964 PDF

Report No
No. 964
Waters Proficiency Testing Program
Round No.
o. 192
- Total Solids, Total Suspended Solids,

Total Dissolved Solids -
March 2016
Acknowledgments
PTA wishes to gratefully acknowledge the technical assistance provided for this program by
Dr M Buckley
Buckley-Smith,
Smith, Global
Global Proficiency Ltd (New Zealand)
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,

Australia 2016
PO Box 7507 SILVERWATER

ILVERWATER NSW 2128,
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
Total Solids (TS).................................................................................................................... A1

Total Suspended Solids (TSS) .............................................................................................. A7
Total Dissolved Solids (TDS) .............................................................................................. A13
APPENDIX B – Sample Homogeneity and Stability
Homogeneity and Stability Testing ........................................................................................ B1
APPENDIX C – Documentation
Instructions to Participants .................................................................................................... C1

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

determination of Total Solids (TS), Total Suspended Solids (TSS) and Total Dissolved
Solids (TDS) in waters. This is round 192 in a planned series of programs involving
the analysis of chemical and physical parameters of waters.
The exercise was conducted in February 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 Coordinators were Mrs K Cividin and 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 – Business Development 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)
containing water samples for the analysis of Total Solids, Total Suspended Solids and
Total Dissolved Solids.
2.4 A total of 43 laboratories received samples, comprising:
- 33 Australian participants; and

- 10 overseas participants, including:
- Brunei Darussalam (1), Indonesia (3), Malaysia (1), Papua New Guinea (1),
Qatar (1), Singapore (1), Tanzania (1), Thailand (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, 2014 (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 14.
2.8 Prior to sample distribution, a number of randomly selected samples were analysed
for homogeneity and stability. Based on the results of this testing (see Appendix B) it
was considered that the samples utilised for this program were homogeneous and
stable. As such, any results later identified as outliers could not be attributed to any
notable sample variability.
3. Statistical Format
For each test, where appropriate, the following information is given:
- a table of results and calculated z-scores;

- a list of summary statistics; and
- ordered z-score charts.
3.1 Outlier Results and Z-scores
In order to assess laboratories’ testing performance, a robust statistical approach,

using z-scores, was utilised. Z-scores give a measure of how far a result is from the
consensus value (i.e. the median), and gives a "score" to each result relative to the
other results in the group.
A z-score with an absolute value less than or equal to 2.0 is considered to be

satisfactory, whereas, a z-score with an absolute value greater than or equal to 3.0 is
considered to be an outlier and is marked by the symbol “§”. Laboratories are also
encouraged to review results which have an absolute z-score value between 2.0 and
3.0 (i.e. 2.0 < |z-score| < 3.0). These are considered to be questionable results.
Each determination was examined for outliers with all methods pooled. The table on
page 14 summarises the outlier results detected.
3.2 Results Tables and Summary Statistics
The tables in Appendix A contain the results returned by each laboratory, including
the code number for the method used and the robust z-score calculated for each
result.
Results have been entered exactly as reported by participants. That is, laboratories
which did not report results to the precision (i.e. number of significant figures)
requested on the Results Sheet have not been rounded to the requested precision
before being included in the statistical analysis.
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A list of summary statistics appears at the bottom of each of the results tables and
consists of:
- No. of Results: the total number of results for that test/sample;

- Median: the middle value of the results;
- Normalised IQR: the normalised interquartile range of the results;
- Uncertainty of the Median: a robust estimate of the standard deviation of the
Median;
- Robust CV: the robust coefficient of variation expressed as a percentage, i.e. 100 x
Normalised IQR / Median;
- Minimum: the lowest laboratory result;
- Maximum: the highest laboratory result; and
- Range: the difference between the Maximum and Minimum.
The median is a measure of the centre of the data.
The normalised IQR is a measure of the spread of the results. It is calculated by

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

2 √
= number of results.
Please see reference [1] for further details on these robust summary statistics.
3.3 Ordered Z-score Charts
The charts in Appendix A indicate each laboratory's robust z-score, in order of

magnitude, marked with its laboratory code number. From these charts, each
laboratory can readily compare its performance relative to the other laboratories.
These charts contain solid lines at +3.0 and -3.0, so that outliers are clearly
identifiable as those laboratories whose "bar" extends beyond these "cut-off" lines.
The y-axis of these charts has been limited, so very large z-scores appear to extend
beyond the chart boundary.
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4. PTA and Technical Adviser’s Comments
4.1 Metrological Traceability and 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, and medians obtained from this proficiency
round were in consistent agreement with the expected levels (dope concentration), 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 Table 1 below.
Table 1. Comparison of expected levels (dope concentration) and proficiency medians. The
values of the calculated uncertainty of the median are also presented.
Dope Uncertainty
Median
Analyte Sample Concentration of the Median
(mg/L)
(mg/L) (mg/L)
PTA 1 610 607.5 5.9

