report no. 1102

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Report No. 1102

Waters Proficiency Testing Program

Round No. 231 - Bromide, Chloride, Fluoride, Iodide -

September 2018

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

© Copyright Proficiency Testing Australia, 2018

PO Box 7507 SILVERWATER NSW 2128, Australia

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CONTENTS

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

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

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

4. PTA and Technical Advisers' Comments ........................................................................ 4

5. Outlier Results ...............................................................................................................16

6. References ....................................................................................................................16

APPENDIX A – Results and Data Analysis

Bromide (Br) ........................................................................................................................ A1

Chloride (Cl) ........................................................................................................................ A5

Fluoride (F) .......................................................................................................................... A9

Iodide (I) ............................................................................................................................ A13

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 Bromide, Chloride, Fluoride and Iodide in waters. This is round 231 in a planned series of programs involving the analysis of chemical and physical parameters of waters. This program is accredited to ISO/IEC 17043:2010 “Conformity assessment - General requirements for proficiency testing” by International Accreditation New Zealand (IANZ). The exercise was conducted in July 2018 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 Manager.

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. Please note that a number of laboratories reported more than one set of results and, therefore, their code numbers (with letter) could appear several times in the same data set.

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 two 500 mL plastic bottles (labelled PTA 1 and

PTA 2) containing solutions of NaF, NaCl, KBr and KI analytical reagents in distilled water.

2.4 A total of 25 laboratories received samples, comprising:

- 16 Australian participants; and

- 9 overseas participants, including:

- Brunei Darussalam (1), Indonesia (2), Japan (1), Malaysia (2), Papua New Guinea (1), Qatar (1), Russia (1).

All laboratories submitted 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.

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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.

2.7 A tabulated listing of laboratories (by code number) identified as having outlier results

can be found on page 16. 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 16 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:

√𝜋

2 ×

𝑛𝑜𝑟𝑚𝐼𝑄𝑅

√𝑛

𝑛 = 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 Measurement 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 for Bromide, Chloride and Fluoride, and medians obtained from this proficiency round were in good agreement with the expected levels (dope concentration), as shown in Table 1. Median analyte recoveries were also within expected parameters published for method APHA 4110 B (Ion Chromatography with Chemical Suppression of Eluent Conductivity), which were estimated to be between 75%-125% [2]. 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 also presented in Table 1. Please note that these statistics could not be calculated for Iodide, as there were insufficient reported results.

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)

Bromide (Br)

PTA 1 10 10.00 100.0% 0.15

PTA 2 15 15.00 100.0% 0.20

Chloride (Cl)

PTA 1 200 210.0 105.0% 1.4

PTA 2 75 78.95 105.3% 1.65

Fluoride (F)

PTA 1 2 1.985 99.3% 0.026

PTA 2 4 3.920 98.0% 0.037

Iodide (I)

PTA 1 0.9 na na na

PTA 2 1.7 na na na

Overall, the performance of participants in this round was good, with robust CVs below 10% for Bromide, Chloride and Fluoride; and the uncertainty of their respective medians contributing ≤ 2%.

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4.2 Analysis of Round 231 Results 4.2.1 Bromide (Br) Table 2 compares the Bromide medians and robust CVs from this round to those obtained in previous PTA rounds. These were comparable to the published precision information in APHA 4110, which indicated that CVs of 3.1%-5.6% could be expected for Bromide analysis using Ion Chromatography with Chemical Suppression [2]. Table 2. Comparison of current round variability and proficiency median of Bromide testing with the results of the previous two rounds.

Round Sample Median (mg/L)

Robust CV (%) Participants

This study PTA 1 10.00 4.6 15

PTA 2 15.00 4.2 15

Report 1050 PTA 1 8.105 3.0 16

PTA 2 13.80 2.4 16

Report 993 PTA 1 6.820 2.3 16

PTA 2 16.85 3.4 16

Bias / Accuracy The Bromide testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0) ranging between 9.85 – 10.7 mg/L for sample PTA 1 and 14.4 – 16.0 mg/L for sample PTA 2. Out of 15 participants, one questionable result (2.0 < |z-score| < 3.0) was reported for sample PTA 1 (laboratory 227). No questionable results were reported for sample PTA 2. Three outlier results (|z-score| ≥ 3.0) were obtained for each of the samples PTA 1 and PTA 2, requiring follow-up action by laboratories 390, 540A and 540B. The Bromide data sets formed approximately normal distributions with no notable bias attributable to any one method (Figures 1 and 2). The method most frequently used for Bromide testing in this round was APHA 4110 B (Ion Chromatography with Chemical Suppression of Eluent Conductivity), which was used by 47% of participants. For laboratories that need to carry out troubleshooting, the most common sources of error include contaminants in reagent water, glassware, sample processing apparatus, or carry-over from prior high concentration samples. APHA section 4020 B Quality Control Practices recommends a minimum of daily use of Method Blanks (MB), Laboratory Fortified Blanks (LFB), Laboratory Fortified Matrix (LFM) and duplicates (LFMD), or every 20th sample [2]. In addition, APHA 4110 B recommended allowing the system to come to equilibrium over a 15-20 minute period, to give a stable base line. They also recommend verifying calibration curves with a mid-range concentration check standard from a source

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independent of the calibration standards. The results of the check standard should be within 10% of the original calibration curve [2].

