Report No. 996: Seawaters Proficiency Testing Program

Report No.
996
SeaWaters
Proficiency Testing Program
Round No. 1
- Metals -
(Aluminium, Boron, Cadmium, Chromium,
Copper, Iron, Mercury, Selenium)
October 2016
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, 2016
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 ................................................................................................................. 14
6. References ...................................................................................................................... 14
APPENDIX A – Results and Data Analysis
Aluminium (Al) ....................................................................................................................... A1

Boron (B) ............................................................................................................................... A3
Cadmium (Cd) ....................................................................................................................... A5
Chromium (Cr)....................................................................................................................... A7
Copper (Cu)........................................................................................................................... A9
Iron (Fe)............................................................................................................................... A11
Mercury (Hg) ....................................................................................................................... A13
Selenium (Se)...................................................................................................................... A15
APPENDIX B – Sample Homogeneity and Stability
Homogeneity and Stability Testing ........................................................................................ B1
APPENDIX C – Documentation
Instructions to Participants .................................................................................................... C1

Method Codes ....................................................................................................................... C3
Digestion Codes .................................................................................................................... C4
Results Sheet ........................................................................................................................ C5
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1. Foreword
This report summarises the results of a proficiency testing program on the

determination of Aluminium, Boron, Cadmium, Chromium, Copper, Iron, Mercury and
Selenium in seawaters. This is round 1 in a planned series of programs involving the
analysis of chemical and physical parameters of seawaters.
The exercise was conducted in August 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. 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 one plastic bottle (labelled PTA 1) containing
solutions of Aluminium, Boron, Cadmium, Chromium, Copper, Iron, Mercury and
Selenium.
2.4 A total of 12 laboratories received samples, comprising:
- 9 Australian participants; and

- 3 overseas participants, including:
- Indonesia (1), Malaysia (1), Qatar (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 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 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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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 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 sample used in this study was a natural estuarine seawater
sample, where the analyte concentrations were fortified by a minimum of 8.5 times
the limit of detection of Inductively Coupled Plasma - Mass Spectrometry ultra trace
(LOD: ICP-MS ultra trace) for all analytes except Mercury (22x LOD) and Boron (nil
fortification), to ensure all analytes were at easily detectable levels.
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.
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
Median
Analyte Sample Concentration of the Median
(µg/L)
(µg/L) (µg/L)
Aluminium
PTA 1 158 171.0 9.9
(Al)
Boron
PTA 1 4060 4290.0 158.7
(B)
Cadmium
PTA 1 1.5 1.547 0.182
(Cd)
Chromium
PTA 1 3.53 3.385 0.302
(Cr)
Copper
PTA 1 10 10.90 0.42
(Cu)
Iron
PTA 1 95.3 100.00 4.54
(Fe)
Mercury
PTA 1 1.9 1.800 0.146
(Hg)
Selenium
PTA 1 39 37.00 3.32
(Se)
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 25% for all analytes, except
Cadmium, which obtained a robust CVs of 31%. This high CV was likely due to the
proximity of the fortified sample concentration to the detection limit for ICP (APHA
3120 B).
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4.2 Analysis of Round 1 Results
4.2.1 Aluminium
Table 2 presents the Aluminium median and robust CV obtained in this round. This
was comparable to the CV observed in a recent proficiency round (14.8%) with 13
participants [3], and to those published in US EPA 6020A for ICP-MS (11%-14%) and
APHA 3120 B for ICP (16.2%).
Table 2. Current round variability and proficiency median of Aluminium testing.

Round Sample Median (µg/L) Robust CV (%) Participants
This study PTA 1 171.0 15.4 11
Bias / Accuracy
The Aluminium testing was successfully performed, with satisfactory results (|z-score|
≤ 2.0) ranging between 145 – 210.5 µg/L. Out of 11 participants, no questionable
results (2.0 < |z-score| < 3.0) and no outlier results (|z-score| ≥ 3.0) were obtained.
The Aluminium dataset formed a normal distribution with no significant bias

attributable to any one analysis method (Figure 1). The method most frequently used
for Aluminium testing in this round was APHA 3120 B (ICP-OES), which was used by
six out of eleven participants.
Aluminium - Sample PTA 1
5
APHA 3120 B
APHA 3125 B
4
In house modified ICP
OES/AES
3 Other
Frequency
0
90 110 130 150 170 190 210 230 250 270
Results (µg/L)
Figure 1. Spread of results for Aluminium testing of sample PTA 1, with a median of
171.0 µg/L.
Laboratories testing Aluminium using ICP-OES had to overcome severe interference

from ≈ 11 µg/L Molybdenum (ICP-OES line 396.152 nm) and ≈ 100 µg/L Iron (ICP-
OES line 167.078 nm) [4].
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4.2.2 Boron
Table 3 presents the Boron median and robust CV obtained in this round. This was
better than the CV observed in a recent proficiency round (13.9%) with 13 participants
[3], and published precision information in APHA 3120 B for ICP (10.5%).
Table 3. Current round variability and proficiency median of Boron testing.

