusion in the final report.

b) Participating laboratories were supplied one 250 gram sample of washed coal labelled

PTA 1/06. c) The following tests were performed on each sample in duplicate:

• Moisture • Ash • Volatile Matter • Gross Calorific Value • Total Sulfur • Pyritic Sulfur • Sulphate Sulfur • Chlorine • Carbon (total) • Hydrogen • Nitrogen • Carbonate Carbon • Phosphorus in Coal • Relative Density • Fluorine • Mercury • Selenium • Arsenic

Not all laboratories reported results for each analyte. d) Prior to distribution the samples were analysed for homogeneity. Based on the results of

this preliminary testing it was concluded that the samples were sufficiently homogeneous. Therefore, any results later identified as outliers could not be attributed to any significant sample variability. (Appendix B)

e) Laboratories were requested to perform the tests according to their copy of the

"Instructions to Participants" and to record their results on the accompanying "Results Sheet", both of which were distributed to participants with the sample. (Appendix C)

f) Each laboratory was randomly allocated a unique code number for the program to enable

confidentiality of results. Reference to each laboratory in this report is made by its code number.

2

3. FORMAT OF APPENDICES APPENDIX A (i) The duplicate results reported by laboratories and the calculated average result for

each test on each sample. (ii) Robust z-scores and z-score charts calculated on the average of the submitted

results (except for Pyritic Sulfur, Sulphate Sulfur, Fluorine, Mercury, Selenium and Arsenic).

(iii) A table of robust statistics for each test - number of results, median, normalised

IQR, robust CV, minimum, maximum and range (except for Pyritic Sulfur, Sulphate Sulfur, Fluorine, Mercury, Selenium and Arsenic).

APPENDIX B Appendix B contains details of sample preparation and homogeneity testing data.

APPENDIX C Appendix C contains a copy of the “Instructions to Participants” and the “Results Sheet” supplied to participants.

4. STATISTICAL DESIGN OF THE PROGRAM

Robust statistical procedures were used to generate the z-scores and summary statistics for the sample. • number of results • median • normalised interquartile range • minimum • maximum • range

Robust z-scores were calculated for each laboratory based on the average of results submitted for each analyte. Where only one result was submitted, that result was used to calculate the z-score. Z-scores were not calculated for Pyritic Sulfur, Sulphate Sulfur, Fluorine, Mercury, Selenium and Arsenic as there were no more than four results reported for any of these analytes.

3

TABLE A: Summary Statistics

Test No. of Results Median Normalised IQR Moisture (air-dry basis) (0.01%) 31 1.345 0.315

Ash (0.01%) 31 9.950 0.098

Volatile Matter (0.01%) 30 20.235 0.187

Gross Calorific Value (0.001 MJ/kg) 28 32.4373 0.1115

Total Sulfur (0.001%) 28 0.5785 0.0226

Pyritic Sulfur (0.001%) 4 0.0493 0.0113

Sulphate Sulfur (0.001%) 4 0.0203 0.0033

Chlorine (0.001%) 14 0.0605 0.0107

Carbon (total) (0.01%) 9 79.535 0.630

Hydrogen (0.01%) 8 4.403 0.163

Nitrogen (0.01%) 8 1.778 0.061

Carbonate Carbon (0.001%) 7 0.0300 0.0044

Phosphorus in Coal (0.001%) 12 0.0320 0.0025

Relative Density (0.001%) 21 1.3625 0.0259

Fluorine (1mg/kg) 4 88.0 11.9

Mercury (0.01mg/kg) 2 0.030 0.000

Selenium (0.1mg/kg) 2 0.68 0.06

Arsenic (0.1mg/kg) 2 0.40 0.00

5. OUTLIER RESULTS In order to achieve the program's aim of assessing laboratories' testing performance, a

robust statistical approach, which uses z-scores to assess participants performance has been utilised. The z-score is a measure of how far the result(s) is from the consensus value - a normalised value which gives a "score" to each result relative to the other results in the group. Therefore a z-score close to zero means that the result agrees well with those from other laboratories. An outlier will be any result(s) which has an absolute z-score value greater than three.