Total Solids
(TS)
PTA 2 270 266.5 4.7
Total PTA 1 215 208.0 3.0

Suspended
Solids (TSS) PTA 2 110 100.0 3.0
Total PTA 1 395 406.0 2.2

Dissolved
Solids (TDS) PTA 2 160 170.5 3.0
Overall, the performance of participants in this round was good, with robust CVs
below 10% for all analytes, except TSS sample PTA 2 which showed a CV of 15.5%.
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4.2 Analysis of Round 192 Results
4.2.1 Total Solids (TS)
Table 2 compares the Total Solids (TS) medians and robust CVs from this round to
those obtained in previous PTA rounds.
Table 2. Comparison of current round variability and proficiency medians of TS testing with the
results of the previous two rounds.
Median
Round Sample Robust CV (%) Participants
(mg/L)
PTA 1 607.5 4.3 30
This study
PTA 2 266.5 7.6 30
PTA 1 541.0 2.6 33
Report 925
PTA 2 358.0 4.1 33
PTA 1 275.0 6.2 41
Report 892
PTA 2 435.0 4.0 42
Bias / Accuracy
The TS testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0)
ranging between 567.5 – 640 mg/L for sample PTA 1 and 228 – 304 mg/L for sample
PTA 2.
Out of 30 participants, one questionable results (2.0 < |z-score| < 3.0) was reported,
for sample PTA 2 (laboratory 135).
One outlier result (|z-score| ≥ 3.0) was obtained for sample PTA 1, requiring follow-up
action by laboratory 480. No outlier results were obtained for sample PTA 2.
The most likely source of error, causing low bias when testing these proficiency
samples, is incomplete transfer of the entire contents of the bottle into the volumetric
flask with rinsing as per the Instructions to Participants. It is important to rinse the
sides of the bottle, the cap, the funnel and the stem of the funnel. Once the entire
sample has been transferred, the vessel should be brought to volume and mixed
thoroughly. Vigorous shaking for at least thirty seconds will mix the sample, but a
magnetic stir bar for 5-10 minutes will ensure a more homogeneous sample.
APHA also recommends analysing at least 10% of samples in duplicate, with the
duplicate determinations agreeing within 5% of their average weight. Laboratories
low biasing on sample PTA 2 may wish to implement the APHA recommended quality
control procedures [3].
The TS data set formed an approximately normal distribution with no notable bias
attributable to any one method (Figures 1 and 2). The method most frequently used
for TS analysis was APHA 2540 B (Total Solids Dried at 103-105ºC - method code 1),
which was used by approximately 87% of participants.
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Total Solids - Sample PTA 1
10
APHA 2540 B
9 AS 3550.4
Calculation
8
6
Frequency
0
520 535 550 565 580 595 610 625 640 655 670 685 700 715
Results (mg/L)
Figure 1. Spread of results for TS testing of sample PTA 1, with a median of 607.5 mg/L.
Total Solids - Sample PTA 2
8
APHA 2540 B
AS 3550.4
7
Calculation
5
Frequency
0
200 210 220 230 240 250 260 270 280 290 300 310 320 330
Results (mg/L)
Figure 2. Spread of results for TS testing of sample PTA 2, with a median of 266.5 mg/L.
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4.2.2 Total Suspended Solids (TSS)
Table 3 compares the Total Suspended Solids (TSS) medians and robust CVs from
this round to those obtained in previous PTA rounds. Despite the higher CV on
sample PTA 2, they were both well within the APHA published precision range which
states that a CV of between 10% - 33% is normal, depending on the concentration of
the sample.
Table 3. Comparison of current round variability and proficiency medians of TSS testing with
the results of the previous two rounds.
Median
(mg/L)
PTA 1 208.0 7.5 42
This study
PTA 2 100.0 15.5 43
PTA 1 45.50 9.8 45
Report 925
PTA 2 97.60 6.1 45
PTA 1 66.00 6.1 54
Report 892
PTA 2 82.00 6.3 55
Bias / Accuracy
The TSS testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0)
ranging between 178 – 230 mg/L for sample PTA 1 and 70 – 125 mg/L for sample
PTA 2.
Out of 42 results submitted for sample PTA 1 and 43 results for sample PTA 2, one
questionable result (2.0 < |z-score| < 3.0) was reported for sample PTA 1 (laboratory
215) and four questionable results were reported for sample PTA 2 (laboratories 135,
231, 633 and 676).
No outlier results (|z-score| ≥ 3.0) were obtained.
For those laboratories struggling with their TSS testing, APHA [3] recommends
method blanks using your dilution water, and that duplicate analyses be carried out
for TSS testing. Duplicate determinations should agree within 5% of their average
weight. If you are pipetting a measured volume onto the seated glass-fibre filter,
APHA [3] recommends you pipette from the approximate midpoint of the container but
not in the vortex created by the magnetic stirrer, to get a more homogeneous sample.
Subsampling is a major source of error in this testing.
Laboratories whose results biased low on the TSS test, and high on the TDS test may
have used a filter with pores that were larger than those used by other laboratories,
allowing a greater proportion of the finer solids particles to pass through. Filter pore
sizes used by laboratories ranged between 0.3 – 4.5 µm and the median was 1.2 µm.
Nearly half of laboratories who stated their filter brand were using Whatman, while
others included Advantec, Merck Millipore, Pall, Sartorius and Filtech filters.
The TSS data set formed an approximately normal distribution with no notable bias
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for TSS analysis was APHA 2540 D (Total Suspended Solids Dried at 103-105ºC -
method code 6), which was used by approximately 84% of participants.
Total Suspended Solids - Sample PTA 1
14
APHA 2540 B
APHA 2540 D
12
AS 3550.4
Other
10
Frequency
0
146 156 166 176 186 196 206 216 226 236 246 256 266 276
Results (mg/L)
Figure 3. Spread of results for TSS testing of sample PTA 1, with a median of 208.0 mg/L.
Total Suspended Solids - Sample PTA 2
12
APHA 2540 B
APHA 2540 D
10 AS 3550.4
Other
8
Frequency
0
42.5 50 57.5 65 72.5 80 87.5 95 102.5 110 117.5 125 132.5 140
Results (mg/L)
Figure 4. Spread of results for TSS testing of sample PTA 2, with a median of 100.0 mg/L.
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4.2.3 Total Dissolved Solids
Table 4 compares the Total Dissolved Solids (TDS) medians and robust CVs from
this round to those obtained in previous PTA rounds.
Table 4. Comparison of current round variability and proficiency medians of TDS testing with
the results of the previous two rounds.
Median
(mg/L)
PTA 1 406.0 2.6 36
This study
PTA 2 170.5 8.4 36
PTA 1 498.0 4.5 37
Report 925
PTA 2 260.0 7.7 37
PTA 1 208.0 6.3 48
Report 892
PTA 2 356.0 6.3 48
Bias / Accuracy
The TDS testing was successfully performed, with satisfactory results (|z-score| ≤ 2.0)
ranging between 389 – 426 mg/L for sample PTA 1 and 147 – 198 mg/L for sample
PTA 2.
Out of 36 participants, two questionable results (2.0 < |z-score| < 3.0) were reported
for sample PTA 1 (laboratories 188 and 322) and three questionable results were
reported for sample PTA 2 (laboratories 160, 397 and 572).
Six outlier results (|z-score| ≥ 3.0) were obtained for sample PTA 1, requiring follow-
up action by laboratories 215, 240, 281, 397, 402 and 648. Two outlier results were
obtained for sample PTA 2, requiring follow-up action by laboratories 188 and 240.
For laboratories struggling with their TDS testing, it is important to recognize that the
drying time required in the TDS method is sensitive to the composition of the TDS
sample. Samples with a high mineral concentration can absorb moisture and will
require an extended drying time, and must be weighed quickly to ensure that moisture
from the air does not affect the result (i.e. storing in a desiccator until the sample
reaches room temperature prior to weighing). Adding successive aliquots of the
sample until a final yield of between 2.5 – 200 mg of dried residue is achieved, and
repeating the cycle of drying, cooling, desiccating and weighing until a constant
weight is obtained or until the weight change is less than 4% of the previous weight,
will help to improve the accuracy and precision of test results.
The TDS data set formed an approximately normal distribution with no notable bias
for TDS analysis was APHA 2540 C (Total Dissolved Solids Dried at 180ºC - method
code 11), which was used by approximately 92% of participants.
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Total Dissolved Solids - Sample PTA 1
16
APHA 2540 C
AS 3550.4
14
Conductivity
12
10
Frequency
0
340 350 360 370 380 390 400 410 420 430 440 450 460 470
Results (mg/L)
Figure 5. Spread of results for TDS testing of sample PTA 1, with a median of 406.0 mg/L.
Total Dissolved Solids - Sample PTA 2
16
APHA 2540 C
AS 3550.4
14
Conductivity
12
10
Frequency
0
85 97 109 121 133 145 157 169 181 193 205 217 229 241
Results (mg/L)
Figure 6. Spread of results for TDS testing of sample PTA 2, with a median of 170.5 mg/L.
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4.3 Measurement Uncertainty (MU)
The majority of participants in this round (73%-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 192
Participants
Total
Analyte Sample reporting MU
participants
(percentage)
PTA 1 30 22 (73%)
Total Solids
(TS)
PTA 2 30 22 (73%)
PTA 1 42 32 (76%)
Total Suspended
Solids (TSS)
PTA 2 43 32(74%)
PTA 1 36 28 (78%)
Total Dissolved
Solids (TDS)
PTA 2 36 28 (78%)
Most of the stated MUs for sample PTA 1 accurately reflect the difference between
the median and the participant’s result for these proficiency samples. The lower
concentration sample PTA 2 seemed to be more challenging for laboratories.
Some laboratories may have notably 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 overestimated their MU.1
It is, however, worth noting that a large number of participants (40% of those who
reported MU) indicated a MU which was greater than three times the normalised IQR
for TDS, sample PTA 1. Taking into account that the majority of these laboratories’
MUs were in the vicinity of the average reproducibility observed over previous
proficiency rounds, and based on the increased variability expected for natural
samples, these MUs would therefore be considered acceptable.
1
MU evaluation is based on minimum / maximum uncertainty criteria (umin and umax)
described in ISO 13528:2015 [2]. It should be noted, however, that these are
informative indicators only and cannot be solely used to validate or invalidate the MUs
reported.
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4.4 Analysis of Results by Method Groups
Further analysis of results by method groups is undertaken to provide specific