Bias / Accuracy
The Boron testing was successfully performed, with satisfactory results (|z-score| ≤
2.0) ranging between 4016 – 5020 µg/L. Out of 11 participants, no questionable
The Boron dataset formed a normal distribution with no significant bias attributable to
any one analysis method (Figure 2). The method most frequently used for Boron
testing in this round was APHA 3120 B (ICP-OES), which was used by six out of
eleven participants.
Boron - Sample PTA 1
6 APHA 3120 B
APHA 3125 B
5

OES/AES
4
Other
Frequency
0
2500 2900 3300 3700 4100 4500 4900 5300 5700 6100
Results (µg/L)
Figure 2. Spread of results for Boron testing of sample PTA 1, with a median of 4290.0 µg/L.
Laboratories testing Boron using ICP-OES had to overcome interferences from ≈ 5

µg/L Cobalt (lines 249.773 nm and 249.678 nm), ≈ 11 µg/L Molybdenum (lines
249.773 nm and 208.959 nm), ≈ 880 µg/L Manganese and ≈ 100 µg/L Iron (line
249.773 nm) and ≈ 3.4 µg/L Chromium (line 249.678 nm) [4].
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4.2.3 Cadmium
Table 4 presents the Cadmium median and robust CV obtained in this round. This
was notably more varied than the CV observed in a recent proficiency round (22.75%)
with 15 participants [3], and to those published in US EPA 6020A for ICP-MS (4.6%-
7.2%) for aqueous solutions.
Table 4. Current round variability and proficiency median of Cadmium testing.

Bias / Accuracy
The Cadmium testing was successfully performed, with satisfactory results (|z-score|
≤ 2.0) ranging between 0.8 – 2.029 µg/L. Out of 11 participants, two questionable
results (2.0 < |z-score| < 3.0) were reported (laboratories 497A and 498). No outlier
results (|z-score| ≥ 3.0) were obtained.
The Cadmium dataset formed a normal distribution with no significant bias

attributable to any one analysis method (Figure 3). The method most frequently used
for Cadmium testing in this round was APHA 3125 B (ICP-MS), which was used by
six out of eleven participants.
Cadmium - Sample PTA 1
6
APHA 3120 B
5 APHA 3125 B

4 OES/AES
Other
Frequency
0
0.2 0.7 1.2 1.7 2.2 2.7 3.2 3.7 4.2 4.7
Results (µg/L)
Figure 3. Spread of results for Cadmium testing of sample PTA 1, with a median of
1.547 µg/L.
Concentrations of Cadmium were below the estimated detection level (4 µg/L) for
APHA 3120 B (ICP). Laboratories with questionable results may have had problems
with severe interference from ≈ 11.2 µg/L Arsenic (ICP-OES line 228.802 nm) or ≈ 5
µg/L Cobalt [4].
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4.2.4 Chromium
Table 5 presents the Chromium median and robust CV obtained in this round. This
participants [3], and to those published in US EPA 6020A for ICP-MS (13%-27%).
Table 5. Current round variability and proficiency median of Chromium.

Bias / Accuracy
The Chromium testing was successfully performed, with satisfactory results (|z-score|
≤ 2.0) ranging between 2.70 – 4.01 µg/L. Out of ten participants, one questionable
result (2.0 < |z-score| < 3.0) was reported (laboratory 129). No outlier results (|z-
score| ≥ 3.0) were obtained.
The Chromium dataset formed a normal distribution with no significant bias

attributable to any one analysis method (Figure 4). The methods most frequently used
for Chromium testing in this round were APHA 3120 B (ICP-OES) and APHA 3125 B
(ICP-MS), which were used by four and three participants, respectively (out of ten
participants).
Chromium - Sample PTA 1
6
APHA 3120 B
5 APHA 3125 B

