Report No Waters Proficiency Te Round

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Waters Proficiency Testing

- Total Kjeldahl

PTA wishes to gratefully acknowledge the technical assistance provided for this program by Dr M BuckleyProficiency Ltd (New Zealand) and to Global Proficiency Pty Ltd (Australia) for the supply and distribution of the samples.

SD 9.17.11


Total Kjeldahl

PTA wishes to gratefully acknowledge the technical assistance provided for this program by Dr M Buckley-Smith, GlobaProficiency Ltd (New Zealand) and to Global Proficiency Pty Ltd (Australia) for the supply and distribution of the samples.

PO Box 7507

Report No


Round

Total Kjeldahl

December 2016

PTA wishes to gratefully acknowledge the technical assistance provided for this program by Smith, Global Proficiency Ltd (New Zealand)

Proficiency Ltd (New Zealand) and to Global Proficiency Pty Ltd (Australia) for the supply and distribution of the samples.

© Copyright

PO Box 7507

Report No


Round

Total Kjeldahl Nitrogen, Total Phosphorus

December 2016

Acknowledgments

PTA wishes to gratefully acknowledge the technical assistance provided for this program by l Proficiency Ltd (New Zealand)

Proficiency Ltd (New Zealand) and to Global Proficiency Pty Ltd (Australia) for the supply and distribution of the samples.

© Copyright Proficiency Testing Australia

PO Box 7507 SILVERWATER

Report No .


Round No.

Nitrogen, Total Phosphorus

December 2016

Acknowledgments

PTA wishes to gratefully acknowledge the technical assistance provided for this program by l Proficiency Ltd (New Zealand)

Proficiency Ltd (New Zealand) and to Global Proficiency Pty Ltd (Australia) for the supply

Proficiency Testing Australia

ILVERWATER NSW

. 1006


o. 203


December 2016

Acknowledgments

PTA wishes to gratefully acknowledge the technical assistance provided for this program by l Proficiency Ltd (New Zealand).


Proficiency Testing Australia

NSW 2128

1006

Waters Proficiency Testing Program

203


December 2016

PTA wishes to gratefully acknowledge the technical assistance provided for this program by . Also our thanks go to Global


Proficiency Testing Australia , 2016

2128, Australia

Program


PTA wishes to gratefully acknowledge the technical assistance provided for this program by Also our thanks go to Global


2016

, Australia

Program

Nitrogen, Total Phosphorus -

PTA wishes to gratefully acknowledge the technical assistance provided for this program by Also our thanks go to Global


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CONTENTS

1. Foreword ............................................................................................................................ 1

2. Program Features and Design ........................................................................................... 1

3. Statistical Format ............................................................................................................... 2

4. PTA and Technical Adviser’s Comments .......................................................................... 4

5. Outlier Results ................................................................................................................. 14

6. References ...................................................................................................................... 14

APPENDIX A – Results and Data Analysis

Total Kjeldahl Nitrogen (TKN) ............................................................................................... A1

Total Phosphorus (TP) .......................................................................................................... A7

APPENDIX B – Sample Homogeneity and Stability

Homogeneity and Stability Testing ........................................................................................ B1

APPENDIX C – Documentation

Instructions to Participants .................................................................................................... C1

Method Codes ....................................................................................................................... C3

Results Sheet ........................................................................................................................ C6

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1. Foreword

This report summarises the results of a proficiency testing program on the determination of Total Kjeldahl Nitrogen and Total Phosphorus in waters. This is round 203 in a planned series of programs involving the analysis of chemical and physical parameters of waters. The exercise was conducted in October 2016 by Proficiency Testing Australia (PTA). The main aim of the program was to assess laboratories’ abilities to competently perform the prescribed analyses. The Program Coordinator was Mrs D Mihaila and the Technical Adviser was Dr M Buckley-Smith, Global Proficiency Ltd (New Zealand). This report was authorised by Mrs K Cividin, PTA Quality Coordinator / Senior Scientific Officer.

2. Program Features and Design 2.1 Each laboratory was randomly allocated a unique code number for the program to

ensure confidentiality of results. Reference to each laboratory in this report is by code number only.

2.2 Laboratories were provided with the "Instructions to Participants" and "Results Sheet"

(see Appendix C). Laboratories were requested to perform the tests according to their routine methods.

2.3 Participants were provided with three plastic vials (labelled PTA 1, PTA 2 and PTA 3)

containing artificial potable water concentrates for testing of Total Kjeldahl Nitrogen and Total Phosphorus.

2.4 A total of 27 laboratories received samples, comprising:

- 22 Australian participants; and

- 5 overseas participants, including:

- Indonesia (2), Malaysia (1), Singapore (1), Vietnam (1). Of these 27 laboratories, one was unable to submit results by the due date. 2.5 Results (as reported by participants) with corresponding summary statistics (i.e.

number of results, median, normalised interquartile range, uncertainty of the median, robust coefficient of variation, minimum, maximum and range) are presented in Appendix A (for each sample and for each of the analyses performed).

2.6 A robust statistical approach, using z-scores, was utilised to assess laboratories’

testing performance (see Section 3). Robust z-scores and ordered z-score charts relevant to each test are presented in Appendix A. The document entitled Guide to Proficiency Testing Australia, 2016 (reference [1]) defines the statistical terms and details the statistical procedures referred to in this report.

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2.7 A tabulated listing of laboratories (by code number) identified as having outlier results can be found on page 14.

2.8 Prior to sample distribution, a number of randomly selected samples were analysed

for homogeneity and stability. Based on the results of this testing (see Appendix B) it was considered that the samples utilised for this program were homogeneous and stable. As such, any results later identified as outliers could not be attributed to any notable sample variability.

3. Statistical Format

For each test, where appropriate, the following information is given:

- a table of results and calculated z-scores;

- a list of summary statistics; and

- ordered z-score charts.

3.1 Outlier Results and Z-scores In order to assess laboratories’ testing performance, a robust statistical approach,

using z-scores, was utilised. Z-scores give a measure of how far a result is from the consensus value (i.e. the median), and gives a "score" to each result relative to the other results in the group.

A z-score with an absolute value less than or equal to 2.0 is considered to be satisfactory, whereas, a z-score with an absolute value greater than or equal to 3.0 is considered to be an outlier and is marked by the symbol “§”. Laboratories are also encouraged to review results which have an absolute z-score value between 2.0 and 3.0 (i.e. 2.0 < |z-score| < 3.0). These are considered to be questionable results.

Each determination was examined for outliers with all methods pooled. The table on

page 14 summarises the outlier results detected. 3.2 Results Tables and Summary Statistics The tables in Appendix A contain the results returned by each laboratory, including

the code number for the method used and the robust z-score calculated for each result.

Results have been entered exactly as reported by participants. That is, laboratories

which did not report results to the precision (i.e. number of significant figures) requested on the Results Sheet have not been rounded to the requested precision before being included in the statistical analysis.

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A list of summary statistics appears at the bottom of each of the results tables and consists of:

- No. of Results: the total number of results for that test/sample;

- Median: the middle value of the results;

- Normalised IQR: the normalised interquartile range of the results;

- Uncertainty of the Median: a robust estimate of the standard deviation of the Median;

- Robust CV: the robust coefficient of variation expressed as a percentage, i.e. 100 x Normalised IQR / Median;

- Minimum: the lowest laboratory result;

- Maximum: the highest laboratory result; and

- Range: the difference between the Maximum and Minimum.

