Report No.

1032

SeaWaters
Proficiency Testing Program

Round No. 2

- Salinity, pH, Conductivity -

July 2017

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, 2017

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 Adviser’s Comments .......................................................................... 4
5. Outlier Results ................................................................................................................. 12
6. References ...................................................................................................................... 12

APPENDIX A – Results and Data Analysis

Salinity ................................................................................................................................... A1
pH ........................................................................................................................................ A5
Conductivity ........................................................................................................................... A9

APPENDIX B – Sample Homogeneity and Stability

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

APPENDIX C – Documentation

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

Method Codes ................................................................................................................. C3-C4
Results Sheet ........................................................................................................................ C5

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 1

1. Foreword

This report summarises the results of a proficiency testing program on the

determination of Salinity, pH and Conductivity in seawaters. This is round 2 in a
planned series of programs involving the analysis of chemical and physical
parameters of seawaters.

The exercise was conducted in May 2017 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 F Watton, 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 plastic bottles (labelled PTA 1 and PTA 2) for
analysis of Salinity, pH and Conductivity.

2.4 A total of 13 laboratories received samples, comprising:

- 10 Australian participants; and

- 3 overseas participants, including:
- Indonesia (1), Philippines (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.

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 12.

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 12 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 decimal places) requested
on the Results Sheet have not been rounded to the requested precision before being
included in the statistical analysis.

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 3

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 (NIQR) 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 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 (Appendix B). The samples used in this study were fortified natural estuarine
and ocean beach seawater samples.

Samples were stable and homogeneous, and medians obtained from this proficiency
round were in consistent agreement with the expected levels from previous testing, as
shown in Table 1.

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 the Table 1 below. In all samples analysed for
the three tests, the uncertainty of the median was larger than 0.3xNIQR.

Table 1. Comparison of expected levels (from previous testing [3]) and proficiency medians.
The values of the calculated uncertainty of the median are also presented.

Expected Uncertainty
Analyte Sample Median
Levels of the Median

PTA 1 34.65 33.9000 1.0129

Salinity
PTA 2 30.0 29.6000 0.6845

PTA 1 8.32 8.260 0.041

pH
PTA 2 8.20 8.285 0.041

PTA 1 52.7 51.900 0.891

Conductivity
(mS/cm)
PTA 2 46.0 46.400 0.749

Overall, the performance of participants in this round was good considering the
challenging matrix that seawater poses. Robust CVs were comparable to those
obtained in previous testing [3] and were below 7% for all analytes.

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4.2 Analysis of Round 2 Results

4.2.1 Salinity

Table 2 presents the Salinity medians and robust CVs obtained in this round. The
results of this round were slightly more variable than previous round results, where 12
laboratories submitted results and gave medians of 34.65 and 30.0, and CVs of 1.9%
and 1.4%, respectively for the same two samples [3]. Published precision information
available for APHA, when using a salinometer or densimeter, indicated that
laboratories should be able to obtain a precision better than ±0.01, with careful
analysis and the use of bracketing standards.

Table 2. Current round variability and proficiency medians of Salinity testing.

Round Sample Median Robust CV (%) Participants
PTA 1 33.9000 6.3 7
This study
PTA 2 29.6000 4.9 7

Bias / Accuracy

The Salinity testing was successfully performed, with satisfactory results (|z-score| ≤
2.0) ranging between 31.0 – 36.1 for sample PTA 1 and 28.957 – 31.2 for sample
PTA 2.

Out of seven participants, one questionable result (2.0 < |z-score| < 3.0) was reported
for each of the samples PTA 1 and PTA 2 (both for laboratory 498).

One outlier result (|z-score| ≥ 3.0) was obtained for sample PTA 2, requiring follow-up
action by laboratory 575. No outlier results were obtained for sample PTA 1.

Laboratories who obtained questionable or outlier results may need to closely

examine the Quality Control (QC) procedures recommended in APHA 2510. In
addition, calibration standards, QC samples and duplicates need to be carried out at
least once daily, or with every batch of 20 or fewer samples. The accuracy of
temperature measurement equipment can also have a notable effect on Salinity
results and laboratories are recommended to have all temperature devices calibrated
annually against an in-house reference thermometer, with the reference thermometer
re-certified every 5 years.