information on individual method performance.
In order for methods to be grouped for analysis, PTA requires at least 11 sets of
results from the same method group. For methods other than those presented below,
there were less than 11 results submitted, therefore reliable conclusions cannot be
drawn from analysing them separately on this occasion.
4.4.1. Total Solids (TS)
The method APHA 2540 B (Total Solids Dried at 103-105ºC - method code 1) was
most frequently employed for TS analysis, with 26 out of 30 participants indicating the
use of this method.
Table 6 below presents the median, uncertainty of the medians and robust CVs for
TS results obtained by this method in round 192.
Table 6. Variability and proficiency medians of TS results obtained by method APHA 2540 B.
Median ±
Robust
Analyte Sample Participants Uncertainty of the Median
CV (%)
(mg/L)
PTA 1 26 616.0 ± 6.0 4.0
Total Solids
PTA 2 26 266.5 ± 4.8 7.3
The robust CVs obtained using this method were slightly smaller, for both PTA 1 and
PTA 2 samples, than those the general population of methods was able to achieve
(CVPTA1 = 4.3%, CVPTA2 = 7.6%).
4.4.2. Total Suspended Solids (TSS)
The method APHA 2540 D (Total Suspended Solids Dried at 103-105ºC - method
code 6) was most frequently employed for TSS analysis, with approximately 84% of
participants indicating the use of this method (35 out of 42 for sample PTA 1 and 36
out of 43 for sample PTA 2).
Table 7 below presents the median, uncertainty of the median and robust CV for TSS
results obtained by this method in round 192.
Table 7. Variability and proficiency medians of TSS results obtained by method APHA 2540 D.
Median ±
Robust
CV (%)
(mg/L)
Total PTA 1 35 207.0 ± 3.5 7.9
Suspended
Solids PTA 2 36 99.4 ± 2.9 14.2
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The robust CV obtained using this method was slightly larger for sample PTA 1
compared to the general population of methods (CVPTA1 = 7.6%). For sample PTA 2
the CV was slightly smaller (14.2% compared to 15.5% for the general population).
4.4.3. Total Dissolved Solids (TDS)
The method APHA 2540 C (Total Dissolved Solids Dried at 180ºC - method code 11)
was most frequently employed for TDS analysis, with 33 out of 36 participants
indicating the use of this method.
Table 8 below presents the median, uncertainty of the median and robust CV for TDS
results obtained by this method in round 192. The robust CVs obtained using this
method were equal to or better than those the general population of methods was
able to achieve (CVPTA1 = 2.6%, CVPTA2 = 8.4%).
Table 8. Variability and proficiency medians of TDS results obtained by method APHA 2540 C.
Median ±
Robust
CV (%)
(mg/L)
Total PTA 1 33 406.0 ± 2.3 2.6
Dissolved
Solids PTA 2 33 171.0 ± 3.1 8.2
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5. Outlier Results
Laboratories reporting results that have been identified as outliers are listed in
Table 9 below.
Table 9. Laboratory results identified as outliers for each analysis performed.

