LCMS-8050 Application - Multi-Residue Analysis of Pyrethroids in Soil and Sediment Using QuEChERS by LC - MS - MS (Japan)
LCMS-8050 Application - Multi-Residue Analysis of Pyrethroids in Soil and Sediment Using QuEChERS by LC - MS - MS (Japan)
Introduction
Pytrethroids are one of the most widely used commercial to the influence on the insects and aquatic invertebrates.
household insecticides in agricultural or non-agricultural Therefore, quick, high-sensitive and universal analysis
application sites. Synthetic pyrethroids are poorly methods are required. The analysis of pyrethroids is
water-soluble, but are strongly adsorbed to soil, therefore typically performed by GC or GC/MS because of their
these compounds are increasingly being found in soil or hydrophobicity. In this study, we report the development
sediments. Recently, soil and sediment contamination by of a simultaneous analysis technique for trace amounts of
pyrethroids has been detected in both urban and pyrethroids by LC/MS/MS.
agricultural area, and it’s becoming a global concern due
Permethrin
Tefluthrin
Esfenvalerate
Sample preparation
Sample preparation was carried out by the use of the amount of the soil and water added, we finally adopted a
QuEChERS method. In case of the soil samples, hydration combination of 5 g soil (or 10 g sediment) and 5 mL water,
of sample with water before acetonitrile extraction is and the following procedures were based on the original
required to improve the recovery and operability. Result of QuEChERS method.
several different extraction methods that changed the
2
Multi-residue analysis of pyrethroids in soil and sediment
using QuEChERS by LC/MS/MS
*1 : Q-sep QuEChERS Extraction Salts (RESTEK) *2 : Q-sep QuEChERS dSPE Tubes (RESTEK)
LC/MS/MS analsis
HPLC conditions (Nexera UHPLC system, Shimadzu)
3
Multi-residue analysis of pyrethroids in soil and sediment
using QuEChERS by LC/MS/MS
Result
MRM of pyrethroid standards
In this study, we selected and evaluated 15 pyrethroids agrocultural insecticides worldwide.
(pyrethrin, fenpropathrin, cycloprothrin, deltamethrin, Except for tefluthrin, which was not ionized by LC/MS under
esfenvarelate, cypermethrin, cyfluthrin, ethofenprox, conditions tested, all other 14 compounds were successfully
permethrin, cyhalothrin, bifenthrin, acrinathrin, tefluthrin, detected in ESI positive mode or in both positive and
silafruofen) which are the most widely used for household or negative mode.
4
Multi-residue analysis of pyrethroids in soil and sediment
using QuEChERS by LC/MS/MS
9.0 9.5 9.5 10.0 9.5 10.0 10.5 10.0 10.5 11.0
5
Multi-residue analysis of pyrethroids in soil and sediment
using QuEChERS by LC/MS/MS
100 100
Recovery (%)
80 80
60 60
40 40
20 20
0 0
Cy nv rin
pe alr n
D ro in
D pro rin
Si at n
flu in
Es me rin
s- fen in
Cy et in
Pe et x
Es m rin
s- fen rin
Cy t in
Pe et x
flu in
A ent n
en
tr Eth ut in
fe rin
en
Fe ret in-2
Cy rop n-1
np th 2
Cy rop in-1
lo n
flu n
lo in
rm ate
e e
Cy nv hri
ci erm pro
o
in ri
in ri
i
Fe yre in-
ha hri
op hr
la ri
rm at
la hr
an o hr
rm hr
rm hr
Cy thr
Bi thr
fl r
ha hr
ci erm pr
fe th
cr h
of
o h
cr h
of
ta th
ta th
an o h
Cy th
Bi th
Si ath
i
pe alr
fe et
cl at
cl at
A nt
tr th t
Py thr
np hr
P thr
r
e
e
re
re
f
Py
Py
el
el
P
P
E
s-
s-
Figure 5 Recovery of 14 pyrethroids from soil and sediment matrices (10 ppb spiked)
ethofenprox permethrin Table 3 Result of quantitative analysis in the soil and sediment
soil sediment
pyrethrin-I n.d. n.d.
soil blank pyrethrin-II n.d. n.d.
fenpropathrin n.d. n.d.
cycloprothrin n.d. n.d.
solvent blank
deltamethrin n.d. n.d.
esfenvalrate n.d. n.d.
cypermethrin n.d. n.d.
cyfluthrin n.d. n.d.
ethofenprox 0.01 ppb* n.d.
Figure 6 Chromatograms of prethroids in the soil permethrin 0.03 ppb n.d.
cyhalothrin n.d. n.d.
bifenthrin n.d. n.d.
acrinathrin n.d. n.d.
silafluofen n.d. n.d.
n.d. : not detected
* : <LOQ
6
Multi-residue analysis of pyrethroids in soil and sediment
using QuEChERS by LC/MS/MS
Conclusions
• A method for quantification of 14 pyrethroids in soil and sediment at ppt-level concentrations was developed by
LC/MS/MS.
• In this study, neither matrix effect nor sample preparation losses were observed in the recovery test, demonstrating the
applicability of QuEChERS method to sample preparation of soil and sediment.