36
Oil Spill identification - Round Robin 20045
Table 3.
Normalizing the peak heights on peak
4-M-pyrane (e) of mass 216 (LVA)
Fig 12
Ratio plot of Cedre including error bars
showing a 95% interval calculated
from
Another example is the ratio calculation of LVA shown in Table 3. The
table highlights the difference in ratio between B(a)F/ 4-methylpyrene
for Source II.
Ratio
EXTR I
EXTR II
Source I
Source II
a/e
0.23
0.23
0.25
0.16
b/e
1.0
0.94
0.93
0.36
c/e
0.19
0.16
0.16
0.1
d/e
0.79
0.76
0.8
0.72
f/e
0.73
0.70
0.75
0.60
Such tables show differences, but what is acceptable is still a personal
decision.
In the CEN guideline it is defined that differences caused by the
analytical method may not lead to the conclusion that samples are
different:
positive match
differences in chromatographic patterns and diagnostic ratios of the samples
submitted for comparison are lower than the analytical variance of the method
or can clearly be explained by weathering. The samples are identical beyond
reasonable doubt
Several labs have used numerical limitations to estimate the acceptable
difference.
70
60
50
40
30
20
10
0
Figure 5 Aromatics distribution of 4 samples (in/z = 216 and 234) (error bars represent 95%
confidence level intervals, N=3)
m Source I ■ Source II □ Extract I □ Extract II
B(a)F/4-Mpy B(b+c)F/4-Mpy 2-Mpy/4-Mpy 1-Mpy/4-Mpy Retene/C4-Phe
Fig 12 shows a bar graph of Cedre with error bars:
The analyses were run in triplicates for each sample, and error bars
considering 95% confidence level intervals were plotted on the histogram.
In the report of Cedre also graphs with a 95% and 98% confidence are
shown and used to estimate, whether differences are significant or not.