Figure 1. Spread of results for Bromide testing of sample PTA 1, with a median of 10.00 mg/L.

Figure 2. Spread of results for Bromide testing of sample PTA 2, with a median of 15.00 mg/L.

The most common interference with Bromide testing by Phenol Red Colorimetric Method (APHA 4500-Br- B 1.b.) is high concentrations of chloride. Sample PTA 1

0

1

2

3

4

5

6

7

7.4 7.8 8.2 8.6 9 9.4 9.8 10.2 10.6 11 11.4 11.8 12.2 12.6

Fre

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Results (mg/L)

Bromide - Sample PTA 1

APHA 4500 – Br¯ B

APHA 4110 B

APHA 4110 C

ISO 10304–1:2007

US EPA 300.1

ICP MS

ICP OES/AES

Ion Chromatography(In-house method)

<

0

1

2

3

4

5

6

7

8.2 9 9.8 10.6 11.4 12.2 13 13.8 14.6 15.4 16.2 17 17.8 18.6

Fre

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Results (mg/L)

Bromide - Sample PTA 2

APHA 4500 – Br¯ B

APHA 4110 B

APHA 4110 C

ISO 10304–1:2007

US EPA 300.1

ICP MS

ICP OES/AES

Ion Chromatography(In-house method)

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contained 210 mg/L Chloride, and APHA recommends addition of substantial amounts of chloride to the Acetate buffer solution to eliminate chloride interference [2]. The majority of laboratories had a good understanding of their measurement uncertainty (MU), giving MU values ranging between 3.2% - 11%. Figure 3 highlights where laboratories 356, 390 and 447 have underestimated their MU, in comparison to the median and doping concentration (both 10 mg/L for sample PTA 1). Also, figure 3 indicates that laboratory 402 may have overestimated their MU in comparison to other laboratories and 3x NIQR (Umax) [4].

Figure 3. Spread of results for Bromide testing of sample PTA 1, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -]. If these laboratories continue to underestimate or overestimate their MU in successive proficiency rounds, they may wish to use a passive empirical approach which includes their proficiency results and reference material testing in their statistical MU calculations (Eurachem 2012) [3].

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4.2.2 Chloride (Cl) Table 3 compares the Chloride medians and robust CVs from this round to those obtained in previous PTA rounds. These were comparable to the published precision information in APHA 4110, which indicated that CVs of 2.2%-11% could be expected for Chloride analysis using Ion Chromatography with Chemical Suppression. Table 3. Comparison of current round variability and proficiency median of Chloride testing with the results of the previous two rounds.




PTA 2 78.95 8.2 24

Report 1050 PTA 1 70.30 5.6 31

PTA 2 123.0 6.6 31

Report 993 PTA 1 60.60 3.2 25

PTA 2 142.0 5.7 25

Bias / Accuracy The Chloride testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0) ranging between 201 – 221 mg/L for sample PTA 1 and 67.7 – 90.0 mg/L for sample PTA 2. Out of 24 participants, one questionable result (2.0 < |z-score| < 3.0) was reported for sample PTA 1 (laboratory 189) and two questionable results were reported for sample PTA 2 (laboratories 189 and 634). Three outlier results (|z-score| ≥ 3.0) were obtained for sample PTA 1, requiring follow-up action by laboratories 540A, 540B and 720. For sample PTA 2, two outlier results were obtained, requiring follow-up action by laboratories 540A and 540B. The Chloride data sets formed approximately normal distributions with no notable bias attributable to any one method (Figures 4 and 5). There was a large variety of methods used for Chloride testing in this round. The method used most frequently was APHA 4110 B (Ion Chromatography with Chemical Suppression of Eluent Conductivity), which was used by 33% of participants. Laboratories wishing to investigate their results, may find the suggestions in the Bromide section of this report useful with respect to APHA 4110 B. The majority of laboratories had a good understanding of their MU, giving MU values ranging between 1.7% - 8.7%. Figures 6 and 7 highlight where laboratories 277, 292, 356, 447 and 476 submitted MU values that did not encompass the median for one or both samples. These laboratories may have relied too heavily on their in-house repeatability to estimate their MU and, if they continue to underestimate their MU in successive proficiency rounds, they may wish to use a passive empirical approach which includes their proficiency results and reference material testing in their statistical MU calculations [3].

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Figure 4. Spread of results for Chloride testing of sample PTA 1, with a median of 210.0 mg/L.

Figure 5. Spread of results for Chloride testing of sample PTA 2, with a median of 78.95 mg/L.