The median is a measure of the centre of the data. The normalised IQR is a measure of the spread of the results. It is calculated by multiplying the interquartile range (IQR) by a correction factor, which converts the IQR to an estimate of the standard deviation. The IQR is the difference between the upper and lower quartiles (i.e. the values above and below which a quarter of the results lie, respectively). For normally distributed data, the uncertainty of the median is approximated by:

��2 ��

√�

� = number of results. Please see reference [1] for further details on these robust summary statistics.

3.3 Ordered Z-score Charts The charts in Appendix A indicate each laboratory's robust z-score, in order of

magnitude, marked with its laboratory code number. From these charts, each laboratory can readily compare its performance relative to the other laboratories.

These charts contain solid lines at +3.0 and -3.0, so that outliers are clearly

identifiable as those laboratories whose "bar" extends beyond these "cut-off" lines. The y-axis of these charts has been limited, so very large z-scores appear to extend beyond the chart boundary.

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4. PTA and Technical Adviser’s Comments 4.1 Metrological Traceability and Uncertainty of Assigned Values

Consensus values (median) derived from participants’ results are used in this program. These values are not metrologically traceable to an external reference. Sample preparation was undertaken according to Global Proficiency Ltd’s Standard Operating Procedures to ensure samples were fit-for-purpose, homogeneous and stable. Solutions were stable and homogeneous, and medians obtained from this proficiency round were in consistent agreement with the expected levels (dope concentration), as shown in Table 1. Average recoveries were similar to those published in APHA 4500-Norg B (Macro-Kjeldahl) and APHA 4500-Norg D (Block Digestion – Flow Injection Analysis, FIA). Samples PTA 1 and PTA 2 were prepared from Ammonium Chloride, Sulphanilamide and Potassium Dihydrogen Orthophosphate in distilled water. Sample PTA 3 was prepared from Nicotinic Acid and Tetra Potassium Pyrophosphate in distilled water. All samples were preserved with Sulphuric Acid. The sample format was designed so that two samples had unbound target analyte, with a more challenging third sample which had organically bound analyte, requiring rigorous digestion prior to being analysed. This was intended to provide more realistic and demanding samples for analysis while maintaining homogeneity and stability, continuity with previous rounds, and challenging the ability to troubleshoot any problems. As the assigned value for each analyte in this program is the median of the results submitted by the participants, the uncertainty of the median for each analyte has been calculated and is presented in Table 1 below, together with the average analyte recovery data. Table 1. Comparison of expected levels (dope concentration) and proficiency medians. The values of the calculated uncertainty of the median are also presented.

Analyte Sample Dope

Concentration (mg/L)

Median (mg/L)

Analyte Recovery

(%)

Uncertainty of the median

(mg/L)

Total Kjeldahl Nitrogen

PTA 1 9.5 9.320 98.1% 0.167 [1.8%]

PTA 2 45 43.10 95.8% 0.42 [1.0%]

PTA 3 20 19.00 95.0% 1.10 [5.8%]

Total Phosphorus

PTA 1 8 8.000 100.0% 0.062 [0.8%]

PTA 2 1.5 1.460 97.3% 0.011 [0.8%]

PTA 3 4 4.210 105.3% 0.065 [1.5%]

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4.2 Analysis of Round 203 Results 4.2.1 Total Kjeldahl Nitrogen (TKN) Table 2 compares the TKN medians and robust CVs from this round to those obtained in previous PTA rounds. These CV were higher than those published in APHA 4500 – Norg B (Macro-Kjeldahl), where repeatability relative standard deviations (RSD) were between 0.84%-3.46% for concentration ranges of 5-20 mg/L. APHA 4500 – Norg D (Block Digestion-FIA) published RSD of between 3.3%-7.3%, which were closer to CVs observed in this round. Table 2. Comparison of current round variability and proficiency medians of TKN testing with the results of the previous two rounds.

Round Sample Median (mg/L) Robust CV (%) No. of Res ults

This study

PTA 1 9.320 7.2 25

PTA 2 43.10 3.9 25

PTA 3 19.00 22.2 23

Report 938

PTA 1 7.070 6.2 22

PTA 2 33.90 5.6 24

PTA 3 14.30 8.3 23

Report 815

PTA 1 8.235 5.2 28

PTA 2 25.50 7.8 28

PTA 3 11.40 13.9 27

A considerable increase in CV was observed for the more challenging sample PTA 3 (22.2%) when compared to the more easily digestible samples PTA 1 and PTA 2 (7.2% and 3.9%, respectively). If the grossly under recovered results (<50% recovery) were removed from statistical analysis of TKN results for sample PTA 3, the CV would reduce to a more realistic value of 10.5%. Bias / Accuracy

TKN testing was successfully performed, with satisfactory results (|z-scores| ≤ 2.0) ranging between 8.43 – 10.2 mg/L for sample PTA 1, 41.7 – 44.7 mg/L for sample PTA 2 and 13.9 – 26.6 mg/L for sample PTA 3. Out of 25 participants for sample PTA 1, two questionable results (2.0 < |z-scores| < 3.0) were obtained (laboratories 473 and 526). For sample PTA 2, out of 25 participants, one questionable result was obtained (laboratory 445) and for sample PTA 3, out of 23 participants, two questionable results were obtained (laboratories 213 and 603). Five outlier results (|z-scores| ≥ 3.0) were obtained for sample PTA 1 requiring follow-up action by laboratories 233, 345, 407, 498 and 603. Six outlier results were obtained for sample PTA 2, requiring follow-up action by laboratories 181, 233, 345, 473, 579 and 603. Four outlier results were obtained for sample PTA 3, requiring follow-up action by laboratories 129, 181, 400 and 467.

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Figure 1. Spread of results for TKN testing of sample PTA 1, with a median concentration of 9.320 mg/L.

Figure 2. Spread of results for TKN testing of sample PTA 2, with a median concentration of 43.10 mg/L.

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Results (mg/L)

Total Kjeldahl Nitrogen - Sample PTA 1

APHA 4500 – Norg B.

APHA 4500 – Norg C.

APHA 4500 – Norg D.

US EPA 351.1 - 351.4

ISO 11905–1:1997

Calculation

Other

APHA 4500 – NH₃ H.

Modified StandardMethod

0

2

4

6

8

10

12

24 26 28 30 32 34 36 38 40 42 44 46 48 50

Fre

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Results (mg/L)





US EPA 351.1 - 351.4

ISO 11905–1:1997

Calculation

Other

APHA 4500 – NH₃ H.


