Summary of laboratory means

Transcription

1 Ringversuch VOC 2011 Summary of laboratory means Sample sample 1 NBUAC Z score NHEPTAN Z score TOLUOL Z score PXYLOL Z score NDODECAN Z score TETRADEC Measurement unit 23,9 2,6 35,400 5,900 75,1 18,864 21,9 2,9 12,400-1,386 18,8 19,000 0,754 19,0 0,291 20,100 0,162 16,900 0,498 15,9 0,125 20,7 21,0 1,731 20,0 0,610 21,0 0,8 20,0 2,024 20,000 1,8 25,000 15,3-0,671 24,9 2,190 19,800 0,0 16,0 0,328 14,100-0,662 20,3 15,800-0,496 20,0 0,451 15,6-1,3 14,8-0,371 16,0 0,274 11,0 13,5-1,374 13,0-1,4 13,0-2,233 12,1-1,516 12,2-1,4 14,8 18,2 0,461,100 1,178 19,5-0,025 18,1 1,028 12,9-1,152 11,5 14,0-1,003 24,4 2,013 15,000-1,571 11,9-1,0 16,3 0,296 15,1 42,000 9,737,0 1,320 29,000 3, 35,0 8,383 24,000 3,553 28,0 18,5 0,578 19,5 0,273 23,8 1,436 16,8 0,477 17,6 0,849 20,100 13,0-1,472 11,0-2,549 7,100-4,255 11,800-1,664 16,700 0,5 7,0 1 18,775 0,666 19,535 0,2 20,895 0,432 18,2 1,062 17,020 0,581 18,880 11,0-2,136 10,7-2,851 6,0-4,526 9,5-2,618 10,9-2,004 12,8 20,400 1,1 21,900 1,107 21,1 0,519 14,800-0,392 17,200 0,658 21,400 16,1-0,359,0 9,059 29,0 3,355 14,100-0,9 12,9-1,152 14,7 13,0-1,3 21,000 0,788 26,000 2,166 12,0-1,367 6,0-3,899 8,0 8,0-3,347 11,000-2,762 19,0-0,042 19,0 1,0 16,000 0,147 24,000 19,000 0,754,000 1,143 62,0 14,566 12,0-1,367 10,0-2,195 13,0 20,400 1,1 25,700 2,456 24,0 1,589 19,000 1,388 18,1 1,062 20,000 21,0 1,770 19,0 0,156,710 3,766 28,520 5,424 17,805 0,915 20, 17,0 0,1 18,0-0,099 17,000-0,891 15,000-0,7 15,0-0,066 18,0 19,0 0,9 17,0-0,454 18,0-0,382 16,0 0,328 17,000 0,573 20,0 16,200-0,339 15,900-1,0 15,700-1,333 17,000 0,540 17,6 0,849 20,700 16,5-0,203 10,7-2,851 13,0-2, 14,900-0,3 17,200 0,658 17,700 Page 1

2 Ringversuch VOC NBUAC Z score NHEPTAN Z score TOLUOL Z score PXYLOL Z score NDODECAN Z score TETRADEC 18,0 0,559 20,000 0,433 19,000-0,212 16,0 0,328 17,0 0,785 21,000 Method Assessment Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 17,069 18,780 19,623 15,725 15,655 17,855 Reproducibility s.d. 3,599 4,731 4,737 3,298 2,755 4,497 Rel. reproducibility s.d. 21,08 % 25,19 % 24,14 % 20,97 % 17,59 % 25,19 % Reference value 18,0 17,0 16,900 16,000 16,0 20,900 Target s.d. 2,5 2,817 2,4 2,359 2,348 2,678 Rel. target s.d. 15,00 % 15,00 % 15,00 % 15,00 % 15,00 % 15,00 % Low er limit of tolerance 11,8 13,146 13,736 11,008 10,959 12,498 Upper limit of tolerance,190 24,414 25,510 20,3 20,352 23,211 Low er confidence limit 15,7 16,865 17,8 14,432 14,5 16,088 Upper confidence limit 18,1 20,695 21,559 17,019 16,706 19,621 Type B outliers Type outliers No. of laboratories w ith E outliers Intermed. s.d. Explanation of outlier types A: Single outlier B: Differing laboratory mean C: excessive laboratory s.d. D: Excluded manually E: score outside tolerance limits : Score >3,5 Z score BUETOH Z score TRIMEBEN Z score CAREN Z score DMCPS Z score Measurement unit 0,372 38,4 10,0 15,3 0,006 15,9-1, 29,4 5,419 Page 2