4

TABLE B: Outlier Results

Test Lab Code

Moisture (air-dry basis) 21A, 21B, 23, 28, 33, 36

Ash 21A, 21B

Volatile Matter -

Gross Calorific Value -

Total Sulfur -

Pyritic Sulfur Not calculated

Sulphate Sulfur Not calculated

Chlorine -

Carbon (total) 29

Hydrogen 19

Nitrogen -

Carbonate Carbon 30

Phosphorus in Coal 18, 30, 34

Relative Density -

Fluorine Not calculated

Mercury Not calculated

Selenium Not calculated

Arsenic Not calculated

6. TECHNICAL COMMENTS General Comments –

For the fourteen tests, the 31 laboratories reported a total of 245 results (after averaging). In total 14 outlier results were reported from 11 laboratories. This means 5.71% of the total results reported for this program were outlier results. The results appear to be typical values for the coal types used for this program. Moisture and Ash values achieved for the program closely matched those of the homogeneity testing. The following tables give a comparison of performances for tests common to the previous programs.

5

TABLE C: Robust Co-efficient of Variation (%)

Test Round 20 Round 21 Round 22

* Moisture 30.1 11.1 23.42

Ash 1.2 1.5 0.99

Volatile Matter 1.1 0.9 0.93

Gross Calorific Value 0.4 0.3 0.34

Total Sulfur 3.2 4.0 3.91

Chlorine 14.4 13.2 17.61

Phosphorus 4.6 4.5 7.82

* Moisture analysis is required purely as a correctional value, to enable calculation of other results to dry basis. Any statistical analysis is for interest only.

The Robust Co-efficient of Variation for these tests is comparable to previous programs.

TABLE D: Outlier Results – Previous Rounds

Test Round 20 Round 21 Round 22

Total Results 284 290 245

No. of Outlier Results 19 14 14

% of Total 6.7% 4.8% 5.71%

The ratio of outliers is comparable with previous programs. Outlier laboratories not only need to review their method but perhaps ensure results are to the correct basis or value. The majority of outliers were outside the repeatability/reproducibility values stated in the relevant AS1038 series so if laboratories are reporting to Australian Standards they should carry out investigations. Also any laboratories reporting results with a |z-scorebetween 2 and 3 are also encouraged to review procedures. The specified method for performing the tests was AS1038 (relevant sections). The majority of participating laboratories followed this method. Other methods reported included relevant ASTM, BS, ISO and in-house methods.

6

Overall the results compared favourably to previous programs. Measurement Uncertainty For this program participating laboratories were asked to report Measurement Uncertainty. Of the 31 laboratories who returned results, only 29 responded with varying tests and values. Most laboratories are using the published reproducibility figures of the relevant standards as their measure of uncertainty value for e.g.: Standards Australia table listed below

Standards Australia Precision Data Standard Test Repeatability Reproducability AS1038.3 Moisture 0.10% N/A AS1038.3 Ash 0.15% 0.25% AS1038.3 Volatile Matter 0.2% 1.0% AS1038.5 Gross Calorific Value 0.13 MJ/kg 0.30 MJ/kg AS1038.6.3.2 Total Sulfur 0.03% 0.08% AS1038.6.3.3 Total sulfur 0.03% 0.05% AS1038.8.1 Chlorine 0.01% 0.02% AS1038.8.2 Chlorine 0.01% 0.02% AS1038.9.1 Phosphorus 10% of mean 15% of mean AS1038.9.2 Phosphorus 10% of mean 15% of mean AS1038.9.3 Phosphorus 10% of mean 15% of mean AS1038.15 AFT (IDT) 30ºC 80ºC AS1038.15 AFT (ST) 30ºC 60ºC AS1038.15 AFT (HT) 30ºC 60ºC AS1038.15 AFT (Flow) 40ºC 80ºC

7. REFERENCE

[1] “Guide to Proficiency Testing Australia” – February 2006 (this document is located on the PTA website at www.pta.asn.au under “Publications”).