<

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Figure 3. Spread of results for TKN testing of sample PTA 3, with a median concentration of 19.00 mg/L. The TKN datasets formed a normal distribution with no significant bias attributable to any digestion / analysis method (Figures 1 to 3). The most frequently used method to determine TKN was APHA 4500 – Norg B (Macro-Kjeldahl), which was used by approximately 30-32% of participants. Calculation methods (TN – NOx = TKN) were used by approximately 24-26% of participants. It is recommended that laboratories who recovered less than 50% of the 20 mg/L nicotinic acid doped into sample PTA 3 (Laboratories 129, 181, 213 and 603), follow up on the Quality Control (QC) procedures recommended in APHA 4020 B and Table 4020:I, including mandatory Method blanks, Laboratory Fortified Blanks, Laboratory Fortified Matrix and Duplicates every 20th sample, or batch of samples tested. For troubleshooting and ongoing QC, section APHA 4500-Norg A 4 recommends the use of known additions of nicotinic acid to determine nitrogen recovery and the completeness of digestion, and known additions of ammonium chloride to test for loss of nitrogen. Laboratory 400 reported satisfactory results for samples PTA 1 and PTA 2, and outlier results for sample PTA 3 (for both TKN and TP). After investigation, it was found that TKN in samples PTA 1 and PTA 2 was analysed using Block Digestion – FIA, whereas the results reported for sample PTA 3 were obtained by Macro-Kjeldahl technique. A dilution error in preparation of sample PTA 3 was found to be the cause of these outlier results. Published precision information in APHA 4500-Norg D (Block Digestion – FIA) indicated that recoveries of between 81% - 119% for influent and effluent type matrices are achievable for the FIA method. APHA 4500-Norg B (Macro-Kjeldahl) indicated recoveries of between 84.3% - 112% were achievable for nicotinic acid.

0

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6

7

8

3 5.5 8 10.5 13 15.5 18 20.5 23 25.5 28 30.5 33 35.5

Fre

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Results (mg/L)





US EPA 351.1 - 351.4

ISO 11905–1:1997

Calculation

Other

APHA 4500 – NH₃ C.


/ >

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Catalyst

The move away from use of Mercury as a catalyst for Kjeldahl digestion, because of its toxicity and legal disposal issues, has been widely implemented. A large number of participants in this round (approximately 40-44%) used the Copper catalyst in the digestion of TKN, with a small number of laboratories reporting Persulphate, Selenium, Sodium Nitroferricyanide or other catalysts. APHA 4500-Norg A 4 indicates that effective digestion results can be obtained using a salt/acid ratio of 1 g/mL with copper; and if a change is made in the reagent formula, it is important to report the change and indicate the percentage recovery relative to the results for similar samples analysed using the previous formula. Carrying out the demonstration of capability indicated in APHA 4020 B 1a or method validation in APHA 1040 B, are also recommended for any modifications to standard methods. Final Ammonia Method

The most frequently used final Ammonia method in this round was the titrimetric method (APHA 4500 – NH3 C), which was used by approximately 16-22% of participants. A relatively large number of laboratories (approximately 38%) did not report the final Ammonia method. This could be at least in part attributed to the sample analysis procedures being included with the digestion procedures in some methods. APHA recommends the use of titration, ammonia selective electrode, manual phenate or automated phenate methods (APHA 4500-NH3. C, D, F, and G, respectively), however a number of laboratories used the colorimetric methods recommended by US EPA, and FIA for total N and NOx.

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4.2.2 Total Phosphorus (TP) Table 3 compares the TP medians and robust CVs from this round to those obtained in previous PTA rounds. These CV were better than those published in APHA 4500-P:I for TP at levels similar (10 mg/L) to those used in the current study, and ranged between 6.5% - 11.7% for various Persulphate, Sulphuric/Nitric acids or Perchloric acid digestion procedures. As seen previously in Table 1, the average recoveries of participants were very good compared to the doping concentrations, with the relative errors similar to those published in APHA 4500-P:I which ranged between 0.3% - 4.3% for TP. Table 3. Comparison of current round variability and proficiency medians of TP testing with the results of the previous two rounds.

Round Sample Median (mg/L) Robust CV (%) No. of Res ults

This study

PTA 1 8.000 3.1 25

PTA 2 1.460 3.0 25

PTA 3 4.210 6.2 25

Report 938

PTA 1 4.990 3.5 32

PTA 2 1.240 6.9 34

PTA 3 7.510 4.4 32

Report 815

PTA 1 4.250 5.4 33

PTA 2 1.110 6.3 34

PTA 3 2.305 9.5 34 Bias / Accuracy Total Phosphorus testing was successfully performed, with satisfactory results (|z-scores| ≤ 2.0) ranging between 7.70 – 8.40 mg/L for sample PTA 1, 1.38 – 1.5 mg/L for sample PTA 2 and 3.83 – 4.62 for sample PTA 3. Out of 25 participants, four questionable results (2.0 < |z-scores| < 3.0) were obtained for each of the samples PTA 1 and PTA 2 (PTA 1: laboratories 205, 345, 575 and 579; PTA 2: laboratories 205, 432, 473 and 498). No questionable results were obtained for sample PTA 3. Two outlier results (|z-scores| ≥ 3.0) were obtained for sample PTA 1 requiring follow-up action by laboratories 364 and 603. Five outlier results were obtained for sample PTA 2, requiring follow-up action by laboratories 364, 579, 590, 603 and 646. Two outlier results were obtained for sample PTA 3, requiring follow-up action by laboratories 400 and 603. In general, participants performed remarkably well, analysing samples containing Monopotassium phosphate in samples PTA 1 and PTA 2; and Tetra Potassium Pyro Phosphate (TPPP) in sample PTA 3. The TP datasets formed a normal distribution with no significant bias attributable to any one analysis method (Figures 4 to 6). There was a large variety of methods used for TP analysis in this round, including: Vanado-

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molybdophosphoric Acid Colorimetric, Ascorbic Acid, FIA, Persulfate, Ammonium Molybdate, Discrete Analyser, In-house ICP - MS/OES, etc.

Figure 4. Spread of results for TP testing of sample PTA 1, with a median concentration of 8.000 mg/L.

Figure 5. Spread of results for TP testing of sample PTA 2, with a median concentration of 1.460 mg/L.

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6.7 6.9 7.1 7.3 7.5 7.7 7.9 8.1 8.3 8.5 8.7 8.9 9.1 9.3

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Results (mg/L)

Total Phosphorus - Sample PTA 1

APHA 4500 – P C.

APHA 4500 – P E.

APHA 4500 – P F.

APHA 4500 – P H.

APHA 4500 – P I.

APHA 4500 – P J.

US EPA 365.1 - 365.4

Discrete Analyser

AA/FIA

In-house ICP - MS/OES

Other

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16

1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3

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Results (mg/L)


APHA 4500 – P C.

APHA 4500 – P E.

APHA 4500 – P F.

APHA 4500 – P H.

APHA 4500 – P I.

APHA 4500 – P J.

US EPA 365.1 - 365.4

Discrete Analyser

AA/FIA


Other

/>

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Figure 6. Spread of results for TP testing of sample PTA 3, with a median concentration of 4.210 mg/L. Digestion Method

The most frequently used digestion method to determine TP was the APHA 4500 – P B5 (Persulfate Method), which was used by 44% of participants. Other methods used included US EPA methods, Sulphuric-Nitric acid digestion, modified standard methods, and In-house methods. No laboratory indicated they were using the more drastic and time-consuming perchloric acid method, as it is primarily recommended only for particularly difficult samples, such as sediments. The nitric acid/sulfuric acid method is recommended for most samples, however persulfate oxidation method has proven popular as it is by far the simplest method. It is recommended that persulfate oxidation methods be checked against one or more of the more drastic digestion techniques, and only be adopted if identical recoveries are obtained on your natural matrices. QC procedures recommended in APHA 4020 B and Table 4020:I continued, included mandatory Method blanks, Laboratory Fortified Blanks, Laboratory Fortified Matrix and Duplicates every 20th sample, or batch of samples tested.

