Proficiency test SPIL-1 (2018) - Eurofins Scientific...4 CONCLUSION The quality control performed, including test of sample stability and homogeneity as well as test of recovery of

Quality Documentation

May 2018

Proficiency test SPIL-1 (2018) Organic matter, phosphorus, chloride, sulphate and suspended matter in wastewater (effluent)

Proficiency test SPIL-1 (2018) Quality Documentation May 2018

Eurofins Miljø A/S Smedeskovvej 38 DK-8464 Galten Denmark Tlf: +45 7022 4266 e-mail: [email protected] Web: www.eurofins.dk

Client

Environmental laboratories

Client’s representative

Project

Proficiency test SPIL-1 (2018)

Project No

20404-81

Authors

Stine Ottsen

Date 2018-05-23

Approved by Peter Rerup

Quality Documentation Report SJN PRE 2018-05-23

Revision Description By Approved Date

Key words Analytical quality, assigned value, precision, trueness, homogeneity, stability, CODCr, BOD5 (w. ATU), BOD7 (w. ATU), NVOC/TOC, total phosphorus, chloride, sulphate, suspended matter, wastewater

Classification

Open

Internal

Proprietary

Distribution

DANAK Eurofins:

Stine Ottsen, Peter Rerup

CONTENTS

1 INTRODUCTION ........................................................................................................... 1

2 FEATURES OF THE PROFICIENCY TEST .................................................................. 2 2.1 Sample preparation ....................................................................................................... 2 2.2 Statistical analysis of participants’ data ......................................................................... 2 2.3 Assigned and spike value .............................................................................................. 2 2.3.1 Assigned and spike values ............................................................................................ 3 2.3.2 Test of spike values ...................................................................................................... 3 2.3.3 Test of assigned values ................................................................................................. 4

3 HOMOGENEITY AND STABILITY OF SAMPLES ......................................................... 5

4 CONCLUSION .............................................................................................................. 6

5 REFERENCES ............................................................................................................. 7

ANNEX A LIST OF PARTICIPANTS ..................................................................................... 9

ANNEX B SAMPLE PREPARATION .................................................................................. 11

ANNEX C CONTROL OF SPIKE VALUES ......................................................................... 13

ANNEX D CONTROL OF RECOVERY ............................................................................... 21

ANNEX E CONCENTRATION LEVEL ................................................................................ 29

ANNEX F HOMOGENEITY AND STABILITY ..................................................................... 30

1

1 INTRODUCTION

A proficiency test on the analysis of organic matter, phosphorus, chloride, sulphate and suspended matter in wastewater was conducted on 15 March 2018. The proficiency test was organised by Eurofins Miljø A/S.

The present report contains Eurofins’ documentation for the quality of the proficiency test. Results of the proficiency test including data from participating laboratories and statistical analysis of these data were issued in a report to all participants /1/ on 19 April 2018.

2

2 FEATURES OF THE PROFICIENCY TEST

Participants in the proficiency test were a total of 71 laboratories from Denmark, Ger-many, Norway and Sweden. A list of participants is shown in Appendix A.

The closing date for submission of results was 4 april 2018. All participants had submit-ted their results before the dead-line.

2.1 Sample preparation

The parameters covered in the proficiency test are listed in Table 2 as are the abbrevi-ations used in this report.

Six samples were dispatched for the proficiency test. The samples were sample pairs covering the parameters as described in Table 1. The matrix of the samples represent-ed wastewater, in this case effluent. Sample preparation is described in Appendix B.

Table 1 Samples in the proficiency test

Sample name Parameters A1/B1 BOD BOD5 w. ATU, BOD7 w. ATU A1/B1 COD/NVOC CODCr, NVOC/TOC A2/B2 TP, Cl, SO4

A3/B3 TSS

2.2 Statistical analysis of participants’ data

A split-level design was used. The data analysis was performed in accordance with ISO 5725: “Accuracy (trueness and precision) of measurement methods and results” (1994) /2/ and as described in detail in Spliid (1992) /3/. A short introduction to the sta-tistics and a list of symbols and abbreviations used is given in Eurofins document “Schedule for a proficiency test”, which is available at Eurofins’ home page /4/.

The statistical model used is based on the assumption that the variances for the two samples in a sample pair are identical. The assumption was tested (F-test, 95% confi-dence level) and the result was that the two variances may be assumed to be identical for all parameters.

2.3 Assigned and spike value

An overview of the concentrations in the samples (the assigned values) and the differ-ence in concentration between the two samples of a sample pair (spike value) are shown in Table 2 compared to the range of concentrations normally encountered in effluent. The table also gives the expanded uncertainty of the assigned values.

3

Table 2 Assigned and spike values..

Parameter Abbreviation Unit Typical Range

Assigned value

Uncertainty of assigned value

Spike value

CODCr CODCr mg/L O2 5-75 48 2.4 6 BOD5 (w. ATU) BOD5 w. ATU mg/L O2 2-6 *) - - BOD7 (w. ATU) BOD7 w. ATU mg/L O2 2-6 4.2 0.24 0.7 NVOC/TOC NVOC/TOC mg/L C 2-30 18.9 0.90 3.0 Total phosphorus TP mg/L P 0.2-2 1.14 0.022 0.22 Chloride Cl mg/L 50-700 130 2.7 22 Sulphate SO4 mg/L 20-200 72 2.2 10 Total suspended solids

TSS mg/L 20-100 36.2 0.37 7.5

*) Only three laboratories reported results for BOD5 w. ATU using a standardised method and therefore no assigned value is given.

