Results of the 6 th deposition and soil solution ring test 2013

Transcription

1 Meeting of the heads of the Labs 19./20. September, Zadar (Croatia) Results of the 6 th deposition and soil solution ring test 2013 Kirsti Derome, Nils Koenig

2 Meeting of the heads of the Labs 19./20. September, Zadar (Croatia) Participants and funding 40 laboratories from 22 countries + 2 more labs registered, but didn t send the results Number of participants has stayed quite stabile during ten years time of WRT s (2002, 2005, 2009, 2010, 2011, 2013) The costs of the ring test budgeted for 40 to 50 participants, max 400 each, finally 360 Covers the costs for preparing, mailing and analyzing the samples in laboratory + web interface + overheads, but not coordinator s costs

3 Meeting of the heads of the Labs 19./20. September, Zadar (Croatia) Natural samples Samples Sample 1. Bulk deposition from Finland (NH 4 Cl added) Sample 2. Throughfall sample from Finland (NH 4 SO 4 added) Sample 3. Stemflow from Germany Sample 4. Soil solution from Germany Synthetic samples SYN 5. For measuring anions and kations, prepared from salts (Ca, K, Na, Mg, NH 4, SO 4, N0 3, PO 4, Cl, EDTA and tartrates) SYN 6. For measuring alkalinity only Smell in Sample 5??

4 Meeting of the heads of the Labs 19./20. September, Zadar (Croatia) Samples Accounting of the 6th WRT Estimation Real costs updated updated participants 40 participants 5 samples 4 real samples + 2 synthetic samples Consumables (boxes, bottles, labels, filters etc.) Analyses etc Delivery Sending 1-2 raw samples to Rovaniemi Sum direct costs Work (incl. overheads) technicians only Sum total Alfred: database Grand total per participant Income 360 Income total Overheads include administrative costs Kirsti Derome's working costs not included