APPENDIX A

Summary of Results

and

Robust Z-Score Charts

A1

MOISTURE (air-dry basis) (0.01%) Lab

Code Result 1 Result 2 Average Robust Z-Score Method/ Technique MU

1 1.30 1.25 1.28 -0.22 AS1038.3-2000 2 1.19 1.15 1.17 -0.56 AS1038.3 5 1.62 1.61 1.62 0.86 AS1038.3.2 0.0028 7 1.68 1.68 1.68 1.06 AS1038.3 8 1.26 1.24 1.25 -0.30 ISO5068-1983 0.07

10 1.41 1.43 1.42 0.24 AS1038.3 0.1 11 1.21 1.12 1.17 -0.57 AS1038.3 0.10 13 1.22 1.23 1.23 -0.38 BS1016 Section 104.1 0.01 14 0.94 0.97 0.96 -1.24 AS1038.3 15 1.31 1.32 1.32 -0.10 AS1038.3 16 1.36 1.33 1.35 0.00 AS1038 Part 3 0.1 17 1.33 1.30 1.32 -0.10 AS1038.3 18 1.23 1.21 1.22 -0.40 AS1038.3 0.20 19 1.31 1.30 1.31 -0.13 20 1.36 1.34 1.35 0.02 AS1038.3-2000

21A 2.33 2.28 2.31 3.05 § ASTM: D3173-03 1.84% 21B 2.44 2.48 2.46 3.54 § ASTM: D5142-04 1.30% 22 1.35 1.37 1.36 0.05 AS1038.3 23 3.11 3.05 3.08 5.51 § In house method 24 1.56 1.60 1.58 0.75 AS1038 Part 3 0.1 25 1.17 1.18 1.18 -0.54 0.1 26 1.38 1.40 1.39 0.14 AS1038.3

27 1.0 1.2 1.10 -0.78 EMS-HV-M-SP001.4.5 TGA Method 0.15

28 2.925 2.925 2.93 5.02 § AS1038.3 0.1

29 1.14 1.19 1.17 -0.57 In house based on ASTM D3173-00 0.06

30 1.27 1.27 1.27 -0.24 AS1038.3 31 1.18 1.13 1.16 -0.60 AS1038.3 33 2.32 2.27 2.30 3.02 § AS1038.3 0.1 34 1.4 1.40 0.17 35 1.75 1.77 1.76 1.32 AS1038.3 0.1 36 3.29 3.29 3.29 6.17 § ISO11722-1999 0.53

No. of Results 31 Median 1.345 Normalised IQR 0.315 Robust CV 23.42% Minimum 0.96 Maximum 3.29 Range 2.34

Note: § Denotes an outlier

A2

Moisture (air-dry basis) (0.01%)

1427 31 11 29 2

25 18 138 30 1 19 15 17

16 20 22 26 3410

24 57

35

3321A21B

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00

Laboratory Code Number

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36

A3

ASH (0.01%) Lab


1 9.77 9.83 9.80 -1.53 In House Rapid Method 2 10.00 9.96 9.98 0.31 AS1038.3 5 9.81 9.76 9.79 -1.68 AS1038.3.3 0.15% 7 10.00 9.97 9.99 0.36 AS1038.3 8 9.93 9.90 9.92 -0.36 ISO1171-1997 0.07

10 9.94 9.95 9.95 -0.05 AS1038.3 0.1 11 9.92 9.89 9.91 -0.46 AS1038.3 0.1 13 9.95 9.96 9.96 0.05 ISO1171:1997 0.23 14 10.12 10.14 10.13 1.83 AS1038.3 15 9.93 9.97 9.95 0.00 AS1038.3 16 9.95 9.91 9.93 -0.20 AS1038 Part 3 0.25 17 10.01 9.98 10.00 0.46 AS1038.3 0.25 18 10.02 10.06 10.04 0.92 AS1038.3 0.25 19 10.05 9.98 10.02 0.66 20 9.89 9.87 9.88 -0.71 AS1038.3-2000 0.15

21A 10.37 10.29 10.33 3.87 § ASTM: D3174-04 4.30% 21B 10.40 10.33 10.37 4.23 § ASTM: D5142-04 2.70% 22 10.14 10.21 10.18 2.29 AS1038 23 9.97 10.01 9.99 0.41 In house method 24 9.80 9.78 9.79 -1.63 AS1038 Part 3 0.25 25 10.02 10.00 10.01 0.61 AS1038.3 0.15 26 9.81 9.84 9.83 -1.27 AS1038.3 0.15