2.3.1 Assigned and spike values The content of each parameter in each sample is given an assigned value for the sam-ple with the lower content and a spike value, the spike value being the difference in concentration between the two samples of the sample pair.

In order to ensure optimal use of the data, the assigned value is calculated as the av-erage of the median for both samples in the sample pair after subtraction of the spike value. The spike values are calculated from sample preparation except for CODCr where the spike value is the difference between median values for the two samples in the sample pair.

The assigned values for all parameters except Cl and SO4 are operationally defined and are consensus values based upon the median for method no. 62, 77 and 77A (CODCr), method no. 1 (NVOC), method no. 1 and 2 (TP), or method no. 1 and 2 (TSS), which are the methods required by the Danish EPA /5/. The assigned value for BOD7 is based upon standardised methods (method no. 1 - 4). A list of method identifi-cation numbers is found in the report to participants /1/. Assigned values for Cl and SO4 are consensus values for all laboratories based on the median. For BOD5 it was not possible to set an assigned value because only three laboratories had used a stand-ardised method.

2.3.2 Test of spike values A comparison was made (t-test, 95% confidence level) between the spike value and the difference in concentration between the two samples in the sample pair found from the laboratories’ results, see Appendix C. The test revealed a significant difference be-tween the two for CODCr and BOD7.

The difference for CODCr was significant and could not be attributed to specific meth-ods or other conditions. Furthermore, the difference had a significant influence on the general quality of analyses. It was therefore decided to change the spike value from the calculated value based on sample preparation to a value based on consensus between participating laboratories, i.e. the difference between the medians for sample A1 and B1.

For BOD7 the difference could be attributed to influence from laboratories using meth-ods other than the one prescribed by the Danish EPA. The test was repeated after ex-clusion of the results for method no. 9, and 52 and now showed no significant differ-ence. The spike value is therefore kept unchanged.

4

2.3.3 Test of assigned values The assigned value and the average of the results obtained from all laboratories were also compared (t-test, 95% confidence level), see Appendix D. The test showed no significant difference between the two and the control of assigned value at Eurofins confirmed the value (Appendix E).

5

3 HOMOGENEITY AND STABILITY OF SAMPLES

The homogeneity and stability of samples were tested using the following parameters as indicators:

CODCr Homogeneity test

TP Combined homogeneity and stability test

TSS Combined homogeneity and stability test

The results of control measurements are shown in Appendix F. The appendix also gives the results of the statistical evaluation of the control data. The data are analysed by analysis of variance (ANOVA) giving:

1. the standard deviation/variance for replicates (the contribution from analytical vari-ability),

2. the between bottle standard deviation/variance (the contribution from heterogenei-ty) and

3. the between days concentration difference (the contribution from instability).

Homogeneity is evaluated by comparing the between bottle variance to 0.3 * the standard deviation for evaluation of participants’ performance (0.3 ∙ σ�) specified by the Danish EPA /5/, whereas the stability is evaluated by comparing the concentration change of the samples to 0.3 ∙ σ�. This test ensures that heterogeneity and instability will not have negative influence on the evaluation of participant performance /6/.

The appendix also shows the standard deviation within and between laboratories from the proficiency test to allow comparison between tests performed and average quality from participating laboratories.

The tests for stability and homogeneity show that the samples are stable and homoge-neous.

6

4 CONCLUSION

The quality control performed, including test of sample stability and homogeneity as well as test of recovery of spike and assigned values, shows that the samples and their assigned values are suitable for testing the proficiency of the participating laboratories for all parameters. The results are also suitable for estimation of the general quality of analyses among all participating laboratories.

For BOD5 it was not possible to set an assigned value because too few laboratories have used a standardised method.

For BOD7 the participants could not recover the spike value. The difference between the calculated spike value and that found by the participants is small and the influence on evaluation of participant performance or estimation of general quality of analyses is insignificant.

7

5 REFERENCES

/1/ Eurofins A/S, Proficiency test SPIL-1 (2018), Report to participants, April 2018.

/2/ ISO 5725-2, Accuracy (trueness and precision) of measurement methods and re-sults – Part 2: Basic method for the determination of repeatability and reproduci-bility of a standard measurement method, 1994.

/3/ Spliid, H., Procedure and analysis of data for proficiency tests and environmental analyses, Report to Danish Environmental Protection Agency, 1994 (in Danish).

/4/ Eurofins A/S, Schedule for a proficiency test, document may be downloaded from www.eurofins.dk/proficiencytest.

/5/ Ministry of Environment regulation no. 1146 on quality criteria for environmental measurements, 24 October 2017 (in Danish).

/6/ ISO 13528, Statistical methods for use in proficiency testing by interlaboratory comparison, 2005.