The Salinity data sets formed approximately normal distributions (Figures 1 and 2). All
participants used the method APHA 2520 B (Electrical Conductivity) for Salinity
testing in this round.

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 6

Salinity - Sample PTA 1

4
APHA 2520 B

3
Frequency

0
27 28.5 30 31.5 33 34.5 36 37.5 39
Salinity Results

Figure 1. Spread of results for Salinity testing of sample PTA 1, with a median of 33.9000.

Salinity - Sample PTA 2

5
APHA 2520 B

3
Frequency

0
19 22 25 28 31 34 37 40 43
Salinity Results

Figure 2. Spread of results for Salinity testing of sample PTA 2, with a median of 29.6000.

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4.2.2 pH

Table 3 presents the pH medians and robust CVs obtained in this round. The results
of this round were comparable to previous round results, where 26-28 laboratories
submitted results and gave medians of 8.32 and 8.20, and CVs of 1.2% and 0.8%,
respectively for the same two samples [3]. Published APHA precision information
indicated that laboratories should be able to achieve a standard deviation of ±0.13 on
a well buffered solution [4]. Laboratories participating in this round preformed well,
achieving NIQRs of 0.113 for both samples PTA 1 and PTA 2.

Table 3. Current round variability and proficiency medians of pH testing.

Round Sample Median Robust CV (%) Participants
PTA 1 8.260 1.4 12
This study
PTA 2 8.285 1.4 12

Bias / Accuracy

The pH testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0)
ranging between 8.03 – 8.47 for sample PTA 1 and 8.17 – 8.40 for sample PTA 2.

Out of 12 participants, one questionable result (2.0 < |z-score| < 3.0) was reported for
each of the samples PTA 1 (laboratory 214B) and PTA 2 (laboratory 424).

One outlier result (|z-score| ≥ 3.0) was also obtained for each sample, requiring
follow-up action by laboratory 472.

Laboratories who obtained questionable or outlier results may need to look at

cleaning or replacing their electrode. Glass electrodes generally fail because of
scratches, deterioration, or accumulation of debris on the glass surface. Laboratories
may also need to check the expiry of their calibration buffers. APHA recommends
measurement of a magnetically stirred sample, and to equilibrate electrodes after
calibration by immersing in successive portions of the sample (hold in stirring sample
for 1 minute); then take a fresh portion of the sample to measure the pH [4].

The pH data sets formed approximately normal distributions (Figures 3 and 4). The
method most frequently used for pH testing in this round was APHA 4500-H+ B
(Electrometric), which was used by nine out of 12 participants.

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pH - Sample PTA 1

7
APHA 4500 – pH B
ASTM D1293
6
In-house pH Meter

5
Frequency

0
6.8 6.95 7.1 7.25 7.4 7.55 7.7 7.85 8 8.15 8.3 8.45 8.6 8.75
pH Results

Figure 3. Spread of results for pH testing of sample PTA 1, with a median of 8.260.

pH - Sample PTA 2

7
APHA 4500 – pH B
ASTM D1293
6
In-house pH Meter

5
Frequency

0
7.52 7.64 7.76 7.88 8 8.12 8.24 8.36 8.48 8.6 8.72
pH Results

Figure 4. Spread of results for pH testing of sample PTA 2, with a median of 8.285.

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4.2.3 Conductivity

Table 4 presents the Conductivity medians and robust CVs obtained in this round.
The results of this round were slightly more variable than previous round results,
where 26 laboratories submitted results and gave medians of 52.7 and 46.0 mS/cm,
and CVs of 2.9% and 2.4%, respectively for the same two samples [3].

Table 4. Current round variability and proficiency medians of Conductivity testing.