27 10.0 9.9 9.95 0.00 EMS-HV-M-SP001.4.5 TGA Method 0.079

28 9.99 10.00 10.00 0.46 AS1038.3 0.1

29 9.91 9.91 9.91 -0.41 In house based on ASTM D3174-00 0.16

30 9.85 9.87 9.86 -0.92 AS1038.3 31 10.2 10.1 10.15 2.04 AS1038.3 0.25 33 9.92 9.96 9.94 -0.10 AS1038.3 0.15 34 9.84 9.84 -1.12 35 9.81 9.8 9.81 -1.48 AS1038.3 0.1 36 9.73 9.76 9.75 -2.09 ISO1171-1997 0.19


Notes: § Denotes an outlier

A4

Ash (0.01%)

365 24 1 35

26 3430 20

11 29 816 33

10 15 27 132 7 23 17 28

25 1918

14 3122

21A

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00


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21B

A5

VOLATILE MATTER (0.01%) Lab


1 20.09 20.22 20.16 -0.43 AS1038.3-2000 2 20.17 20.01 20.09 -0.77 AS1038.3 7 19.94 20.10 20.02 -1.15 AS1038.3 8 20.00 19.93 19.97 -1.44 ISO562-1988 0.13

10 20.08 20.04 20.06 -0.93 AS1038.3 0.2 11 20.16 20.24 20.20 -0.19 AS1038.3 0.20 13 19.97 19.73 19.85 -2.06 ISO562:1998 0.8 14 20.36 20.2 20.28 0.24 AS1038.3 15 20.33 20.37 20.35 0.61 AS1038.3 16 20.18 20.17 20.18 -0.32 AS1038 Part 3 1.00 17 20.26 20.06 20.16 -0.40 AS1038.3 0.1 18 20.34 20.41 20.38 0.75 AS1038.3 0.5 19 20.26 20.17 20.22 -0.11 20 20.38 20.29 20.34 0.53 AS1038.3-2000 1

21A 19.78 19.85 19.82 -2.24 ASTM: D3175-02 5.10% 21B 20.12 20.11 20.12 -0.64 ASTM: D5142-04 1.40% 22 20.14 20.07 20.11 -0.69 AS1038 23 19.92 19.81 19.87 -1.98 AS1038.3 24 20.32 20.27 20.30 0.32 AS1038 Part 3 1 25 20.59 20.43 20.51 1.47 AS1038.3 0.15 26 20.43 20.38 20.41 0.91 AS1038.3 0.5 27 20.3 20.3 20.30 0.35 AS1038.3 0.1 28 20.45 20.36 20.41 0.91 AS1038.3 0.2 29 20.61 20.64 20.63 2.08 In house based on D3175-89a 2.44 30 20.51 20.29 20.40 0.88 AS1038.3 31 19.82 19.69 19.76 -2.56 AS1038.3 1.0 33 20.31 20.20 20.26 0.11 AS1038.3 0.50 34 20.28 20.28 0.24 35 20.32 20.25 20.29 0.27 AS1038.3 0.2 36 20.60 20.59 20.60 1.92 ISO562-1998 3.5


A6

Volatile Matter (0.01%)

3121A13

238

7 102 2221B

1 17 16 1119

33 14 34 35 2427 20

15 1830 26 28

2536 29

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-2.00

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0.00

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3.00

4.00


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A7

GROSS CALORIFIC VALUE (0.001MJ/kg) Lab


2 32.471 32.518 32.495 0.51 AS1038.5.1 5 32.334 32.384 32.359 -0.70 AS1038.5 0.30 7 32.560 32.540 32.550 1.01 AS1038.5 0 8 32.453 32.436 32.445 0.07 ISO1928-1995 0.11

10 32.617 32.672 32.645 1.86 AS1038.5 0.1 11 32.477 32.528 32.503 0.59 AS1038.5 0.13 13 32.395 32.373 32.384 -0.48 ISO1928:1995 0.181 14 32.304 32.294 32.299 -1.24 AS1038.5 15 32.48 32.55 32.515 0.70 AS1038.5 16 32.460 32.476 32.468 0.28 AS1038 Part 5 0.30 17 32.60 32.49 32.545 0.97 AS1038.5 0.30 18 32.382 32.414 32.398 -0.35 AS1038.5 0.3 19 32.378 32.459 32.419 -0.17 20 32.351 32.372 32.362 -0.68 AS1038.5-1998 0.3