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Results (mg/L)


APHA 4500 – P C.

APHA 4500 – P E.

APHA 4500 – P F.

APHA 4500 – P H.

APHA 4500 – P I.

APHA 4500 – P J.

US EPA 365.1 - 365.4

Discrete Analyser

AA/FIA


Other

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4.3 Measurement Uncertainty (MU)

The majority of participants in this round (72%-78%) reported the measurement uncertainty (MU) associated with their results. Table 4 below presents the number and percentage of laboratories reporting the MU for each analyte. Table 4. The number and percentage of laboratories reporting MU for analytes in round 203

Analyte Sample Total participants

Participants reporting MU (percentage)

Total Kjeldahl Nitrogen

PTA 1 25 18 (72%)

PTA 2 25 18 (72%)

PTA 3 23 18 (78%)

Total Phosphorus

PTA 1 25 19 (76%)

PTA 2 25 19 (76%)

PTA 3 25 19 (76%)

Many of the stated MUs did not accurately reflect the difference between the median and the participant’s result for these proficiency samples. Some laboratories may have under estimated their MU, as they indicated that their MU was less than two times the uncertainty of the median, however their results were further from the median than the MU value.1

Conversely, laboratories which indicated a MU which was greater than three times the normalised IQR may have over estimated their MU.1 Laboratory 498 submitted an unusually large MU for TP analysis of sample PTA 2, which was most likely a calculation/typographical error. If laboratories over estimate or under estimate MU in successive proficiency testing rounds, they are recommended to re-examine their measurement uncertainty calculations.

1 MU evaluation is based on minimum / maximum uncertainty criteria (umin and umax) described in ISO 13528:2015 [2]. It should be noted, however, that these are informative indicators only and cannot be solely used to validate or invalidate the MUs reported.

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4.4 Analysis of Results by Method Groups In order for methods to be grouped for analysis, PTA requires at least 11 sets of results from the same method group. As there were less than 11 results submitted for each method, reliable conclusions cannot be drawn from analysing grouped methods on this occasion. Therefore, results from all method groups have been pooled for analysis.

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5. Outlier Results Laboratories reporting results that have been identified as outliers are listed in Table 5 below.

Table 5. Laboratory results identified as outliers for each analysis performed.

Lab Code

Analysis

Total Kjeldahl Nitrogen Total Phosphorus

PTA 1 PTA 2 PTA 3 PTA 1 PTA 2 PTA 3

129 §

181 § §

233 § §

345 § §

364 § §

400 § §

407 §

467 §

473 §

498 §

579 § §

590 §

603 § § § § §

646 §

Note: 1. A “§” indicates the occurrence of a z-score outlier result (i.e. those results for which

|z-score| ≥ 3.0).

6. References

[1] Guide to Proficiency Testing Australia, 2016 (This document can be found on the PTA website, www.pta.asn.au)

[2] APHA Standard Methods For the Examination of Water and Wastewater, 2012. 22nd Edition by APHA, AWWA, WEF. American Public Health Association, Washington DC, USA.

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APPENDIX A

Results and Data Analysis Total Kjeldahl Nitrogen (TKN) ............................................................................................... A1

Total Phosphorus (TP) .......................................................................................................... A7

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Total Kjeldahl Nitrogen (TKN) Results

Samples PTA 1, PTA 2 and PTA 3

A1

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Total Kjeldahl Nitrogen (TKN) Results by Laboratory Code

Sample PTA 1

Lab Code Result ± MU1

(mg/L) Robust z-score2

Method Code3

Catalyst Code3

Final Ammonia Method Code3

103 9.46 ± 0.540 0.21 25 41 57 129 8.90 ± 0.62 -0.63 26 45 # 181 9.66 # 0.51 25 41 46 205 9.15 ± 0.65 -0.25 25 45 # 213 9.26 ± 1.26 -0.09 25 41 46 233 11.5 # 3.27 § 25 41 47 317 9.32 ± 0.93 0.00 32 20 # 345 13.3 ± 1.33 5.97 § 28 45 52 364 8.43 ± 0.8 -1.33 53 25, 41 53 400 8.80 # -0.78 51 41 51 407 12.2 ± 0.5 4.32 § 38 # # 445 9.7 ± 0.7 0.57 27 41 50 467 8.774 # -0.82 28 43 52 473 10.7 ± 3.2 2.07 27 41 51 485 8.58 ± 0.98 -1.11 38 # # 498 6.74 ± 1.48 -3.87 § 38 # # 526 7.66 ± 0.73 -2.49 38 45 57 575 9.36 ± 1.87 0.06 38 45 57 579 8.60 # -1.08 26 41 49 590 8.95 # -0.55 25 42 46 597 9.45 ± 1.0 0.19 38 45 57 603 15.0 # 8.51 § 25 # # 607 9.06 ± 1 -0.39 27 # # 646 10.2 ± 0.4 1.32 25 41 46 690 9.52 ± 0.952 0.30 39 41, 42 57 No of Results: 25

Median: 9.320

Normalised IQR: 0.667

Uncertainty of the Median:

0.167

Robust CV: 7.2%

Minimum: 6.74

Maximum: 15.0

Range: 8.26

1 Where reported, results are shown with their corresponding measurement uncertainty (MU). 2 "§" denotes an outlier (i.e. those results for which |z-score| ≥ 3.0). Robust z-scores are

calculated as: z = (A - median) ÷ normalised IQR, where A is the participant laboratory's result.

3 Please refer to Appendix C (pages C3-C5) for method, catalyst and final Ammonia method code descriptions.

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Total Kjeldahl Nitrogen (TKN)- Sample PTA 1 - Robus t Z-Scores

Ordered R

obust Z-S

core Charts

Total K

jeldahl Nitrogen (T

KN

)- Sam

ple PT

A 1

A2

Robust Z-Scores

498

526

364

485

579

467

400

129

590

607

205

213

-5

-4

-3

-2

-1

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z-sc

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lab code

-5

-4

-3

-2

-1

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z-sc

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lab code

A3

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Sample PTA 2



Method Code3

Catalyst Code3


103 44.2 ± 2.28 0.66 25 41 57 129 41.7 ± 1.7 -0.84 26 45 # 181 36.6 # -3.90 § 25 41 46 205 42.6 ± 3.025 -0.30 25 45 # 213 44.0 ± 3.52 0.54 25 41 46 233 35.9 # -4.32 § 25 41 47 317 43.1 ± 4.3 0.00 32 20 # 345 35.6 ± 3.56 -4.50 § 28 45 52 364 42.1 ± 4.2 -0.60 53 25, 41 53 400 44.3 # 0.72 51 41 51 407 44.0 ± 0.5 0.54 38 # # 445 46.8 ± 5 2.22 27 41 50 467 42.965 # -0.08 28 43 52 473 48.9 ± 14.7 3.48 § 27 41 51 485 41.95 ± 4.64 -0.69 38 # # 498 44.4 ± 9.76 0.78 38 # # 526 42.9 ± 4.29 -0.12 38 45 57 575 43.3 ± 8.66 0.12 38 45 57 579 21.1 # -13.19 § 26 41 49 590 42.4 # -0.42 25 42 46 597 41.8 ± 2.0 -0.78 38 45 57 603 48.2 # 3.06 § 25 # # 607 43.8 ± 5 0.42 27 # # 646 43.6 ± 1.7 0.30 25 41 46 690 44.7 ± 4.47 0.96 39 41, 42 57 No of Results: 25

