Preliminärrapport för provningsjämförelse

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1 Preliminärrapport för provningsjämförelse 8- Stockholm, mars 8 Del A Utgående kommunalt avloppsvatten, spikat Suspenderade ämnen, Glödrest Del B Utgående skogsindustriellt avloppsvatten, spikat Suspenderade ämnen, Glödrest, Grova partiklar (Susp7/Vira) Del C Rötslam Torrsubstans, Glödrest, ph, alkalinitet, organiska syror, NHN I preliminärrapporten är resultaten redovisade i figur- och tabellform här följer några förklaringar för tabellrubrikerna: Mean Stdev Range CV% n Excl. medelvärde, konsensus standardavvikelse max min variationskoefficient antal värden i de statistiska beräkningarna uteslutna resultat (outliers, mindre-än värden) Youdendiagram Analysresultaten representeras av värdepar Sample + Sample. Talparens placering visar ifall resultaten innehåller systematiska eller slumpmässiga avvikelser. Ett cirkelformat spridningsmönster indikerar en slumpmässig fördelning utan påtagliga systematiska fel. Är spridningsmönstret däremot samlat utefter 5 linjen är materialet behäftat med systematiska avvikelser. Histogram (eller frekvensdiagram) Hela värdeintervallet är uppdelade i ett antal del-intervall. Stapelhöjden motsvarar antalet mätvärden i del-intervallet. En normal fördelning av det statistiska materialet är jämn och symmetrisk med högsta antalet mätvärden i närheten av medelvärdet. En asymmetrisk fördelning eller flera tydliga maxima tyder på komplikationer som kan bero metoder, homogenitet eller dylikt. Kriterier för beräkning av z-scores i denna rapport För parametrar med minst sex godkända resultat beräknas z-score om proverna bedöms vara homogena och stabila m.a.p. den aktuella parametern. För parametrar med fyra eller fem godkända resultat beräknas z-score om CV% (standardavvikelse /medelvärde) är mindre än % och det finns högst ett outlier. Mindre-än värden och uppenbara rapporteringsmissar räknas inte som outliers. Inga z-scores beräknas för parametrar som inte uppfyller villkoren. För dessa presenteras endast deltagarnas resultat samt, beroende på antal resultat och spridning, eventuellt även grundläggande statistik och Youden-diagram utan konfidensintervall. Vänligen, meddela oss om du upptäcker misstag vi kan ha gjort i preliminärrapporten så vi kan rätta till dem i slutrapporten. Slutrapporten beräknas vara klar senast vecka 5. ACES Provningsjämförelser Stockholms universitet 9 Stockholm Sweden Hemsida: Marsha Hanson: marsha.hanson@aces.su.se Marcus Sundbom: marcus.sundbom@aces.su.se

2 Preliminary Report for Proficiency Test 8- Stockholm, March, 8 Part A Treated municipal wastewater Total suspended solids, Fixed suspended solids Part B Treated paper industry wastewater Total suspended solids, Fixed suspended solids, Susp7 Part C Digested sludge Dry solids, Fixed solids, ph, alkalinity, organic acids, NHN Results in the preliminary report are shown in tables and charts. Explanations for the abbreviations used in the table heads and translations for some key words: Mean Stdev Range CV% n Excl. average, consensus standard deviation max min coefficient of variation number of values used in the statistical calculations excluded values (outliers, less-than values) Youden plots The results are represented as value pairs with sample plotted against sample. The position of the value pairs reveals both systematic and random errors. Data scattered circularly around the intersection of the means are randomly distributed with no specific systematic errors. Data distributed along the 5 axis indicate the presence of systematic errors. Histograms (or frequency diagrams) The result range is divided into equal intervals along the x-axis with each bar representing the number of results in that interval. A normal statistical material is characterised by an even, symmetrical distribution with the majority of data centred around the mean. An asymmetric distribution or more than one obvious maximum indicates complications, for example with the methods or homogeneity. Criteria for the calculation of z-scores in this report For parameters with at least six acceptable results, z-scores are calculated if the samples are homogenous and stabile with respect to that parameter. For parameters with four or five acceptable results, and no more than one outlier, z-scores are calculated if the CV% (standard deviation/mean) is less than %. Less-than values and obvious clerical errors are not counted as outliers. No z-scores are calculated for parameters that do not fulfil the above conditions. Only the results of the participants are presented. Basic statistics and the Youden plot (without the confidence interval) may be included depending on the number of participants and the distribution. Kindly inform us of errors we may have made in the preliminary report so we can correct them in the final report. A final report can be expected by April. ACES Proficiency Tests Stockholm University SE- 9 Stockholm Sweden Website: Marsha Hanson: marsha.hanson@aces.su.se Marcus Sundbom: marcus.sundbom@aces.su.se