21A 32.242 32.275 32.259 -1.60 ASTM: D5865-04 1.00% 22 32.320 32.242 32.281 -1.40 AS1038.5 23 32.300 32.340 32.320 -1.05 AS1038.5 24 32.515 32.480 32.498 0.54 AS1038 Part 5 0.3 26 32.540 32.480 32.510 0.65 AS1038.5 0.30 27 32.410 32.300 32.355 -0.74 AS1038.5 0.14 28 32.5 32.58 32.540 0.92 AS1038.5 0.13 29 32.411 32.37 32.391 -0.42 ASTM D5865-99a 0.115 30 32.51 32.57 32.540 0.92 AS1038.5 31 32.276 32.251 32.264 -1.56 AS1038.5 0.3 33 32.394 32.398 32.396 -0.37 AS1038.5 0.3 34 32.43 32.430 -0.07 35 32.498 32.508 32.503 0.59 AS1038.5 0.13 36 32.588 32.611 32.600 1.46 ISO1928-1995 0.32


A8

Gross Calorific Value (0.001MJ/kg)

21A31 2214 23

27 5 2013 29 33 18

19 34

8 162 24 11 35 26 15

28 30 17 736

10

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A9

TOTAL SULFUR (0.001%) Lab


2 0.567 0.577 0.572 -0.29 AS1038.6.3.3 7 0.581 0.574 0.578 -0.04 AS1038.6.3.3

8 0.577 0.580 0.579 0.00 ASTM D4239-2000 IR Furnace method 0.01

11 0.599 0.596 0.598 0.84 0.03 13 0.577 0.580 0.579 0.00 ASTM D4239-97 0.075 14 0.559 0.547 0.553 -1.13 AS1038.6.3.3 15 0.547 0.543 0.545 -1.48 AS1038.11 16 0.573 0.573 0.573 -0.24 AS1038 Part 6.3.3 0.05 17 0.600 0.592 0.596 0.77 AS1038.6.3.2 0.05 18 0.561 0.563 0.562 -0.73 AS1038.6.3.2 0.08 19 0.588 0.601 0.595 0.71 20 0.558 0.553 0.556 -1.02 AS1038.6.3.3-1997 0.05

21A 0.621 0.627 0.624 2.01 ASTM: D3177-02 Eschka mixture 2.65%

21B 0.613 0.614 0.614 1.55 ASTM: D3177-02 Bomb washing 2.87%

22 0.577 0.574 0.576 -0.13 AS1038.6.3.3 23 0.523 0.525 0.524 -2.41 AS1038.6.3.2 24 0.591 0.595 0.593 0.64 AS1038 Part 6.3.3 0.05 25 0.589 0.597 0.593 0.64 AS1038 Part 6.3.3 0.03 26 0.573 0.577 0.575 -0.15 AS1038.6.3.3 0.05 27 0.58 0.58 0.580 0.07 AS1038.5 0.017 28 0.560 0.556 0.558 -0.91 AS1038.6.3.3 0.03 29 0.588 0.592 0.590 0.51 ASTM D4239-00 0.038 30 0.565 0.560 0.563 -0.71 AS1038.6.3.3 31 0.583 0.591 0.587 0.38 AS1038.6.3.3 0.05 33 0.570 0.555 0.563 -0.71 AS1038.6.3.3 0.050 34 0.62 0.620 1.84 35 0.582 0.584 0.583 0.20 AS1038.6.3.3 0.03 36 0.583 0.581 0.582 0.15 ASTM D4239-04a 0.09


A10

Total Sulfur (0.001%)

23

1514 20

28 18 30 332 16 26 22

7 8 13 27 3635 31

29 24 2519 17 11

21B3421A

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A11

PYRITIC SULFUR (0.001%)

Lab Code Result 1 Result 2 Average Method/ Technique MU

3 0.050 0.043 0.047 Acid Digestion ICP 0.027 8 0.064 0.083 0.074 AS1038Part11-1993 0.02