5 Meeting of the heads of the Labs Monthly stability measurements 19./20. September, Zadar (Croatia) Ca K Mg Na P S Alkalinit yi DOC ph Conducti vity Tot N Amm-N Cl Nitr-N Phos-P Sulf-S Sample mg/l mg/l mg/l mg/l mg/l mg/l mmol/l mg/l ms/m mg/l mg/l mg/l mg/l mg/l mg/l Sample 1 0,0503 0,053 0,0163 0,291 <0,007 0,175 1,996 4,56 2,037 0,415 0,143 0,430 0,236 <0.13 0,189 Sample 1 0,0515 0,055 0,0160 0,296 <0,007 0,177 1,632 4,48 2,162 0,391 0,162 0,440 0,241 <0.13 0,173 Sample 1 0,0502 0,047 0,0159 0,286 <0,007 0,171 1,677 4,38 2,177 0,377 0,128 0,420 0,242<0.13 0,172 Sample 1 0,0496 0,048 0,0154 0,294 <0,007 0,183 4,40 2,141 0,407 0,135 0,416 0,241<0.13 0,176 Sample 1 0,050 0,051 0,016 0,292 0,177 1,768 4,455 2,129 0,398 0,142 0,427 0,240 0,177 mean 0,001 0,003 0,000 0,003 0,004 0,152 0,064 0,046 0,014 0,010 0,009 0,002 0,006 avedev 1,1 6,4 1,6 1,1 2,0 8,6 1,4 2,2 3,4 7,3 2,0 0,9 3,1 % Sample 2 0,0841 0,188 0,0332 0,492 <0,007 0,305 1,515 3,63 11,388 0,33 0,114 9,129 0,194 <0.13 0,435 Sample 2 0,0858 0,190 0,0333 0,497 <0,007 0,302 1,267 3,63 11,340 0,34 0,119 8,833 0,176 <0.13 0,297 Sample 2 0,0851 0,180 0,0320 0,494 <0,007 0,299 1,354 3,61 11,419 0,31 0,101 8,772 0,189<0.13 0,370 Sample 2 0,085 0,182 0,0320 0,509 <0,007 0,313 3,61 11,475 0,35 0,106 8,677 0,191<0.13 0,331 Sample 2 0,085 0,185 0,033 0,498 0,305 1,379 3,620 11,405 0,329 0,110 8,853 0,188 0,358 mean 0,000 0,004 0,001 0,006 0,004 0,091 0,009 0,041 0,012 0,007 0,138 0,006 0,044 avedev 0,53 2,16 1,92 1,10 1,39 6,59 0,26 0,36 3,70 5,91 1,56 3,21 12,30 % Sample 3 0,605 3,59 0,129 1,39 <0,007 0,718 0,081 7,479 6,51 3,613 2,71 1,18 1,658 1,112 <0.13 0,665 Sample 3 0,615 3,60 0,131 1,43 <0,007 0,706 0,079 7,205 6,51 3,634 2,66 1,26 1,638 1,074 <0.13 0,603 Sample 3 0,609 3,51 0,126 1,40 <0,007 0,698 0,079 7,313 6,53 3,674 2,65 1,12 1,576 1,073<0.13 0,611 Sample 3 0,607 3,53 0,129 1,48 <0,007 0,733 0,080 6,51 3,667 2,58 1,15 1,560 1,063<0.13 0,596 Sample 3 0,609 3,558 0,129 1,425 0,714 0,080 7,332 6,514 3,647 2,648 1,177 1,608 1,081 0,619 mean 0,003 0,038 0,001 0,030 0,012 0,001 0,098 0,008 0,024 0,034 0,042 0,040 0,016 0,023 avedev 0,49 1,05 1,07 2,11 1,65 0,81 1,33 0,12 0,65 1,28 3,59 2,49 1,44 3,73 % Sample 4 2,45 3,93 0,759 3,23 0,0583 2,89 0,022 10,61 5,67 7,226 3,894 1,43 5,156 2,030 <0.13 2,960 Sample 4 2,49 3,94 0,778 3,25 0,0589 2,88 0,021 9,18 5,61 7,219 3,678 1,47 5,192 1,954 <0.13 2,760 Sample 4 2,43 3,89 0,751 3,24 0,0598 2,81 0,021 9,42 5,64 7,260 3,68 1,39 5,206 1,974<0.13 2,848 Sample 4 2,43 3,93 0,756 3,25 0,061 2,94 0,023 5,62 7,214 3,86 1,37 4,982 1,950<0.13 2,799 Sample 4 2,45 3,923 0,761 3,243 0,060 2,880 0,022 9,737 5,634 7,229 3,778 1,414 5,134 1,977 2,842 mean 0,020 0,016 0,008 0,007 0,001 0,035 0,000 0,582 0,020 0,015 0,099 0,034 0,076 0,026 0,062 avedev 0,82 0,41 1,12 0,23 1,51 1,22 2,15 5,98 0,35 0,21 2,62 2,40 1,48 1,34 2,20 % SYN 5 16,9 3,23 1,39 8,11 0,581 2,51 0,793 20,78 6,66 14,549 5,768 1,29 4,297 1, ,681 SYN 5 17,0 3,23 1,42 8,24 0,571 2,51 0,813 18,61 7,02 14,685 5,488 1,54 4,151 1,290 0,399 2,527 SYN 5 16,7 3,22 1,39 8,23 0,610 2,48 0,810 20,25 6,75 14,803 5,52 1,47 4,076 1,275 0,399 2,573 SYN 5 16,6 3,25 1,37 8,17 0,623 2,55 0,823 7,11 14,908 5,62 1,54 4,034 1,289 0,481 2,603 SYN 5 16,8 3,233 1,393 8,188 0,596 2,513 0,809 19,88 6,885 14,736 5,599 1,460 4,140 1,289 0,426 2,596 mean 0,150 0,009 0,014 0,048 0,020 0,019 0,008 0,847 0,180 0,119 0,095 0,086 0,085 0,007 0,036 0,046 avedev 0,89 0,27 0,99 0,58 3,40 0,75 1,02 4,26 2,61 0,81 1,70 5,88 2,04 0,55 8,55 1,77 % SYN 6 0,082 SYN 6 0,082 6,68 2,490 SYN 6 0,080 6,73 2,675 SYN 6 0,082 6,75 2,680 SYN 6 0,081 6,719 2,615 mean 0,001 0,029 0,083 avedev 0,98 0,43 3,19 %