3 Ringversuch VOC Z score BUETOH Z score TRIMEBEN Z score CAREN Z score DMCPS Z score 1,081 19,5 1,840 16,4 0,484 24,6 1,678 19,0 1,254 2,6 18,0 1,383,000 2,896 25,0 1,966 19,0 1,336 0,932 13,0-0,749 16,2 0,397,2 0,866 17,8 0,659-2,335 12,3-1,293 12,8-1,081 17,5-0,725 18,800 1,049-1,1 12,200-1,358 11,0-1,755 16,400-1,115 13,0-1,085-2,354 31,3 6,974 16,5 0,527 20,2 0, 17,800 0,8-1,010 9,100-2,707 16,4 0,484 18,900-0,2 10,200-2,481 3,975 26,000 4,646 26,0 4,852 36,000 5,520 36,0 8,312 0,838 19,6 1,883 17,0 0,984 23,5 1,6 18,2 0,823-3,829 12,0-1,315 10,400-2,146 16,0-1,081 14,000-0, ,383 18,165 1, 15,775 0,190 20,475 0,265 17,280 0,425-1,869 18,9 1,579 10,4-2,124 12,7-2,3 11,1-2,091 1,324 16,200 0,382 17,1 0,788,100 0,815 18,0 0,741-1,159 15,200-0,053 11,0-1,624 16,3-1,132 12,5-1,516-3,493 11,0-1,6 11,0-1,6 15,000-1,589 9,0-2,7 2,295 6,0-3,838 20,0 2,2 20,000 0,104 36,0 8,312-1,626 8,0-2,9 12,0-1,233 13,000-2,266 13,000-1,332 0,801 14,400-0,401 17,4 0,918 27,1 2,524 21,2 2,054 0,866 49,810 15,006,0 3,113 20,855 0,393 20,510 1,7 0,241 7,000-3,621 14,0-0,364 16,0-1,081 15,000-0,511 0,988 17,000 0,7 15,0 0,071 20,0 0,273 18,000 0,720 1,062 18,6 1,8 17,3 0,5 21,900 0,747 17,200 0,392-0,058 18,0 1,296 14,700-0,277 23,5 1,6 17,0 0,556 1,174 17,000 0,7 15,000-0,147 21,000 0,2 17,000 0,310 Method Assessment Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 15,3 15,337 19,693 16,245 Reproducibility s.d. 3,612 3,285 3,918 3,628 Rel. reproducibility s.d. 23,57 % 21,42 % 19,89 %,33 % Reference value 16,900 16,0 20,900 18,0 Target s.d. 2,298 2,1 2,954 2,437 Page 3

4 Ringversuch VOC Z score BUETOH Z score TRIMEBEN Z score CAREN Z score DMCPS Z score Rel. target s.d. 15,00 % 15,00 % 15,00 % 15,00 % Low er limit of tolerance 10,725 10,736 13,785 11,372 Upper limit of tolerance 19,918 19,938 25,1 21,119 Low er confidence limit 13,697 14,041 18,118 14,818 Upper confidence limit 16,7 16,4 21,2 17,672 Type B outliers Type outliers No. of laboratories w ith E outliers Intermed. s.d. Explanation of outlier types A: Single outlier B: Differing laboratory mean C: excessive laboratory s.d. D: Excluded manually E: score outside tolerance limits : Score >3,5 Page 4