14 0.053 0.051 0.052 AS1038 Part11 30 0.029 0.029 0.029 AS1038.11 #

SULPHATE SULFUR (0.001%) Lab

Code Result 1 Result 2 Average Method/ Technique MU

3 0.014 0.013 0.0135 0.006 8 0.022 0.016 0.019 AS1038Part11-1993 0.02

14 0.022 0.026 0.024 AS1038 Part11 30 0.025 0.018 0.02 AS1038.11

A12

CHLORINE (0.001%) Lab


2 0.051 0.051 0.051 -0.89 AS1038.8.2.1 7 0.040 0.054 0.047 -1.27 AS1038.8.1 8 0.063 0.068 0.066 0.47 ASTM D4208-88 0.005

14 0.064 0.066 0.065 0.42 In house 15 0.058 0.058 0.058 -0.23 AS1038.8.1 17 0.050 0.052 0.051 -0.89 AS1038.8.2 0.02 19 0.082 0.080 0.081 1.92 20 0.065 0.061 0.063 0.23 ASTM D2361-2001 0.06 22 0.049 0.051 0.050 -0.99 AS1038.8.1 23 0.058 0.051 0.055 -0.56 AS1038.8 24 0.062 0.067 0.065 0.38 AS1038 Part 8.2 0.02 30 0.067 0.067 0.067 0.61 AS1038.8 34 0.036 0.036 -2.30 35 0.073 0.071 0.072 1.08 AS1038.8.1 0.01


A13

Chlorine (0.001%)

34

722 2 17

2315

20 24 14 830

35

19

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0.00

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A14

CARBON (TOTAL) (0.01%) Lab


7 80.09 80.08 80.09 0.87 AS1038.6.4 8 80.82 80.78 80.80 2.01 In house 0.34

14 79.06 78.89 78.98 -0.89 AS1038.6.4 18 79.31 79.30 79.31 -0.37 AS1038.6 0.6 19 79.81 79.82 79.82 0.44 28 79.27 79.20 79.24 -0.48 AS1038.6.1 0.3 29 82.562 82.463 82.51 4.73 § ASTM D5373-93 0.64 30 79.47 79.60 79.54 0.00 In house 35 78.28 78.38 78.33 -1.91 AS1038.6.4 0.3



Carbon (total) (0.01%)

35

1428 18

3019

7

8

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-3.00

-2.00

-1.00

0.00

1.00

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A15

HYDROGEN (0.01%) Lab


7 4.55 4.48 4.52 0.69 AS1038.6.4 14 4.25 4.22 4.24 -1.03 AS1038.6.4 18 4.46 4.47 4.47 0.38 AS1038.6 0.20 19 5.70 5.62 5.66 7.71 § 28 4.35 4.33 4.34 -0.38 AS1038.6.1 0.10 29 4.26 4.29 4.28 -0.78 ASTM D5373-93 0.16 30 4.50 4.45 4.48 0.44 in house 35 4.21 4.20 4.21 -1.21 AS1038.6.4 0.10



Hydrogen (0.01%)

35 1429

28

18 307

-4.00

-3.00

-2.00

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0.00

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A16

NITROGEN (0.01%) Lab


7 1.77 1.76 1.77 -0.20 AS1038.6.4 14 1.80 1.78 1.79 0.20 AS1038.6.4 18 1.85 1.85 1.85 1.19 AS1038.6 0.08 19 1.38 1.40 1.39 -6.34 § 28 1.84 1.82 1.83 0.86 AS1038.6.2 0.03 29 1.74 1.74 1.74 -0.61 ASTM D5373-93 0.11 30 1.82 1.79 1.81 0.45 in house 35 1.70 1.69 1.70 -1.35 AS1038.6.4 4.00%



Nitrogen (0.01%)

35

297

1430

2818

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00


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A17

CARBONATE CARBON (0.001%) Lab


7 0.020 0.020 0.020 -2.25 AS1038.23 14 0.033 0.028 0.031 0.11 AS1038.23 20 0.026 0.029 0.028 -0.56 AS1038.23-2002 0.02 22 0.023 0.021 0.022 -1.80 AS1038.23 26 0.032 0.030 0.031 0.22 AS1038.23 0.02 30 0.054 0.046 0.050 4.50 § AS1038.23 35 0.033 0.027 0.030 0.00 AS1038.23 0.01


Notes: § Outlier reported

Carbonate Carbon (0.001%)