4 OES/AES
Other
Frequency
0
0.5 1.25 2 2.75 3.5 4.25 5 5.75 6.5 7.25
Results (µg/L)
Figure 4. Spread of results for Chromium testing of sample PTA 1, with a median of
3.385 µg/L.
Concentrations of Chromium were below the estimated detection level (7 µg/L) for
APHA 3120 B (ICP). Laboratories with questionable results may have had problems
with severe interference from Vanadium (unknown concentration) and ≈ 10 µg/L
Copper (ICP-OES line 276.654 nm) [4].
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4.2.5 Copper
Table 6 presents the Copper median and robust CV obtained in this round. This was
comparable to the CV observed in a recent proficiency round (12.2%) with 12
participants [3], and to those published in US EPA 6020A for ICP-MS (6.1%-27%)
and APHA 3120 B for ICP (30.1%).
Table 6. Current round variability and proficiency median of Copper testing.

Bias / Accuracy
The Copper testing was successfully performed, with satisfactory results (|z-score| ≤
2.0) ranging between 10.07 – 12.38 µg/L. Out of eleven participants, one
questionable result (2.0 < |z-score| < 3.0) was reported (laboratory 498). Two outlier
results (|z-score| ≥ 3.0) were obtained, requiring follow-up action by laboratories 160
and 359.
The Copper dataset formed a normal distribution with no significant bias attributable
to any one analysis method (Figure 5). The method most frequently used for Copper
testing in this round was APHA 3125 B (ICP-MS), which was used by five out of
eleven participants.
Copper - Sample PTA 1
6
APHA 3120 B
5 APHA 3125 B

4 OES/AES
Other
Frequency
0
1.5 3.5 5.5 7.5 9.5 11.5 13.5 15.5 17.5 19.5
Results (µg/L)
Figure 5. Spread of results for Copper testing of sample PTA 1, with a median of 10.90 µg/L.
Laboratories with questionable or outlier results may have had problems with severe
interference from Lead (ICP-OES line 224.700 nm) which was present at a
concentration of ≈ 9.5 µg/L, or Nickel at ≈ 26.4 µg/L. ICP-OES line 324.754 nm was
also likely to suffer interference from Molybdenum which had a concentration of
≈ 11 µg/L [4].
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4.2.6 Iron
Table 7 presents the Iron median and robust CV obtained in this round. This was
participants [3], and to published precision information in US EPA 6020A for ICP-MS
(11%-150%) and APHA 3120 B for ICP (18.0%).
Table 7. Current round variability and proficiency median of Iron testing.

This study PTA 1 100.00 13.0 13
Bias / Accuracy
The Iron testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0)
ranging between 74.6 – 112.2 µg/L. Out of 13 participants, no questionable results
(2.0 < |z-score| < 3.0) were reported. Two outlier results (|z-score| ≥ 3.0) were
obtained, requiring follow-up action by laboratories 451 and 497B.
The Iron dataset formed a normal distribution with no significant bias attributable to
any one analysis method (Figure 6). The method most frequently used for Iron testing
in this round was APHA 3120 B (ICP-OES), which was used by six out of 13
participants.
Iron - Sample PTA 1
5
APHA 3120 B
APHA 3125 B
4
OES/AES
Other
3
Frequency
0
65 75 85 95 105 115 125 135 145 155 165 175 185 195
Results (µg/L)
Figure 6. Spread of results for Iron testing of sample PTA 1, with a median of 100.00 µg/L.
Laboratories with outlier results may have had problems with interference from
≈ 5 µg/L Cobalt (ICP-OES line 238.204 nm and 239.562 nm) or ≈ 3.4 µg/ L Chromium
[4].
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4.2.7 Mercury
Table 8 presents the Mercury median and robust CV obtained in this round. This was
participants [3], and to those published in APHA 3112 B for Cold Vapour Atomic
Absorption Spectrometry (13.3%-22.6%) for inorganic Mercury.
Table 8. Current round variability and proficiency median of Mercury testing.

Bias / Accuracy
The Mercury testing was successfully performed, with satisfactory results (|z-score| ≤
2.0) ranging between 1.261 – 2.32 µg/L. Out of nine participants, no questionable
The Mercury dataset formed a normal distribution with no significant bias attributable
to any one analysis method (Figure 7). The methods most frequently used for
Mercury testing in this round were APHA 3112 B (Cold Vapour Atomic Absorption
Spectrometric Method), which was used by five out of nine participants. The method
APHA 3125 B (ICP-MS) used by three participants.
Mercury - Sample PTA 1
5
APHA 3112 B
APHA 3125 B
Other
4
3
Frequency
0
0.5 0.8 1.1 1.4 1.7 2 2.3 2.6 2.9 3.2
Results (µg/L)
Figure 7. Spread of results for Mercury testing of sample PTA 1, with a median of 1.800 µg/L.
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4.2.8 Selenium
Table 9 presents the Selenium median and robust CV obtained in this round. This
participants [3], and to those published in US EPA 6020A for ICP-MS (15%-25%).
Table 9. Current round variability and proficiency median of Selenium testing.