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8

10

12

14

16

115 125 135 145 155 165 175 185 195 205 215 225 235 245

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Results (mg/L)

Chloride - Sample PTA 1 APHA 4500 – Cl¯ B

APHA 4500 – Cl¯ C

APHA 4500 – Cl¯ D

APHA 4500 – Cl¯ E

APHA 4110 B

APHA 4110 C

ISO 10304–1:2007

Discrete Analyser

FIA Lachat

ICP OES/AES

Ion Chromatography(In house method)

Other

#N/A

0

1

2

3

4

5

6

7

8

34 40 46 52 58 64 70 76 82 88 94 100 106 112

Fre

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Results (mg/L)

Chloride - Sample PTA 2 APHA 4500 – Cl¯ B

APHA 4500 – Cl¯ C

APHA 4500 – Cl¯ D

APHA 4500 – Cl¯ E

APHA 4110 B

APHA 4110 C

ASTM D 512 – 04

ISO 10304–1:2007

Discrete Analyser

FIA Lachat

ICP OES/AES


Other

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Figure 6. Spread of results for Chloride testing of sample PTA 1, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -].

Figure 7. Spread of results for Chloride testing of sample PTA 2, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -].

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4.2.3 Fluoride (F) Table 4 compares the Fluoride medians and robust CVs from this round to those obtained in previous PTA rounds. These are comparable to the published precision information in APHA 4110, which indicated that CVs of 2.9%-8.8% could be expected for Fluoride analysis using Ion Chromatography with Chemical Suppression; and CVs of between 2.9%-4.8% for the Ion Selective Electrode Method (APHA 4500-F- C). Table 4. Comparison of current round variability and proficiency median of Fluoride testing with the results of the previous two rounds.




PTA 2 3.920 3.5 22

Report 1050 PTA 1 2.470 4.1 27

PTA 2 3.460 3.1 27

Report 993 PTA 1 1.490 5.5 25

PTA 2 4.430 3.0 25

Bias / Accuracy The Fluoride testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0) ranging between 1.86 – 2.06 mg/L for sample PTA 1 and 3.80 – 4.11 mg/L for sample PTA 2. Out of 22 participants, one questionable result (2.0 < |z-score| < 3.0) was reported for sample PTA 1 (laboratory 277) and four questionable results were reported for sample PTA 2 (laboratories 277, 390, 402 and 699). Two outlier results (|z-score| ≥ 3.0) were obtained for sample PTA 1, requiring follow-up action by laboratories 390 and 540A. Two outlier results were also obtained for sample PTA 2, requiring follow-up action by laboratories 540A and 540B. The Fluoride data sets formed approximately normal distributions with no notable bias attributable to any one method (Figures 8 and 9). The methods most frequently used for Fluoride testing in this round were APHA 4110 B (Ion Chromatography with Chemical Suppression of Eluent Conductivity) and APHA 4500- F¯ C (Ion Selective Electrode Method), with 36% and 27% of participants, respectively. As Fluoride is the first analyte to elute in Ion Chromatography columns, it is important to minimise the effect of the “water dip” for fluoride analysis. APHA 4110 B makes the following recommendations as potential options for improving fluoride analysis results:

laboratories should analyse standards that bracket the expected result,

eliminate the water dip by diluting the sample with eluent,

add concentrated eluent to the sample to give the name HCO3−/CO3

2− concentration as the eluent,

gradient elution using an NaOH eluent,

try alternative columns.

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Figure 8. Spread of results for Fluoride testing of sample PTA 1, with a median of 1.985 mg/L.

Figure 9. Spread of results for Fluoride testing of sample PTA 2, with a median of 3.920 mg/L.

The majority of laboratories had a good understanding of their MU, giving MU ranging between 4%-10%. Laboratories 277, 356, 390 and 699 submitted MU values that did not encompass the median for one or both samples; as can be seen in Figures 10 and 11. These laboratories may have relied too heavily on their in-house repeatability

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8

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1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7

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Results (mg/L)

Fluoride - Sample PTA 1

APHA 4500 – F¯ C

APHA 4500 – F¯ D

APHA 4110 B

APHA 4110 C

ISO 10304–1:2007

Fluoride Electrode


Other

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7

3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4 4.1 4.2 4.3 4.4

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Results (mg/L)

Fluoride - Sample PTA 2

APHA 4500 – F¯ C

APHA 4500 – F¯ D

APHA 4110 B

APHA 4110 C

ISO 10304–1:2007

Fluoride Electrode


Other

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to estimate their MU and, if they continue to underestimate their MU in successive proficiency rounds, they may wish to use a passive empirical approach which includes their proficiency results and reference material testing in their statistical MU calculations [3].

Figure 10. Spread of results for Fluoride testing of sample PTA 1, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -].

Figure 11. Spread of results for Fluoride testing of sample PTA 2, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -].