Median: 43.10



0.42

Robust CV: 3.9%

Minimum: 21.1

Maximum: 48.9

Range: 27.8




SD 9.17.11


Ordered R

obust Z-S

core Charts

Total K

jeldahl Nitrogen (T

KN

)- Sam

ple PT

A 2

A4

Robust Z-Scores

579 34

5

233 18

1

129

597

485

364

590

205

526

467

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

A5

SD 9.17.11


Sample PTA 3



Method Code3

Catalyst Code3


103 18.7 ± 1.01 -0.07 25 41 57 129 6.32 ± 0.54 -3.00 § 26 45 # 181 3.64 # -3.64 § 25 41 46 205 23.6 ± 1.676 1.09 25 45 # 213 8.13 ± 1.06 -2.57 25 41 46 317 20.5 ± 2.1 0.35 32 20 # 345 26.6 ± 2.66 1.80 28 45 52 364 16.3 ± 1.6 -0.64 53 25, 41 53 400 37.3 # 4.33 § 46 41 46 407 21.0 ± 0.5 0.47 38 # # 445 24.1 ± 2 1.21 27 41 50 467 6.121 # -3.05 § 28 43 52 473 17.4 ± 5.3 -0.38 27 41 51 485 20.39 ± 2.27 0.33 38 # # 498 20.0 ± 4.40 0.24 38 # # 526 19.0 ± 1.90 0.00 38 45 57 575 19.3 ± 3.86 0.07 38 45 57 590 16.0 # -0.71 25 42 46 597 20.8 ± 1.0 0.43 38 45 57 603 6.58 # -2.94 25 # # 607 20.3 ± 2.5 0.31 27 # # 646 17.9 ± 0.7 -0.26 25 41 46 690 13.9 ± 1.39 -1.21 39 41, 42 57 No of Results: 23

Median: 19.00



1.10

Robust CV: 22.2%

Minimum: 3.64

Maximum: 37.3

Range: 33.66




SD 9.17.11


Ordered R

obust Z-S

core Charts

Total K

jeldahl Nitrogen (T

KN

)- Sam

ple PT

A 3

A6

Robust Z-Scores

181 46

7

129

603 21

3

690 59

0

364

473

646

103

526

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

SD 9.17.11

Total Phosphorus (TP) Results

Samples PTA 1, PTA 2 and PTA 3

A7

SD 9.17.11

Total Phosphorus (TP) Results by Laboratory Code

Sample PTA 1



Method Code3

Digestion Code3

103 8.12 ± 0.248 0.48 4 22 181 7.70 # -1.21 3 20 205 7.50 ± 0.623 -2.01 13 20 213 8.40 ± 1.26 1.61 13 20 233 7.73 ± 0.250 -1.09 16 # 317 8.10 ± 0.81 0.40 8 20 345 7.5 ± 0.324 -2.01 16 22 364 6.73 ± 0.7 -5.11 § 4 20 400 7.90 # -0.40 6 20 407 7.71 ± 0.05 -1.17 16 23 432 8.11 ± 0.05 0.44 16 24 445 8.0 ± 0.7 0.00 6 20 467 7.785 # -0.87 9 9 473 8.01 ± 1.60 0.04 7 20 485 8.33 ± 1.70 1.33 14 22 498 8.38 ± 1.56 1.53 8 20 526 7.95 ± 0.80 -0.20 8 24 575 8.58 ± 1.72 2.34 4 20 579 8.72 # 2.90 1 19 590 7.85 # -0.60 4 19 597 8.04 ± 0.2 0.16 6 20 603 8.91 # 3.66 § 16 24 607 8.00 ± 1 0.00 8 # 646 7.85 ± 0.74 -0.60 3 19 690 7.92 ± 0.792 -0.32 17 24 No of Results: 25

Median: 8.000



0.062

Robust CV: 3.1%

Minimum: 6.73

Maximum: 8.91

Range: 2.18

1 Where reported, results are shown with their corresponding measurement

uncertainty (MU). 2 "§" denotes an outlier (i.e. those results for which |z-score| ≥ 3.0). Robust z-

scores are calculated as: z = (A - median) ÷ normalised IQR, where A is the participant laboratory's result.

3 Please refer to Appendix C (pages C3-C5) for method and digestion code descriptions.

SD 9.17.11

Total Phosphorus (TP)- Sample PTA 1 - Robust Z-Scor es

Ordered R

obust Z-S

core Charts

Total P

hosphorus (TP

) - Sam

ple PT

A 1

A8

Robust Z-Scores

364

205

345 18

1

407

233

467

590

646

400

690

526

-5

-4

-3

-2

-1

0

1

2

3

4

5z-

scor

e

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

A9

SD 9.17.11


Sample PTA 2



Method Code3

Digestion Code3

103 1.50 ± 0.049 0.90 4 22 181 1.40 # -1.35 3 20 205 1.34 ± 0.111 -2.70 13 20 213 1.47 ± 0.22 0.22 13 20 233 1.44 ± 0.250 -0.45 16 # 317 1.47 ± 0.15 0.22 8 20 345 1.38 ± 0.06 -1.80 16 22 364 1.27 ± 0.2 -4.27 § 4 20 400 1.41 # -1.12 6 20 407 1.44 ± 0.05 -0.45 16 23 432 1.57 ± 0.02 2.47 16 24 445 1.5 ± 0.5 0.90 6 20 467 1.450 # -0.22 9 9 473 1.55 ± 0.31 2.02 7 20 485 1.46 ± 0.30 0.00 14 22 498 1.56 ± 2.91 2.25 8 20 526 1.47 ± 0.15 0.22 8 24 575 1.44 ± 0.29 -0.45 4 20 579 4.27 # 63.18 § 1 19 590 1.28 # -4.05 § 4 19 597 1.46 ± 0.05 0.00 6 20 603 1.77 # 6.97 § 16 24 607 1.47 ± 0.2 0.22 8 # 646 1.80 ± 0.17 7.64 § 3 19 690 1.45 ± 0.145 -0.22 17 24 No of Results: 25