Bias / Accuracy
The Selenium testing was successfully performed, with satisfactory results (|z-score|
≤ 2.0) ranging between 33.1 – 48 µg/L. Out of nine participants, no questionable
The Selenium dataset formed a normal distribution with no significant bias attributable
to any one analysis method (Figure 8). The method most frequently used for
Selenium testing in this round was APHA 3125 B (ICP-MS), which was used by six
out of nine participants.
Selenium - Sample PTA 1
5
APHA 3125 B

OES/AES
4
Other
3
Frequency
0
6 13 20 27 34 41 48 55 62 69
Results (µg/L)
Figure 8. Spread of results for Selenium testing of sample PTA 1, with a median of 37.00 µg/L.
Concentrations of Selenium were below the estimated detection level (75 µg/L) for
APHA 3120 B (ICP). Laboratories testing Selenium using ICP-OES also had to
overcome severe interference from 3.4 µg/L Chromium (ICP-OES line 203.985 nm
and 206.279 nm), 3.0 µg/L Antimony (ICP-OES line 203.985 nm) and 9.5 µg/L Iron
(ICP-OES 196.026 nm) [4].
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4.3 Measurement Uncertainty (MU)
All participants in this round reported the measurement uncertainty (MU) associated
with their results, with the exception of laboratory 160 which did not report the MU for
Mercury.
Many of the stated MUs did not accurately reflect the difference between the median
and the participant’s result for this proficiency sample. If this is occurring in
successive rounds, laboratories may wish to reassess their MU.
Some laboratories may have underestimated 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 this value.
Conversely, laboratories which indicated a MU which was greater than three times
the normalised IQR may have over-estimated their MU.1
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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5. Outlier Results
Laboratories reporting results that have been identified as outliers are listed in Table
10 below.
Table 10. Laboratory results identified as outliers for each analysis performed.
Analysis
Aluminium
Chromium
Boron (B)
Cadmium
Selenium
Lab
Iron (Fe)
Mercury
Copper
(Cd)
(Cu)
(Hg)
(Se)
Code
(Cr)
(Al)
160 §
359 §
451 §
497B §
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 WCS1606.
[4] Inorganic Ventures, 2016. Interactive Periodic Table – Analytical ICP Data.
https://www.inorganicventures.com/periodic-table
[5] US EPA 6020A, 1998. Inductively Coupled Plasma – Mass Spectrometry,

Table 4. https://www.epa.gov/sites/production/files/2015-07/documents/epa-
6020a.pdf
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APPENDIX A
Results and Data Analysis

Aluminium (Al) ....................................................................................................................... A1
Boron (B) ............................................................................................................................... A3
Cadmium (Cd) ....................................................................................................................... A5
Chromium (Cr)....................................................................................................................... A7
Copper (Cu)........................................................................................................................... A9
Iron (Fe)............................................................................................................................... A11
Mercury (Hg) ....................................................................................................................... A13
Selenium (Se)...................................................................................................................... A15
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Aluminium Results
Sample PTA 1
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A1
Aluminium
Results by Laboratory Code
Sample PTA 1
Laboratory Code
Result ± MU1 Robust Method Digestion
µg/L z-score2 Code3 Code3
103 194 ± 33 0.87 8 14
129 188 ± 12.3 0.65 7 15
160 192 ± 17 0.80 13 14
359 158 ± 16 -0.49 7 14
432 186.1 ± 7.9 0.57 12 14
476 151 ± 20 -0.76 7 14
497A 150.2 ± 15.09 -0.79 12 14
497B 160.7 ± 16.13 -0.39 7 14
498 145 ± 23.2 -0.99 7 #
532 210.5 ± 28.6 1.50 8 14
575 171 ± 42 0.00 7 14
No of Results: 11
Median: 171.0
Normalised IQR: 26.3
Uncertainty of the Median: 9.9
Robust CV: 15.4%
Minimum: 145
Maximum: 210.5
Range: 65.5
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 and digestion code descriptions.
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Aluminium - Sample PTA 1 - Robust Z-Scores
Aluminium - Sample PTA 1