Median
Round Sample Robust CV (%) Participants
(mS/cm)
PTA 1 51.900 4.1 9
This study
PTA 2 46.400 3.9 9

Bias / Accuracy

The Conductivity testing was successfully performed, with satisfactory results (|z-
score| ≤ 2.0) ranging between 50.33 – 54.2 mS/cm for sample PTA 1 and 44.79 –
47.5 mS/cm for sample PTA 2.

Out of nine participants, one questionable result (2.0 < |z-score| < 3.0) was reported
for sample PTA 2 (laboratory 424). No questionable results were reported for sample
PTA 1.

Two outlier results (|z-score| ≥ 3.0) were obtained for sample PTA 1, requiring follow-
up action by laboratories 424 and 498. Two outlier results were also obtained for
sample PTA 2, requiring follow-up action by laboratories 498 and 575.

Laboratories struggling with their Conductivity testing are recommended to look at the
QC practices identified in APHA 2020 and 2510 for precision of duplicates, testing of
blanks and QC samples (KCl), calibration using standards, at least daily or with each
batch of 20 samples tested. APHA also recommend rinsing the device with one or
more portions of the sample before measuring an additional portion [4].

The Conductivity data sets formed approximately normal distributions (Figures 5 and
6). The method most frequently used for Conductivity testing in this round was APHA
2510 B (Conductivity Meter), which was used by seven out of nine participants.

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Conductivity - Sample PTA 1

5
APHA 2510 B

ASTM D1125 - 95
(2009) Non-Flowing
4
In-house Conductivity
Meter

3
Frequency

0
41.5 43.5 45.5 47.5 49.5 51.5 53.5 55.5 57.5 59.5 61.5 63.5 65.5 67.5
Results (mS/cm)

Figure 5. Spread of results for Conductivity testing of sample PTA 1, with a median of 51.900
mS/cm.

Conductivity - Sample PTA 2

5
APHA 2510 B

ASTM D1125 - 95
(2009) Non-Flowing
4
In-house Conductivity
Meter

3
Frequency

0
34 37 40 43 46 49 52 55 58 61 64 67 70 73
Results (mS/cm)

Figure 6. Spread of results for Conductivity testing of sample PTA 2, with a median of 46.400
mS/cm.

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 11

4.3 Measurement Uncertainty (MU)

The majority of participants in this round (71%-78%) 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 2.
Participants
Total
Analyte Sample reporting MU
participants
(percentage)

PTA 1 7 5 (71%)
Salinity
PTA 2 7 5 (71%)

PTA 1 12 9 (75%)
pH
PTA 2 12 9 (75%)

PTA 1 9 7 (78%)
Conductivity
(mS/cm)
PTA 2 9 7 (78%)

Some laboratories may have notably underestimated their MU, as they indicated that
their MU was less than two times the uncertainty of the median (see Table 1), yet
their results were further from the median than this value. This guideline is very
approximate however, given that the uncertainty of the median was more than
0.3xNIQR.

Conversely, laboratories which indicated a MU which was greater than three times
the normalised IQR may have overestimated their MU.1 If either of these situations
continue to occur over successive proficiency rounds, laboratories are recommended
to re-visit their MU calculations.

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.

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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 12

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.

Analysis
Lab
Salinity pH Conductivity
Code
PTA 1 PTA 2 PTA 1 PTA 2 PTA 1 PTA 2

424 §

472 § §

498 § §

575 § §
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] ISO 13528:2015 Statistical methods for use in proficiency testing by

interlaboratory comparisons.

[3] Global Proficiency, 2016. WaterChek Proficiency Round WCS1706.

[4] Standard Methods For the Examination of Water and Wastewater, 2012.
Published by APHA, AWWA, WEF (22nd Edition).