8

A N N E X E S

9

ANNEX A LIST OF PARTICIPANTS

Laboratory Town Country AquaDjurs A/S Grenaa Denmark

Biofos A/S København K Denmark

Bjergmarken R/A, Fors Spildevand Roskilde Roskilde Denmark

BlueKolding A/S Kolding Denmark

CP Kelco, Spildevandslaboratoriet Ll. Skensved Denmark

Eurofins Miljø A/S Vejen Denmark

Faxe Forsyning Faxe Denmark

Fors Spildevand Holbæk Holbæk Denmark

Holstebro Centralrenseanlæg, Vestforsyning Spildevand

Holstebro Denmark

Kerteminde Forsyning - Spildevand A/S Kerteminde Denmark

Klarforsyning, Køge-Egnens Renseanlæg Køge Denmark

Melby Renseanlæg Liseleje Denmark

Nyborg Renseanlæg Nyborg Denmark

Næstved Central Renseanlæg, NK-Spildevand Næstved Denmark

Provas Haderslev Denmark

RGS Nordic A/S Skælskør Denmark

Ringkøbing-Skjern Forsyning A/S Skjern Denmark

Rønne Renseanlæg Rønne Denmark

Slagelse Renseanlæg (5 participants) Slagelse Denmark

Spildevandslaboratoriet (2 participants) Esbjerg Denmark

Svendborg Centralrenseanlæg Skårup Fyn Denmark

Vandmiljø Randers A/S Randers SØ Denmark

Vejle Renseanlæg Vejle Denmark

Macherey-Nagel GmbH & Co KG Düren Germany

Eurofins Environment Testing Norway AS Moss Norway

AB Borlänge Energi, Reningsverket Borlänge Sweden

Akzo Nobel Functional Chemicals AB, Cellulosic Specialties, QHSE

Örnsköldsvik Sweden

Arctic Paper Munkedals AB Munkedal Sweden

Campus Roslagen, Utvecklingscentrum för Vatten Norrtälje Sweden

Ernemar Laboratorium Oskarshamn Sweden

Fiskeby Board AB Norrköping Sweden

GRYAAB AB Göteborg Sweden

10

Gästrike Vatten AB Skutskär Sweden

Hallsta Pappersbruk Hallstavik Sweden

Holmen Paper AB, Bravikens Pappersbruk Norrköping Sweden

Iggesund Paperboard AB, Iggesunds Bruk, Cell & Miljölab

Iggesund Sweden

INOVYN Sweden AB Stenungsund Sweden

Kalmar Vatten AB, VA-lab Kalmar Sweden

Klippans Reningsverk Klippan Sweden

Kristianstad Kommun Kristianstad Sweden

Käppalaverket Lidingö Sweden

Laboratoriet vid Smedjeholms avolppsreningsverk Falkenberg Sweden

Ljungby Kommun, Avloppsreningsverket Ljungby Sweden

Mjölby Kommun Mjölby Sweden

Motala Kommun Motala Sweden

Nordic Sugar, Örtofta Sockerbruk Eslöv Sweden

Norrköping Vatten och Avfall AB, Laboratoriet Slottshagens Reningsverk

Norrköping Sweden

NSVA/Öresundsverket Helsingborg Sweden

Nynäshamn Kommun, VA-avd. Laboratoriet Nynäshamn Sweden

Preem AB Göteborg Göteborg Sweden

Preemraff Lysekil Lysekil Sweden

Reningsverket Aggerud Karlskoga Sweden

Rottneros Bruk AB Rottneros Sweden

Smurfit Kappa Piteå Piteå Sweden

St1 Refinery AB Göteborg Sweden

Stora Enso Paper AB Hyltebruk Sweden

Södra Cell AB Mönsterås Mönsterås Sweden

Södra Cell AB, Värö Väröbacka Sweden

Södra Cell Mörrum Mörrum Sweden

Tekniska förvaltningen, Verksamhetsstöd VA, Labo-ratoriet

Örebro Sweden

Uddebo Laboratorium Luleå Sweden

VA SYD Källby Avloppsreningsverk Malmö Sweden

VA SYD Sjölundalaboratoriet Malmö Sweden

VA SYD, Ellingelaboratoriet Malmö Sweden

Vallviks Bruk Vallvik Sweden

Västervik Miljö & Energi AB, Vattenlaboratoriet Västervik Sweden

11

ANNEX B SAMPLE PREPARATION

Stock solution Prepared from Concentration Concentrate A1 BOD

9.6010 g D-glucose 9.5996 g L-glutamic acid milli-Q water up to 13000 g

BOD: 1.034 g/kg

Concentrate B1 BOD


BOD: 1.295 g/kg

Concentrate A1 COD/NVOC


CODCr: 1.510 g/kg NVOC: 0.597 g/kg

Concentrate B1 COD/NVOC


CODCr: 1.892 g/kg NVOC: 0.747 g/kg

Stock TP 1.5006 g Na-B.glycerophosphate milli-Q water up to 1000.0 g

TP: 151.8 mg/kg

Stock Cl 10.003 g Sodium chloride (NaCl) milli-Q water up to 1000.0 g

Cl: 6.068 g/kg

Stock SO4 5.0057 g Sodium sulphate (Na2SO4) milli-Q water up to 1000.0 g

SO4: 3.385 g/kg

Stock TSS 15.03 g Microcrystalline cellulose milli-Q water up to 1000.0 g

TSS: 15.030 g/kg

12

Sample Sample prepared from CODCr mg/L O2

BOD (w. ATU) mg/L O2

NVOC mg/L C

TP mg/L P

Cl mg/L

SO4 mg/L

TSS mg/L

A1-BOD At the laboratory 5.00 mL of concen-trate A1 is diluted up to 2000.0 mL with filtered water from Vejen sewage treatment plant