5
Ordered Robust Z-Score Charts

4
3
532
2
103
160
129
432
575
1
z-score
A2
497B
-1
359
476
497A
498
-2
-3
-4
-5
lab code
Robust Z-Scores
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Boron Results
Sample PTA 1
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A3
Boron
Sample PTA 1
Laboratory Code
103 4016 ± 112 -0.65 8 14
129 4675 ± 44 0.92 7 15
160 4165 ± 300 -0.30 13 14
359 4730 ± 473 1.05 7 14
432 4393 ± 56 0.25 12 14
476 4290 ± 645 0.00 7 14
497A 4102 ± 328.2 -0.45 12 14
497B 4208 ± 338.7 -0.20 7 14
498 5020 ± 1305 1.74 7 #
532 4725 ± 548 1.04 8 14
575 4063 ± 520 -0.54 7 14
No of Results: 11
Median: 4290.0
Robust CV: 9.8%
Minimum: 4016
Maximum: 5020
Range: 1004
1
2
3
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Boron - Sample PTA 1 - Robust Z-Scores
Boron - Sample PTA 1

4
3
498
359
532
2
129
432
476
1
z-score
A4
497B
160
-1
497A
575
103
-2
-3
-4
-5
lab code
Robust Z-Scores
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Cadmium Results
Sample PTA 1
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A5
Cadmium
Sample PTA 1
Laboratory Code
103 1.6 ± 0.2 0.11 8 14
129 1.5 ± 0.5 -0.10 7 23
160 1.11 ± 0.8 -0.91 13 14
359 2.00 ± 0.24 0.94 8 14
432 1.547 ± 0.082 0.00 12 14
476 1.40 ± 0.48 -0.31 8 14
497A 2.750 ± 0.834 2.50 12 14
497B 2.029 ± 0.609 1.00 7 14
498 2.57 ± 0.05 2.12 8 #
532 1.33 ± 0.08 -0.45 8 14
575 0.8 ± 0.3 -1.55 8 14
No of Results: 11
Median: 1.547
Robust CV: 31.1%
Minimum: 0.8
Maximum: 2.750
Range: 1.950
1
2
3
SD 9.17.11
Cadmium - Sample PTA 1 - Robust Z-Scores
Cadmium - Sample PTA 1

5

4
497A
498
3
497B
359
2
103
432
1
z-score
A6
129
476
-1
532
160
-2
575
-3
-4
-5
lab code
Robust Z-Scores
SD 9.17.11
Chromium Results
Sample PTA 1
SD 9.17.11
A7
Chromium
Sample PTA 1
Laboratory Code
103 3.5 ± 0.9 0.15 8 14
129 5.0 ± 1.4 2.12 7 15
160 4.01 ± 0.6 0.82 13 14
359 4.00 ± 0.40 0.81 7 14
432 2.869 ± 0.110 -0.68 12 14
476 3.27 ± 1.25 -0.15 8 14
497A 3.143 ± 0.943 -0.32 12 14
497B 3.713 ± 1.135 0.43 7 14
532 2.70 ± 0.29 -0.90 8 14
575 3 ± 2 -0.51 7 14
No of Results: 10
Median: 3.385
Robust CV: 22.5%
Minimum: 2.70
Maximum: 5.0
Range: 2.30
1
2
3
SD 9.17.11
Chromium - Sample PTA 1 - Robust Z-Scores
Chromium - Sample PTA 1

5

4
129
3
2
160
359
497B
103
1
z-score
A8
476
497A
-1
575
432
532
-2
-3
-4
-5
lab code
Robust Z-Scores
SD 9.17.11
Copper Results
Sample PTA 1
SD 9.17.11
A9
Copper
Sample PTA 1
Laboratory Code
103 12.0 ± 0.6 0.98 8 14
129 10.9 ± 1.6 0.00 7 23
160 15.2 ± 0.9 3.83 § 13 14
359 2 ± 0.20 -7.92 § 8 14
432 10.07 ± 0.22 -0.74 12 14
476 10.9 ± 2.4 0.00 8 14
497A 11.34 ± 3.405 0.39 12 14
497B 12.38 ± 3.892 1.32 7 14
498 7.93 ± 0.16 -2.64 8 #
532 10.9 ± 1.3 0.00 8 14
685 12 ± 1 0.98 12 22
No of Results: 11
Median: 10.90
Robust CV: 10.3%
Minimum: 2
Maximum: 15.2
Range: 13.2
1
2
3
SD 9.17.11
A1
Copper - Sample PTA 1 - Robust Z-Scores
160
Copper - Sample PTA 1