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 APPENDIX A

Results and Data Analysis

Salinity ................................................................................................................................... A1
pH ........................................................................................................................................ A5
Conductivity ........................................................................................................................... A9

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 Salinity Results

Samples PTA 1 and PTA 2

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 A1

Salinity
Results by Laboratory Code

Sample PTA 1
Laboratory Code
Result ± MU1 Robust Method
z-score2 Code3
214B 35.100 ± 3.245 0.56 1
237 36.1 ± 1 1.03 1
447 33.900 # 0.00 1
464 33.353 # -0.26 1
498 29.417 ± 2.9 -2.10 1
575 31.000 ± 4.34 -1.36 1
579 34.0 ± 0.19 0.05 1

No of Results: 7
Median: 33.9000
Normalised IQR: 2.1383
Uncertainty of the Median: 1.0129
Robust CV: 6.3%
Minimum: 29.417
Maximum: 36.1
Range: 6.683
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-C4) for method code descriptions.
4
"#" indicates that no result was returned for this sample/test.

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 Salinity - Sample PTA 1 - Robust Z-Scores

Ordered Robust Z-Score Charts

Salinity - Sample PTA 1

4
3

237
2

214B
579
447
1
z-score

A2
464
-1
575

-2
498

-3
-4
-5
lab code

Robust Z-Scores

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 A3

Salinity
Results by Laboratory Code

Sample PTA 2
Laboratory Code
Result ± MU1 Robust Method
z-score2 Code3
214B 29.965 ± 2.770 0.25 1
237 31.2 ± 1 1.11 1
447 29.600 # 0.00 1
464 28.957 # -0.44 1
498 25.740 ± 2.6 -2.67 1
575 36.300 ± 5.08 4.64 § 1
579 29.0 ± 0.19 -0.42 1

No of Results: 7
Median: 29.6000
Normalised IQR: 1.4450
Uncertainty of the Median: 0.6845
Robust CV: 4.9%
Minimum: 25.740
Maximum: 36.300
Range: 10.560
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-C4) for method code descriptions.
4
"#" indicates that no result was returned for this sample/test.

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 Salinity - Sample PTA 2 - Robust Z-Scores

575
5

Ordered Robust Z-Score Charts

Salinity - Sample PTA 2

4
3

237
2

214B
447
1
z-score

A4
-1

579
464

-2
-3
498

-4
-5
lab code

Robust Z-Scores

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 pH Results

Samples PTA 1 and PTA 2

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 A5

pH
Results by Laboratory Code

Sample PTA 1
Laboratory Code
Result ± MU1 Robust Method
z-score2 Code3
156 8.26 ± 0.13 0.00 10
214B 7.98 ± 0.17 -2.48 5
237 8.3 ± 0.2 0.35 5
317 8.26 ± 0.15 0.00 5
424 8.03 ± 0.16 -2.03 5
432 8.28 # 0.18 5
447 8.47 # 1.86 5
451 8.21 ± 0.02 -0.44 10
464 8.41 # 1.33 6
472 6.99 ± 0.11 -11.23 § 5
498 8.22 ± 0.2 -0.35 5
575 8.37 ± 0.13 0.97 5

No of Results: 12
Median: 8.260
Normalised IQR: 0.113
Uncertainty of the Median: 0.041
Robust CV: 1.4%
Minimum: 6.99
Maximum: 8.47
Range: 1.48
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-C4) for method code descriptions.
4
"#" indicates that no result was returned for this sample/test.

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 pH - Sample PTA 1 - Robust Z-Scores

Ordered Robust Z-Score Charts

4

pH - Sample PTA 1
3

447
464
575
2

237
432
156

317
1
z-score

A6
498
-1
451

-2
424

-3
214B

-4
-5
472

lab code

Robust Z-Scores

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 A7

pH
Results by Laboratory Code

Sample PTA 2
Laboratory Code
Result ± MU1 Robust Method
z-score2 Code3
156 8.36 ± 0.13 0.66 10
214B 8.17 ± 0.18 -1.02 5
237 8.3 ± 0.2 0.13 5
317 8.39 ± 0.15 0.93 5
424 8.00 ± 0.16 -2.52 5
432 8.36 # 0.66 5
447 8.26 # -0.22 5
451 8.36 ± 0.02 0.66 10
464 8.40 # 1.02 6
472 7.80 ± 0.13 -4.29 § 5
498 8.22 ± 0.2 -0.57 5
575 8.27 ± 0.13 -0.13 5

No of Results: 12
Median: 8.285
Normalised IQR: 0.113
Uncertainty of the Median: 0.041
Robust CV: 1.4%
Minimum: 7.80
Maximum: 8.40
Range: 0.60
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-C4) for method code descriptions.
4
"#" indicates that no result was returned for this sample/test.

