procedure for LC-MS analysis and the use of very advanced mass spectrometers,
GC-MS-based methods are still the most sensitive methods available.
Despite the availability of numerous modern and miniaturized techniques of
extraction and purification of samples before instrumental analysis, in principle the
only valid techniques remain classical extraction techniques: liquid-liquid and solidphase extraction. The latter can be performed automatically by robotic systems both
in the format of cartridges and 96-well plates. Automation increases the precision of
determinations but also significantly reduces the labor cost, which is of great
importance in population studies with hundreds or thousands of samples.
Analytical methods are also being developed for the metabolite determination
of new pyrethroids and those less frequently used or hitherto not covered by
biomonitoring. The problem is the commercial availability of reference substances
and relevant isotopically labeled internal standards.
A very important tool that facilitates the achievement of reliable results by
analytical laboratories is the availability of interlaboratory comparison programs.
This type of harmonization of analytical methods makes it possible to compare the
results of human biomonitoring studies carried out in different countries by various
laboratories.
References
1. Kaneko H (2011) Pyrethroids: mammalian metabolism and toxicity. J Agric Food Chem
59:2786–2791. https://doi.org/10.1021/jf102567z
2. Krieger RI, Doull J, Vega H (2010) Hayes’ handbook of pesticide toxicology, vol 1. Elsevier,
Amsterdam. https://books.google.pl/books/about/Hayes_Handbook_of_Pesticide_Toxicology.
html?id¼sUrLT9z9i3IC&redir_esc¼y. Accessed 29 May 2019
3. Kühn K-H, Leng G, Bucholski KA, Dunemann L, Idel H (1996) Determination of pyrethroid
metabolites in human urine by capillary gas chromatography-mass spectrometry.
Chromatographia 43:285–292. https://doi.org/10.1007/BF02270996
4. Leng G, Kühn KH, Idel H (1997) Biological monitoring of pyrethroids in blood and pyrethroid
metabolites in urine: applications and limitations. Sci Total Environ 199:173–181. https://doi.
org/10.1016/S0048-9697(97)05493-4
5. Aprea C, Stridori A, Sciarra G (1997) Analytical method for the determination of urinary
3-phenoxybenzoic acid in subjects occupationally exposed to pyrethroid insecticides.
J Chromatogr B Biomed Sci Appl 695:227–236. https://doi.org/10.1016/S0378-4347(97)
00190-4
6. Angerer J, Ritter A (1997) Determination of metabolites of pyrethroids in human urine using
solid-phase extraction and gas chromatography–mass spectrometry. J Chromatogr B Biomed
Sci Appl 695:217–226. https://doi.org/10.1016/S0378-4347(97)00174-6
7. Arrebola F, Martı́ nez-Vidal J, Fernández-Gutiérrez A, Akhtar M (1999) Monitoring of pyrethroid metabolites in human urine using solid-phase extraction followed by gas
chromatography-tandem mass spectrometry. Anal Chim Acta 401:45–54. https://doi.org/10.
1016/S0003-2670(99)00519-X
8. Ueda Y, Oda M, Saito I, Hamada R, Kondo T, Kamijima M, Ueyama J (2018) A sensitive and
efficient procedure for the high-throughput determination of nine urinary metabolites of pyrethroids by GC-MS/MS and its application in a sample of Japanese children. Anal Bioanal Chem
410:6207–6217. https://doi.org/10.1007/s00216-018-1229-x
Analytical Methods for Determination Urinary Metabolites of Synthetic. . .
77
GC-MS-based methods are still the most sensitive methods available.
Despite the availability of numerous modern and miniaturized techniques of
extraction and purification of samples before instrumental analysis, in principle the
only valid techniques remain classical extraction techniques: liquid-liquid and solidphase extraction. The latter can be performed automatically by robotic systems both
in the format of cartridges and 96-well plates. Automation increases the precision of
determinations but also significantly reduces the labor cost, which is of great
importance in population studies with hundreds or thousands of samples.
Analytical methods are also being developed for the metabolite determination
of new pyrethroids and those less frequently used or hitherto not covered by
biomonitoring. The problem is the commercial availability of reference substances
and relevant isotopically labeled internal standards.
A very important tool that facilitates the achievement of reliable results by
analytical laboratories is the availability of interlaboratory comparison programs.
This type of harmonization of analytical methods makes it possible to compare the
results of human biomonitoring studies carried out in different countries by various
laboratories.
References
1. Kaneko H (2011) Pyrethroids: mammalian metabolism and toxicity. J Agric Food Chem
59:2786–2791. https://doi.org/10.1021/jf102567z
2. Krieger RI, Doull J, Vega H (2010) Hayes’ handbook of pesticide toxicology, vol 1. Elsevier,
Amsterdam. https://books.google.pl/books/about/Hayes_Handbook_of_Pesticide_Toxicology.
html?id¼sUrLT9z9i3IC&redir_esc¼y. Accessed 29 May 2019
3. Kühn K-H, Leng G, Bucholski KA, Dunemann L, Idel H (1996) Determination of pyrethroid
metabolites in human urine by capillary gas chromatography-mass spectrometry.
Chromatographia 43:285–292. https://doi.org/10.1007/BF02270996
4. Leng G, Kühn KH, Idel H (1997) Biological monitoring of pyrethroids in blood and pyrethroid
metabolites in urine: applications and limitations. Sci Total Environ 199:173–181. https://doi.
org/10.1016/S0048-9697(97)05493-4
5. Aprea C, Stridori A, Sciarra G (1997) Analytical method for the determination of urinary
3-phenoxybenzoic acid in subjects occupationally exposed to pyrethroid insecticides.
J Chromatogr B Biomed Sci Appl 695:227–236. https://doi.org/10.1016/S0378-4347(97)
00190-4
6. Angerer J, Ritter A (1997) Determination of metabolites of pyrethroids in human urine using
solid-phase extraction and gas chromatography–mass spectrometry. J Chromatogr B Biomed
Sci Appl 695:217–226. https://doi.org/10.1016/S0378-4347(97)00174-6
7. Arrebola F, Martı́ nez-Vidal J, Fernández-Gutiérrez A, Akhtar M (1999) Monitoring of pyrethroid metabolites in human urine using solid-phase extraction followed by gas
chromatography-tandem mass spectrometry. Anal Chim Acta 401:45–54. https://doi.org/10.
1016/S0003-2670(99)00519-X
8. Ueda Y, Oda M, Saito I, Hamada R, Kondo T, Kamijima M, Ueyama J (2018) A sensitive and
efficient procedure for the high-throughput determination of nine urinary metabolites of pyrethroids by GC-MS/MS and its application in a sample of Japanese children. Anal Bioanal Chem
410:6207–6217. https://doi.org/10.1007/s00216-018-1229-x
Analytical Methods for Determination Urinary Metabolites of Synthetic. . .
77