8th WorkingRing Test for Depositionand Soilsolution

Transcription

1 8th WorkingRing Test for Depositionand Soilsolution Organization Samples Results Requalification New parameters Conclusion Anna Kowalska Forest Research Institute, Poland Combined session UNECE ICP-Forests EP s + WG QA/QC Zagreb, 29 March 2017

2 8th WRT Deposition and Soil Solution organization Timetable: Invitation letter 10 October 2016 (to water, foliar, and soil labs, EP s, and NFC s) Deadline for registration- 28 October 2016 Sendingsamples -28 November 2016 Deadline for data submission- 22 January 2017(ca. 7 weeks for analyses) Deadline for requalification 30 January - 28 February 2017 (4 weeks for requalification) Fee: 320 Euro In total: 4 months from the registration till the end of requalification

3 Participants 40 labs registered 39 sent back results 10 Germany 3(2) Italy 2 Austria, Belgium, Russia, Sweden 19 otherlabs: Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Greece, Ireland, Kosovo, Latvia, Norway, Poland, Romania, Slovakia, Slovenija, Spain, Switzerland, Turkey, UK

4 Participants 33 labs participated also in the previous round 7thWRT 2015 New labsin 8thWRT 2017: - Sweden - Kosovo - Italy(no results) - Turkey (no results in previous WRT) Reasons why labs did not participate: - 2 labsfrom Bulgaria othercommitments - Portugal financial constraints - Italy(Bolzano) survey suspended due to cost-saving measures

5 Parameters measured in WRT Manual: Soil Solutions Manual: Deposition(bulk and throughfall) Variable Reporting Unit Mandatory/Optional Variable Reporting Unit Mandatory/Optional ph ph unit Mandatory ph ph unit Mandatory EC µs/cm Mandatory EC µs/cm Mandatory Ca mg/l Mandatory Ca mg/l Mandatory Mg mg/l Mandatory Mg mg/l Mandatory Na mg/l Mandatory Na mg/l Mandatory K mg/l Mandatory K mg/l Mandatory NH4-N mg N/L Mandatory NH4-N mg N/L Mandatory SO4-S mg S/L Mandatory SO4-S mg S/L Mandatory NO3-N mg N/L Mandatory NO3-N mg N/L Mandatory Cl mg/l Mandatory Cl mg/l Mandatory Alkalinity µmolc/l Mandatory if ph >5 Alkalinity µeq/l Mandatory if ph >5 Total N mg/l Mandatory Total N mg N/L Mandatory* DOC mg/l Mandatory DOC mg/l Mandatory Ptotal mg/l Optional Ptotal, P-PO4mg P/L Optional Altotal mg/l Mandatory (if ph <5) Al µg/l Optional Fe mg/l Mandatory (if ph <5) Fe µg/l Optional Mn mg/l Mandatory (if ph <5) Mn µg/l Optional Zn µg/l Optional Zn µg/l Optional Cu µg/l Optional Cu µg/l Optional Ni µg/l Optional Ni µg/l Optional Pb µg/l Optional Pb µg/l Optional Cd µg/l Optional Cd µg/l Optional Si mg/l Optional Co µg/l Optional Cr µg/l Optional Mo µg/l Optional Allabile mg/l Optional Hg µg/l Optional Stotal mg/l Optional Ctotal mg/l Optional Norg mg N/L Optional HCO3 Optional measured regularly in WRT s started in 8WRT 2017 not evaluatedin 6-8 WRT s

6 Samples/parameters measured in 8thWRT CondpH Cl N- NO3 P- PO4 S- SO4 N- NH4 Ca Mg Na K Alk DOCNtot Fe Al Mn Deposition M M M M O M M M M M M M ph>5 M M O O O Soil solution M M M M - M M M M M M M M M M M M ph<5 ph<5 ph<5 S 1 Stemflow x x x x x x x x x x x x* x x x x x S 2 Throughfall x x x x x x x x x x x x* x x x x x S 3 Bulk Deposition x x x x x x x x x x x x* x x x x x S 4 Soil Solutionx x x x x x x x x x x x* x x x x x S 5 Soil Solutionx x x x x x x x x x x x* x x x x x S 6 Syntetic x M mandatory O optional

7 Samples tolerable limits Parameter Unit Conc. Range low TolerableConc. Limit Range low*) high Tolerable Limit high*) max. LOQ**) Alkalinity μeq/l 100 ± 40% >100 ± 25% 10 Ammonium mg-n/l 0.25 ± 25% > 0.25 ± 15% 0,08 Calcium mg/l 0.25 ± 20 % > 0.25 ± 15% 0,2 Chloride mg/l 1.5 ± 25 % > 1.5 ± 15% 0,2 Conductivity(at25 C) μs/cm 10 ±20 % > 10 ±10% 5 Dissolved Organic Carbon mg-c/l 1 ± 30 % > 1 ± 20% 1 Magnesium mg/l 0.25 ± 25 % > 0.25 ± 15% 0,1 Nitrate mg-n/l 0.5 ± 25 % > 0.5 ± 15% 0,08 ph ph > units units - Phosphate mg P/l ± 20 % ± 20% 0,1 Potassium mg/l 0.5 ± 25 % > 0.5 ± 15% 0,4 Sodium mg/l 0.5 ± 25 % > 0.5 ± 15% 0,1 Sulphate mg-s/l 1 ± 20 % > 1 ± 10% 0,1 Total Nitrogen mg-n/l 0.5 ± 40 % > 0.5 ± 20% 0,5 *) Based on the tolerable limits (see Manual Part XVI Quality Assurance and Control in Laboratories) **) Maximum accepted LOQ