5 Ringversuch VOC Summary of laboratory means Sample sample 2 NBUAC Z score NHEPTAN Z score TOLUOL Z score PXYLOL Z score NDODECAN Z score TETRADEC Measurement unit 43,4 0,814 56,2 3,9 124,0 15,740 37,700 0,719 47,5 0,3,900 42,4 0,642 41,0 0,711 42,800 1,0 36,0 0,3 49,4 0,610 36,4 51,000 2,114,0 1,5 46,0 1,695 45,0 2,247 62,000 2,456 43,000 31,000-1,329 43,000 0,959 36,7-0,058 35,6 0,317 43,0-0,266 34,1 31,5-1, 36,7-0,149,2-1,7 28,0-1,084 45,8 0,080 18,4,7-1,372 29,400-1,453,000-1,272 28,0-1,084 37,200-1,193 25,0 36,9-0,5 36,9-0,114 32,6-0,795 32,1-0,3 41,8-0,9 26,400 34,400-0,7 46,4 1,571 33,2-0,6 29,4-0,897 24,2-3,098 12,800 56,0 3,061 32,000-0,992 36,0-0,103 47,000 2,541 48,000 0,396 34,0 39,3 0,108 38,700 0,197 35,900-0,211 34,900 0,,7 0,801 33,4 28,3-1,786 35,3-0,397 32,0-0,8 24,200-1,926 40,3-0,729,0 1 42,0 0,573 38,5 0,112 43,525 1,1 39,995 1,1 48,815 0,516 31, 26,100-2,173 23,700-2,464 19,000-3,2,800-2,200 34,200-1,4,200 45,000 1,081 47,0 1,757 45,5 1,524 33,5-0,0 55,7 1,537 38,000 36,900-0,314 42,800 0,924 41,2 0,751 32,200-0,359 39,700-0,825 26,100 29,0-1,588,0-1,258 31,000-1,092 26,000-1,573 31,0-2,032 17,000 16,0-3,826 20,0-3,031 36,0-0,103 38,0 0,5,0-0,119 37,000,0-1,415 29,000-1,524 53,000 2,864 25,0-1,671 27,000-2,6 23,000,8 1,055 47,9 1,837,700 1,372 39,4 1,062 53,700 1, 33,2,5 0,961 42,4 0,862 66,610 5,312,410 5,1 51,640 0,932 36,475 40,0 0,6 39,0 0,339 38,000 0,167 36,000 0,386 49,000 0,5 32,000 43,000 0,737 36,000-0,282 37,0 0,077 36,000 0,386 52,0 1,059 34,0 40,100 0, 35,700-0,335 37,0-0,004 35,700 0,327,5 0,772 34,6 36,2-0,425 25,200-2,197 28,0-1,542 32,400-0,320 49,5 0,624,2 Page 5

6 Ringversuch VOC NBUAC Z score NHEPTAN Z score TOLUOL Z score PXYLOL Z score NDODECAN Z score TETRADEC,0 0,995 42,000 0,782 40,000 0,526 38,0 0,5 53,0 1,206 34,0 Method Assessment Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 38,721 37,591 37,073 34,031 45,6,3 Reproducibility s.d. 7,649 8,8 7,693 6,409 9,435 6,724 Rel. reproducibility s.d. 19,75 % 23,49 % 20,75 % 18,83 % 20,82 % 21,95 % Reference value 40,000 35,900 35,0 33,0 51,400 35,200 Target s.d. 5,808 5,9 5,561 5,105 6,796 4,595 Rel. target s.d. 15,00 % 15,00 % 15,00 % 15,00 % 15,00 % 15,00 % Low er limit of tolerance 27,105 26,314 25,951 23,8 31,714 21,3 Upper limit of tolerance,337 48,8 48,195,240 58,898 39,8 Low er confidence limit 35,646 34,9 34,038 31,491 41,675 27,937 Upper confidence limit 41,796 40,953 40,107 36,571 48,938 33,328 Type B outliers Type outliers No. of laboratories w ith E outliers Intermed. s.d. Explanation of outlier types A: Single outlier B: Differing laboratory mean C: excessive laboratory s.d. D: Excluded manually E: score outside tolerance limits : Score >3,5 Z score BUETOH Z score TRIMEBEN Z score CAREN Z score DMCPS Z score Measurement unit 0,058 49,9 2,833 28,0-0,984 25,000-1,236 38,700 1,0 Page 6