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4.2.4 Iodide (I) and Total Iodine As mentioned previously, statistics could not be calculated for Iodide or Total Iodine, as there were insufficient reported results. Figures 12 and 13 have been displayed for informational purposes only, as they also contain the Homogeneity and Stability averaged results (see Appendix B) and the doping concentration. It is hoped that this information will reassure laboratories that no gross error had occurred in their testing.

Figure 12. Spread of results for Iodide/Total Iodine testing of sample PTA 1, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -].

Figure 13. Spread of results for Iodide/Total Iodine testing of sample PTA 2, with MU error bars for each laboratory result, 3x NIQR [- - -], and the uncertainty of the median [- - -].

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4.3 Measurement Uncertainty (MU)

The majority of participants in this round (63%-100%) reported the measurement uncertainty (MU) associated with their results. Table 5 below presents the number and percentage of laboratories reporting the MU for each analyte.

Table 5. The number and percentage of laboratories reporting MU for analytes in round 231.

Analyte Sample Total

participants

Participants reporting MU (percentage)

Bromide (Br)

PTA 1 15 10 (67%)

PTA 2 15 10 (67%)

Chloride (Cl)

PTA 1 24 15 (63%)

PTA 2 24 15 (63%)

Fluoride (F)

PTA 1 22 16(73%)

PTA 2 22 16(73%)

Iodide (I)

PTA 1 4 4 (100%)

PTA 2 4 4 (100%)

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 underestimated their MU, as they indicated that their MU was less than two times the uncertainty of the median (see Table 1), however, their results were further from the median than the MU value.1

Conversely, laboratories that indicated a MU which was greater than three times the normalised IQR may have overestimated their MU.1 If laboratories overestimate or underestimate 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 [4]. 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.

5. Outlier Results

Laboratories reporting results that have been identified as outliers are listed in Table 6 below. Table 6. Laboratory results identified as outliers for each analysis performed.

Lab Code

Analysis

Bromide Chloride Fluoride Iodide

PTA 1 PTA 2 PTA 1 PTA 2 PTA 1 PTA 2 PTA 1 PTA 2

390 § § §

540A § § § § § §

540B § § § § §

720 §

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 Published by APHA, AWWA & WEF. [3] EURACHEM / CITAC Guide CG 4 (2012). Quantifying Uncertainty in

Analytical Measurement; S. Ellison & A. Williams (Eds), Third Edition, Section 7.8, pg 20. https://www.eurachem.org/images/stories/Guides/pdf/QUAM2012_P1.pdf

[4] ISO 13528:2015 Statistical methods for use in proficiency testing by

interlaboratory comparisons.

http://www.pta.asn.au/

https://www.eurachem.org/images/stories/Guides/pdf/QUAM2012_P1.pdf

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APPENDIX A

Results and Data Analysis Bromide (Br) ........................................................................................................................ A1

Chloride (Cl) ........................................................................................................................ A5

Fluoride (F) .......................................................................................................................... A9

Iodide (I) ............................................................................................................................ A13

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Bromide (Br) Results

Samples PTA 1 and PTA 2

A1

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Bromide (Br)

Results by Laboratory Code

Laboratory Code

Sample PTA 1

Result ± MU1 Robust

z-score2

Method Code

3 mg/L

108 10.7 # 1.52 3

227 11.1 ± 1.2 2.39 9

277 9.93 ± 1.40 -0.15 3

292 9.87 ± 0.12 -0.28 11

356 10.5 ± 0.3 1.09 3

390 12.4 ± 0.62 5.22 § 1

402 10.4 ± 2.6 0.87 1

447 10.3 ± 0.15 0.65 4

472 10 # 0.00 3

476 9.96 ± 0.59 -0.09 7

540A 4.82 # -11.27 § 3

540B 4.53 # -11.90 § 3

545 9.89 # -0.24 10

699 9.85 ± 0.42 -0.33 3

705 10.5 ± 0.57 1.09 8

No of Results: 15

Median: 10.00

Normalised IQR: 0.46

Uncertainty of the Median: 0.15

Robust CV: 4.6%

Minimum: 4.53

Maximum: 12.4

Range: 7.87

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 code descriptions.

4 "na" indicates "not applicable".

5 "#" indicates that no result was returned for this sample/test.

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Bromide - Sample PTA 1 - Robust Z-Scores

Ord

ere

d R

ob

ust Z

-Sc

ore

Ch

arts

Bro

mid

e - S

am

ple

PT

A 1

A2

Robust Z-Scores

540B

540A

699

292

545

277

476

472

447

402

356

705

108

227

390

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

A3

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Bromide (Br)