b + 2.59

B1-BOD At the laboratory 5.00 mL of concen-trate B1 is diluted up to 2000.0 mL with filtered water from Vejen sewage treatment plant

b + 3.24

A1-COD/NVOC

At the laboratory 2.00 mL of concen-trate A1 is diluted up to 100.0 mL with filtered water from Vejen sewage treatment plant

a + 30.2 c + 11.9

B1-COD/NVOC

At the laboratory 2.00 mL of concen-trate B1 is diluted up to 100.0 mL with filtered water from Vejen sewage treatment plant

a + 37.8 c + 14.9

A2 100.03 g stock TP 500.0 g stock Cl 850.0 g stock SO4 Filtered water from Vejen sewage treatment plant up to 70.0 kg

d + 0.217 e + 43.3 f + 41.1

B2 60.04 g stock TP 150.01 g stock Cl 125.03 g stock SO4 Sample A2 up to 40.0 kg

0.992·

(d+0.217) + 0.228

0.992· (e + 43.3) +

22.8

0.992· ( f + 41.1) +

10.6

A3 At the laboratory 1000.0 mL of filtered water from Vejen sewage treatment plant is added to 3.0 mL stock TSS

g + 45.0

B3 At the laboratory 1000.0 mL of filtered water from Vejen sewage treatment plant is added to 2.5 mL stock TSS

g + 37.5

13

ANNEX C CONTROL OF SPIKE VALUES CODCr, mg/L 02 Control of differences within sample pairs

Laboratory Difference AB

1 -5.80 2 - 3 - 4 - 5 -0.30 6 -0.20 7 -0.60 8 - 9 4.00

10 1.80 11 -2.40 12 - 13 -1.30 14 11.80 UC 15 0.70 16 - 17 - 18 0.50 19 - 20 -0.50 21 - 22 -0.90 23 -1.40 24 -4.70 25 - 26 - 27 -8.70 28 - 29 - 30 -2.70 31 0.80 32 -2.20 33 - 34 -1.60 35 - 36 -1.10 37 -2.00 38 0.30 39 - 40 0.60 41 -1.20 42 -0.30 43 -0.50 44 -0.30 45 -0.80 46 - 47 - 48 -0.10 49 0.80 50 - 51 -

52A -1.10


52B -0.20 53 -1.60 54 7.80 55 -1.30 UG 56 -0.50 57 - 58 -1.00 59 1.20 60 -1.60 61 2.10 62 0.30 63 -2.40 64 - 65 - 66 -0.45 67 0.90 68 0.30 69 6.30 70 -0.50 71 -2.30

No of labs., p 47 No of repl., n 2

d -0.49 s² 6.56 s 2.56

t = √p · (d/s) -1.3010 Sign. level, p(t) 0.1997 No test statistics were found to be significant UC denotes a Cochran outlier UG denotes a Grubbs outlier

14

BOD5, mg/L 02 Control of differences within sample pairs


1 - 2 - 3 - 4 - 5 - 6 -1.940 7 - 8 - 9 -2.070

10 - 11 - 12 - 13 - 14 -0.700 15 - 16 - 17 - 18 - 19 - 20 - 21 -0.450 22 - 23 - 24 - 25 - 26 - 27 - 28 - 29 - 30 - 31 - 32 - 33 - 34 - 35 - 36 0.000 37 - 38 - 39 - 40 - 41 0.730 42 - 43 -0.590 44 - 45 0.000 46 - 47 - 48 -0.500 49 - 50 - 51 -

52A - 52B -0.910

53 -1.930 54 - 55 -


56 - 57 - 58 - 59 - 60 - 61 - 62 -0.170 63 - 64 - 65 - 66 0.000 67 - 68 - 69 - 70 0.510 71 -


d -0.573 s² 0.778 s 0.882

t = √p · (d/s) -2.4294 Sign. level, p(t) 0.0304 * * denotes that there is a significant difference (t-test, 5%-level) ** denotes that there is a significant difference (t-test, 1%-level) *** denotes that there is a significant difference (t-test, 0.1%-level) Difference for sample pair AB is significantly different from 0, and data should be corrected with the differ-ence (in spike value), during execution of Cochran's test.

15

BOD7, mg/L 02 Control of differences within sample pairs


1 0.270 2 - 3 - 4 - 5 - 6 - 7 - 8 0.007 9 -

10 - 11 - 12 0.200 13 - 14 - 15 - 16 -0.400 17 0.450 18 2.710 UC 19 0.200 20 - 21 - 22 - 23 0.000 24 - 25 - 26 - 27 - 28 0.300 29 - 30 0.080 31 - 32 - 33 - 34 - 35 - 36 - 37 0.800 38 -0.010 39 - 40 - 41 - 42 - 43 - 44 - 45 - 46 0.300 47 - 48 - 49 - 50 0.140 51 0.000

52A - 52B -

53 - 54 0.330 55 -


56 - 57 - 58 - 59 - 60 - 61 - 62 -0.360 63 0.080 64 - 65 - 66 - 67 0.000 68 - 69 - 70 - 71 0.300


d 0.141 s² 0.073 s 0.270

t = √p · (d/s) 2.2794 Sign. level, p(t) 0.0351 * * denotes that there is a significant difference (t-test, 5%-level) ** denotes that there is a significant difference (t-test, 1%-level) *** denotes that there is a significant difference (t-test, 0.1%-level) UC denotes a Cochran outlier Difference for sample pair AB is significantly different from 0, and data should be corrected with the differ-ence (in spike value), during execution of Cochran's test.