Analysis
Lab Total Solids
Total Suspended Total Dissolved
Code Solids Solids
PTA 1 PTA 2 PTA 1 PTA 2 PTA 1 PTA 2
188 §
215 §
240 § §
281 §
397 §
402 §
480 §
648 §
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, 2014 (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] 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

Total Solids (TS).................................................................................................................... A1
Total Suspended Solids (TSS) .............................................................................................. A7
Total Dissolved Solids (TDS) .............................................................................................. A13
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Total Solids (TS) Results
Samples PTA 1 and PTA 2
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A1
Total Solids (TS)

Results by Laboratory Code
Sample PTA 1
Laboratory Code
Result ± MU1 Robust Method
mg/L z-score2 Code3
111 584 ± 25 -0.91 3
135 600 ± 60 -0.29 1
160 572 ± 15 -1.37 1
215 624 # 0.64 1
231 575 # -1.25 1
281 631 ± 113 0.91 1
308 640 ± 64 1.25 1
322 600 ± 1 -0.29 1
350 581 ± 58.1 -1.02 1
376 592 # -0.60 4
397 567.5 # -1.54 1
400 621 ± 13 0.52 1
402 602 # -0.21 1
403 625 ± 63 0.67 1
408a 620 ± 8.37 0.48 1
433 611 ± 16.74 0.13 1
449 586 # -0.83 1
464 627 ± 30 0.75 1
468 619 ± 40 0.44 1
480 700 # 3.57 § 1
486 600 ± 6.28 -0.29 1
514 624 ± 64.90 0.64 1
555 588 # -0.75 1
593 619 ± 31.7 0.44 1
598 634 ± 15 1.02 3
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 (page C3) for method code descriptions.
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A2
Total Solids (TS) - cont.

Sample PTA 1
Laboratory Code
mg/L z-score2 Code3
619 624 ± 10 0.64 1
622 604 ± 72 -0.13 4
648 578 ± 58 -1.14 1
654 601 ± 60 -0.25 1
676 633 ± 40 0.98 1
No of Results: 30
Median: 607.5
Normalised IQR: 25.9
Uncertainty of the Median: 5.9
Robust CV: 4.3%
Minimum: 567.5
Maximum: 700
Range: 132.5
uncertainty (MU).
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Total Solids - Sample PTA 1 - Robust Z-Scores
5
4
3
2
1
z-score
Total Solids (TS) - Sample PTA 1

0
622
402
654
135
322
486
-1
376
555
449
111
350
Ordered Robust Z-Score Charts

648
231
160
-2
397
-3
-4
-5
lab code
A3
Robust Z-Scores
5
4
3
2
1
z-score
0
-1
-2
-3
-4
-5
lab code
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A4
Total Solids (TS)