3 Preliminär Rapport Provningsjämförelse 8- Suspenderade ämnen och slam Proficiency Test 8- Suspended solids and sludge Marsha Hanson Marcus Sundbom ACES, Stockholms universitet

4 Innehåll / Table of Contents STR Suspenderade ämnen / Total suspended solids... SFR Glödrest / Fixed solids... S7 Grova partiklar (Susp7/Vira) / Susp TS Torrsubstans / Dry solids... 8 TFR Glödrest (slam) / Dry fixed solids (sludge)... ph ph (slam) / ph (sludge)... Alk Alkalinitet (slam) / Alkalinity (sludge)... 7 VFA Organiska syror (slam) / Organic acids (sludge)... NHN Ammoniumkväve (slam) / Ammonium nitrogen (sludge)... Provmatriser / Sample matrices A Kommunalt avloppsvatten, spikat Municipal wastewater, spiked B Skogsindustriellt avloppsvatten, spikat Paper industry wastewater, spiked C Rötslam Digested sludge

5 STR Suspenderade ämnen / Total suspended solids Analyskoder & metoder STR-STG Glasfiberfilter. Torkat i 5 C. SS 8 (upphävd); SS-EN 87:5 STR-XX Lab 7: Membranfilter, µm. Egen metod. Lab 97:Glasfiberfilter torkas i mikrovågsugn i 7 min. Analysis codes & methods STR-STG Glass fiber filter. Dried at 5 C. SS 8 (upphävd); SS-EN 87:5 STR-XX Lab 7: Membrane filter. µm. Own method. Lab 97: Glas fiber filter dried 7 min. in microwave oven.

6 Sample A, <= >.7 <= >5.555 STR Del A / Part A STR Sample A Total STG XX STR Sample A STR Sample A Total STG XX STR Sample A STR Part A Youdendiagram Mean Mean 5º STG XX Sample A,

7 STR Del A / Part A Lab Method Sample Z-score Excl. Sample Z-score Excl. 8 STG XX STG STG STG STG STG STG STG STG STG STG STG STG XX STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG X.. 5 STG STG STG STG STG STG STG STG STG STG STG STG

8 STR Del A / Part A z-score for STR Lab Code (Method) 5 (STG) 8 (STG) (STG) (STG) 97 (XX) (STG) 5 (STG) (STG) 75 (STG) 8 (STG) 7 (STG) (STG) 7 (STG) 5 (STG) 9 (STG) 5 (STG) 5 (STG) 8 (STG) 7 (STG) 5 (STG) 89 (STG) 7 (STG) 7 (STG) (STG) 8 (STG) (STG) 9 (STG) 7 (XX) 9 (STG) (STG) 5 (STG) 9 (STG) 7 (STG) (STG) (STG) 7 (STG) 7 (STG) 7 (STG) 9 (STG) (STG) 7 (STG) (STG) 7 (STG) (STG) (STG) z-score A z-score A Unsatisfactory Questionable

9 Sample B, <= >8.5 <= >.95 STR Del B / Part B STR Sample B Total STG STR Sample B Total STG STR Sample B STR Sample B STR Part B Youdendiagram 8 8 Mean Mean 5º STG Sample B, 7

10 STR Del B / Part B Lab Method Sample Z-score Excl. Sample Z-score Excl. 9 STG STG STG STG STG STG STG STG STG STG X STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG X STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG STG

