Table 3
Liquid 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
Notice
Ref.
cis-DCCA
(0.5;
nd); DF, 36%
trans-DCCA
(0.5;
nd); DF, 50%
DBCA (0.2; nd);
DF, 3.2%
3PBA (0.1; nd);
DF, 64%
4F3PBA (0.3; nd);
DF, 8.6%
V: 5 mL
H: enzymatic
E: SPE (waters Oasis HLB 6 cc)
I: HPLC-MS/MS (triple quadrupole, negative mode)
SPE:
• Conditioning: 4 mL MeOH, 4 mL
water
• Sample
• Washing: 2 mL 5% MeOH
• Elution: 2 mL MeOH
• Evaporation (TurboVap)
• Reconstitution: 50
μL ACN
• Evaporation
• Reconstitution: 7
μL ACN
• Population: half the cohort was
suspected to have residential exposure
(n
¼ 217), USA
[29]
3PBA (15; 50);
DF, nd
4OH3PBA (15;
50); DF, nd
V: 1 mL
H: acidic (0.2 mL HCl; 90 min,
95
C)
E: HF-LPME
I: HPLC-DAD
HF-LPME
• +100 mg NaCl
• Extraction (solvent dihexyl ether)
120 min
• Desorption: 0.1 mL 0.1 M NaOH
120 min
• Hollow-fiber microextraction
[12]
cis-DCCA
(0.4;
nd); DF, 14.5%
trans-DCCA
(0.4;
nd); DF, 16.4%
DBCA (0.4; nd);
DF, nd
3PBA (0.03; nd);
DF, 52.7%
4F3PBA (0.03;
nd); DF, 5.5%
V: 1 mL
H: enzymatic
E: automated SPE (OASIS HLB
96-well 30 mg, Waters)
I: HPLC-MS/MS (quadrupole,
negative mode)
SPE:
• Conditioning: 0.5 mL acetone,
0.5 mL 1% acetic acid
• Sample
• Washing: 25% MeOH in 1% acetic
acid
• Drying (TurboVap under stream of
nitrogen)
• Elution: 2
 325
μL acetone
• Evaporation
• Reconstitution: 10
μL internal standard (3-chloro-2-phenoxybenzoic acid)
and 110
μL 25% MeOH in water
• 96-well plate SPE
• External quality control: G-EQUAS
• Population: diverse group of male and
female adult volunteers with no
documented occupational exposure to the
target pesticides or their precursors
(n
¼ 55), USA
[16]
68
B. Wielgomas et al.
Liquid 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
Notice
Ref.
cis-DCCA
(0.5;
nd); DF, 36%
trans-DCCA
(0.5;
nd); DF, 50%
DBCA (0.2; nd);
DF, 3.2%
3PBA (0.1; nd);
DF, 64%
4F3PBA (0.3; nd);
DF, 8.6%
V: 5 mL
H: enzymatic
E: SPE (waters Oasis HLB 6 cc)
I: HPLC-MS/MS (triple quadrupole, negative mode)
SPE:
• Conditioning: 4 mL MeOH, 4 mL
water
• Sample
• Washing: 2 mL 5% MeOH
• Elution: 2 mL MeOH
• Evaporation (TurboVap)
• Reconstitution: 50
μL ACN
• Evaporation
• Reconstitution: 7
μL ACN
• Population: half the cohort was
suspected to have residential exposure
(n
¼ 217), USA
[29]
3PBA (15; 50);
DF, nd
4OH3PBA (15;
50); DF, nd
V: 1 mL
H: acidic (0.2 mL HCl; 90 min,
95
C)
E: HF-LPME
I: HPLC-DAD
HF-LPME
• +100 mg NaCl
• Extraction (solvent dihexyl ether)
120 min
• Desorption: 0.1 mL 0.1 M NaOH
120 min
• Hollow-fiber microextraction
[12]
cis-DCCA
(0.4;
nd); DF, 14.5%
trans-DCCA
(0.4;
nd); DF, 16.4%
DBCA (0.4; nd);
DF, nd
3PBA (0.03; nd);
DF, 52.7%
4F3PBA (0.03;
nd); DF, 5.5%
V: 1 mL
H: enzymatic
E: automated SPE (OASIS HLB
96-well 30 mg, Waters)
I: HPLC-MS/MS (quadrupole,
negative mode)
SPE:
• Conditioning: 0.5 mL acetone,
0.5 mL 1% acetic acid
• Sample
• Washing: 25% MeOH in 1% acetic
acid
• Drying (TurboVap under stream of
nitrogen)
• Elution: 2
 325
μL acetone
• Evaporation
• Reconstitution: 10
μL internal standard (3-chloro-2-phenoxybenzoic acid)
and 110
μL 25% MeOH in water
• 96-well plate SPE
• External quality control: G-EQUAS
• Population: diverse group of male and
female adult volunteers with no
documented occupational exposure to the
target pesticides or their precursors
(n
¼ 55), USA
[16]
68
B. Wielgomas et al.