16

NVOC/TOC, mg/L C Control of differences within sample pairs


1 -0.50 2 -0.20 3 -0.25 4 - 5 -0.20 6 - 7 1.16 8 -0.23 9 -

10 - 11 - 12 0.30 13 - 14 - 15 - 16 0.30 17 - 18 - 19 -0.68 20 - 21 2.00 22 -0.20 23 -0.15 24 0.60 25 0.44 26 0.28 27 - 28 0.20 29 0.20 30 - 31 - 32 -0.34 33 -0.60 34 - 35 0.30 36 0.10 37 0.43 38 - 39 0.20 40 - 41 - 42 - 43 0.60 44 - 45 -0.20 46 0.20 47 0.57 48 -0.20 49 -0.02 50 -0.10 51 -0.08

52A - 52B -

53 - 54 - 55 -


56 - 57 1.78 UG 58 0.30 59 - 60 - 61 - 62 -0.73 63 -0.20 64 1.20 UG 65 -0.10 66 0.75 67 0.50 68 0.20 69 - 70 0.80 71 -


d 0.14 s² 0.27 s 0.52

t = √p · (d/s) 1.6831 Sign. level, p(t) 0.1005 No test statistics were found to be significant UG denotes a Grubbs outlier

17

Total phosphorus, mg/L P Control of differences within sample pairs


1 0.020 2 -0.010 3 -0.026 4 -0.020 5 0.070 6 0.050 7 -0.030 8 0.060 9 -0.020

10 -0.020 11 -0.040 12 -0.040 UG 13 0.010 14 0.042 15 0.000 16 0.240 UC 17 0.046 18 -0.020 19 0.030 20 0.020 21 -0.003 22 -0.030 23 0.010 24 0.000 25 - 26 0.040 27 0.000 28 0.010 29 -0.020 30 - 31 0.010 32 0.018 33 -0.030 34 -0.000 35 -0.030 36 0.040 37 0.160 UC 38 0.054 39 -0.020 40 0.040 41 -0.020 42 0.080 43 -0.080 44 -0.020 45 -0.010 46 0.000 47 0.030 48 -0.050 49 0.430 UC 50 0.020 51 -0.026

52A 0.010 52B 0.000

53 0.040 54 0.017 55 -0.000


56 -0.000 57 - 58 -0.010 59 -0.017 60 -0.020 61 -0.030 62 -0.050 63 -0.040 64 0.050 65 -0.160 UC 66 0.180 UC 67 0.000 68 0.020 69 0.020 70 0.070 71 0.014


d 0.004 s² 0.001 s 0.033

t = √p · (d/s) 0.9545 Sign. level, p(t) 0.3435 No test statistics were found to be significant UC denotes a Cochran outlier UG denotes a Grubbs outlier

18

Chloride, mg/L Control of differences within sample pairs


1 - 2 10.7 3 - 4 - 5 -5.0 6 -6.0 7 - 8 - 9 -

10 -20.0 UG 11 -0.5 12 - 13 - 14 -6.0 15 -6.0 16 - 17 - 18 -4.0 19 1.8 20 -14.8 UG 21 2.0 22 - 23 - 24 - 25 1.4 26 - 27 - 28 - 29 -27.0 UC 30 - 31 -1.0 32 - 33 - 34 3.4 35 - 36 - 37 - 38 - 39 - 40 1.0 41 -12.0 42 -6.0 43 -2.0 44 - 45 -3.0 46 - 47 - 48 0.0 49 -1.0 50 - 51 -

52A -5.0 52B -4.0

53 1.0 54 - 55 -


56 12.0 57 - 58 1.0 59 0.2 60 -39.0 UC 61 - 62 2.3 63 - 64 - 65 1.0 66 -2.5 67 - 68 2.0 69 -11.0 70 -0.7 71 1.7


d -1.1 s² 24.9 s 5.0


19

Sulphate, mg/L Control of differences within sample pairs


1 - 2 0.80 3 - 4 - 5 -0.70 6 2.30 7 - 8 - 9 -

10 - 11 - 12 - 13 - 14 0.60 15 - 16 - 17 - 18 - 19 - 20 -1.20 21 - 22 - 23 - 24 - 25 - 26 - 27 - 28 - 29 0.10 30 - 31 - 32 - 33 - 34 - 35 - 36 - 37 - 38 - 39 - 40 -2.70 41 - 42 - 43 - 44 - 45 3.60 46 - 47 - 48 - 49 3.20 50 - 51 -

52A - 52B 0.10

53 -2.10 54 - 55 -


56 - 57 - 58 0.00 59 - 60 - 61 - 62 0.72 63 - 64 - 65 0.00 66 - 67 - 68 -9.50 69 10.90 70 0.30 71 -


d 0.38 s² 15.65 s 3.96

t = √p · (d/s) 0.3936 Sign. level, p(t) 0.6991 No test statistics were found to be significant