6 Meeting of the heads of the Labs 19./20. September, Zadar (Croatia) Remarks for future ring tests Requalification reports on tables made by Alfred will help evaluation: Updated database will help with registering and invoicing: take care that all information (contact person, addresses etc.) is updated for your laboratory Feedback for the next ringtest is valuable: Type of samples, samples collected by participants Concentrations of parameters Possibility to analyze metals Timing of the ring test How much time is needed for doing the analyses Use always lab code in correspondence (in mail subject, file name etc.)

7 Participating labs: 40 percentage of labs which has not measured this parameter Percentage Alk N-NH4 Ca Cl Cond DOC Mg N-NO3 ph P-PO4 K Na S-SO4 TN Parameter

8 Labcod e Alk N-NH4 Ca Cl Cond DOC Mg N-NO3 ph P-PO4 K A A A A A A A D D D D D D D D D D D F F F F F F F

9 Percentage of accepted results for each parameter (only labs which have measured the parameter) Cl TN N-NO3 Cond Na N-NH4 Mg DOC K S-SO4 ph Alk Ca P-PO

10 Parameter without problems: Cl, Conductivity, Na, N-NO 3, N tot (90 96 % correct results) Parameter with problems at very low concentrations: Alkalinity, Ca, DOC, K, Mg, P-PO 4 Parameter with other problems: Alkalinity, N-NH 4, N-NO 3, ph, S-SO 4

11 problems with low concentrations: Parameter % passed Problematic samples problems comments % passed without problematic samples Alk 76 S4 low alkalinity (20) 16 of 34 labs wrong 87 Ca 70 S1 + 2 very low conc. (0,06/0,08) S1: 6 labs correct, S2: 18 labs correct 84 DOC 84 S1 low conc. (1,85) 9 of 34 labs wrong 89 K 84 S1 very low conc. (0,046) 20 of 39 labs wrong 94 Mg 85 S1 + 2 very low conc. (0,018/0,032) 94 P-PO4 49 S1-3 below quant. limit 66

12 other problems: Parameter % passed Problematic samples problems comments Alk S labs with measured results % passed without problematic samples N-NH4 87 S5 smelling /changes? 9 of 37 labs wrong 92 N-NO3 92 S5 smelling /changes? 5 of 39 labs wrong 95 ph 83 S3 + 5 ph higher than 6,5 S-SO4 83 S1 Interference org. compounds 20 of 39 labs wrong 88

13 Percentage of accepted results before and after elimination of problematic samples percentage Alk N-NH4 Ca Cl Cond DOC Mg N-NO3 ph P-PO4 K Na S-SO4 TN parameter

14 percentage acceptable results per lab F25 F08 F12 S03 D33 F27 A61 D39 D27 D35 F03 F07 F16 A49 F05 D47 F18 F32 F28 F23 F14 F15 F02 S25 A47 D69 F01 A60 D60 F06 A39 D05 D34 F04 A55 A83 F21 S01 D06 D68

15 Water ring tests nontolerable results (%) RT 2002 RT 2005 RT 2009 RT 2010 RT 2011 RT 2013 Cond ph Ca Mg Na K NH4 Cl SO4 NO3 TDN DOC Alk much better results for TDN and DOC! Northwest Forest Research Station

16 Water ring tests nontolerable results (%) RT 2002 RT 2005 RT 2009 RT 2010 RT 2011 RT2013 Cond ph Ca Mg Na K NH4 Cl SO4 NO3 TDN DOC Alk without low conc. samples

17 Thanks to Kirsti Derome and her team for preparing and organizing the ringtest and Alfred Fürst for the evaluation software and the data management!