11 STR Del B / Part B z-score for STR Lab Code (Method) 55 (STG) 9 (STG) 7 (STG) (STG) 7 (STG) 8 (STG) 95 (STG) 99 (STG) 7 (STG) (STG) (STG) (STG) 7 (STG) (STG) 9 (STG) (STG) (STG) (STG) 85 (STG) 7 (STG) 8 (STG) 7 (STG) (STG) (STG) 5 (STG) 7 (STG) (STG) (STG) 99 (STG) 9 (STG) 5 (STG) 5 (STG) 75 (STG) 89 (STG) (STG) 5 (STG) 9 (STG) 9 (STG) 8 (STG) (STG) 9 (STG) (STG) 7 (STG) (STG) (STG) (STG) z-score B z-score B Unsatisfactory Questionable 9

12 SFR Glödrest / Fixed suspended solids Analyskoder & metoder SFR-STG Glasfiberfilter. Bränt i 55 C. SS 8 (upphävd); SS-EN 87:5 Analysis codes & methods SFR-STG Glass fiber filter. Ignited at 55 C. SS 8 (upphävd); SS-EN 87:5

13 Sample A, <= >.8 <= >. SFR Del A / Part A SFR Sample A Total STG XX. 5 SFR Sample A SFR Sample A Total STG XX SFR Sample A SFR Part A Youdendiagram 5 9 Mean Mean 5º STG XX Sample A,

14 8 (STG) 5 (STG) (STG) (STG) (STG) 97 (STG) (STG) 7 (STG) 7 (STG) 7 (XX) (STG) 7 (STG) (STG) 8 (STG) 7 (STG) (STG) (STG) 5 (STG) z-score for SFR SFR Del A / Part A Lab Method Sample Z-score Excl. Sample Z-score Excl. 8 STG X X STG STG STG X X 8 STG STG STG...7. STG STG XX....7 STG STG STG STG STG STG STG STG z-score A z-score A Unsatisfactory Questionable Lab Code (Method)

15 Sample B, <= >5.5 <= >. SFR Del B / Part B SFR Sample B Total STG SFR Sample B SFR Sample B Total STG SFR Sample B SFR Part B Youdendiagram 5 Mean Mean 5º STG Sample B,

16 (STG) (STG) (STG) (STG) 7 (STG) (STG) 7 (STG) 8 (STG) 7 (STG) z-score for SFR SFR Del B / Part B Lab Method Sample Z-score Excl. Sample Z-score Excl. STG STG X STG STG STG....9 STG STG STG STG z-score B z-score B Unsatisfactory Questionable Lab Code (Method)

17 S7 Grova partiklar (Susp7/Vira) / Susp7 Analyskoder & metoder S7-STV Vira-duk filter (~7 µm). Torkat i 5 C. SS 88 Analysis codes & methods S7-STV "Vira"-mesh filter (~7 µm). Dried at 5 C. SS 88 5

18 Sample B, <= >.5 S7 Del B / Part B S7 Sample B Total STV S7 Sample B S7 Sample B Total STV S7 Part B Youdendiagram Mean Mean 5º STV Sample B,

19 55 (STV) 7 (STV) 9 (STV) 9 (STV) 5 (STV) 7 (STV) (STV) z-score for S7 S7 Del B / Part B Lab Method Sample Z-score Excl. Sample Z-score Excl. 5 STV STV X 9 STV STV STV STV X 7 STV X z-score B z-score B Unsatisfactory Questionable Lab Code (Method) 7

20 TS Torrsubstans / Dry solids Analyskoder & metoder TS-SF Total torrsubstans vid 5 C, frystorkat prov. TS-ST Total torrsubstans vid 5 C. SS 8; SS-EN 88 TS-XX Lab 5: Ugn som väger provet, bränner bort och bestämmer när provet är klart. Lab 97: C. Analysis codes & methods TS-SF Total solids (the residue) at 5 C, freeze-dried sample. TS-ST Total solids (the residue) at 5 C. SS 8; SS-EN 88 TS-XX Lab 5: Oven that weighs and dries the sample, and determines when the endpoint is reached. Lab 97: C. 8