Sample PTA 2
Laboratory Code
mg/L z-score2 Code3
111 243 ± 22 -1.15 3
135 225 ± 25 -2.04 1
160 242 ± 15 -1.20 1
215 237 # -1.45 1
231 230 # -1.79 1
281 268 ± 48 0.07 1
308 270 ± 27 0.17 1
322 228 ± 1 -1.89 1
350 260 ± 26.0 -0.32 1
376 275 # 0.42 4
397 235 # -1.55 1
400 299 ± 13 1.59 1
402 271 # 0.22 1
403 265 ± 27 -0.07 1
408a 283 ± 8.37 0.81 1
433 277 ± 7.79 0.52 1
449 262 # -0.22 1
464 272 ± 15 0.27 1
468 262 ± 40 -0.22 1
480 300 # 1.64 1
486 270 ± 6.06 0.17 1
514 264 ± 27.46 -0.12 1
555 247 # -0.96 1
593 304 ± 24.3 1.84 1
598 289 ± 15 1.10 3
uncertainty (MU).
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A5
Total Solids (TS) - cont.

Sample PTA 2
Laboratory Code
mg/L z-score2 Code3
619 278 ± 10 0.56 1
622 255 ± 31 -0.56 4
648 257 ± 26 -0.47 1
654 271 ± 27 0.22 1
676 285 ± 20 0.91 1
No of Results: 30
Median: 266.5
Robust CV: 7.6%
Minimum: 225
Maximum: 304
Range: 79
uncertainty (MU).
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Total Solids - Sample PTA 2 - Robust Z-Scores
5
4
3
2
1
z-score
Total Solids (TS) - Sample PTA 2

0
403
514
449
468
350
-1
648
622
555

111
160
-2
215
397
231
322
135
-3
-4
-5
lab code
A6
Robust Z-Scores
5
4
3
2
1
z-score
0
-1
-2
-3
-4
-5
lab code
SD 9.17.11
Total Suspended Solids (TSS) Results
SD 9.17.11
A7
Total Suspended Solids (TSS)

Sample PTA 1
Laboratory Code
mg/L z-score2 Code3
111 200 ± 6 -0.51 7
113 204 # -0.26 10
135 195 ± 20 -0.84 6
137 216 # 0.51 10
160 192 ± 10 -1.03 6
188 209 # 0.06 6
215 176 # -2.06 6
231 180 # -1.80 6
240 185 ± 7.6 -1.48 6
281 190 ± 34 -1.16 6
308 230 ± 23 1.41 6
322 222 ± 1 0.90 6
350 181 ± 18.1 -1.73 6
376 182 # -1.67 6
397 195 # -0.84 6
400 223 ± 1.7 0.96 6
402 226 # 1.16 6
403 201 ± 20 -0.45 6
408a 213 ± 10.58 0.32 6
433 214 ± 5.79 0.39 6
449 178 # -1.93 6
464 207 ± 15 -0.06 6
468 209 ± 15 0.06 6
480 211 ± 21 0.19 6
486 203 ± 3.02 -0.32 6
514 218 ± 27.47 0.64 6
538 226 ± 32.3 1.16 10
555 182 # -1.67 6
556 213 ± 6 0.32 6
uncertainty (MU).
SD 9.17.11
A8
Total Suspended Solids (TSS) - cont.

Sample PTA 1
Laboratory Code
mg/L z-score2 Code3
567 216 ± 15.1 0.51 6
572 220 ± 44 0.77 1
593 213 ± 26.3 0.32 6
598 219 ± 15 0.71 7
604 202 ± 5.0% -0.39 6
619 220 ± 10 0.77 6
622 210 ± 18 0.13 6
633 202 ± 10 -0.39 6
638 199 ± 15 -0.58 10
648 205 ± 21 -0.19 6
654 224 ± 22 1.03 6
676 193 ± 10 -0.96 6
695 215 ± 6.10 0.45 6
No of Results: 42
Median: 208.0
Robust CV: 7.5%
Minimum: 176
Maximum: 230
Range: 54
uncertainty (MU).
SD 9.17.11
Total Suspended Solids - Sample PTA 1 - Robust Z-Scores
5
4
3
Total Suspended Solids (TSS) - Sample PTA 1

2
1
z-score
464
648
113
486
604
633
-1
403
111
638
135
397
676
160

281
-2
240
376
555
350
231
449
215
-3
-4
-5
lab code
A9
Robust Z-Scores
5
4
3
2
1
z-score
0
-1
-2
-3
-4
-5
lab code
SD 9.17.11
A10
Total Suspended Solids (TSS)

Sample PTA 2
Laboratory Code
mg/L z-score2 Code3
111 91.7 ± 4.3 -0.54 7
113 87.3 # -0.82 10
135 55 ± 10 -2.91 6
137 104 # 0.26 10
160 88 ± 10 -0.78 6
188 100 # 0.00 6
215 73 # -1.75 6
231 60 # -2.59 6
240 85.0 ± 7.5 -0.97 6
281 103 ± 19 0.19 6
308 110 ± 11 0.65 6
322 111 ± 1 0.71 6
325 113 # 0.84 6
350 94.2 ± 9.42 -0.38 6
376 97.0 # -0.19 6
397 82.5 # -1.13 6
400 113 ± 1.7 0.84 6
402 114 # 0.91 6
403 98 ± 10 -0.13 6
408a 104 ± 10.58 0.26 6
433 97.6 ± 3.92 -0.16 6
449 106 # 0.39 6
464 102 ± 10 0.13 6
468 119 ± 15 1.23 6
480 102 ± 10 0.13 6
486 100 ± 3.01 0.00 6
514 94.9 ± 11.96 -0.33 6
538 119 ± 17.0 1.23 10
555 78 # -1.42 6
uncertainty (MU).
SD 9.17.11
A11
Total Suspended Solids (TSS) - cont.