Median: 1.460



0.011

Robust CV: 3.0%

Minimum: 1.27

Maximum: 4.27

Range: 3.00





SD 9.17.11

Total Phosphorus (TP)- Sample PTA 2 - Robust Z-Scor es

Ordered R

obust Z-S

core Charts

Total P

hosphorus (TP

) - Sam

ple PT

A 2

A10

Robust Z-Scores

364

590

205

345 18

1

400 23

3

407

575

467

690

485

-5

-4

-3

-2

-1

0

1

2

3

4

5z-

scor

e

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

A11

SD 9.17.11


Sample PTA 3



Method Code3

Digestion Code3

103 4.43 ± 0.137 0.85 4 22 181 3.92 # -1.12 3 20 205 3.83 ± 0.318 -1.46 13 20 213 4.36 ± 0.66 0.58 13 20 233 4.17 ± 0.250 -0.15 16 # 317 4.37 ± 0.44 0.62 8 20 345 4.08 ± 0.176 -0.50 16 22 364 3.87 ± 0.4 -1.31 4 20 400 8.65 # 17.11 § 6 20 407 4.21 ± 0.05 0.00 16 23 432 4.62 ± 0.04 1.58 16 24 445 4.3 ± 0.5 0.35 6 20 467 4.076 # -0.52 9 9 473 3.91 ± 0.78 -1.16 7 20 485 4.49 ± 0.92 1.08 14 22 498 4.19 ± 0.78 -0.08 8 20 526 4.22 ± 0.42 0.04 8 24 575 4.12 ± 0.82 -0.35 4 20 579 4.61 # 1.54 1 19 590 4.30 # 0.35 4 19 597 4.21 ± 0.1 0.00 6 20 603 5.48 # 4.89 § 16 24 607 4.10 ± 0.5 -0.42 8 # 646 4.57 ± 0.43 1.39 3 19 690 4.08 ± 0.408 -0.50 17 24 No of Results: 25

Median: 4.210



0.065

Robust CV: 6.2%

Minimum: 3.83

Maximum: 8.65

Range: 4.82





SD 9.17.11

Total Phosphorus (TP) - Sample PTA 3 - Robust Z-Sco res

Ordered R

obust Z-S

core Charts

Total P

hosphorus (TP

) - Sam

ple PT

A 3

A12

Robust Z-Scores

205

364

473

181 46

7

345

690

607

575

233

498

407

-5

-4

-3

-2

-1

0

1

2

3

4

5z-

scor

e

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-sc

ore

lab code

SD 9.17.11

APPENDIX B

Sample Homogeneity and Stability

Homogeneity and Stability Testing ........................................................................................ B1

B1

SD 9.17.11

Homogeneity and Stability Testing Samples for this program were obtained from Global Proficiency Ltd, New Zealand. As such, all samples are subjected to rigorous quality control and homogeneity / stability testing. A random selection of ten samples was chosen from sample sets PTA 1 and PTA 3 for homogeneity and stability testing. Seven of each set were stored frozen, the remaining three were subjected to 35ºC for three days for an accelerated ageing stability trial. The samples were then analysed in duplicate by Hill Laboratories, New Zealand. The TKN method used by Hill Laboratories was a Sulphuric acid digestion with copper sulphate catalyst then phenol/hypochlorite colorimetry using a Discrete Analyser [APHA 4500-Norg D. (modified) 4500 NH3 F (modified) 22nd ed. 2012]. Samples PTA 1 and PTA 2 were analysed for Dissolved Reactive Phosphorus using Molybdenum blue colorimetry using a Discrete Analyser [APHA 4500-P E (modified from manual analysis) 22nd ed. 2012]; and sample PTA 3 analysed for Total Phosphorus using Acid persulphate digestion and ascorbic acid colorimetry by Discrete Analyser [APHA 4500-P B and E (modified from manual analysis) 22nd ed. 2012]. For sample set PTA 2, two samples were randomly selected, stored frozen in the same conditions as the homogeneity samples and subjected to a verification testing (one replicate per sample) by Hill Laboratories. Homogeneity and stability characteristics were assumed to be similar to samples PTA 1 and PTA 3, based on identical manufacturing procedure and sample handling. All stability samples showed no notable differences when compared to homogeneity samples. Based on the assumption that the rate of ageing doubles with every 10ºC elevated temperature, these samples were assumed stable for more than 118 days (3 days*2(53/10)) from the date of manufacture, for all analytes. From statistical analyses based on the results of this testing and rigorous quality control, it was considered that all samples were sufficiently homogeneous and stable, so that any results later identified as outliers should not be attributed to any notable sample variability. The results of homogeneity and stability testing are presented in Tables B1 to B3 below. Please note that the mean results for these tests are not intended to be used as reference values. Table B1. Homogeneity and stability testing of PTA 1 samples.

Round PTA 203

Samples PTA 1

Sample ID Total Kjeldahl Nitrogen

(mg/L) Dissolved Reactive Phosphorus (mg/L)

Duplicate 1 Duplicate 2 Duplicate 1 Duplicate 2 Homogeneity H1 8.221 8.391 7.952 7.849

H2 7.836 8.081 7.708 7.809 H3 8.451 8.251 7.687 7.629 H4 8.426 8.561 7.881 7.853 H5 9.326 9.051 7.828 7.742 H6 9.026 9.001 7.783 7.945 H7 9.531 9.641 7.753 7.795

Stability S1 8.636 8.611 7.886 7.677 S2 8.766 9.036 7.742 7.935 S3 9.356 9.896 7.787 7.897

RSD 6.26% 6.65% 1.09% 1.35%

B2

SD 9.17.11

Table B2. Homogeneity testing of PTA 2 samples.

Round PTA 203

Samples PTA 2



Duplicate 1 Duplicate 1 Homogeneity H1 41.78 1.48

H2 45.74 1.48 RSD 6.40% 0.24%

Table B3. Homogeneity and stability testing of PTA 3 samples.

Round PTA 203

Samples PTA 3



Duplicate 1 Duplicate 2 Duplicate 1 Duplicate 2 Homogeneity H1 19.366 18.426 4.367 4.304

H2 17.076 19.526 4.447 4.272 H3 17.0891 17.931 4.458 4.045 H4 19.231 17.771 4.125 4.146 H5 19.174 18.369 4.227 4.055 H6 19.314 18.614 4.024 4.164 H7 19.889 18.939 4.171 4.059

Stability S1 19.099 18.609 4.125 4.188 S2 19.834 20.134 4.304 4.111 S3 20.599 20.824 4.293 4.122

RSD 5.97% 5.14% 3.41% 2.14%

SD 9.17.11

APPENDIX C

Documentation

Instructions to Participants .................................................................................................... C1

Method Codes ....................................................................................................................... C3

Results Sheet ........................................................................................................................ C6

SD 9.17.11

CHEMICAL ANALYSIS Total Kjeldahl Nitrogen, Total Phosphorus

Please note the following before commencing the analysis 1. Samples

i)

ii)

iii)

Please Note:laboratory sample.

2. Sample Preparation

Caution:

i)

ii)

iii)

iv)

v)

vi)

vii)

viii)

Please report results for the diluted sample.

SD 9.17.11

CHEMICAL ANALYSIS


**Please record (on the Results Sheet) the approximate tempe rature

Please note the following before commencing the analysis

Samples

Three plastic bottles labelled PTA 1, PTA 2 and PTA 3The bottles contain approximately 22 mL of artificial potable water concentrate for analysis of Total KjeldahlH2SO4, samples PTA 1 and PTA 2 to pH ~2, and sample PTA 3 to pH ~3.