21 Sample C, % <= >. <= >.7 TS Del C / Part C TS Sample C % Total SF. ST XX TS Sample C TS Sample C % Total SF. ST XX. 5 % TS Sample C % TS Part C Youdendiagram Sample C, % Mean Mean 5º SF ST XX 9

22 97 (XX) (ST) 8 (ST) 5 (XX) (ST) 7 (ST) 9 (ST) (ST) (ST) (ST) 5 (ST) 7 (ST) (ST) 8 (ST) (ST) (ST) 7 (ST) 5 (ST) (ST) (ST) 8 (ST) 89 (ST) 9 (ST) 5 (ST) 7 (ST) 5 (ST) (SF) z-score for TS TS Del C / Part C Lab Method Sample Z-score Excl. Sample Z-score Excl. 8 ST ST ST ST XX ST ST ST ST XX X X 7 ST....5 ST ST ST ST ST ST ST ST ST ST ST SF ST ST ST ST z-score C z-score C Unsatisfactory Questionable Lab Code (Method)

23 TFR Glödrest (slam) / Dry fixed residue (sludge) Analyskoder & metoder TFR-ST Total substans. Glödrest efter bränning i 55 C. SS 8; SS-EN 879 Analysis codes & methods TFR-ST Total fixed solids ignited at 55 C. SS 8; SS-EN 879

24 Sample C, % TS <= >.855 <= >7. TFR Del C / Part C TFR Sample C % TS Total ST TFR Sample C % TS Total ST TFR Sample C % TS TFR Sample C % TS TFR Part C Youdendiagram Mean Mean 5º ST Sample C, % TS

25 89 (ST) 5 (ST) (ST) (ST) (ST) (ST) 5 (ST) 9 (ST) 8 (ST) (ST) 7 (ST) 7 (ST) 5 (ST) (ST) 8 (ST) 7 (ST) (ST) 9 (ST) 8 (ST) (ST) 5 (ST) 7 (ST) (ST) 97 (ST) (ST) z-score for TFR TFR Del C / Part C Lab Method Sample Z-score Excl. Sample Z-score Excl. 8 ST ST ST ST ST ST ST ST X. -. X 97 ST X. 7. X 7 ST ST ST ST ST ST ST X.. X 9 ST ST ST ST ST ST ST ST ST z-score C z-score C Unsatisfactory Questionable Lab Code (Method)

26 ph ph (slam) / ph (sludge) Analyskoder & metoder PH- Elektrometrisk bestämning vid C. SS 8 mod.; SS-EN ISO 5: PH-5 Elektrometrisk bestämning vid 5 C. SS 8; SS-EN ISO 5: PH-5T Elektrometrisk bestämning med titroprocessor vid 5 C. SS 8; SS-EN ISO 5: PH-K Kontinuerlig elektrometrisk mätning med temperaturkompensering. SS 8; SS-EN ISO 5: PH-R Elektrometrisk bestämning vid rumstemperatur. SS-EN ISO 5: PH-XX Lab 8,, 7: SS-EN 59:. Lab 7: SS-EN 59:. Rumstemperaturmätning. Analysis codes & methods PH- Electrometric measurement at C. SS 8 mod.; SS-EN ISO 5: PH-5 Electrometric measurement at 5 C. SS 8; SS-EN ISO 5: PH-5T Electrometric measurement with titroprocessor at 5 C. SS 8; SS-EN ISO 5: PH-K Continuous electrometric measurement with temperature compensation. SS 8; SS-EN ISO 5: PH-R Electrometric measurement at room temperature. SS-EN ISO 5: PH-XX Lab 8,, 7: SS-EN 59:. Lab 7: SS-EN 59:. Room temperature.