4
3
497B
103
685
2
497A
129
476
532
1
z-score
A10
0
-1
432
-2
-3
498
-4
-5
359
lab code
Robust Z-Scores
SD 9.17.11
Iron Results
Sample PTA 1
SD 9.17.11
A11
Iron
Sample PTA 1
Laboratory Code
103 100 ± 20 0.00 8 14
129 82.7 ± 7 -1.33 7 23
160 106 ± 3 0.46 13 14
359 90 ± 9 -0.77 7 14
432 100.2 ± 1.9 0.02 12 14
451 194.4 ± 120 7.24 § 13 #
476 74.6 ± 21.0 -1.95 7 14
497A 112.2 ± 22.45 0.94 12 14
497B 147.2 ± 29.4 3.62 § 7 14
498 88.4 ± 17.7 -0.89 7 #
532 104.3 ± 14.0 0.33 8 14
575 83.4 ± 35 -1.27 7 14
685 99 ± 3 -0.08 12 22
No of Results: 13
Median: 100.00
Robust CV: 13.0%
Minimum: 74.6
Maximum: 194.4
Range: 119.8
1
2
3
SD 9.17.11
Iron - Sample PTA 1 - Robust Z-Scores
451
497B
5

4
Iron - Sample PTA 1

3
497A
2
160
532
432
103
1
z-score
A12
0
685
-1
359
498
575
129
-2
476
-3
-4
-5
lab code
Robust Z-Scores
SD 9.17.11
Mercury Results
Sample PTA 1
SD 9.17.11
A13
Mercury
Sample PTA 1
Laboratory Code
103 1.9 ± 0.2 0.29 8 14
129 1.8 ± 0.05 0.00 5 23
160 1.41 # -1.12 13 23
359 1.60 ± 0.40 -0.57 8 14
432 1.261 ± 0.099 -1.54 5 14
476 1.99 ± 0.29 0.54 5 23
497A <5.0 # na 12 14
497B <5.0 # na 7 14
498 1.50 ± 0.10 -0.86 5 #
532 1.85 ± 0.36 0.14 8 14
575 2.32 ± 0.5 1.49 5 18
No of Results: 9
Median: 1.800
Robust CV: 19.4%
Minimum: 1.261
Maximum: 2.32
Range: 1.059
1
2
3
SD 9.17.11
Mercury - Sample PTA 1 - Robust Z-Scores
Mercury - Sample PTA 1

4
3
575
2
476
103
532
129
1
z-score
A14
0
-1
359
498
160
-2
432
-3
-4
-5
lab code
Robust Z-Scores
SD 9.17.11
Selenium Results
Sample PTA 1
SD 9.17.11
A15
Selenium
Sample PTA 1
Laboratory Code
103 33.1 ± 3.0 -0.49 8 14
129 37 ± 1.2 0.00 13 23
160 43.2 ± 15 0.78 13 14
359 48 ± 7 1.38 8 14
432 34.11 ± 1.99 -0.36 12 14
476 40.2 ± 6.2 0.40 8 14
498 33.4 ± 1.17 -0.45 8 #
532 35.8 ± 5.01 -0.15 8 14
575 43.3 ± 12 0.79 8 14
No of Results: 9
Median: 37.00
Robust CV: 21.5%
Minimum: 33.1
Maximum: 48
Range: 14.9
1
2
3
SD 9.17.11
Selenium - Sample PTA 1 - Robust Z-Scores
Selenium - Sample PTA 1

4
3
359
2
575
160
476
129
1
z-score
A16
0
532
432
-1
498
103
-2
-3
-4
-5
lab code
Robust Z-Scores
SD 9.17.11
APPENDIX B
Sample Homogeneity and Stability
Homogeneity and Stability Testing ........................................................................................ B1
SD 9.17.11
B1
Homogeneity and Stability Testing
Samples for this program consisted of acidified estuarine seawater and 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 the manufactured batch for
homogeneity and stability testing. Seven 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 Global Proficiency Ltd using Conductivity as an
indicator test (Conductivity meter, 250C / APHA 2510 B, 22nd ed. 2012).
All stability samples showed no notable differences when compared to homogeneity

samples.
Based on the combined results of the indicator test for homogeneity and stability, the
standard operating procedures for sample manufacture, and the normality of participant
results from the proficiency testing program conducted by Global Proficiency (round
WCS1606, sample WST1606-2), 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 the table B1. 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).
Samples PTA 1
SeaWaters
Round 1 Sample Conductivity (mS/cm)
ID Rep 1 Rep 2
Homogeneity H1 9.10 9.09
H2 9.05 9.05
H3 9.02 9.02
H4 9.02 9.01
H5 9.00 8.98
H6 9.04 9.02
H7 9.04 9.02
Stability S1 9.02 8.99
S2 9.02 9.02
S3 9.00 9.01
RSD 0.32% 0.34%
SD 9.17.11
APPENDIX C
Documentation
Instructions to Participants .................................................................................................... C1