The samples must be thoroughly mixed prior to analysis.

The samples will require dilution in reagent grade waterPreparation

Please Note: laboratory sample.

Sample Preparation

Caution: Analysis must begin immediately after bottle is opened.

Adjust bottle temperature to 20ºC and mix thoroughly to ensure any precipitate has fully redissolved prior to dilution step. If any precipitate remains, microwave for 20and swirl to dissolve, returning sample to 20ºC before dilution.

Add approximately

Record bottle ID number. Open bottle.

Using a volumetric pipette transfer 10.00 mL from the bottle into the flask.

Bring to volume with reagent grade water.

Close with stopper and mix by inversio

Test according to your normal procedures.

viii) Repeat steps


PROFICIENCY TESTING AUSTRALIA

WATERS PROFICIENCY TESTING PROGRAM

CHEMICAL ANALYSIS ROUND 203


INSTRUCTIONS TO PARTICIPANTS



Three plastic bottles labelled PTA 1, PTA 2 and PTA 3The bottles contain approximately 22 mL of artificial potable water concentrate for analysis of Total Kjeldahl Nitrogen and Total Phosphorus. The concentrate samples are stabilised with

, samples PTA 1 and PTA 2 to pH ~2, and sample PTA 3 to pH ~3.


The samples will require dilution in reagent grade waterPreparation steps below)

Where possible, proficiency testing samples should be treated as a routine laboratory sample.

Sample Preparation

Analysis must begin immediately after bottle is opened.

bottle temperature to 20ºC and mix thoroughly to ensure any precipitate has fully redissolved prior to dilution step. If any precipitate remains, microwave for 20and swirl to dissolve, returning sample to 20ºC before dilution.

Add approximately 900 mL reagent grade water to a one






Repeat steps i) to vii) for the second and third sample.




ROUND 203



**Please record (on the Results Sheet) the approximate tempe rature of the samples upon receipt**


Three plastic bottles labelled PTA 1, PTA 2 and PTA 3The bottles contain approximately 22 mL of artificial potable water concentrate for analysis of

Nitrogen and Total Phosphorus. The concentrate samples are stabilised with , samples PTA 1 and PTA 2 to pH ~2, and sample PTA 3 to pH ~3.


The samples will require dilution in reagent grade waterbelow).

Where possible, proficiency testing samples should be treated as a routine



900 mL reagent grade water to a one






for the second and third sample.


C1







Three plastic bottles labelled PTA 1, PTA 2 and PTA 3The bottles contain approximately 22 mL of artificial potable water concentrate for analysis of



The samples will require dilution in reagent grade water




900 mL reagent grade water to a one




Close with stopper and mix by inversion.








Please note the following before commencing the analysis of the samples.

Three plastic bottles labelled PTA 1, PTA 2 and PTA 3, supplied by Global Proficiency Ltd. The bottles contain approximately 22 mL of artificial potable water concentrate for analysis of



The samples will require dilution in reagent grade water




900 mL reagent grade water to a one-litre volumetric flask.







of the samples.

, supplied by Global Proficiency Ltd. The bottles contain approximately 22 mL of artificial potable water concentrate for analysis of


The samples will require dilution in reagent grade water (please follow the




litre volumetric flask.


OCTOBER, 2016




(please follow the


bottle temperature to 20ºC and mix thoroughly to ensure any precipitate has fully redissolved prior to dilution step. If any precipitate remains, microwave for 20-30 seconds

litre volumetric flask.


OCTOBER, 2016


Nitrogen and Total Phosphorus. The concentrate samples are stabilised with

(please follow the Sample


bottle temperature to 20ºC and mix thoroughly to ensure any precipitate has fully 30 seconds

C2

SD 9.17.11

3. Tests Requested

For each of the samples prepared from the three bottles:

i) Total Kjeldahl Nitrogen (TKN)

ii) Total Phosphorus (TP)

(It is recommended that a reagent water blank is analysed by the same method used to analyse the samples.)

If unable to perform the above please note this on your Results Sheet.

4. Safety

i) Samples are for laboratory use only.

ii) Participants should have sufficient experience and training to take the necessary precautions when handling the samples and reagent chemicals and during disposal.

iii) Use of personal protective equipment such as safety glasses, gloves, laboratory coats and fume hoods, where appropriate during the determinations, is recommended.

5. Reporting

i) Report results using three significant figures (e.g.: 0.0123, 0.123, 1.23, 12.3).

ii) Report results in milligrams per litre (mg/L).

iii) Do not correct results for recovery.

iv) Select the appropriate method code for each test from the Method Code Table and record it on the Results Sheet.

v) Calculate the measurement uncertainty (MU) for each reported result. All estimates of MU must be given as a 95% confidence interval (coverage factor k ≈ 2) and reported in mg/L. Report MU using the same number of decimal places as for the result.

6. Testing should commence as soon as possible after receiving the samples and results reported

NO LATER THAN 21 OCTOBER 2016 to:

Delfina Mihaila Proficiency Testing Australia PO Box 7507 SILVERWATER NSW 2128 AUSTRALIA Phone: +612 9736 8397 Fax: +612 9743 6664 Email: [email protected]

7. For this program your laboratory has been allocated the code number shown on the attached

Results Sheet. All reference to your laboratory in reports associated with the program will be through this code number, thus ensuring the confidentiality of your results.

8. As a guide, ranges for the samples can be expected to be:

Analyte Range (mg/L) Total Kjeldahl Nitrogen (TKN) 5 - 50 Total Phosphorus (TP) 0.5 - 10

C3

SD 9.17.11

Method Codes to be used for the Results Sheet

ANALYSIS METHOD REFERENCE METHOD DESCRIPTION CODE

Total Phosphorus (TP)

APHA APHA 4500 – P C. Vanadomolybdophosphoric Acid Colorimetric Method

1

APHA 4500 – P D. Stannous Chloride Method

2

APHA 4500 – P E. Ascorbic Acid Method

3

APHA 4500 – P F. Automated Ascorbic Acid Reduction Method

4

APHA 4500 – P G. Flow Injection Analysis for Orthophosphate

5

APHA 4500 – P H. Manual Digestion and Flow Injection Analysis for Total Phosphorus

6

APHA 4500 – P I. In-line UV/Persulfate Digestion and Flow Injection Analysis for Total Phosphorus

7

APHA 4500 – P J. Persulfate Method for Simultaneous Determination of Total Nitrogen and Total Phosphorus

8

USEPA US EPA 0365.1 – 0.365.4 0365.1 Orthophosphate (as P) - Automated Colorimetry 0365.1 Phosphorus, All Forms - Colorimetric/Automated 0365.2 Phosphorus - manual colorimetric/1 reagent 0365.3 Phosphorus - colorimetric/ 2 reagents 0365.4 Phosphorus, Total -Colorimetric/Automated

9

ESS Method 230.1: Total Phosphorus and Total Kjeldahl Nitrogen, Semi-Automated Method

10

ISO / CEN EN ISO 6878:2004 Water Quality - Determination Of Phosphorus - Ammonium Molybdate Spectrometric Method

11

Other Modified Standard Method 12

Discrete Analyser 13

AA / FIA 14

Test Kit, Colorimeter (HACH, Fluka… specify). 15

In-house ICP – MS/ OES 16

Other (please specify) 17

Digestion Procedure for TP

APHA APHA 4500 – P B3. Perchloric Acid 18

APHA 4500 – P B4. Sulfuric-Nitric 19

APHA 4500 – P B5. Persulfate 20

USEPA US EPA 0200.2 Phosphorus - Sample Preparation 21

Other In-house method 22

Modified Standard Method 23


C4

SD 9.17.11

Method Codes to be used for the Results Sheet (cont .)