7 Ringversuch VOC Z score BUETOH Z score TRIMEBEN Z score CAREN Z score DMCPS Z score 1,266 43,0 1,5 35,7 0,437 38,0 1,599 35,700 0,959 2,692 46,0 2,573 41,000 2,240 37,000 1,236 0,766 29,0-1,037 38,3 0,953 35,100 0,958 32,8 0,3-2,651 23,2-2,245 26,2-1,451 24,8-1,2 33,100 0,403-1,161 29,700-1,018 24,8-1,729 23,2-1,616 24,7-1,380-0,921 55,9 3,974 31,000-0,7,8 0,035 29,5-0,355-3,881 17,8-3,272 35,9 0,477 29,000-0,367 17,0-2,971 0,842 40,000 0,1 39,0 1,182 36,0 1,262 43,000 2,518 0,613 43,800 1,6 35,8 0,457 35,0 1,067 33,0 0,6-1,770 28,800-1, 21,1-2,464 26,0-0,953 29,7-0, ,114 39,740 0,891 35,315 0,3 31,085 0,086 31,980 0,164-1,835,000 1,701 23,0-1,997 19,000-2,539 19,8-2,427 1,3 42,8 1,483 38,800 1,043 36,6 1,295 37,0 1,365-0,986 32,0-0,486 26,7-1,351 25,0-1,105 25,6-1,188-2,967 26,000-1,7 27,000-1,2,000-1,888,0-1,861 1,386 13,000-4,1 41,0 1,579 32,000 0,285 66,0 7,538-1,661 28,000-1,342 27,0-1,202 20,0-2,213,0-1,861 0,570 33,1-0,362 37,1 0,715 42,700 2,9 41,400 2,176 1,272,0 4,756,5 2,2 34,340 0,793 36,845 1,203 0,298 17,000-3,434 34,000 0,089 26,000-1,019 29,000-0,472 0,842 48,0 2,557 32,0-0,209 33,000 0,2 33,0 0,489 0,4 41,9 1,311 38,400 0,9 33,1 0,535 32,200 0,211-0,083 37,700 0,3 31,7-0,358 34,200 0,7 29,5-0,355 0,842 38,0 0,655 36,000 0,486 31,0 0,176 31,0 0,062 Method Assessment Z <=2,000 Z <=2,000 Z <=2,000 Z <=2,000 35,054 33,552,9 31,211 Reproducibility s.d. 9,592 6,759 6,417 6,809 Rel. reproducibility s.d. 27,36 % 20,15 % 20,91 % 21,81 % Reference value 36,000 34,100 31,200 33,800 Target s.d. 5,258 5,033 4,3 4,2 Page 7

8 Ringversuch VOC Z score BUETOH Z score TRIMEBEN Z score CAREN Z score DMCPS Z score Rel. target s.d. 15,00 % 15,00 % 15,00 % 15,00 % Low er limit of tolerance 24,538 23,486 21,482 21,848 Upper limit of tolerance 45,571 43,617 39,896 40,575 Low er confidence limit,912,904 28, 28,517 Upper confidence limit 39,196 36,199 33,5 33,906 Type B outliers Type outliers No. of laboratories w ith E outliers Intermed. s.d. Explanation of outlier types A: Single outlier B: Differing laboratory mean C: excessive laboratory s.d. D: Excluded manually E: score outside tolerance limits : Score >3,5 Page 8

9 15,337 sample 1 3, ,00 34,00 32,00,00 28,00 26,00 24,00,00 20,00 18,00 16,00 14,00 12,00 10,00 8,00 1 Page 9

10 3-Carene sample 1 19,693 3, ,00,00 45,00 40,00 35,00,00 25,00 20,00 15,00 10,00 1 Page 10