27 Sample C, <= >8.5 <= >7.9 ph Del C / Part C ph Sample C ph Sample C Total T 7.8 K R XX ph Sample C ph Sample C Total T 7.55 K R XX ph Part C Youdendiagram Mean Mean 7.7 5º T K 7. R XX Sample C, 5

28 5 (R) 8 (XX) 9 (5) 7 () 5 (K) 89 (K) 8 () 7 () 5 () 9 (5) 7 (R) 97 (5T) (5) 5 (5) (5) (R) 7 (XX) (XX) (K) 7 (XX) z-score for ph ph Del C / Part C Lab Method Sample Z-score Excl. Sample Z-score Excl. 8 XX XX K R K T XX K R R XX z-score C z-score C Unsatisfactory Questionable Lab Code (Method)

29 Alk Alkalinitet (slam) / Alkalinity (sludge) Analyskoder & metoder ALK-HACH Bestämt enligt Hach eller liknande metod. HACH 8 ALK-NN Total alkalinitet: slutpunkt ph.5. Titrimetrisk bestämning med indikator. SS-EN ISO 99-; Standard Methods B ALK-NN5 Karbonatalkalinitet: slutpunkt ph 5.. Titrimetrisk bestämning med indikator. SS-EN ISO 99- ALK-NP Total alkalinitet: slutpunkt ph.5. Titrimetrisk bestämning. Potentiometriskt slutpunktsbestämning med ph-meter eller liknande. SS-EN ISO 99-; Standard Methods B ALK-NP5 Karbonatalkalinitet: slutpunkt ph 5.. Titrimetrisk bestämning. Potentiometriskt slutpunktsbestämning med ph-meter eller liknande. SS-EN ISO 99- ALK-XX Annan metod. Slutpunkt mellan och.5. Samtliga VAV P5 Slutpunkt.: lab, 9, 5 Slutpunkt.5: lab 7 ALK-XX5 Annan metod. Slutpunkt mellan 5. och Samtliga VAV P5 Slutpunkt 5.75: lab, 9, 5 Slutpunkt 5.: lab 7 Analysis codes & methods ALK-HACH Procedure according to Hach or equivalent method. HACH 8 ALK-NN Total alkalinity: endpoint ph.5. Titrimetric determination with indicator. SS-EN ISO 99-; Standard Methods B ALK-NN5 Carbonate alkalinity: endpoint ph 5.. Titrimetric determination with indicator. SS-EN ISO 99- ALK-NP Total alkalinity: endpoint ph.5. Titrimetric determination. Potentiometric endpoint determination with ph-meter or equivalent. SS-EN ISO 99-; Standard Methods B ALK-NP5 Carbonate alkalinity: endpoint ph 5.. Titrimetric determination. Potentiometric endpoint determination with phmeter or equivalent. SS-EN ISO 99- ALK-XX Other method. Endpoint between and.5. All according to VAV P5 Endpoint.: lab, 9, 5 Endpoint.5: lab 7 ALK-XX5 Other method. Endpoint between 5. and All according to VAV P5 Endpoint 5.75: lab, 9, 5 Endpoint 5.: lab 7 7

30 Sample C, mmol/l <= >5. <= >5. Alk Del C / Part C ALK Sample C mmol/l Total HACH. NN NN NP NP XX XX ALK Sample C mmol/l ALK Sample C mmol/l Total HACH 7.7 NN NN NP NP XX XX ALK Sample C 8 mmol/l ALK Part C Youdendiagram Mean Mean 5º HACH NN NN5 NP NP5 XX XX Sample C, mmol/l 8

31 8 (NN5) 7 (XX5) 5 (NN) 9 (NN5) (NN5) 5 (HACH) (NP) (NN) 5 (NP5) (NN) (NP5) 5 (NP) 5 (XX5) (XX5) 97 (NP) 7 (XX) 9 (XX5) 7 (NN5) 7 (NP5) (XX) 8 (NP) (NP) 7 (NP) 9 (XX) 5 (XX) z-score for ALK Alk Del C / Part C Lab Method Sample Z-score Excl. Sample Z-score Excl. 8 NN NP NP NN NN NP NP NN HACH NP NP NP NN NP NN NP XX XX NN XX XX XX XX XX XX z-score C z-score C Unsatisfactory Questionable Lab Code (Method) 9