Sample PTA 2
Laboratory Code
mg/L z-score2 Code3
556 100 ± 3 0.00 6
567 89.0 ± 6.23 -0.71 6
572 112 ± 22 0.78 1
593 107 ± 15.1 0.45 6
598 81 ± 15 -1.23 7
604 70 ± 5.0% -1.94 6
619 110 ± 10 0.65 6
622 88.7 ± 14 -0.73 6
633 55.5 ± 2.8 -2.88 6
638 125 ± 9 1.62 10
648 98.7 ± 9.9 -0.08 6
654 102 ± 10 0.13 6
676 66.5 ± 5 -2.17 6
695 111 ± 3.15 0.71 6
No of Results: 43
Median: 100.0
Robust CV: 15.5%
Minimum: 55
Maximum: 125
Range: 70
uncertainty (MU).
SD 9.17.11
Total Suspended Solids - Sample PTA 2 - Robust Z-Scores
5
4
3
Total Suspended Solids (TSS) - Sample PTA 2

2
188
1
z-score
648
403
433
376
514
350
-1
111
567
622
160
113
240

397
598
-2
555
215
604
676
-3
231
633
135
-4
-5
lab code
A12
Robust Z-Scores
5
4
3
2
1
z-score
0
-1
-2
-3
-4
-5
lab code
SD 9.17.11
Total Dissolved Solids (TDS) Results
SD 9.17.11
A13
Total Dissolved Solids (TDS)

Sample PTA 1
Laboratory Code
mg/L z-score2 Code3
111 389 ± 25 -1.58 12
135 405 ± 40 -0.09 11
160 406 ± 20 0.00 11
188 431 # 2.33 11
215 444 # 3.54 § 11
231 410 # 0.37 11
240 351 ± 8.6 -5.12 § 11
281 360 ± 36 -4.28 § 16
308 410 ± 41 0.37 11
322 432 ± 1 2.42 11
350 395 ± 39.5 -1.02 11
376 410 # 0.37 11
397 370 # -3.35 § 11
400 426 ± 10 1.86 11
402 368 # -3.54 § 11
403 413 ± 41 0.65 11
408a 407 ± 7.53 0.09 11
433 402 ± 4.21 -0.37 11
449 396 # -0.93 11
464 408 ± 20 0.19 11
480 398 ± 60 -0.74 11
486 409 ± 6.13 0.28 11
514 406 ± 28.42 0.00 11
555 405 # -0.09 11
567 410 ± 20.5 0.37 11
572 390 ± 59 -1.49 11
593 396 ± 47.5 -0.93 11
598 411 ± 15 0.47 11
604 404 ± 8.8% -0.19 11
uncertainty (MU).
3 Please refer to Appendix C (pages C3-C5) for method code descriptions.
SD 9.17.11
A14
Total Dissolved Solids (TDS) - cont.

Sample PTA 1
Laboratory Code
mg/L z-score2 Code3
619 419 ± 10 1.21 11
622 394 ± 47 -1.12 11
633 423 ± 21 1.58 16
648 372 ± 37 -3.16 § 11
654 398 ± 40 -0.74 11
676 406 ± 30 0.00 11
695 412 ± 19.0 0.56 11
No of Results: 36
Median: 406.0
Robust CV: 2.6%
Minimum: 351
Maximum: 444
Range: 93
uncertainty (MU).
SD 9.17.11
Total Dissolved Solids - Sample PTA 1 - Robust Z-Scores
5
4
3
Total Dissolved Solids (TDS) - Sample PTA 1

2
160
1
z-score
135
555
604
433
-1
480
654
449
593
350

622
-2
572
111
-3
648
397
-4
402
281
-5
240
lab code
A15
Robust Z-Scores
5
4
3
2
1
z-score
0
-1
-2
-3
-4
-5
lab code
SD 9.17.11
A16

Sample PTA 2
Laboratory Code
mg/L z-score2 Code3
111 147 ± 25 -1.65 12
135 170 ± 20 -0.04 11
160 135 ± 20 -2.49 11
188 215 # 3.12 § 11
215 188 # 1.23 11
231 180 # 0.67 11
240 86.0 ± 8.6 -5.92 § 11
281 163 ± 16 -0.53 16
308 160 ± 16 -0.74 11
322 198 ± 1 1.93 11
350 165 ± 16.5 -0.39 11
376 178 # 0.53 11
397 140 # -2.14 11
400 179 ± 10 0.60 11
402 164 # -0.46 11
403 171 ± 17 0.04 11
408a 179 ± 7.53 0.60 11
433 172 ± 4.04 0.11 11
449 158 # -0.88 11
464 184 ± 15 0.95 11
480 167 ± 25 -0.25 11
486 184 ± 6.03 0.95 11
514 172 ± 12.04 0.11 11
555 178 # 0.53 11
567 160 ± 8.0 -0.74 11
572 140 ± 50 -2.14 11
593 186 ± 28.3 1.09 11
598 178 ± 15 0.53 11
604 170 ± 8.8% -0.04 11
uncertainty (MU).
SD 9.17.11
A17
Total Dissolved Solids (TDS) - cont.