11 16,245 sample 1 3,628 55,00,00 45,00 40,00 35,00,00 25,00 20,00 15,00 10,00 5,00 1 Page 11

12 15,3 sample 1 3, ,00 38,00 36,00 34,00 32,00,00 B 49,810 28,00 26,00 24,00,00 20,00 18,00 16,00 14,00 12,00 10,00 8,00 6,00 1 Page 12

13 n-butyl acetate sample 1 17,069 3, B Page 13

14 n-dodecane sample 1 15,655 2, ,00 34,00 32,00,00 28,00 26,00 24,00,00 20,00 18,00 16,00 14,00 12,00 10,00 8,00 6,00 1 Page 14

15 n-heptane sample 1 18,780 4, B,00 B 45,00 40,00 35,00,00 25,00 20,00 15,00 10,00 1 Page 15

16 p-xylene sample 1 15,725 3,298 23,00 28,00 26,00 24,00,00 B 35,0 20,00 18,00 16,00 14,00 12, ,00 8,00 Page 16

17 n-tetradecane sample 1 17,855 4, ,00 35,00,00 25,00 20,00 15,00 10,00 5,00 1 Page 17

18 Toluene sample 1 19,623 4,737 19,00 45,00 62,075,1 40,00 35,00,00 25,00 20,00 15,00 10,00 5,00 1 0,00 Page 18

19 Sample chart of Z scores Sample: sample 1 NBUAC NHEPTAN TOLUOL NDODECAN Measurand TETRADEC BUETOH TRIMEBEN CAREN DMCPS 1 2,6 9,737-2,549-2,136-2,851-3,347-2,762-2,851 5,900 2,190-2,233 2,013-4,255-4,526 9,059 2,456-2, 18,864 3, -2,618 3,355 2,166 14,566 3,766 2,9 2,024 8,383-2,004-3,899-2,195 5,424 2,6-2,335-2,354-2,707 3,553 3,975-3,829-3,493-3,838 2,295-2,9-3,621 10,0 2,896 6,974 4,646 4,852-2,146-2,124-2,3 2,2-2,266 15,006 3,113 5,419-2,481 5,520 8,312-2,091-2,7 8,312 2,524 2, Z score quo data Demo version Page 19

20 33,552 sample 2 6, ,00,00 48,00 46,00,00 42,00 40,00 38,00 36,00 34,00 32,00,00 28,00 26,00 24,00,00 20,00 1 Page 20

21 3-Carene sample 2,9 6, ,00 40,00 38,00 36,00 34,00 32,00,00 28,00 26,00 24,00,00 20,00 1 Page 21

22 31,211 sample 2 6,809 24,00 48,00 46,00 66,0,00 42,00 40,00 38,00 36,00 34,00 32,00,00 28,00 26,00 24,00,00 20,00 18,00 16,00 14,00 1 Page

23 35,054 sample 2 9,592 21,00 55,00,00 45,00 40,00 35,00,00 25,00 20,00 15,00 1 Page 23

24 n-butyl acetate sample 2 38,721 7, ,00,00 45,00 40,00 35,00,00 25,00 20,00 1 Page 24

25 n-dodecane sample 2 45,6 9,435 25,00 55,00,00 45,00 40,00 35,00,00 25,00 20,00 15,00 10,00 1 Page 25

26 n-heptane sample 2 37,591 8,8 25,00 55,00,00 45,00 40,00 35,00,00 25,00 20,00 1 Page 26

27 n-tetradecane sample 2,3 6,724 24,00 42,00 40,00 38,00 36,00 34,00 32,00,00 28,00 26,00 24,00,00 20,00 18,00 16,00 14,00 12,00 10,00 8,00 1 Page 27

28 p-xylene sample 2 34,031 6, B,00 58,00 56,00 54,00 52,00,00 48,00 46,00,00 42,00 40,00 38,00 36,00 34,00 32,00,00 28,00 26,00 24,00,00 1 Page 28