Method Codes ....................................................................................................................... C3
Digestion Codes .................................................................................................................... C4
Results Sheet ........................................................................................................................ C5
SD 9.17.11
C1
PROFICIENCY TESTING AUSTRALIA
SeaWaters Proficiency Testing Program
SeaWaters (Chemical) Round 1 AUGUST, 2016
Metals (Aluminium, Boron, Cadmium, Chromium, Copper, Iron, Mercury, Selenium)
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) One plastic bottle labelled SeaWaters Round 1 Sample: PTA 1, supplied by Global
Proficiency Ltd. The bottle contains approximately 200 mL of modified sea water sample,
acidified with 0.1% nitric acid, for analysis of Aluminium, Boron, Cadmium, Chromium,
Copper, Iron, Mercury and Selenium.
ii) The sample must be thoroughly mixed prior to analysis.
iii) The sample has been acidified with high purity nitric acid (HNO3) to pH 2, and is ready to use
as received.
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 sample PTA 1 are as follows:
i) Aluminium (Al).
ii) Boron (B).
iii) Cadmium (Cd).
iv) Chromium (Cr).
v) Copper (Cu).
vi) Iron (Fe).
vii) Mercury (Hg).
viii) Selenium (Se).
(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.
SD 9.17.11
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) Report results using three or four significant figures as appropriate (e.g.: 0.0123, 1.23, 12.3,
1234).
ii) Report results in micrograms per litre (µg/L).
iii) Do not correct results for recovery.
iv) Select the appropriate method code and preparation procedure code for each test (see page
3 for method codes and preparation procedures codes) and record them 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 µg/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 2 SEPTEMBER 2016 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 (in µg/L):

Analyte Range
Aluminium (Al) 50 – 500 µg/L
Boron (B) 1000 – 10000 µg/L
Cadmium (Cd) 0.5 – 5 µg/L
Chromium (Cr) 0.5 – 5 µg/L
Copper (Cu) 5 – 50 µg/L
Iron (Fe) 50 – 500 µg/L
Mercury (Hg) 0.5 – 5 µg/L
Selenium (Se) 10 – 100 µg/L
SD 9.17.11
C3
Method Codes to be used for the Results Sheet
METHOD
ANALYSIS METHOD DESCRIPTION CODE
REFERENCE
APHA SM APHA 3111 B. 1
Aluminium (Al)
Direct Air-Acetylene Flame Method
Boron (B) APHA 3111 C. 2
Cadmium (Cd) Extraction/Air-Acetylene Flame Method
Chromium (Cr) APHA 3111 D.
Direct Nitrous Oxide-Acetylene Flame 3
Copper (Cu) Method
Iron (Fe) APHA 3111 E.
Extraction/Nitrous Oxide-Acetylene Flame 4
Mercury (Hg)
Method
Selenium (Se)
APHA 3112 B.
Cold Vapour Atomic Absorption 5
Spectrometric Method
APHA 3113 B.
Electrothermal Atomic Absorption 6
Spectrometric Method
APHA 3120 B. 7
Inductively Coupled Plasma (ICP) Method
APHA 3125 B.
Inductively-Coupled Plasma/Mass 8
Spectrometry (ICP/MS) Method
APHA 19th Edition (1995) 9

Dithizone Method
US EPA US EPA Method 245.7 (2005),

Bromine Oxidation followed by Atomic 10
Fluorescence.
US EPA Method 1631 (2002)

Mercury in Water by Oxidation, Purge and 11
Trap, and Cold Vapor Atomic Fluorescence
Spectrometry
In house Modified ICP-OES/AES 12
Other (please specify) 13
SD 9.17.11
C4
Sample Preparation Codes to be used for the Results Sheet
Sample Preparation Procedure Code
APHA (18, 19, 20, 21 and 22 Edition):
No pre-treatment 14
Part 3030 B Filtration 15
Part 3030 E (HNO3) Digestion 16
Part 3030 F (HNO3/HCl) Digestion 17
Part 3030 G (HNO3/H2SO4) Digestion 18
Part 3030 H (HNO3/HClO4) Digestion 19
Part 3030 I (HNO3/HClO4/HF) Digestion 20
Part 3030 J (Dry Ashing) Digestion 21
Part 3030 K (Microwave Assisted) Digestion 22
Other (please specify) 23
Method Reference Key
i) APHA SM APHA “Standard Methods for the Examination of Water and Wastewater” (18,
19, 20, 21 and 22 Edition).
ii) USEPA U.S Environmental Protection Agency,
http://www.epa.gov/osa/fem/methcollectns.htm.
SD 9.17.11
C5
PROFICIENCY TESTING AUSTRALIA