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 pH - Sample PTA 2 - Robust Z-Scores

Ordered Robust Z-Score Charts

4

pH - Sample PTA 2
3

464
317
2

156

432

451
237
1
z-score

A8
575
447
-1
498
214B

-2
-3
424

-4
472

-5
lab code

Robust Z-Scores

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 Conductivity Results

Samples PTA 1 and PTA 2

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 A9

Conductivity
Results by Laboratory Code

Sample PTA 1
Laboratory Code
Result ± MU1 Robust Method
mS/cm z-score2 Code3
156 51.85 ± 0.25 -0.02 17
214B 53.20 ± 4.92 0.61 12
237 54.2 ± 2 1.08 12
317 52.41 ± 5.2 0.24 12
424 61.20 ± 12.24 4.36 § 12
447 51.9 # 0.00 12
464 50.76 # -0.53 13
498 45.26 ± 4.5 -3.11 § 12
575 50.33 ± 7.05 -0.74 12

No of Results: 9
Median: 51.900
Normalised IQR: 2.133
Uncertainty of the Median: 0.891
Robust CV: 4.1%
Minimum: 45.26
Maximum: 61.20
Range: 15.94
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-C4) for method code descriptions.
4
"#" indicates that no result was returned for this sample/test.

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 Conductivity - Sample PTA 1 - Robust Z-Scores

Conductivity - Sample PTA 1

424
5

Ordered Robust Z-Score Charts

4
3

237
214B
2

317
447
1
z-score

A10
0

156
-1
464
575

-2
-3
498

-4
-5
lab code

Robust Z-Scores

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 A11

Conductivity
Results by Laboratory Code

Sample PTA 2
Laboratory Code
Result ± MU1 Robust Method
mS/cm z-score2 Code3
156 45.45 ± 0.25 -0.53 17
214B 46.20 ± 4.27 -0.11 12
237 47.5 ± 2 0.61 12
317 46.68 ± 4.7 0.16 12
424 51.5 ± 10.30 2.85 12
447 46.4 # 0.00 12
464 44.79 # -0.90 13
498 39.60 ± 3.9 -3.79 § 12
575 59.33 ± 8.31 7.22 § 12

No of Results: 9
Median: 46.400
Normalised IQR: 1.792
Uncertainty of the Median: 0.745
Robust CV: 3.9%
Minimum: 39.60
Maximum: 59.33
Range: 19.73
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-C4) for method code descriptions.
4
"#" indicates that no result was returned for this sample/test.

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 Conductivity - Sample PTA 2 - Robust Z-Scores

575

Conductivity - Sample PTA 2

5

Ordered Robust Z-Score Charts

4

424
3
2

237
317
447
1
z-score

A12
0

214B
-1
156
464

-2
-3
-4
498

-5
lab code

Robust Z-Scores

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 APPENDIX B

Sample Homogeneity and Stability

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

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 B1

Homogeneity and Stability Testing

Samples for this program consisted of pasteurised estuarine seawater and ocean beach
seawater and were obtained from Global Proficiency Ltd, New Zealand. As such, all samples
were subjected to rigorous quality control and homogeneity / stability testing.

A random selection of 13 samples were chosen from samples PTA 1 and PTA 2. Ten of
these were stored refrigerated 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
Global Proficiency Ltd for Conductivity (Conductivity meter, 25ºC / APHA 2510 B, 22nd ed.
2012) and pH (pH meter, APHA 4500-H+ B, 22nd ed. 2012).

All stability samples showed no notable differences when compared to homogeneity

samples.

Salinity was also tested to confirm the levels were within the expected range. One of each
sample was randomly selected, stored 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 of salinity were assumed to be similar to
conductivity and pH, based on identical manufacturing procedure and sample handling.