20

Total suspended solids, mg/L Control of differences within sample pairs


1 1.70 2 0.20 3 -1.50 4 - 5 -13.10 UC 6 -0.90 7 1.50 8 -3.00 9 -0.50

10 1.90 UG 11 - 12 -3.00 13 - 14 -1.40 15 0.80 16 -0.30 17 0.61 18 -0.40 19 0.30 20 -5.50 21 - 22 2.80 23 -0.20 24 -0.50 25 - 26 -0.80 27 -3.50 28 0.00 29 -1.50 30 - 31 -0.80 32 -0.10 33 -1.60 34 -0.40 35 -0.30 36 -1.50 37 -2.50 38 2.10 39 -1.20 40 - 41 -0.80 42 -2.50


43 3.10 44 - 45 -1.50 46 1.30 47 0.00 48 -0.90 49 0.80 50 -0.40 51 0.60

52A - 52B 0.30

53 3.30 54 2.50 55 0.90 56 -0.20 57 0.78 58 - 59 -2.48 60 2.60 61 -0.40 62 0.55 63 0.90 64 1.01 65 0.10 66 -6.30 67 -0.50 68 - 69 0.60 70 -0.40 71 0.90


d -0.30 s² 3.34 s 1.83


21

ANNEX D CONTROL OF RECOVERY CODCr, mg/L 02 Control of recovery, average of results

Laboratory Sample pair AB

1 55.40 2 - 3 - 4 - 5 44.25 6 44.70 7 53.80 8 - 9 33.00

10 51.80 11 45.60 12 - 13 48.35 14 40.40 UC 15 42.05 16 - 17 - 18 43.45 19 - 20 42.35 21 - 22 48.65 23 53.25 24 47.65 25 - 26 - 27 56.65 28 - 29 - 30 48.75 31 42.90 32 51.20 33 - 34 51.55 35 - 36 45.75 37 50.00 38 49.75 39 - 40 44.60 41 44.80 42 43.05 43 44.45 44 43.15 45 43.70 46 - 47 - 48 44.55 49 51.20 50 - 51 -

52A 44.35 52B 41.90


53 44.30 54 57.90 55 88.35 UG 56 50.95 57 - 58 48.50 59 48.90 60 45.70 61 55.55 62 44.85 63 50.10 64 - 65 - 66 43.98 67 52.05 68 45.75 69 43.55 70 50.25 71 45.05


m 47.32 s² 22.44 s 4.74

Assigned value, µ 48 Recovery, % 98.6 t = √p · (m-µ)/s -0.9861 Sign. level, p(t) 0.3292 No test statistics were found to be significant UC denotes a Cochran outlier UG denotes a Grubbs outlier

22

BOD5, mg/L 02 Control of recovery, average of results


1 - 2 - 3 - 4 - 5 - 6 6.760 7 - 8 - 9 3.505

10 - 11 - 12 - 13 - 14 3.990 15 - 16 - 17 - 18 - 19 - 20 - 21 4.095 22 - 23 - 24 - 25 - 26 - 27 - 28 - 29 - 30 - 31 - 32 - 33 - 34 - 35 - 36 5.600 37 - 38 - 39 - 40 - 41 2.255 42 - 43 4.105 44 - 45 1.850 46 - 47 - 48 3.150 49 - 50 - 51 -

52A - 52B 5.145

53 5.145 54 - 55 -


56 - 57 - 58 - 59 - 60 - 61 - 62 4.745 63 - 64 - 65 - 66 5.000 67 - 68 - 69 3.580 70 3.405 71 -


m 4.196 s² 1.756 s 1.325

Assigned value, µ - Recovery, % - t = √p · (m-µ)/s - Sign. level, p(t) - No test statistics were found to be significant

23

BOD7, mg/L 02 Control of recovery, average of results


1 3.485 2 - 3 - 4 - 5 - 6 - 7 - 8 4.155 9 -

10 - 11 - 12 4.000 13 - 14 - 15 - 16 3.400 17 4.105 18 7.875 UC 19 3.700 20 - 21 - 22 - 23 3.800 24 - 25 - 26 - 27 - 28 4.450 29 - 30 4.790 31 - 32 - 33 - 34 - 35 - 36 - 37 3.400 38 4.815 39 - 40 - 41 - 42 - 43 - 44 - 45 - 46 4.160 47 - 48 - 49 - 50 4.370 51 4.200

52A - 52B -

53 - 54 3.875 55 -


56 - 57 - 58 - 59 - 60 - 61 - 62 5.090 63 4.540 64 - 65 - 66 - 67 4.300 68 - 69 - 70 - 71 3.500


m 4.112 s² 0.247 s 0.497

Assigned value, µ 4.2 Recovery, % 97.9 t = √p · (m-µ)/s -0.7694 Sign. level, p(t) 0.4516 No test statistics were found to be significant UC denotes a Cochran outlier

24

NVOC/TOC, mg/L C Control of recovery, average of results


1 17.25 2 19.90 3 18.30 4 - 5 19.00 6 - 7 18.31 8 18.55 9 -

10 - 11 - 12 17.05 13 - 14 - 15 - 16 18.85 17 - 18 - 19 18.27 20 - 21 15.94 22 20.20 23 18.68 24 18.10 25 19.35 26 19.94 27 - 28 18.90 29 20.00 30 - 31 - 32 18.28 33 20.90 34 - 35 19.75 36 19.35 37 19.55 38 - 39 19.50 40 - 41 - 42 - 43 20.70 44 - 45 19.00 46 19.30 47 20.05 48 20.00 49 20.69 50 18.75 51 18.51