Laboratory Code

Sample PTA 2


z-score2

Method Code

3 mg/L

108 15.6 # 0.95 3

227 15.8 ± 2 1.27 9

277 14.5 ± 2.04 -0.79 3

292 14.8 ± 0.2 -0.32 11

356 14.4 ± 0.4 -0.95 3

390 16.9 ± 0.86 3.02 § 1

402 16.0 ± 4.0 1.59 1

447 15.1 ± 0.20 0.16 4

472 15 # 0.00 3

476 15.1 ± 0.9 0.16 7

540A 8.29 # -10.65 § 3

540B 8.37 # -10.52 § 3

545 14.6 # -0.63 10

699 14.8 ± 0.64 -0.32 3

705 15.2 ± 0.82 0.32 8

No of Results: 15

Median: 15.00



Robust CV: 4.2%

Minimum: 8.29

Maximum: 16.9

Range: 8.61

1






SD 9.17.12

Bromide - Sample PTA 2 - Robust Z-Scores

Ord

ere

d R

ob

ust Z

-Sc

ore

Ch

arts

Bro

mid

e - S

am

ple

PT

A 2

A4

Robust Z-Scores

540A

540B

356

277

545

292

699

472

447

476

705

108

227

402

390

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

SD 9.17.12

Chloride (Cl) Results


A5

SD 9.17.12

Chloride (Cl)


Laboratory Code

Sample PTA 1


z-score2

Method Code

3 mg/L

108 204 # -1.08 18

120 209 ± 20.9 -0.18 15 124 208 ± 2 -0.36 16 189 223 # 2.34 14 227 220 ± 22 1.80 28 277 211 ± 6.56 0.18 18 292 204 ± 3 -1.08 34 356 201 ± 4 -1.62 18 390 211 ± 2.26 0.18 16 402 212 ± 32 0.36 17 447 206 ± 2.42 -0.72 19 454 212 ± 15.3 0.36 14 472 213 # 0.54 18 476 209 ± 10 -0.18 22 496 212 ± 4 0.36 14 540A 116 # -16.91 § 18 540B 142 # -12.23 § 18 545 221 # 1.98 30 634 207 ± 29.0 -0.54 27 674 206 # -0.72 18 699 215 ± 8.8 0.90 18 705 219 ± 16.1 1.62 34 720 238 # 5.04 § 36 729 207 # -0.54 14

No of Results: 24

Median: 210.0

Normalised IQR: 5.6


Robust CV: 2.6%

Minimum: 116

Maximum: 238

Range: 122

1






SD 9.17.12

Chloride - Sample PTA 1 - Robust Z-Scores

Ord

ere

d R

ob

ust Z

-Sc

ore

Ch

arts

Ch

lorid

e - S

am

ple

PT

A 1

A6

Robust Z-Scores

540A

540B

356

108

292

447

674

634

729

124

120

476

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

A7

SD 9.17.12

Chloride (Cl)


Laboratory Code

Sample PTA 2


z-score2

Method Code

3 mg/L

108 67.7 # -1.74 18

120 78.0 ± 7.80 -0.15 15 124 80.8 ± 0.8 0.29 16 189 92.4 # 2.09 14 227 85.8 ± 9 1.06 28 277 87.7 ± 2.73 1.36 18 292 75.0 ± 0.8 -0.61 34 356 73.4 ± 1.5 -0.86 18 390 82.1 ± 2.06 0.49 16 402 90.0 ± 15 1.71 17 447 76.6 ± 0.90 -0.36 19 454 85.4 ± 6.0 1.00 21 472 78 # -0.15 18 476 74.0 ± 3.6 -0.77 22 496 82.0 ± 2 0.47 14 540A 43.5 # -5.50 § 18 540B 48.1 # -4.78 § 18 545 73.7 # -0.81 30 634 92.2 ± 12.9 2.05 27 674 74.7 # -0.66 18 699 79.9 ± 3.3 0.15 18 705 82.5 ± 6.05 0.55 34 720 75.0 # -0.61 36 729 81.0 # 0.32 14

No of Results: 24

Median: 78.95



Robust CV: 8.2%

Minimum: 43.5

Maximum: 92.4

Range: 48.9

1






SD 9.17.12

Chloride - Sample PTA 2 - Robust Z-Scores

Ord

ere

d R

ob

ust Z

-Sc

ore

Ch

arts

Ch

lorid

e - S

am

ple

PT

A 2

A8

Robust Z-Scores

540A

540B

108

356

545

476

674

292

720

447

120

472

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

SD 9.17.12

Fluoride (F) Results


A9

SD 9.17.12

Fluoride (F)