From statistical analyses based on the results of this testing and rigorous quality control, and
the normality of participant results from the proficiency testing program conducted by Global
Proficiency (round WCS1706, samples WSS1706-1 and WSS1706-2), 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-B3. 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 (diluted x10 for conductivity testing).

Samples PTA 1
SeaWaters
Round 2 Sample Conductivity (mS/cm) pH
ID
Rep 1 Rep 2 Rep 1 Rep 2
Homogeneity H1 5.36 5.35 8.35 8.35
H2 5.33 5.32 8.38 8.38
H3 5.39 5.32 8.38 8.38
H4 5.37 5.32 8.32 8.28
H5 5.39 5.34 8.27 8.26
H6 5.39 5.31 8.28 8.27
H7 5.37 5.31 8.27 8.27
H8 5.36 5.30 8.32 8.31
H9 5.36 5.32 8.33 8.33
H10 5.38 5.35 8.38 8.38
Stability S1 5.38 5.34 8.27 8.26
S2 5.36 5.32 8.30 8.29
S3 5.38 5.36 8.26 8.26
RSD 0.32% 0.34% 0.55% 0.59%

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 B2

Table B2. Homogeneity and stability testing of PTA 2 samples (diluted x10 for conductivity testing).

Samples PTA 2
SeaWaters
Round 2 Sample Conductivity (mS/cm) pH
ID
Rep 1 Rep 2 Rep 1 Rep 2
Homogeneity H1 4.59 4.62 8.26 8.24
H2 4.62 4.60 8.26 8.24
H3 4.57 4.58 8.30 8.30
H4 4.57 4.56 8.29 8.26
H5 4.61 4.59 8.31 8.29
H6 4.61 4.62 8.29 8.24
H7 4.61 4.60 8.27 8.24
H8 4.62 4.63 8.27 8.24
H9 4.61 4.61 8.30 8.30
H10 4.60 4.56 8.29 8.31
Stability S1 4.60 4.57 8.26 8.25
S2 4.58 4.57 8.26 8.26
S3 4.59 4.57 8.26 8.26
RSD 0.37% 0.53% 0.23% 0.32%

Table B3. Confirmatory testing of Salinity.

Salinity
SeaWaters
Round 2 Sample
Samples PTA 1 Samples PTA 2
ID
Confirmatory H1 34.9 ± 1.5 29.8 ± 1.3

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 APPENDIX C

Documentation

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

Method Codes ................................................................................................................. C3-C4
Results Sheet ........................................................................................................................ C5

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 C1

PROFICIENCY TESTING AUSTRALIA

SeaWaters Proficiency Testing Program

SeaWaters (Chemical) Round 2 MAY, 2017

Salinity, pH, Conductivity

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 SeaWaters Round SW2 Sample: PTA 1 and Sample: PTA 2,
supplied by Global Proficiency Ltd. The bottles contain approximately 800 mL of sea water
sample, for analysis of Salinity, pH and Conductivity.
ii) The samples must be thoroughly mixed prior to analysis.
iii) The samples are ready to use as received, with no dilution or filtration required.

iv) The samples were chilled prior to dispatch and any liquid on the outside of the bottles may
be due to condensation rather than leakage. Store refrigerated (2-6ºC).

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

2. Sample Preparation

Caution: Analysis must begin immediately after bottle is opened.

i) Adjust bottle temperature to 20ºC.

ii) Record bottle ID number.
iii) Mix thoroughly by inversion and test according to your normal procedures.

3. Tests Requested

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

i) Salinity.
ii) pH.
iii) Conductivity.

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 C2

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 safety glasses, gloves, and fume hoods, where appropriate during the
determinations, is recommended.