8 Samples concentration level, excluded parameters Sample Cond ph Cl N-NO3 P-PO4 S-SO4 N-NH4 Ca Mg Na K Alk. DOC Ntot Deposition M M M M O M M M M M M M ph>5 M M* Soil solution M M M M - M M M M M M M M M S 1 Stemflow H L H L H H H H L H H L x H S 2 Throughfall H L L L x L L H L H H L H H S 3 Bulk Depo L L L L x L H H L L L L L H S 4 Soil Sol. H H H L x H x H H H L x H H S 5 Soil Sol. H H H H H H L H H H H x H H S 6 Syntetic H * only recommended in Bulk deposition H - concentration range high L - concentration range low x - sample/parameter excluded

9 Sample collection, preparation, homogeneity, stability Collecting of samples from early spring till autumn 2016, stored in +4 C Filtration through glass fiber prefilter and membrane filters 0.45 µm mixed celulose esters(november 2016), samples divided into bottles before the dispatch Homogeneitytests-10% of samplestestedfor ph, EC, DOC OK.! Stabilitytests-every2-3 weeksuntilthe end of February= end of requalification Problem: Sample 1 - DOC unstable excluded from evaluation

10 79% Results completness of results by parameter Cond ph Cl N-NO3 S-SO4 N-NH4 Ca Mg Na K Alk DOC Ntot P-PO4 Fe Al % of totalno of results 100% 0% 100% 0% 100% 0% 99% 1% 97% 3% 95% 5% 100% 0% 100% 0% 100% 0% 100% 0% 79% 21% 89% 11% 87% 13% 77% 23% 79% 21% 82% 18% Mn 21% submitted missing Mandatory parameters missing results: DOC, Ntot, S-SO4, N-NH4, N-NO3 Alkalinity(7% missing in samples ph>5)

11 Results- completness of results by lab A39 A49 A61 A85 D27 D35 D70 D71 D72 F03 F05 F06 F07 F08 F12 F14 F15 F16 F18 F25 F27 F28 F32 A47 A60 S03 D39 S01 A71 D63 F24 D47 S25 D73 F04 F01 F02 A43 D34 No of submitted results mandatory optional missing results of mandatory parameters

12 Results Percentage of acceptable results before requalification labs 8th WRT % acceptable results 14 labs labs S03 D70 D27 A61 F25 D47 F12 F15 D72 A49 F18 D35 F28 S01 F05 D39 F03 F27 F32 A71 F01 A60 F16 F02 D34 F14 F07 A39 F06 D71 S25 F24 A47 F04 F08 A43 A85 D63 D73 Labs that needed requlification - 25 (14 labs- no requalification needed) 1 parameter to requalify - 14 labs 2 parameters to requalify - 5 labs 3 to 9 parameters - 6 labs

13 Results Improvement after requalification % % of acceptable results per lab S03 D70 D27 A61 F25 D47 F12 F15 D72 A49 F18 D35 F28 S01 F05 D39 F03 F27 F32 A71 F01 A60 F16 F02 D34 F14 F07 A39 F06 D71 S25 F24 A47 F04 F08 A43 A85 D63 D73 before requalification after requalification 19 labsout of 25 requalified No attemptto requalify: A47, F04, F08, D73, D39, A71

14 Results Please, read the instructions! More results reported than required: Sample 6 syntetic required Alkalinity only! Reported results for sample 6: AMMONIUM S25 CONDUCTIVITY (at 25 C) A85 F03 F06 DISSOLVED ORGANIC CARBON F06 ph A47 A85 F03 F06

15 Results Too high limit of quantification in relation to maximum acceptable LOQ: Determination method Chloride max LOQ 0,2 mg/l D72 0,25 mg/l IC with suppression F06 0,3 mg/l ICP-OES without Ultrasonic nebulization S25 1 mg/l IC with suppression Dissolved organic carbon max LOQ 1 mg C/L F32 2 mg C/L TOC/TN analyzer Magnesium max LOQ 0,1 mg/l F08 0,11 mg /L ICP-OES without Ultrasonic nebulization Nitrate max LOQ 0,08 mg N/L A60 0,23 mg N/L IC without suppression F06 0,2 mg N/L FI UV-VIS F32 0,1 mg N/L IC with suppression

16 Results % of accepted results per parameter before and after requalification 100% 10 % accepted results 80% 60% 40% 20% No of labsthatfailed 0% Ca ph DOC Alk NH4 SO4 NO3 PO4 Ntot Cond Mg K Cl Na % before requalification % after requalification No of labs failed in WRT 0 Problematic parameters: - <80% acceptableresults: Ca, ph, Alk, NH4,DOC, - 5 labsfailed: Ca, ph, Alk, NH4, Ntot, SO4, Cond.