SeaWaters Proficiency Testing Program
SeaWaters (Chemical) Round 1
METALS
(Aluminium, Boron, Cadmium, Chromium, Copper, Iron, Mercury, Selenium)
AUGUST, 2016
RESULTS SHEET
(µg/L)
Laboratory
Code
*Approximate temperature of samples upon receipt:
SAMPLE PTA 1
METHOD PREPARATION
ANALYSIS ±MU CODE CODE
Result (µg/L)
(µg/L)
Aluminium (Al)
Boron (B)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Iron (Fe)
Mercury (Hg)
Selenium (Se)
Please note: Where possible, proficiency testing samples should be treated as a routine laboratory
sample.
i) For each analyte only a single result is requested.

ii) Report results using three or four significant figures (e.g.: 0.0123, 1.23, 12.3, 1234).
iii) Report results in micrograms per litre (µg/L).
iv) Do not correct results for recovery.
v) MU* Laboratories Measurement Uncertainty (MU) if known for the result. Please report in
µg/L, using the same number of decimal places as for the result.
DATE: ______________________ SIGNATURE: _______________________________
Return results NO LATER THAN 2 SEPTEMBER 2016 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 SeaWaters Prof Test Prog 1
SD 9.17.11
- End of Report -
SD 9.17.11

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© Copyright Proficiency Testing Australia, 2016

PO Box 7507 SILVERWATER NSW 2128, Australia

APPENDIX A – Results and Data Analysis

Aluminium (Al) ....................................................................................................................... A1

APPENDIX B – Sample Homogeneity and Stability

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

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

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

2. Program Features and Design

2.4 A total of 12 laboratories received samples, comprising:

- 9 Australian participants; and

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

- a table of results and calculated z-scores;

3.1 Outlier Results and Z-scores

In order to assess laboratories’ testing performance, a robust statistical approach,

A z-score with an absolute value less than or equal to 2.0 is considered to be

3.2 Results Tables and Summary Statistics

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

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

3.3 Ordered Z-score Charts

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

4. PTA and Technical Adviser’s Comments

4.1 Metrological Traceability and Measurement Uncertainty of Assigned Values

Sample preparation was undertaken according to Global Proficiency Ltd’s Standard

4.2 Analysis of Round 1 Results

Table 2. Current round variability and proficiency median of Aluminium testing.

The Aluminium dataset formed a normal distribution with no significant bias

Aluminium - Sample PTA 1

Laboratories testing Aluminium using ICP-OES had to overcome severe interference

Table 3. Current round variability and proficiency median of Boron testing.

Boron - Sample PTA 1

In house modified ICP

Laboratories testing Boron using ICP-OES had to overcome interferences from ≈ 5

Table 4. Current round variability and proficiency median of Cadmium testing.

The Cadmium dataset formed a normal distribution with no significant bias

Cadmium - Sample PTA 1

In house modified ICP

Table 5. Current round variability and proficiency median of Chromium.

The Chromium dataset formed a normal distribution with no significant bias

Chromium - Sample PTA 1

In house modified ICP

Table 6. Current round variability and proficiency median of Copper testing.

Copper - Sample PTA 1

In house modified ICP

Table 7. Current round variability and proficiency median of Iron testing.

Iron - Sample PTA 1

Table 8. Current round variability and proficiency median of Mercury testing.

Mercury - Sample PTA 1

Table 9. Current round variability and proficiency median of Selenium testing.

Selenium - Sample PTA 1

In house modified ICP

4.3 Measurement Uncertainty (MU)

4.4 Analysis of Results by Method Groups

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

[3] Global Proficiency, 2016. WaterChek Proficiency Round WCS1606.

[5] US EPA 6020A, 1998. Inductively Coupled Plasma – Mass Spectrometry,

Results and Data Analysis

Aluminium - Sample PTA 1

Ordered Robust Z-Score Charts

Ordered Robust Z-Score Charts

Boron - Sample PTA 1

DATE: SIGNATURE: _________