32 VFA Organiska syror (slam) / Organic acids (sludge) Med våra vanliga statistiska rutiner blir 8 av 8 resultat outliers. Spridningen är stor även bland resultaten för samma Hach-Lange kyvettmetod. I preliminärrapporten redovisas därför statistiken för samtliga resultat, utan uteslutning av outliers. Samtliga resultat redovisas även i Youdendiagrammet. Inga z-scores har beräknats. I resultattabellen finns kompletterande information om filtrering, centrifugering och bortdragen egenfärg/blank för att kunna spåra avgörande skillnader. För metoden med fempunktstitrering har analyskoden VFA-T5 skapats. De vanligaste sättet att rapportera resultat är i som ättiksyra-ekvivalenter. (Med LCK 5 kan man även välja smörsyra-ekvivalenter.) Kontakta oss om du inte har använt ättiksyra-ekvivalenter. Our usual statistical routines classify 8 of 8 results as outliers. The variation is large even among results of the same Hach-Lange cuvette method. In the preliminary report we present the statistics for all the results without the removal of outliers. All results are also shown in the Youden plot. No z-scores have been calculated. The results table contains supplementary information concerning filtration, centrifugation and compensation for inherent colour/blank. For the five-point titration method, we have created the analysis code VFA-T5. The usual way to report the results is in as acetic acid equivalents. (With LCK 5 there is also the choice of butanoic acid equivalents.) Contact us if you haven t used acetic acid equivalents. Analyskoder & metoder VFA-CUV Kyvettest. Hach-Lange LCK 5. VFA-T5 Fempunktstitrering. Lab : Ibrahim et. al. JES () 9 9 Lab 97: Moosbrugger Lab : Jönsson, L.-E. (995); Moosbrugger, et. al. (99) VFA-XX Lab : GC-FID egen metod, resultat enbart från ättiksyra Lab 7: Journal of Chromatography A 9 () 9- Analysis codes & methods VFA-CUV Cuvette test. Hach-Lange LCK 5. VFA-T5 Five point titration. Lab : Ibrahim et. al. JES () 9 9 Lab 97: Moosbrugger Lab : Jönsson, L.-E. (995); Moosbrugger, et. al. (99) VFA-XX Lab : GC-FID own method, acetic acid results only Lab 7: Journal of Chromatography A 9 () 9-

33 Sample C, <= >8.5 <= >.5 VFA Del C / Part C VFA Sample C Method Mean Median Stdev Range CV% n Total CUV T XX VFA Sample C VFA Sample C Method Mean Median Stdev Range CV% n Total CUV T XX VFA Sample C VFA Part C Youdendiagram 8 8 Median Median CUV T5 XX 8 8 Sample C,

34 VFA Del C / Part C Grupperad efter metod. Resultat sorterat från lägsta till högsta. Grouped by method. Results sorted from lowest to highest. Lab Method Sample Sample 7 XX 8 5 Egenfärg/blank bortdragen XX Nej Centrifug rpm min Filter.5 µm T5.. Nej Ja Ja T Nej 97 T Munktell kvalitet V5 5 CUV 8 9 Ja Whatman 597 ½ CUV 9 8 CUV 5 Ja Whatman 597 ½ CUV 8 Ja Ja CUV Ja 5 CUV 5 5 CUV 55 7 Nej Whatman 597 ½ 9 CUV 9 7 Ja 7 CUV 8 CUV 97 CUV CUV 7 rpm 5 CUV 5 5 rpm min

35 NHN Ammoniumkväve (slam) / Ammonium nitrogen (sludge) Några av de intresserade labben missade att jämförelsen för NH-N i slam skulle bli av. Därför har endast tre labb rapporterat resultat. Även om det är för få för en riktig utvärdering var spridningen bland resultaten mycket låg och samtliga labb kan anses ha godkända resultat. Several of the interested labs missed the information that there would be a test for NH-N in sludge so only three labs reported results. Although this is too few for a proper evaluation, the variation is very low and the results from all three labs are considered acceptable. Analyskoder & metoder NHN-XX Lab : Kjeldahl Lab 7: Standard Methods 998, 5 mod. Lab : LCK Analysis codes & methods NHN-XX Lab : Kjeldahl Lab 7: Standard Methods 998, 5 mod. Lab : LCK NHN Sample C mg/kg Total XX NHN Sample C mg/kg Total XX Lab Method Sample Sample XX 55 7 XX XX 7 5

36 ACES Institutionen för miljövetenskap och analytisk kemi Department of Environmental Science and Analytical Chemistry 7