29 Toluene sample 2 37,073 7, ,00 85,00 80,00 124,0 75,00 70,00 B 65,00,00 55,00,00 45,00 40,00 35,00,00 25, ,000 20,00 Page 29

30 Sample chart of Z scores Sample: sample 2 NBUAC NHEPTAN TOLUOL NDODECAN Measurand TETRADEC BUETOH TRIMEBEN CAREN DMCPS 1 2,114 3,061-2,173-2,464-3,826-3,031-2,197 3,9 15,740 2,247 2,456-2,651 2,692-2,245-3,098-3,881-3,272 2,541-3,2-2,200-2,032-2,967-4,1-2,6 2,864 5,312 5,1-3,434 2,833 3,974-2,464 4,756 2,557 2,573 2,240-2,971 2,518-2,539-2,427-2,213 7,538 2,9 2,176 2, Z score Page

31 Ringversuch VOC Questions and Answers Participant thermodesorber Tenax TA ISO TENAX TA ISO PE Turbomatrix 3 TENAX TA ISO MARKES UNITY 2 Tenax TA - Carbiograph 5 TD ISO Markes UNITY2-/ Tenax TA ja Shimadzu TD 20 Tenax TA Nein Turbomatrix ATD von PerkinElmer Tenax TA ISO TDS2 (Gerstel) Tenax Ja Gerstel TDSA Tenax TA ja Perkin Elmer TurboMatrix 6 Tenax TA gemäß ISO Perkin ElmerTurboMatrix automatischer Thermodesorber 1 Tenax TA Ja Turbo Matrix 6 Tenax TA EN ISO TurboMatrix 3 Gerstel Tenax TA Adsorber ja Gerstel TDS-2 mit Gerstel TDS A und KAS-4 TenaxTA Ja TDS2 a. Gerstel Tenax TA ja Turbo Matrix 6 Tenax TA Perkin Elmer ATD Turbo Matrix 6 Tenax TA ja Gerstel TDS A tenax atd400 perkin elmer Tenax TA -80 mesh ISO STD DANI 33. TENAX TA ISO/DIS T-Dex II(GL Sciences Inc.) Tenax Ja ATD 400 Tenax TA GC-MS-Thermosdesorption Perkin Elmer TurboMatrix 6 Tenax TA Nein Turbomatrix TENAX TA Nein, Interne Methode SOP-B-25 MARKES ULTRA + UNITY Page 31

32 Ringversuch VOC Participant desorption temperature desorption flow desorption time Tube 280 C; Trap 0 C C ml/min 15 min 280degree ml/min 5min C ml/min 10 min 340 C ml/min 20 min 2 C 13,4 ml/min 25 to 2 C in 11,75 min, 5 min hold time at 2 C 2 C ml / min C / Min. von 40 C bis 2 C, 5 Minuten bei 2 C 280 C C 80 cm3/min 15 min C ml/min 12 min 10 C 0,5min 40 C/min 310 C 8min ml/min Helium ECD 10 C 0,5min 40 C/min 310 C 8min 280 C 100 ml/min 5 Min bis 280 C C ml/min 10 min bis 280 C 1,2 ca. 14 min 2 C 15 2ºC 10 ml/min 10 min 2 degrees 90 ml/min 10min C ml/min 5Min 0 C ml/ min 10 min 280 C ml/min 15min. Participant cyro trap carrier gas flow rate -3 C general purpose hydrophobic trap (C4/5 bis C/32) Stickstoff 0,5-0,6 - C Helium 2 ml/min -degree to 290degree helium C C, max He -10 / 315 Helium 1,5-15 C Helium 1,88 ml/min Page 32

