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Volltext : 56: Usability of gas chromatography techniques (GC-FID, GC-MS and GC-IRMS) for identification of maritime paraffin wax

IRMS  data

25

C22  C23  C24  C25  C26  C27  C28  C29  C30  C31  C32  C33

Fig.  15:  d13C-means  of
sample  1,  10  from  IAEA  with
standard  deviation  as  error
margin.  IAEA  measured  in
triplicates  (n=3).

IAEA  performed  analysis  In  triplicates  and  used  a  more  elaborated  methodology ­
  compared  to  the  NFI,  with  following  steps  Involved:
•  Preparation  of  a  linear  chained  hydrocarbon  fraction  of  the  paraffin  wax  mixture ­

•  Reference  C0 2 ,  calibrated  against  PDB,  was  Introduced  five  times  at  the
beginning,  three  times  at  the  end  of  every  Isotopic  GC  determination.
•  Calibration  standards  of  n-alkanes  were  Introduced  every  4  samples.

For  the  duplicate  analysis,  the  results  of  both  laboratories  show  that  the  8 13 Ccontent
  of  each  Individual  n-alkane  Is  within  the  range  of  1  %o  (Fig.  15  and
Fig.  14).  In  case  of  IAEA’s  duplicate  analysis  (Fig.  15),  sample  10  shows  unstable ­
  13 C-contents  along  the  series  of  n-alkanes.  Especially  the  sudden  Increase
(<  1  per  mil)  from  C28  to  C29  does  not  correspond  to  the  average  composition
of  the  neighbouring  n-alkanes.

However,  there  was  an  outlier  In  the  NFI’s
duplicate  run  of  the  first  sample,  resulting  In
Increased  RSD  (repeatability)  and  very  low
matching-ratios  (<  10%  for  comparison  of
set  1  “1  on  2”  and  “1  on  3”  and  >59%  for  “1
on  10”).  This  was  very  obvious  even  without
the  application  of  any  statistical  test  (e.  g.
Grubbs,  etc.).  After  eliminating  the  outlier  by
Ignoring  the  whole  run  and  using  just  the
data  from  the  second  analysis  (Instead  of  the
mean,  only  values  from  the  second  run  were
considered,  n=1),  the  comparison  turned  out
to  be  very  well  In  accordance  (>  83%  for
comparison  of  set  1  “1  on  2”  and  “1  on  3”
and  100%  for  “1  on  10”).

IAEA

NFI

<1

<1

Set_l  1  on  2

100%

83%

1  on  3

100%

100%

2  on  3

100%

100%

Set_2  4  on  5

8%

31%

4  on  6

0%

8%

5  on  6

0%

0%

Set_3

Dup

7  on  8
7  on  9
8  on  9
Ion  10

92%
77%
85%

92%
92%
92%

83%

100%

Tab.  5:  IRMS-Conclusion  matrix
            
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