Laboratory Code

Sample PTA 1


z-score2

Method Code

3 mg/L

108 1.93 # -0.56 42

120 1.94 ± 0.19 -0.46 38

124 2.05 ± 0.12 0.66 38

227 1.99 ± 0.2 0.05 38

277 1.78 ± 0.185 -2.09 42

292 1.96 ± 0.03 -0.25 52

353 2.06 ± 0.10 0.76 47

356 2.06 ± 0.04 0.76 42

390 2.38 ± 0.18 4.02 § 39

402 1.89 ± 0.38 -0.97 39

447 1.97 ± 0.06 -0.15 43

454 1.90 ± 0.16 -0.87 39

472 2 # 0.15 42

476 1.91 ± 0.13 -0.76 46

496 1.98 ± 0.2 -0.05 38

540A 2.44 # 4.63 § 42

540B 1.86 # -1.27 42

545 2.00 # 0.15 38

634 2.01 ± 0.201 0.25 38

674 2.06 # 0.76 42

680 1.91 ± 0.16 -0.76 54

699 2.04 ± 0.08 0.56 42

No of Results: 22

Median: 1.985



Robust CV: 4.9%

Minimum: 1.78

Maximum: 2.44

Range: 0.66

1






SD 9.17.12

Fluoride - Sample PTA 1 - Robust Z-Scores

Ord

ere

d R

ob

ust Z

-Sc

ore

Ch

arts

Flu

orid

e - S

am

ple

PT

A 1

A10

Robust Z-Scores

277

540B

402

454

476

680

108

120

292

447

496

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

A11

SD 9.17.12

Fluoride (F)


Laboratory Code

Sample PTA 2


z-score2

Method Code

3 mg/L

108 3.82 # -0.72 42

120 4.01 ± 0.40 0.65 38

124 4.00 ± 0.24 0.58 38

227 4.00 ± 0.5 0.58 38

277 3.54 ± 0.368 -2.73 42

292 3.87 ± 0.05 -0.36 52

353 4.06 ± 0.21 1.01 47

356 3.91 ± 0.08 -0.07 42

390 4.29 ± 0.17 2.66 39

402 3.62 ± 0.62 -2.16 39

447 3.97 ± 0.06 0.36 43

454 3.89 ± 0.311 -0.22 39

472 4 # 0.58 42

476 3.82 ± 0.35 -0.72 46

496 3.93 ± 0.2 0.07 38

540A 3.48 # -3.17 § 42

540B 3.29 # -4.53 § 42

545 3.80 # -0.86 38

634 4.11 ± 0.411 1.37 38

674 4.06 # 1.01 42

680 3.87 ± 0.32 -0.36 54

699 4.28 ± 0.17 2.59 42

No of Results: 22

Median: 3.920



Robust CV: 3.5%

Minimum: 3.29

Maximum: 4.29

Range: 1.00

1






SD 9.17.12

Fluoride - Sample PTA 2 - Robust Z-Scores

Ord

ere

d R

ob

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ore

Ch

arts

Flu

orid

e - S

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PT

A 2

A12

Robust Z-Scores

540B

540A

277

402

545

108

476

292

680

454

356

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

-5

-4

-3

-2

-1

0

1

2

3

4

5

z-s

core

lab code

SD 9.17.12

Iodide (I) Results


A13

SD 9.17.12

Iodide (I)


Laboratory Code

Sample PTA 1


z-score2

Method Code

3 mg/L

227 1.52 ± 0.2 na 62

390 0.73 ± 0.07 na 58

699 0.815 ± 0.052 na 57

705 1.51 ± 0.15 na 64

No of Results: 4

Minimum: 0.73

Maximum: 1.52

Range: 0.79

1


2 There were insufficient reported results for Iodide (N=4), therefore no statistical analysis was performed for this analyte on this occasion.




A14

SD 9.17.12

Iodide (I)


Laboratory Code

Sample PTA 2


z-score2

Method Code

3 mg/L

227 2.16 ± 0.3 na 62

390 1.34 ± 0.11 na 58

699 1.39 ± 0.09 na 57

705 1.81 ± 0.18 na 64

No of Results: 4

Minimum: 1.34

Maximum: 2.16

Range: 0.82

1


2 There were insufficient reported results for Iodide (N=4), therefore no statistical analysis was performed for this analyte on this occasion.




SD 9.17.12

APPENDIX B

Sample Homogeneity and Stability

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

B1

SD 9.17.12

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 sample concentrates was chosen from samples PTA 1 (Table B1) for homogeneity and stability testing. Seven of these were stored chilled and 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. Total Iodine underwent TMAH Digestion and analysis with ICP-MS (Inductive Coupled Plasma - Mass Spectrometry) using APHA 3125 B; Bromide and Chloride were analysed using Ion Chromatography method APHA 4110 B; and Fluoride was analysed with an ion selective electrode using method APHA 4500-F-

C.

Stability samples for Bromide, Chloride and Fluoride showed no increased variability when compared to the chilled samples, however, Total Iodine did show a slight increase in the concentration of incubated samples compared to the homogeneity samples. Samples PTA 2 (Table B2) were also tested to confirm the levels were within the expected range. Homogeneity and stability characteristics were assumed to be similar to samples

PTA 1, based on identical manufacturing procedure and sample handling.

From statistical analysis 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 could not be attributed to any notable sample variability. Table B1. Homogeneity and stability testing of PTA 1 samples.

