3PBA (nd; 0.01); DF,
100%
ClF
3 CA (nd; 0.01);
DF, 90%
CPBA (nd; 0.01); DF,
40%
MPA (nd; 0,01); DF,
5%
cis-DCCA
(0.05
μg L
À1
); DF,
52%
trans-DCCA
(0.05
μg L
À1
); DF,
72%
DBCA (0.05
μg L
À1
);
DF, 13%
3PBA (0.05
μg L
À1
);
DF, 70%
4F3PBA
(0.05
μg L
À1
); DF,
4%
V: 10 mL
H: acidic (1 mL HCl; 1 h,
90
C)
E: LLE
C: LLE
I: GC-MS (quadrupole, EI,
SIM)
LLE
• Extraction: 2
 5 mL hexane
• Organic phase + 2 mL 0.1 N
NaOH
• Aqueous phase + 0.1 mL
conc. HCl + 2 mL hexane
• Drying organic phase (vacuum centrifuge)
• Dissolution: 50
μL toluene
10
μL MTBSTFA
• 70
C, 45 min
• External quality
control: yes
• Population: group
without known exposure to pyrethroids
(n
¼ 26 females,
20 males) Germany
[11]
cis-DCCA
(0.006;
0.020); DF, nd
trans-DCCA
(0.005;
0.017); DF, nd
DBCA (0.019;
0.062); DF, nd
3PBA (0.003; 0.010);
DF, nd
CPBA (0.002; 0.007);
DF, nd
V: 3 mL
H: acidic (0.5 mL H
2 SO
4 ;
1 h, 90
C)
E: SPE (C18 Sep-Pak,
500 mg, waters)
C: LLE
I: GC-MS/MS (ion trap)
SPE:
• Conditioning: 7.5 mL MeOH,
5 mL water
• Sample
• 6 mL water
• Drying
• Elution: 10 mL acetone
• Evaporation
Cleanup:
• Residue dissolution in 2 mL
• 10
μL HFIP, 15
μL DIIC
–
3 min, RT
• Wash: 1 mL 5% K
2 CO
3
• High usage of
organic solvents:
about 35 mL
• Population: six
occupationally
exposed, two
non-exposed occupationally, Spain
[7]
(continued)
Analytical Methods for Determination Urinary Metabolites of Synthetic. . .
63