33 Ringversuch VOC Participant cyro trap carrier gas flow rate Helium 15 ml/min helium 1 ml/min He 1.5 ml/min Helium 1,5 Helium 1 Helium 1,8 helium 1,0 ml/min Helium Qualität ECD 1ml/min const low -100 C/280 C Helium 1 ml/min - C/bis 280 C Helium 2 - C C Helium 1,5 ml/min -1 C/bis 280 C Helium 1,2 - C / 280 C azote cryo temperature = -35ºC, heating temperature=0ºc helium 0.8 ml/min Cryo trap at -1 degrees and desorb at +310 degrees helium 2.3ml/min - Helium 1,2 - C Helium 1.2ml/min minus C Helium 0,5 ml/ min -10 C Helium 1.5 ml/min Participant analytical column detector HP1-MSUI Agilent 5973 Inert (Massenselektiver Detektor) Rxi-5ms (Restek) mm x 0.32 mm x 25 µm Mas spectrometer (MSD) : flame ionization (ID) DB-5MS m GC-MS Rxi-5sil MS Agilent 5975C inert XL MSD Restek semi-volatile ( * 0.25mm * 0.) MS Phenomenex ZB 5-MS, m, 0,25 mm ID, 0,25 µm D Shimadzu GC-MS QP 2010 Vocol von Supelco MS HP-1MS, m 0,25 mm ID, 0,25 µm film thickness quadrupool MS Agilent 5973N J&W G, DB-5ms MS RTX-200 MSD Rtx-5HS (m x 0,25mm x 0,5 µm) MS Page 33

34 Ringversuch VOC Participant analytical column detector 1 CPSil 8CB m MS Optima 5MS 0,25mm MS Clarus 0 Agilent HP 5 ms min X0,25mm x 0,5µm Agilent MSD 5973 DB-5MS m X 0,25 mm ID1µm DB-5MS ( m x 0,25 µm x 0,25 mm) 5975 C Agilent Rxi - % Sil MS m ; 2µm ; 1,0µm MSD DB-5MS ( m x 0,200 mm x 0,33 µm) GC-MS 5973 Agilent m*0,25mm*1µm DB5 ID + MS HP5 ( m, 0.2 mm, 0. um) MSD 5972 HP-VOC(m, 0.32mm, I.D. 1.8um) MSD DB 5 MS Rtx Volatile m (ID 0,25mm; D 1µm) von Restek Massenspektrometer Varian Saturn 00 Varian V Xms m, 0.25 mm i.d., 0.5 µm ilm MS HP INNOWAX m x 0.32mm x 0.5µm MSD Participant data evaluation substanzspezifisch mit interner Standard Toluol D8 und Targetionen, aber auch TIC - je nach Bedarf/Überlagerung: 1,2,3-TMB substanzähnlich über 1,3,5-TMB, Toluol über Cyclodekan; Identifizierung über Vergleich Retentionszeit Referenzsubstanz (Kalibrierreihe) und Spektrenbibliothek WILEY275 identification by MSD / quantification by ID internal standard method External calibration Proben im TIC, Proben im SIM Ext. Std., 3-Punkt-Kalibration. Identifizierung mittels MS. quantification using 5 point calibration curves of all target compounds (EIC) Kalibrierung mit Standards, Softew are: Agilent Masshunter externer Standard, quadratischer it IS Toluol D8 1 Kalibrierung aller Komponenten per Kalibrierkurven mit internem Standard external standards, library searching substanzspezifisch externe Kalibrierung ident. über externe Standards, quant. über relative Responsefaktoren, interner Standard Toluen D8 Page 34

35 Ringversuch VOC Participant data evaluation ident. über externe Standars, quant. über relative Responsefaktoren, interner Standard Toluene D identification by MSD and confirmed by standard injection for all the compounds; calibration curve w ith 5 levels of concentration 2-Butoxyethanol w as calculated by using toluene(tic) response factor,and others w ere calculated by using their individual response factor. EIC Originalreferenz, eigene und kommerzielle Bibliotheken Identifizierung: Retentionszeit + substanzspezif. Massen/ Quantifizierung: mittels interner Standardmethode über hinterlegte Mehrpunktkalibrieung TIC und SIR - Mode mit internem Standard Quantifizierung mittels spezifischen Massenfragmenten, Indentifizierung mittels Bibliothek NIST05 Participant date of analysis June 2011, 7th and 9th 2011/7/ /07/2011 Proben am.06., Proben am /06/ / June Jun 2011 Page 35