Round PTA 231

Samples PTA 1 (g/m3)

Sample ID

Total Iodine Bromide Chloride Fluoride

Rep 1 Rep 2 Rep 1 Rep 2 Rep 1 Rep 2 Rep 1 Rep 2

Homogeneity H1 0.83 0.88 9.90 9.91 206 205 2.01 1.99

H2 0.87 0.89 9.76 9.74 201 201 1.98 1.94

H3 0.83 0.87 9.76 9.73 203 203 1.97 1.96

H4 0.84 0.86 9.76 9.76 204 203 1.97 1.96

H5 0.80 0.83 9.75 9.69 199 198 1.97 1.97

H6 0.87 0.87 9.74 9.75 204 202 1.95 1.98

H7 0.86 0.88 9.71 9.74 203 202 1.96 1.97

Stability S1 0.91 0.91 9.74 9.73 202 200 1.97 1.97

S2 0.92 0.92 9.79 9.76 203 204 1.97 1.96

S3 0.91 0.94 9.71 9.68 202 201 1.95 1.94

RSD 4.68% 3.63% 0.54% 0.63% 0.93% 1.03% 0.93% 0.85%

B2

SD 9.17.12

Table B2. Confirmatory testing of PTA 2 samples.

Round PTA 231

Samples PTA 2 (g/m3)

Sample ID Total Iodine Bromide Chloride Fluoride

Homogeneity H1 1.45 14.925 74.26 3.88

H2 1.49 14.806 75.23 3.83

RSD 1.90% 0.57% 0.92% 0.89%

Please note that the mean results for these tests are not intended to be used as reference values.

SD 9.17.12

APPENDIX C

Documentation

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

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

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

C1

SD 9.17.12

PROFICIENCY TESTING AUSTRALIA

WATERS PROFICIENCY TESTING PROGRAM CHEMICAL ANALYSIS ROUND 231 JULY, 2018

Bromide, Chloride, Fluoride, Iodide

INSTRUCTIONS TO PARTICIPANTS

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

Please note the following before commencing the analysis of the samples. 1. Samples

i) Two plastic bottles labelled PTA 1 and PTA 2, supplied by Global Proficiency Limited (New Zealand). The bottles contain approximately 500 mL of artificial potable water for analysis of Bromide, Chloride, Fluoride and Iodide.

ii) To minimise the possibility of change in concentration, do not open the samples until ready to commence analysis.

iii) The samples were refrigerated (1 - 5ºC) prior to dispatch and any liquid on the outside of the bottles may be due to condensation rather than sample leakage.

iv) The samples have not been preserved and if analyses cannot be commenced on the day of receipt, it is recommended that the samples be stored under refrigeration and in the dark.

v) The samples are ready to test (please follow the Sample Preparation steps below).

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

2. Sample Preparation (for each of the PTA 1 and PTA 2 samples)

Caution: Analysis must begin immediately after bottle is opened.

i) Adjust bottle temperature to 20ºC and mix thoroughly.

ii) Record bottle ID number. Open bottle.

iii) Test according to your normal procedures.

iv) Repeat steps i) to iii) for the second sample.

Please report results in mg/L to three significant figures for this ready to test sample.

C2

SD 9.17.12

3. Tests Requested

Tests requested for samples PTA 1 and PTA 2 are as follows:

i) Bromide (Br¯)

ii) Chloride (Cl¯)

iii) Fluoride (F¯)

iv) Iodide (I¯)

v) Total Iodine

(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) For each sample only a single result is requested.

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

iii) For statistical purposes, report results to three significant figures:

e.g. 123 mg/L, 12.3 mg/L or 1.23 mg/L etc.

iv) Do not correct results for recovery.

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

vi) 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 3 AUGUST 2018 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

Bromide (Br¯) 5 – 20 mg/L

Chloride (Cl¯) 50 – 250 mg/L

Fluoride (F¯) 1.0 – 5.0 mg/L

Iodide (I¯) 0.5 – 2.0 mg/L

Total Iodine 0.5 – 2.0 mg/L

mailto:[email protected]

C3

SD 9.17.12

Method Codes to be used for the Results Sheet

ANALYSIS METHOD

REFERENCE METHOD DESCRIPTION CODE

Bromide (Br¯ )

APHA APHA 4500 – Br¯ B. Phenol Red Colorimetric Method

1

APHA 4500 – Br¯ D. Flow Injection Analysis 2

APHA 4110 B. Ion Chromatography with Chemical Suppression of Eluent Conductivity

3

APHA 4110 C. Single-Column Ion Chromatography with Direct Conductivity Detection

4

APHA 4110 D. Ion Chromatographic Determination of Oxyhalides and Bromide

5

APHA 4140 B. Capillary Ion Electrophoresis with Indirect UV Detection

6

ISO ISO 10304–1:2007 Water quality – Determination of dissolved anions by liquid chromatography of ions – Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulphate

7

US EPA US EPA 300.1 Inorganic Anions in DW by Ion Chromatography

8

Other ICP MS 9

ICP OES/AES 10

Ion Chromatography (In-house method) 11

In-house method 12

Other (please specify) 13

Chloride (Cl¯ )