Total Kjeldahl Nitrogen (TKN)

APHA APHA Part 4500 - Norg B. Macro-Kjeldahl Method 25

APHA Part 4500 - Norg C. Semi-Micro Kjeldahl Method 26

APHA Part 4500 - Norg D. Block Digestion and Flow Injection Analysis 27

USEPA USEPA 0351.1 – 0351.4 0351.1 Colorimetric/ Automated 0351.2 Colorimetric 0351.2 Semi-Automated Colorimetric 0351.3 Colorimetric/ Titrimetric 0351.4 Potentiometric

28

ESS Method 230.1: Total Phosphorus and Total Kjeldahl Nitrogen, Semi-Automated Method

29

ASTM ASTM D3590 - 11 Standard Test Methods for Total Kjeldahl Nitrogen in Water 30

ISO / CEN ISO 5663:1984 (EN 25663:1993) Water quality - Determination of Kjeldahl nitrogen - Method after mineralization with selenium

31

ISO 11905-1:1997 Water quality - Determination of nitrogen - Part 1: Method using oxidative digestion with peroxodisulfate

32

EN 12260:2003 Water quality - Determination of nitrogen -Determination of bound nitrogen (TNb), following oxidation to nitrogen oxides

33



AA / FIA 36

Test Kit, Colorimeter (HACH… specify). 37

Calculation (TN-NOx =TKN) 38


TKN Catalyst Mercury 40

Copper 41

Selenium 42

Sodium nitroferricyanide 43

Titanium 44


Continued on next page for Ammonia analysis methods…

C5

SD 9.17.11

Method Codes to be used for the Results Sheet (cont .)


Ammonia Measurement for TKN

APHA APHA 4500 – NH3 C. Titrimetric Method 46

APHA 4500 – NH3 D. Ammonia-Selective Electrode Method 47

APHA 4500 – NH3 E. Ammonia-Selective Electrode Method Using Known Addition 48

APHA 4500 – NH3 F. Phenate Method 49

APHA 4500 – NH3 G. Automated Phenate Method 50

APHA 4500 – NH3 H. Flow Injection Analysis 51

USEPA US EPA 0351.1 – 0351.4 0351.1 Colorimetric/ Automated 0351.2 Colorimetric 0351.2 Semi-Automated Colorimetric 0351.3 Colorimetric/ Titrimetric 0351.4 Potentiometric

52



AA / FIA 55

Test Kit, Colorimeter (e.g. HACH… specify). 56


Method Reference Key i) APHA SM APHA “Standard Methods for the Examination of Water and Wastewater” (18, 19 20,

21, 22 Edition). (http://www.standardmethods.org/) ii) ASTM Annual Book of ASTM Standards, Vol. 11.01(2004). (http://www.astm.org) iii) CEN European Committee for Standardization. (http://www.cen.eu/cen) iv) ISO International Organization for Standardization. (http://www.iso.org) v) US EPA U.S Environmental Protection Agency.

(http://www.epa.gov/osa/fem/methcollectns.htm)

SD 9.17.11

Please note:Where possible, proficiency testing samples should be treated as a routine laboratory

*Approximate temperature of samples upon receipt:

ANALYSIS

Sample PTA 1 Total KjeldahlNitrogen (TKN)Total Phosphorus (TP)

Sample PTA 2 Total Kjeldahl Nitrogen (TKN)Total Phosphorus (TP)

Sample PTA 3 Total Kjeldahl Nitrogen (TKN)Total Phosphorus (TP)

i) For ii) Report results for the diluted sample.

iii) Report results using three significant figures.

iv) Report results in v) Do not correct results for recovery.

vi) MU* Laboratories Measurement Uncertainty (MU) if known for the result. Please report in mg/L

DATE:

INSTRUCT WATERS PROF TEST PROG 203

SD 9.17.11

Please note: Where possible, proficiency testing samples should be treated as a routine laboratory


ANALYSIS

Sample PTA 1 (Bottle diluted x100)


Phosphorus (TP)



Phosphorus (TP)



Phosphorus (TP)

For each prepared sample only a single result is requested.Report results for the diluted sample.

Report results using three significant figures.

Report results in Do not correct results for recovery.

MU* Laboratories Measurement Uncertainty (MU) if known for the result. Please report in mg/L, using the same number of decimal places as for the result.

DATE: ______________________

Return results Delfina MihailaProficiency Testing AustraliaPO Box 7507 SILVERWATER NSW 2128 AUSTRALIA


PROFICIENCY TESTING



Where possible, proficiency testing samples should be treated as a routine laboratory


Result (mg/L)

(Bottle diluted x100)



prepared sample only a single result is requested.Report results for the diluted sample.


Report results in milligrams per litre (mg/L).Do not correct results for recovery.

MU* Laboratories Measurement Uncertainty (MU) if known for the result. Please report in , using the same number of decimal places as for the result.

______________________

Return results NO LATER THAN 21 OCTOBER 2016 Delfina Mihaila Proficiency Testing AustraliaPO Box 7507 SILVERWATER NSW 2128 AUSTRALIA


PROFICIENCY TESTING



Total Kjeldahl Nitrogen, Total PhosphorusOCTOBER, 2016

RESULTS SHEET



Result

±MU*(mg/L)






milligrams per litre (mg/L).Do not correct results for recovery.


______________________

NO LATER THAN 21 OCTOBER 2016

Proficiency Testing Australia PO Box 7507 SILVERWATER NSW 2128


C6

PROFICIENCY TESTING




RESULTS SHEET(mg/L)



±MU* (mg/L)

METHOD



milligrams per litre (mg/L).


SIGNATURE:

NO LATER THAN 21 OCTOBER 2016

PO Box 7507 Phone:SILVERWATER NSW 2128 Fax:

Email:





RESULTS SHEET


METHOD CODE

prepared sample only a single result is requested.


SIGNATURE: _______________________________

NO LATER THAN 21 OCTOBER 2016 to:

Phone: +61 2 9736 8397 +61 2 9743 6664

Email: [email protected]

AUSTRALIA





Laboratory Code

DIGESTION

or CATALYST

CODE


_______________________________

+61 2 9736 8397 +61 2 9743 6664 [email protected]

Where possible, proficiency testing samples should be treated as a routine laboratory sample.

Laboratory Code

DIGESTION

CATALYST CODE

FINAL AMMONIA METHOD

CODE

MU* Laboratories Measurement Uncertainty (MU) if known for the result. Please report in

_______________________________

[email protected]

sample.

FINAL AMMONIA METHOD

CODE

MU* Laboratories Measurement Uncertainty (MU) if known for the result. Please report in

_______________________________

SD 9.17.11

- End of Report -

Report No Waters Proficiency Te Round

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