52A - 52B -

53 - 54 - 55 -


56 - 57 8.27 UG 58 19.25 59 - 60 - 61 - 62 20.45 63 18.30 64 13.30 UG 65 17.75 66 19.32 67 19.65 68 20.50 69 - 70 17.40 71 -


m 19.07 s² 1.21 s 1.10

Assigned value, µ 18.9 Recovery, % 100.9 t = √p · (m-µ)/s 0.9357 Sign. level, p(t) 0.3553 No test statistics were found to be significant UG denotes a Grubbs outlier

25

Total phosphorus, mg/L P Control of recovery, average of results


1 1.130 2 1.155 3 1.073 4 1.100 5 1.125 6 1.175 7 1.165 8 1.066 9 1.060

10 1.110 11 1.210 12 1.440 UG 13 1.205 14 1.065 15 1.200 16 1.040 UC 17 1.099 18 1.180 19 1.135 20 1.160 21 1.131 22 1.115 23 1.173 24 1.170 25 - 26 1.210 27 1.160 28 1.055 29 1.150 30 - 31 1.205 32 1.147 33 1.125 34 1.140 35 1.095 36 1.120 37 1.150 UC 38 1.146 39 1.150 40 1.140 41 1.170 42 1.120 43 1.160 44 1.080 45 1.155 46 1.160 47 1.205 48 1.165 49 1.135 UC 50 1.190 51 1.102

52A 1.145 52B 1.180

53 1.190 54 1.098 55 1.130


56 1.150 57 - 58 1.135 59 1.176 60 1.200 61 1.105 62 1.265 63 1.250 64 1.105 65 1.130 UC 66 1.330 UC 67 1.030 68 1.100 69 1.210 70 0.985 71 1.144


m 1.142 s² 0.003 s 0.051

Assigned value, µ 1.14 Recovery, % 100.2 t = √p · (m-µ)/s 0.3201 Sign. level, p(t) 0.7500 No test statistics were found to be significant UC denotes a Cochran outlier UG denotes a Grubbs outlier

26

Chloride, mg/L Control of recovery, average of results


1 - 2 123.8 3 - 4 - 5 113.5 6 128.0 7 - 8 - 9 -

10 174.0 UG 11 137.3 12 - 13 - 14 132.0 15 128.0 16 - 17 - 18 123.0 19 132.9 20 80.6 UG 21 132.0 22 - 23 - 24 - 25 134.0 26 - 27 - 28 - 29 184.5 UC 30 - 31 122.5 32 - 33 - 34 131.3 35 - 36 - 37 - 38 - 39 - 40 110.5 41 120.0 42 122.0 43 133.0 44 - 45 130.5 46 - 47 - 48 132.0 49 120.5 50 - 51 -

52A 108.5 52B 123.0

53 132.5 54 - 55 -


56 131.0 57 - 58 128.0 59 133.7 60 127.5 UC 61 - 62 127.0 63 - 64 - 65 129.5 66 135.8 67 - 68 141.0 69 130.5 70 133.4 71 133.9


m 128.0 s² 56.5 s 7.5

Assigned value, µ 130 Recovery, % 98.4 t = √p · (m-µ)/s -1.5408 Sign. level, p(t) 0.1335 No test statistics were found to be significant UC denotes a Cochran outlier UG denotes a Grubbs outlier

27

Sulphate, mg/L Control of recovery, average of results


1 - 2 68.20 3 - 4 - 5 71.55 6 74.75 7 - 8 - 9 -

10 - 11 - 12 - 13 - 14 74.40 15 - 16 - 17 - 18 - 19 - 20 84.10 21 - 22 - 23 - 24 - 25 - 26 - 27 - 28 - 29 65.25 30 - 31 - 32 - 33 - 34 - 35 - 36 - 37 - 38 - 39 - 40 77.05 41 - 42 - 43 - 44 - 45 69.50 46 - 47 - 48 - 49 68.40 50 - 51 -

52A - 52B 79.45

53 74.65 54 - 55 -


56 - 57 - 58 75.00 59 - 60 - 61 - 62 72.07 63 - 64 - 65 69.60 66 - 67 - 68 64.55 69 65.05 70 71.45 71 -


m 72.06 s² 27.87 s 5.28

Assigned value, µ 72 Recovery, % 100.1 t = √p · (m-µ)/s 0.0469 Sign. level, p(t) 0.9632 No test statistics were found to be significant

28

Total suspended solids, mg/L Control of recovery, average of results


1 36.85 2 35.20 3 34.85 4 - 5 28.85 UC 6 36.05 7 35.75 8 38.30 9 39.75

10 18.25 UG 11 - 12 34.00 13 - 14 36.40 15 36.20 16 37.05 17 33.41 18 35.00 19 36.45 20 34.25 21 - 22 37.70 23 36.50 24 35.75 25 - 26 36.30 27 37.75 28 37.60 29 37.75 30 - 31 36.50 32 36.85 33 36.20 34 36.30 35 36.45 36 36.35 37 35.25 38 37.45 39 33.70 40 - 41 35.20 42 32.95 43 32.55 44 - 45 35.25 46 35.75 47 35.70 48 32.75 49 36.90 50 36.20 51 36.70