APHA 4500 – Cl¯ B. Argentometric Method 14

4500 – Cl¯ C. Mercuric Nitrate Method 15

4500 – Cl¯ D. Potentiometric Method 16

4500 – Cl¯ E. Automated Ferricyanide Method 17

4110 B. Ion Chromatography with Chemical Suppression of Eluent Conductivity

18

4110 C. Single-Column Ion Chromatography with Direct Conductivity Detection

19

4140 B. Capillary Ion Electrophoresis with Indirect UV Detection

20

ASTMD ASTM D 512 – 04 Standard Test Methods for Chloride Ion in Water

21

ISO ISO 10304–1:2007 Water quality – Determination of dissolved anions by liquid chromatography of ions – Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulphate

22

ISO 10304 – 4: 1997 Water quality – Determination of dissolved anions by liquid chromatography of ions – Part 4: Determination of chlorate, chloride and chlorite in water with low contamination

23

Continued on next page

C4

SD 9.17.12

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

ANALYSIS METHOD


Chloride (Cl¯ ) (cont.)

ISO ISO 15682:2000 Water quality – Determination of chloride by flow analysis (CFA and FIA) and photometric or potentiometric detection

24

ISO 9297:1989 Water quality -- Determination of chloride -- Silver nitrate titration with chromate indicator (Mohr's method)

25

Other Chloride Selective Electrode 26

Discrete Analyser 27

FIA Lachat 28

ICP MS 29

ICP OES/AES 30

Potentiometric Titration 31

Segmented Flow Analysis 32

Spectroquant 33

Ion Chromatography (In house method) 34

In house method 35


Fluoride (F¯)

APHA 4500 – F¯ B. Preliminary Distillation Step 37

4500 – F¯ C. Ion Selective Electrode Method 38

4500 – F¯ D. SPADNS Method 39

4500 – F¯ E. Complexone Method 40

4500 – F¯ G. Ion-Selective Electrode Flow Injection Analysis

41


42

4110 C. Single-Column Ion Chromatography with Direct Conductivity Detection

43

4140 B. Capillary Ion Electrophoresis with Indirect UV Detection

44

ASTM ASTM D 1179 – 04 Standard Test Methods for Fluoride Ion in Water

45

ISO ISO 10304–1:2007 Water quality – Determination of dissolved anions by liquid chromatography of ions – Part 1

46

Other Fluoride Electrode 47

ICP MS 48

ICP OES/AES 49

SPAONS Method 50

SPADNS Discrete Analyser 51


In house method 53


Continued on next page

C5

SD 9.17.12

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

ANALYSIS METHOD


Iodide (I¯) Total Iodine

APHA 3120 B. Inductively coupled Plasma (ICP-OES/AES)

55

3125 B. Inductively Coupled Plasma-Mass Spectrometry (ICP-MS)

56


57

4500 – I¯ B. Leuco Crystal Violet Method 58

4500 – I¯ C. Catalytic Reduction Method 59

4500 – I¯ D. Voltametric Method 60

ISO ISO 10304 –3:1997 Water quality – Determination of dissolved anions by liquid chromatography of ions – Part 3: Determination of chromate, iodide, sulfite, thiocyanate and thiosulfate

61

Other ICP MS (In house method) 62

ICP OES/AES (In house method) 63


In house method 65


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

21, 22, 23 Edition). (http://www.standardmethods.org/) ii) ASTM Annual Book of ASTM Standards, Vol. 11.01(2004). (http://www.astm.org) iii) ISO International Organization for Standardization. (http://www.iso.org). iv) US EPA U.S Environmental Protection Agency.

(https://www.epa.gov/measurements/collection-methods)

C6

SD 9.17.12

PROFICIENCY TESTING AUSTRALIA

WATERS PROFICIENCY TESTING PROGRAM

CHEMICAL ANALYSIS ROUND 231

Bromide, Chloride, Fluoride, Iodide JULY, 2018

RESULTS SHEET (mg/L)

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

Laboratory

Code

*Approximate temperature of samples upon receipt:

ANALYSIS

SAMPLE PTA 1 SAMPLE PTA 2

Result (mg/L)

±MU (mg/L)

METHOD CODE

Result (mg/L)

±MU (mg/L)

METHOD CODE

Bromide (Br¯ )

Chloride (Cl¯ )

Fluoride (F¯ )

Iodide (I¯)

Total Iodine

Total Iodine Digestion Method: i) For each sample only a single result is requested.

ii) For statistical purposes, report results to three significant figures:

e.g. 123 mg/L, 12.3 mg/L or 1.23 mg/L etc. iii) Report results in milligrams per litre (mg/L). iv) Do not correct results for recovery.

v) 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: ______________________ SIGNATURE: _______________________________

Return results NO LATER THAN 3 AUGUST 2018 to: Delfina Mihaila Proficiency Testing Australia PO Box 7507 Phone: +61 2 9736 8397 SILVERWATER NSW 2128 Fax: +61 2 9743 6664 AUSTRALIA Email: [email protected]

INSTRUCT WATERS PROF TEST PROG 231

mailto:[email protected]

SD 9.17.12

- End of Report -

report no. 1102

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