Sample PTA 2
Laboratory Code
mg/L z-score2 Code3
619 179 ± 10 0.60 11
622 166 ± 20 -0.32 11
633 180 ± 9.0 0.67 16
648 155 ± 16 -1.09 11
654 148 ± 15 -1.58 11
676 186 ± 15 1.09 11
695 170 ± 8.02 -0.04 11
No of Results: 36
Median: 170.5
Robust CV: 8.4%
Minimum: 86.0
Maximum: 215
Range: 129.0
uncertainty (MU).
SD 9.17.11
Total Dissolved Solids - Sample PTA 2 - Robust Z-Scores
5
4
3
Total Dissolved Solids(TDS) - Sample PTA 2

2
1
z-score
135
604
695
480
622
350
-1
402
281
308
567
449

648
-2
654
111
397
572
-3
160
-4
-5
240
lab code
A18
Robust Z-Scores
5
4
3
2
1
z-score
0
-1
-2
-3
-4
-5
lab code
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 were obtained from Global Proficiency Ltd, New Zealand. As such,
all samples are subjected to rigorous quality control and homogeneity / stability testing.
Samples were manufactured from two solutions which formed a precipitate in the bottle. A
random selection of ten samples was chosen from samples PTA 1 and PTA 2 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 by Global Proficiency Ltd, using the conductivity method for dissolved
solids.
Based on the known composition, manufacturing procedure and the direct relationship
between TDS, TSS and TS, homogeneity and stability were inferred for TSS and TS based
on the TDS results. All stability samples showed no increased variability when compared to
the chilled samples.
From statistical analyses based on the results of this testing and rigorous quality control, it
was considered that all samples were sufficiently homogeneous and stable, so that any
results later identified as outliers should not be attributed to any notable sample variability.
The results of homogeneity and stability testing are presented in Table B1 below. Please
note that the mean results for these tests are not intended to be used as reference values.
Table B1. Homogeneity testing of Round 192 samples.

Round
PTA 192 Samples PTA 1 (mg/L) Samples PTA 2 (mg/L)
Duplicate (a) Duplicate (b) Duplicate (a) Duplicate (b)
H1 383.0 381.4 167.2 168.0
H2 378.8 380.4 162.4 167.2
H3 378.4 373.4 164.2 167.4
H4 379.6 378.4 166.8 167.0
H5 379.8 378.8 166.2 166.2
H6 378.2 387.8 167.4 166.2
H7 380.2 379.6 167.8 168.8
S1 372.6 379.2 162.2 162.6
S2 372.2 375.8 163.4 162.4
S3 376.8 376.0 161.4 162.8
RSD 0.9% 1.0% 1.5% 1.4%
SD 9.17.11
APPENDIX C
Documentation
Instructions to Participants .................................................................................................... C1

Method Codes ....................................................................................................................... C3
Results Sheet ........................................................................................................................ C4
SD 9.17.11
C1
PROFICIENCY TESTING AUSTRALIA
WATERS PROFICIENCY TESTING PROGRAM
CHEMICAL ANALYSIS ROUND 192 FEBRUARY, 2016
Total Solids (TS), Total Suspended Solids (TSS), Total Dissolved Solids (TDS)
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 Ltd. The
bottles contain 20 mL of artificial water concentrates for analysis of total solids, total
suspended solids and total dissolved solids.
ii) Each bottle will require dilution in reagent grade water. Please follow the Sample Preparation
section below.
iii) The bottles must be thoroughly mixed prior to analysis
Please Note: Where possible, proficiency testing samples should be treated as a routine
laboratory sample.
2. Sample Preparation
Note: The Residue sample colour is white.
Caution: Analysis must begin immediately after bottle is opened.
i) A separate sample must be prepared from each bottle.
ii) Adjust bottle temperature to 20ºC.
iii) Add approximately 800 mL of reagent grade water to a one

one--litre
litre volumetric flask.
iv) Record bottle ID number and mix thoroughly.
v) Quantitatively transfer the entire contents from the bottle into the flask, rinse the sides of the
bottle
tle with reagent grade water and include this in the flask.
vi) Bring to volume with reagent grade water.
vii) Close the flask with a stopper and mix by inversion.
viii) Repeat steps ii) – vii) for second sample.
Please report results for the diluted sample.
SD 9.17.11
C2
3. Tests Requested
For the samples prepared from the two bottles PTA 1 and PTA 2:
i) Total Solids (TS).

ii) Total Suspended Solids (TSS).
iii) Total Dissolved Solids (TDS).
(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 safety glasses, gloves, and fume hoods, where appropriate during the
determinations, is recommended.
5. Reporting
i) Report results using three significant figures.

