Table 2
Gas chromatography methods for determination of synthetic pyrethroid metabolites in human urine
Analytes (LOD
ng/mL; LOQ ng/mL);
DF
Sample volume (V),
hydrolysis (H), extraction
(E), cleanup (C),
instrument (I)
Extraction and cleanup details
Derivatization
Notice
Ref.
cis-DCCA
(0.2; 0.5);
DF, nd
trans-DCCA
(0.2;
0.5); DF, nd
DBCA (0.2; 0.5); DF,
nd
3PBA (0.3; 1.0); DF,
nd
4F3PBA (0.3; 1.0);
DF, nd
V: 5 mL
H: acidic (1 mL HCl; 1 h,
90
C)
E: LLE
C: LLE
I: GC-MS (quadrupole,
SIM)
LLE:
• 2
 4 mL hexane
• Evaporation
• 10% H
2 SO
4 in MeOH (v/v)
–
1 h
• Dilution with 10 mL water
and 15 mL 1 M NaOH
• Re-extraction: 3
 10 mL
hexane
• Drying with 2 g anhydr.
Na
2 SO
4
• Evaporation
– gentle stream
of nitrogen
• Reconstitution: 0.5 mL
iso-octane
51.5 mL of organic
solvents per sample
[3]
NCI-detection
trans-CDCA
(0.05;
nd); DF, 91%
cis-DCCA
(0.02; nd);
DF, 69%
trans-DCCA
(0.02;
nd); DF, 90%
DBCA (0.02; nd); DF,
nd
3PBA (0.01; nd); DF,
97%
4F3PBA (0.005; nd);
DF, nd
EI+ detection
trans-CDCA
(0.05;
V: 2 mL
H: acidic
E: LLE
C: No
I: GC-HRMS (NCI- or EI+
mode; SIM)
LLE:
• 4 mL MTBE
• Drying of organic layer
–
gentle stream of nitrogen
• Reconstitution: 250
μL ACN
• 30
μL HFIP, 20
μL DIC
–
10 min, RT
• Wash: 1 mL 1 M NaHCO
3
• Re-extraction to 250
μL isooctane (EI+ mode) or 2 mL isooctane (NCI- mode)
External Quality
Control: yes
Population: 30 persons, who applied
commercially available vaporizer plates
or sprays containing
pyrethrum (Germany)
[10]
(continued)
Analytical Methods for Determination Urinary Metabolites of Synthetic. . .
59
Gas chromatography methods for determination of synthetic pyrethroid metabolites in human urine
Analytes (LOD
ng/mL; LOQ ng/mL);
DF
Sample volume (V),
hydrolysis (H), extraction
(E), cleanup (C),
instrument (I)
Extraction and cleanup details
Derivatization
Notice
Ref.
cis-DCCA
(0.2; 0.5);
DF, nd
trans-DCCA
(0.2;
0.5); DF, nd
DBCA (0.2; 0.5); DF,
nd
3PBA (0.3; 1.0); DF,
nd
4F3PBA (0.3; 1.0);
DF, nd
V: 5 mL
H: acidic (1 mL HCl; 1 h,
90
C)
E: LLE
C: LLE
I: GC-MS (quadrupole,
SIM)
LLE:
• 2
 4 mL hexane
• Evaporation
• 10% H
2 SO
4 in MeOH (v/v)
–
1 h
• Dilution with 10 mL water
and 15 mL 1 M NaOH
• Re-extraction: 3
 10 mL
hexane
• Drying with 2 g anhydr.
Na
2 SO
4
• Evaporation
– gentle stream
of nitrogen
• Reconstitution: 0.5 mL
iso-octane
51.5 mL of organic
solvents per sample
[3]
NCI-detection
trans-CDCA
(0.05;
nd); DF, 91%
cis-DCCA
(0.02; nd);
DF, 69%
trans-DCCA
(0.02;
nd); DF, 90%
DBCA (0.02; nd); DF,
nd
3PBA (0.01; nd); DF,
97%
4F3PBA (0.005; nd);
DF, nd
EI+ detection
trans-CDCA
(0.05;
V: 2 mL
H: acidic
E: LLE
C: No
I: GC-HRMS (NCI- or EI+
mode; SIM)
LLE:
• 4 mL MTBE
• Drying of organic layer
–
gentle stream of nitrogen
• Reconstitution: 250
μL ACN
• 30
μL HFIP, 20
μL DIC
–
10 min, RT
• Wash: 1 mL 1 M NaHCO
3
• Re-extraction to 250
μL isooctane (EI+ mode) or 2 mL isooctane (NCI- mode)
External Quality
Control: yes
Population: 30 persons, who applied
commercially available vaporizer plates
or sprays containing
pyrethrum (Germany)
[10]
(continued)
Analytical Methods for Determination Urinary Metabolites of Synthetic. . .
59