36 Ringversuch VOC Participant date of analysis Page 36

37 TNN 3- Carene n-butyl acetate p-xylene Toluene n-heptane Dodecane blank value correction y/n DMCS <1 <1 <1 5,9 5,6 69,2 <1 5,5 10,5 14,3 n <1 <1 <1 <1 <1 <1 <1 <1 <1 8 n 1,0 <1 <1 <1 <1 <1 <1 <1 <1 <1 n <1 <1 <1 1,9 3,6 5,3 7,6 1,3 4,0 6,1 n <3 <3 <3 <3 <3 4,0 <3 <3 <3 <3 n 0,42 0,0 0,0 0,0 0,42 0, 0,0 0,0 0,40 0,86 n 0,0 7,4 0,0 0,0 0,0 1,8 2,9 0,0 0,0 4,8 n 0,3 0,2 0,3 0,2 y 0, 0,0 0,0 0,0 0,10 108,0 0, 0, 1,10 0,90 y n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. <5 <5 <5 <5 <5 8,0 5,4 <5 6,7 6,3 y/n 1 1,8 0,92 1,11 1,55 2,98 4,5 2,9 3,79 3,8 2,1 n 0,3 0,2 0 0, ,2 0,1 0,2 0 n 2,0 2,3 n 1,4 5 19,6 y 1,0 2 2,0 20 6,0 1,0 n n 1,0 5 1,0 32 4,0 1,0 1,0 1,0 n 2 2,2 n 0,0 7,8 0,0 6,1 <1 1,8 0,0 1,7 1,8 5,2 y/n <1 <1 <1 <1 <1 <1 <1 <1 <1 <1 n n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. 0,59 0, 0,46 0,48 0,54 0,19 0,39 0,18 y/n n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. 1,0 0 0,0 1 0,0 1 1,0 1,0 1,0 1,0 n IA n 3- Carene Blank values RRT VOC 2011 blank value adjustment 1 () blank value adjustment2 () n-butyl acetate p-xylene Toluene n-heptane Dodecane 1,2,3- Trimethylbenzene 2-Butoxyethanol n-tetradecane 1,2,3- Trimethylbenzene 2-Butoxyethanol n-tetradecane TNN DMCS <1 <1 <1 7,1 5,7 75,3 <1 <1 8,7 13,5 n <1 <1 <1 <1 1,1 1,1 <1 <1 <1 <1 n <1 <1 <1 <1 <1 <1 <1 <1 <1 <1 n <1 <1 <1 <1 1,8 2,2 2,4 <1 3,2 3,6 n <3 <3 <3 <3 <3 <3 <3 <3 <3 <3 n 0,66 0,0 0,0 0,0 0,54 0,53 0,0 0,0 0,25 0,83 n 0,0 1,1 0,0 0,0 3,0 1,1 2,2 0,0 0,0 0,0 n 0,4 0,6 0,3 0,9 1,4 0,2 y 0,7 0,2 0,00 0,0 0,7 1, 0,10 0,2 0,7 0,6 y n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 n 1 1, 1, 0,99 2,39 2,65 4,23 3,06 3,14 3, 1,71 n 0, , ,2 0,1 0,2 0,0 n 4 2,6 n 1,4 5,9 24,4 y 1,0 1,0 20,0 4,0 1,0 n n 1,0 9,0 2,0 86,0 10,0 1,0 1 1,0 n 1,1 4,0 4,8 2,0 n 0,0 8 0,0 5,2 0,0 2,2 0,0 1,7 0 6,6 y/n <1 <1 <1 <1 <1 <1 <1 <1 <1 <1 n n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. 0,41 0,38 0,29 0,26 0,29 0,15 0,25 0,19 y/n n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. n.c. 1,0 2 0,0 1,0 0,0 1,0 3,0 0,0 1 1,0 n IA n Page 37