ii) Report results in milligrams per litre (mg/L).
iii) Do not correct results for recovery.
iv) Select the appropriate method code for each test from the Method Code Table and record it
on the Results Sheet.
v) Calculate the measurement uncertainty (MU) for each reported result. All estimates of MU
must be given as a 95% confidence interval (coverage factor k ≈ 2) and reported in mg/L.
Report MU using the same number of decimal places as for the result.
6. Testing should commence as soon as possible after receiving the samples and results reported
NO LATER THAN 26 FEBRUARY 2016 to:
Karen Cividin
Proficiency Testing Australia
PO Box 7507
SILVERWATER NSW 2128
AUSTRALIA
Phone: +612 9736 8397
Fax: +612 9743 6664
Email: kcividin@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 mg/L):

Analyte Range
Total Solids 140 – 675 mg/L
Total Suspended Solids 20 – 250 mg/L
Total Dissolved Solids 140 – 650 mg/L
SD 9.17.11
C3
Method Codes to be used for the Results Sheet
METHOD
ANALYSIS METHOD DESCRIPTION CODE
REFERENCE
Total Solids APHA SM 2540 B. Total Solids Dried at 103–105°C 1
US EPA 2
0160.3 Residue, Total. Dried at 103–105°C
AS 3550.4 Waters - Determination of solids - 3

Gravimetric method
Other Calculation: Suspended + Dissolved 4
Other (please specify) 5
Total Suspended APHA SM 2540 D. Total Suspended Solids Dried at

6
Solids 103–105°C
AS 3550.4 Waters - Determination of solids -

7
Gravimetric method
ASTM D5907 Standard Test Methods for

8
Filterable Matter
US EPA 0160.2 Residue, Non-Filterable & Total 9

Suspended Solids Dried at 103–105°C
Other Other (please specify) 10
Total Dissolved APHA SM 2540 C. Total Dissolved Solids Dried at

11
Solids 180°C
AS 3550.4 Waters - Determination of solids -

12
Gravimetric method
ASTM D5907 Standard Test Methods for

13
Filterable Matter
US EPA 0160.1 Residue, Filterable. Dried at 180°C 14
Other Calculation: Total – Suspended 15
Conductivity 16
Other (please specify) 17
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.
iii) AS Australian Standard www.standards.org.au
iv) ASTM ASTM International www.astm.org
SD 9.17.11
C4
PROFICIENCY TESTING AUSTRALIA
WATERS PROFICIENCY TESTING PROGRAM
CHEMICAL ANALYSIS ROUND 192
Total Solids (TS), Total Suspended Solids (TSS), Total Dissolved Solids (TDS)
FEBRUARY, 2016
RESULTS SHEET
(mg/L)
Laboratory
Code
*Approximate temperature of samples upon receipt:
SAMPLE PTA 1 SAMPLE PTA 2

METHOD
ANALYSIS
Result ±MU Result ±MU CODE
(mg/L) (mg/L) (mg/L) (mg/L)
Total Solids
Dried at 103
103–105°
105°C
Total Suspended Solids
Dried at 103
103–105°
105°C
Total Dissolved Solids
Dried at 180°C
Please state: Brand of filter used
Nominal pore size Diameter
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) Report results using three significant figures.
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
mg/L,, using the same number of decimal places as for the result.
DATE: ______________________ SIGNATURE: _______________________________
Return results NO LATER THAN 26 FEBRUARY 2016 to:

Karen Cividin
Proficiency Testing Australia
PO Box 7507 Phone: +61 2 9736 8397
SILVERWATER NSW 2128 Fax: +61 2 9743 6664
AUSTRALIA Email: kcividin@pta.asn.au
INSTRUCT WATERS PROF TEST PROG 192
SD 9.17.11
- End of Report -
SD 9.17.11

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Report No

Waters Proficiency Testing Program

- Total Solids, Total Suspended Solids,

© Copyright Proficiency Testing Australia,

PO Box 7507 SILVERWATER

APPENDIX A – Results and Data Analysis

Total Solids (TS).................................................................................................................... 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 43 laboratories received samples, comprising:

- 33 Australian participants; and

All laboratories submitted results by the due date.

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

PTA 1 610 607.5 5.9

Total PTA 1 215 208.0 3.0

Total PTA 1 395 406.0 2.2

4.2 Analysis of Round 192 Results

4.2.1 Total Solids (TS)

Total Solids - Sample PTA 1

Total Solids - Sample PTA 2

4.2.2 Total Suspended Solids (TSS)

No outlier results (|z-score| ≥ 3.0) were obtained.

Total Suspended Solids - Sample PTA 1

Total Suspended Solids - Sample PTA 2

4.2.3 Total Dissolved Solids

Total Dissolved Solids - Sample PTA 1

Total Dissolved Solids - Sample PTA 2

4.3 Measurement Uncertainty (MU)

The majority of participants in this round (73%-78%) reported the measurement

4.4 Analysis of Results by Method Groups

Further analysis of results by method groups is undertaken to provide specific

4.4.1. Total Solids (TS)

4.4.2. Total Suspended Solids (TSS)

4.4.3. Total Dissolved Solids (TDS)

Table 9. Laboratory results identified as outliers for each analysis performed.

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

Results and Data Analysis

Samples PTA 1 and PTA 2

Total Solids (TS)

Total Solids (TS) - cont.

Total Solids (TS) - Sample PTA 1

Ordered Robust Z-Score Charts

Total Solids (TS)

Total Solids (TS) - cont.

Total Solids (TS) - Sample PTA 2

Ordered Robust Z-Score Charts

Samples PTA 1 and PTA 2

DATE: SIGNATURE: _________