722

20

35 14 26

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00


Rob

ust Z

-Sco

re

30

A18

PHOSPHORUS IN COAL (0.001%) Lab


2 0.033 0.033 0.033 0.40 AS1038.9.3 3 0.029 0.031 0.030 -0.80 NQ854 XRF 0.002

14 0.028 0.029 0.029 -1.40 AS1038.14.3 17 0.0327 0.0327 0.033 0.28 AS1038.9.2 0.003 18 0.046 0.042 0.044 4.80 § AS1038.9.2 0.15 20 0.032 0.031 0.032 -0.20 AS1038.9.1-2000 0.009 22 0.028 0.027 0.028 -1.80 AS1038.9.3 24 0.033 0.033 0.033 0.40 AS1038 Part 9.3 0.014 30 0.043 0.044 0.044 4.60 § BS1016.14 # 31 0.032 0.033 0.033 0.20 AS1038.9.2 0.15 34 0.021 0.021 -4.40 § 0 35 0.031 0.031 0.031 -0.40 AS1038.9.1 0.003



A19

Phosphorus in Coal (0.001%)

2214

335 20

31 17 2 24

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00


Rob

ust Z

-Sco

re

30

34

18

A20

RELATIVE DENSITY (0.001%) Lab


2 1.390 1.380 1.385 0.87 AS1038.21.1.2 7 1.390 1.370 1.380 0.67 AS1038.21.1.2 8 1.345 1.341 1.343 -0.75 AS1038.21-1983 0.01

11 1.384 1.394 1.389 1.02 AS1038.21.1.1 0.02 14 1.358 1.343 1.351 -0.46 AS1038.21.1.2 15 1.355 1.356 1.356 -0.27 AS1038.21.1.1 17 1.36 1.34 1.350 -0.48 AS1038.21.1.2 0.1 18 1.354 1.362 1.358 -0.17 AS1038.21.1.1 0.08 19 1.339 1.377 1.358 -0.17 20 1.380 1.381 1.381 0.69 AS1038.21.1.1-2002 0.03 22 1.398 1.405 1.402 1.50 AS1038.21.1.1 24 1.369 1.377 1.373 0.40 AS1038 Part 21.1.2 0.03 25 1.348 1.348 1.348 -0.56 AS1038 Part 21.1.1 0.03 26 1.358 1.337 1.348 -0.58 AS1038.21.1.1 0.08 27 1.35 1.34 1.345 -0.67 AS1038.21.1.2 0.016 28 1.371 1.354 1.363 0.00 AS1038.21.1.1 0.03 30 1.401 1.385 1.393 1.18 AS1038.21.1.1 31 1.345 1.334 1.340 -0.89 AS1038.21.1.1 0.08 33 1.382 1.412 1.397 1.33 AS1038.21.1.2 0.1 34 1.4 1.400 1.45 35 1.378 1.374 1.376 0.52 AS1038.21.1.1 0.03


A21

Relative Density (0.001%)

31 8 2726 25 17 14

15 18 19

2824 35

7 20 211 30

33 34 22

-4.00

-3.00

-2.00

-1.00

0.00

1.00

2.00

3.00

4.00


Rob

ust Z

-Sco

re

A22

FLUORINE (1mg/kg)

Lab Code Result 1 Result 2 Average Method/ Technique MU

3 90 100 95 Pyrohydrolysis ISE Measurement 1000%

7 76 86 81 AS1038.10.4 8 71 86 79 ASTM D3761-96 15

14 100 101 101 AS1038.10.4

MERCURY (0.01mg/kg) Lab


3 0.03 0.03 0.03 Acid Digestion 0.007 8 0.03 0.03 0.03 ASTM D3684-01

SELENIUM (0.1mg/kg) Lab


3 0.6 0.6 0.6 Eschka Fusion 0.08 8 0.7 0.8 0.8 In house

ARSENIC (0.1mg/kg) Lab


3 0.4 0.4 0.4 Eschka Fusion 0.04

8 0.4 0.4 0.4 Low temp ash-microwave acid

digestion - ICPMS

APPENDIX B

Sample Preparation

and

Homogeneity Testing

B1

SAMPLE PREPARATION A typical Bowen Basin Coal sample with Ash level of approximately 10% and Total Sulfur level of approximately 0.6% was obtained from ACTest Gladstone. The sample was split into lots of approximately 250g each and placed into labelled soft plastic jars for distribution to laboratories.