5. Reporting

i) For each sample only a single result on the Results Sheet is requested.
ii) Report results in the appropriate units.
For statistical purposes, please report:
Salinity report to ≥ 3 decimal places (e.g. 35.001)
pH report to 2 decimal places (e.g. 7.91)
Conductivity (at 250C) report to nearest 0.01 mS/cm [0.01 m mho/cm]
(e.g. 54.49 mS/cm)
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 the
appropriate units. 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 19 MAY 2017 to:

Delfina Mihaila
Proficiency Testing Australia
PO Box 7507
SILVERWATER NSW 2128
AUSTRALIA
Phone: +612 9736 8397
Fax: +612 9743 6664
Email: dmihaila@pta.asn.au

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

Salinity 25-40
pH 4 – 10
Conductivity 10 – 200 mS/cm

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 C3

Method Codes to be used for the Results Sheet

METHOD
ANALYSIS METHOD DESCRIPTION CODE
REFERENCE
Salinity APHA SM APHA 2520 B.
1
Electrical Conductivity Method

APHA 2520 C.
2
Density Method

APHA 2520 D.
3
Algorithm of Practical Salinity

Other (please specify) 4

pH APHA SM APHA 4500 – H+ B.

5
Electrometric Method

ASTM ASTM D1293

6
Standard Test Methods for pH of Water

USP USP 38 (791)

7
pH

BS BS1377 P-3:1990
8
Part 9. Determination of the pH value.
AS 2300
AS
Methods of Chemical and Physical Testing 9
for the Dairying Industry
Other
In-house method, pH Meter 10

Other (please specify) 11

Method Reference Key

i) APHA SM APHA “Standard Methods for the Examination of Water and Wastewater”
(18, 19, 20, 21 and 22 Edition).
ii) ASTM ASTM International www.astm.org
iii) AS Australian Standards www.saiglobal.com
iv) BS British Standards Institution www.bsigroup.com
v) ISO International Organization for Standardization www.iso.org
vi) USEPA U.S Environmental Protection Agency, http://www.epa.gov.
vii) USP The United States Pharmacopeial Convention https://hmc.usp.org/

Method Codes Continued on next page…

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 C4

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

METHOD
ANALYSIS METHOD DESCRIPTION CODE
REFERENCE
Conductivity APHA SM APHA 2510 B.
12
(at 25°C) Laboratory Method (conductivity meter)

ASTM ASTM D1125 - 95(2009)

Test Method A—Field and Routine
13
Laboratory Measurement of Static (Non-
Flowing) Samples

ASTM D1125 - 95(2009)

Test Method B— Continuous In-Line 14
Measurement

USP USP 38 (645)

15
Water Conductivity

US EPA Method 120.1: Specific Conductance at

16
25°C by Conductivity Meter

Other
In-house method, Conductivity Meter 17

Other (please specify) 18

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 C5

PROFICIENCY TESTING AUSTRALIA

SeaWaters Proficiency Testing Program

SeaWaters (Chemical) Round 2

Salinity, pH, Conductivity,

MAY 2017
RESULTS SHEET

Laboratory
Code

*Approximate temperature of samples upon receipt:

PTA 1 PTA 2
ANALYSIS Method Method
Result ±MU* Result ±MU*
Code Code

Salinity

pH

Conductivity
at 25°C (mS/cm)
Please note: Where possible, proficiency testing samples should be treated as a routine
laboratory sample.

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

ii) For statistical purposes, please report:
Salinity report to ≥ 3 decimal places (e.g. 35.001)
pH report to 2 decimal places (e.g. 7.91)
0
Conductivity (at 25 C) report to nearest 0.01 mS/cm (0.01 m mho/cm)
(e.g. 54.49 mS/cm)
iii) Do not correct results for recovery.
iv) MU* Laboratories Measurement Uncertainty (MU) if known for the result.
Please report in the corresponding unit of measurement as the testing sample.

DATE: ______________________ SIGNATURE: _______________________________

Return results NO LATER THAN 19 MAY 2017 to:

Delfina Mihaila
Proficiency Testing Australia
PO Box 7507 Phone: +61 2 9736 8397
SILVERWATER NSW 2128 Fax: +61 2 9743 6664
AUSTRALIA Email: dmihaila@pta.asn.au
INSTRUCT WATERS PROF TEST PROG SW2

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 - End of Report -

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