52A - 52B 38.55

53 33.65 54 34.85 55 34.65


56 33.90 57 34.31 58 - 59 35.99 60 37.90 61 36.10 62 35.91 63 36.15 64 37.11 65 36.65 66 33.45 67 39.05 68 - 69 36.80 70 36.30 71 36.25


m 35.96 s² 2.39 s 1.54

Assigned value, µ 36.2 Recovery, % 99.3 t = √p · (m-µ)/s -1.2107 Sign. level, p(t) 0.2309 No test statistics were found to be significant UC denotes a Cochran outlier UG denotes a Grubbs outlier

29

ANNEX E CONCENTRATION LEVEL

Parameter Unit Sample Bottle no. I II Bottle Sample Assigned Spike

Average Average value Measured Assigned

COD mg/L O2 A1 91-8 43.5 43.8 43.65 43.72 48 6 6

52-32 44.0 44.1 44.05

13-58 43.8 43.1 43.45

B1 8-20 49.4 49.2 49.30 49.63 54

48-41 50.0 48.8 49.40

71-53 50.1 50.3 50.20

Total phosphorus mg/L P A2 11 1.18 1.18 1.18 1.17 1.14 0.22 0.22

69 1.12 1.15 1.14

35 1.20 1.18 1.19

B2 12 1.40 1.41 1.41 1.39 1.36

56 1.40 1.39 1.40

88 1.36 1.38 1.37

Chloride mg/L A2 11 117 114 115.5 112.3 130 19 22

69 114 115 114.5

35 106 108 107.0

B2 12 131 131 131.0 131.0 152

56 132 130 131.0

88 131 131 131.0

Sulphate mg/L A2 11 63.1 59.7 61.40 61.7 72 11 10

69 60.9 63.0 61.95

35 61.6 61.8 61.70

B2 12 74.2 70.7 72.45 72.5 82

56 71.1 72.1 71.60

88 71.8 75.3 73.55

Total suspended mg/L A3 27-19 44.2

44.2 44.9 43.7 -7.8 -7.5 solids

50-38 46.8

46.8

66,52 43.7

43.7

B3 9-11 36.9

36.9 37.1 36.2

54-41 37.5

37.5

84-68 36.8

36.8

30

ANNEX F HOMOGENEITY AND STABILITY

PT: SPIL-1 Parameter: TP

Unit: mg/L P

Sigma: 0.075

Responsible for tests: IRL

Homogeneity test Date: 2018-02-28

Stability test Date: 2018-03-15

Sample x(a) x(b) average sd sd^2

Sample x(a) x(b) B2-9 1.43 1.38 1.4 0.035 0.001

B2-12 1.40 1.41

B2-14 1.45 1.40 1.4 0.035 0.00

B2-56 1.40 1.39 B2-23 1.40 1.40 1.4 0.000 0.000

B2-88 1.36 1.38

B2-27 1.40 1.39 1.4 0.007 0.000

B2-36 1.39 1.38 1.4 0.007 0.000

B2-48 1.34 1.3

For stability B2-59 1.36 1.36 1.4 0.000 0.000

General average (y): 1.39

B2-70 1.44 1.39 1.4 0.035 0.001

/x-y/ =

0.0045833 B2-78 1.39 1.39 1.4 0.000 0.000

B2-81 1.40 1.41 1.4 0.007 0.000

B2-85 1.39 1.40 1.4 0.007 0.000

B2-94 1.41 1.43 1.4 0.014 0.000 Conclusions

ss = 0.020 0.3*sigma= 0.02

For homogeneity

/x-y/ = 0.0045833

General average (x) 1.39

Sample average sd (sx) 0.024

Within-sample sd (sw): 0.019

Between-samples sd (ss): 0.0201

Homogeneity: Is ss < 0.3*sigma?

SL in the Proficiency Test: 0.049

YES

SR in the Proficiency Test: 0.054

Stability: /x-y/ < 0.3*sigma?

YES

31

PT: SPIL-1

Parameter: TSS

Unit: mg/L

Sigma: 3.6

Responsible for tests: IRL

Homogeneity test Date: 2018-02-28

Stability test Date: 2018-03-15

Sample x(a) x(b) average sd sd^2

Sample x(a) x(b) B3-14-77 36.8 36.8

B3-9-11 36.9

B3-20-6 36.7 36.7

B3-54-41 37.5 B3-21-58 35.4 35.4

B3-84-68 36.8

B3-31-60 36.8 36.8

B3-40-24 36.6 36.6

B3-41-30

For stability B3-51-13 37.9 37.9

General average (y): 37.066667

B3-57-79 37.1 37.1

/x-y/ =

0.1757576 B3-72-67 37.2 37.2

B3-74-31 37.1 37.1

B3-83-86 37.1 37.1

B3-85-42 37.1 37.1 Conclusions

ss = 0.60 0.3*sigma= 1.08

For homogeneity

/x-y/ = 0.1757576

General average (x) 36.9

Sample average sd (sx) 0.604

Within-sample sd (sw):

Between-samples sd (ss): 0.604

Homogeneity: Is ss < 0.3*sigma?

SL in the Proficiency Test: 1.25

YES

SR in the Proficiency Test: 1.79

Stability: /x-y/ < 0.3*sigma?

YES

Documents

Proficiency test SPIL-1 (2018) - Eurofins Scientific...4 CONCLUSION The quality control performed, including test of sample stability and homogeneity as well as test of recovery of