HOMOGENEITY TESTING 10 samples were selected at random and analysed in duplicate for moisture (air-dry basis) and ash (dry basis) content by ACTest Gladstone. Statistical analysis of the results indicated that no significant sample variability existed. Therefore, it was concluded that any outlier results subsequently identified could not be attributed to sample variability.

NO MOISTURE adb% ASH adb% ASH db%

3 3.6 9.6 9.91 8 3.4 9.6 9.94 10 3.5 9.6 9.96 14 1.2 9.8 9.92 20 1.3 9.8 9.93 25 1.2 9.9 10.02 34 1.2 9.8 9.92 37 3.8 9.6 9.96 43 1.1 9.9 10.01 49 3.9 9.5 9.93

MINIMUM 9.91 MAXIUMUM 10.02 STD DEVIATION 0.039 MEAN 9.949

APPENDIX C

Instructions to Participants

and

Results Sheet

C1

PROFICIENCY TESTING AUSTRALIA COAL PROFICIENCY TESTING PROGRAM (ROUND 22) INSTRUCTIONS TO PARTICIPANTS To ensure that results from this program can be analysed properly, participants are asked to adhere carefully to the following instructions. 1. One 250 gram coal sample labelled PTA Sample 1/06 has been supplied to each laboratory. 2. For the sample the following determinations are required in duplicate: *Moisture Pyritic Sulfur Nitrogen Ash Sulphate Sulfur Carbonate Carbon Volatile Matter Chlorine Phosphorus in Coal Gross Calorific Value Carbon (total) Relative Density Total Sulfur Hydrogen Trace Elements – Fluorine, Mercury, Selenium, Arsenic Results for Moisture are to be reported to air-dry basis. All other tests are to be reported to DRY basis. (*Results obtained from proximate analysis) 3. Laboratories are required to perform all tests for which accreditation is held and are welcome

to report results for any remaining tests. 4. These tests are to be conducted in accordance with AS 1038 (relevant sections). However

laboratories accredited for performing their tests solely to other methods are required to follow their accredited methods and note this on the attached result sheet.

5. For each test on the sample, two replicate results are to be reported to the accuracy and

reporting basis indicated on the result sheet. 6. The following additional information is required for each test: a) Method - relevant AS, ISO or in-house method number (include part numbers, eg AS

1038 Part 6.3.2.) b) Technique - if there are alternative options in a particular method, state which option is

used. 7. Laboratories are also requested to calculate and report an estimate of measurement

uncertainty (MU) for each reported measurement result. All estimates of measurement uncertainty must be given as a 95% confidence interval (coverage factor k ≈ 2).

8. Testing may commence as soon as the sample is received. All laboratories must return the

results sheet no later than 17 November 2006 to: Ms Kate Wiggins Proficiency Testing Australia PO Box 7507 SILVERWATER NSW 2128 Phone: (02) 9736 8397 Fax: (02) 9743 6664

C2

PROFICIENCY TESTING AUSTRALIA COAL PROFICIENCY TESTING PROGRAM (ROUND 22)

RESULTS SHEET

The reporting basis for all tests is dry except for Moisture (air-dry).

Lab Code

Sample 1/06 TEST (report to) Result 1 Result 2

MU (±) a. Method b. Technique

MOISTURE (air-dry basis)

(0.01%)

ASH (0.01%)

VOLATILE MATTER (0.01%)

GROSS CALORIFIC VALUE

(0.001 MJ/kg)

TOTAL SULFUR

(0.001%)

PYRITIC SULFUR

(0.001%)

SULPHATE SULFUR

(0.001%)

CHLORINE

(0.001%)

CARBON (total)

(0.01%)

HYDROGEN

(0.01%)

NITROGEN

(0.01%)

CARBONATE CARBON

(0.001%)

PHOSPHORUS IN COAL

(0.001%)

RELATIVE DENSITY

(0.001%)

C3

FLUORINE (1 mg/kg)

MERCURY (0.01 mg/kg)

SELENIUM (0.1 mg/kg)

ARSENIC (0.1 mg/kg)

Signed: Date:

coal (round 22) proficiency testing programpta.asn.au/phocadownload/reports/2007/531.pdf · 2015....

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