Duration
Retention
Precursor
Quantifier
Qualifier
Ion
Collision
Segment
(min)
PAH and IS Time (min)
Ion
Ion (
m/z
)
Ion (
m/z
)
Ratio
Energy (V)
1
10.50
Naph
8.65
127.9
102.0
77.8
0.38
15
2
2.50
Acy
12.12
152.0
151.1
126.0
0.11
10
Ace
12.34
154.0
153.0
152.0
0.12
10
3
1.50
Fln
13.36
165.9
165.0
162.9
0.03
10
4
3.00
Ant
15.84
178.0
176.0
152.0
0.70
30
Ant-D10
15.86
188.1
160.2
158.2
0.38
30
Phe
15.91
178.0
176.0
152.0
0.65
30
5
4.50
Flu
19.08
202.0
201.1
200.1
0.18
10
Pyr
19.93
202.0
201.0
200.1
0.17
10
6
3.70
B(a)A
23.47
228.1
226.0
202.1
0.15
20
Chr-D12
23.62
240.2
238.1
215.1
0.11
30
Chr
23.70
228.1
226.2
202.2
0.15
20
5MChr
24.94
242.1
241.1
227.5
0.15
30
7
3.80
B(b)F
26.72
252.1
250.1
226.1
0.18
30
B(k)F
26.80
252.1
250.1
226.1
0.18
30
B(a)P-D12
27.85
264.1
260.1
236.0
0.38
30
B(a)P
27.93
252.1
250.1
226.1
0.18
30
8
5.50
I(1,2,3-c,d)P
30.91
276.1
274.0
250.0
0.05
35
D(a,h)A
30.93
278.0
276.0
226.1
0.05
35
B(g,h,i)P-D12
31.84
288.2
286.1
125.1
0.06
35
B(g,h.i)P
31.95
276.1
274.0
250.0
0.05
35
Table 1: Parameters for SRM analysis of PAHs grouped according to Figure 1
PAH
Assigned Value [ng/g]
Measured Value [ng/g]
Recovery [%]
B(a)A
28.12
30.20
107
B(a)P
11.05
12.40
112
I(1,2,3-c,d)P
1.71
1.40
82
B(g,h,i)P
17.07
17.40
102
Table 3: Analysis of spiked fish with NIST 1582 crude oil (values given in
ng/g, n=4)
Assigned
Satisfactory
Measured
PAH
Value [ng/g]
Range
Value [ng/g]
Recovery [%]
B(a)A
6.35
3.56 - 9.14
6.43
101
B (b)F
1.31
0.73 - 1.89
1.26
96
B (a)P
3.41
1.91 - 4.90
3.32
97
I (1,2,3-cd)P
2.53
1.42 - 3.64
2.38
94
B (g,h,i)P
4.37
2.45 - 6.30
5.11
116
Table 2: Analysis of FAPAS
®
smoked fish T0642 proficiency test material
(values given in ng/g, n=4)
Page 5 of 8
13.3 Limits of Detection
The limits of detection in fish were found to be in the
range 1-7 ng/g depending on the individual PAH.
13.4 Accuracy
Accuracy was demonstrated by analysis of a smoked fish
proficiency test material (FAPAS
®
T0642) which had
assigned values for the significant PAHs. After following
the full extraction and cleanup procedure, the FAPAS
®
sample was analyzed by GC-MS/MS and the results are
shown in Table 2. Average recoveries of (B(a)A, B(a)F,
B(a)P, I(1,2,3-c,d)P and B(g,h,i)P were 101, 96, 97, 116
and 94 % respectively. The accuracy of this method for
these critical PAHs in fish was thus demonstrated.
Accuracy was demonstrated by analysis of blank fish
spiked with a solution of NIST crude oil containing certi-
fied levels of PAHs. After following the full extraction and
cleanup procedure, samples were analyzed by GC-MS/MS
and the results are shown in Table 3. Average recoveries
of (B(a)A,, B(a)P, I(1,2,3-c,d)P and B(g,h,i)P were 107,
112, 82 and 112 % respectively. The accuracy of this
method for determining these critical PAHs in fish in the
presence of crude oil was thus demonstrated.