17 Requalification Labs are usually capable of identifying the reasons for nontolerable results. Reasons: - technicalproblems(instruments, sensors, electrodesfailure/ageing): Ca, Alkalinity, Ntot, ph, NH4, DOC, Conductivity - Quality control material or standards of poor quality: Ca, Alkalinity, Ntot, ph, DOC - Calibration(failed for low concentration samples): Ca, Ntot, DOC - Contamination of samples: Ca - Spectral interferences: Ca - Temperature compensation: ph, Conductivity - New instrument/method not fully validated: Ntot - Poor method: IC with suppression N-NH4, 1-end point Alkalinity - Not understanding instructions(not reading instructions?): Alkalinity - Typo errors: N-NH4 - Calculation errors, wrong units: Alkalinity, S-SO4, N-NH4, N-NO3, P-PO4 - happens also to the labs participating regularly in WRT s! - unknown

18 Results- Comparison with previous rounds % of acceptableresults-comparisonof 6t, 7th and 8th WRT S03 S25 F01 F02 F03 F04 F05 F06 F07 F08 F12 F14 F15 F16 F18 F21 F23 F24 F25 F27 F28 F32 S01 D72 D73 A39 A43 A47 A49 A55 A60 A61 A71 A83 A85 D05 D06 D27 D33 D34 D35 D39 D47 D60 D68 D69 D63 D70 D thWRT thWRT thWRT 2017

19 Results- Comparison with previous rounds 8th WRT: nontolerable results % 70,0 60,0 nontolerable results (%) 50,0 40,0 30,0 20,0 10,0 Ca Mg Na K NH4 0,0 RT 2002 RT 2005 RT 2009 RT 2010 RT 2011 RT 2013 RT 2015 RT 2017

20 Results- Comparison with previous rounds 8th WRT: nontolerable results % nontolerable results (%) Cond ph Alk TDN DOC 0 RT 2002 RT 2005 RT 2009 RT 2010 RT 2011 RT 2013 RT 2015 RT 2017

21 Results- Comparison with previous WRT rounds 70 8th WRT: nontolerable results (%) 60 nontolerable results (%) Cl SO4 NO3 0 RT 2002 RT 2005 RT 2009 RT 2010 RT 2011 RT 2013 RT 2015 RT 2017

22 New parameters Al, Fe, Mn Al, Fe, Mn mandatory parameters for soil solutions if ph<5 Haveto be implementedin WRT -not measuredin 6th and 7th WRT s Resultssubmitted: Al 32labs, Fe and Mn 31labs Concentrationµg/L: S1 SF S2 THR S3 BOF S4 Ssol S5 Ssol Al Fe Mn Detection limits, proposal: Al 15 µg/l Fe 15 µg/l Mn 10 µg/l

23 New parameters Al, Fe, Mn, proposal: max LOQ, tolerable limits Al µg/l Fe µg/l Sampleno. Concentration 8WRTresultswithoutoutliers fall within limits: 2 12,31 30% 1 12,69 30% % % Sampleno. Concentration 8WRTresultswithoutoutliers fall within limits: 1 11,39 30% 4 128,95 30% 5 399,29 30% 30% 100 µg/l > 15% Proposal: 30% Low tolerable limit Conc. Range High tolerable limit Tolerable limit Mn µg/l Sampleno. Concentration 8WRTresultswithoutoutliers fall within limits: 3 2,03 20% 2 9,65 15% 1 26,68 10% 4 69,86 10% 5 101,2 10% 15% 25 µg/l > 10% Low tolerable limit Conc. Range High tolerable limit

24 Conclusion(1) % of non-tolerableresultsisbelow20% for allmandatoryparametersin a high range of concentration, except for Ca. Quality tests(conductivity, ionic balance, N check) not performed routinely? Reading WRT instructions would help to avoid common mistakes. Needed change of rules submission of all requested parameters in all the samples. Tolerablelimitsand max LOQ for newparametersfe, Al, Mn needto be agreed=> Headof LabsMeeting, Sept WRT results are now submitted by WRT organizer directly to the ICP-Forests databaseof depositionand soilsolution=> no morewrt resultsin LQA files

25 Conclusion(2) Need to update of the database of contacts/addresses information flow between NFC EP s WG QA/QC highlydesirable Next WRT planned for 2018/2019, start autumn 2018 Registration page open for the new WRT!

26 8th WRT Deposition and Soil Solution- Reports

27 8th WRT Deposition and Soil Solution Special thanks To Kirsti for know-how and collecting of soil solution sample To Alfred for web-interface management and cooperation in evaluation process, for proposal for tolerable limits for Al, Fe, Mn To Nilsfor trendsin WRT and To Tillfor helpwith the databaseand web-page Thankyoufor yourattention