Académique Documents
Professionnel Documents
Culture Documents
using QuEChERS
method
Acidic pesticides
pH-issue: Ionization of pesticides at low or high pH-values
1
Acids: HX 1 H+ + X-
Bases: B + H+ 1 BH+
pH-range of agricultural
samples: ~2.5 7
MCPB
123456457895
837 123456 789
pH
pH
pH
pH
Bromacil
Fluazifop
Bromoxynil
Bentazon
Ioxynil
Propyzamid
2,4-DP
2,4,5-TP
Triclopyr
Mecoprop
2,4,5-T
Fluoxypyr
Naphthylacetic acid
Imazaquin
2,4-D
MCPA
Dicamba
Imazethapyr
4-CPA
Imazapyr
Clopyralid
Picloram
Benazolin
Acidic pesticides
influence of pH on recovery
120
Recovery
%
100
80
max. pH 5.5
60
40
20
12
Citrate-Buffered
Sample pH 5.1
pH=7.8
mg/mL
7Losses of acidic
components after
cleanup
pH=8.3
pH
10
7
8
6
5
6
4
pH=3.5
4
7Acidic compounds
interact with PSA
2,4
2
1,0
0,5
0
Raw Extract PSA 25 PSA 50
mg/mL
mg/mL
mg co-extractives/mL Extract
pH
1
0
pKa-value
2,85
2,84
2,73
4,8
3,67
3,56
3,2
3,2
3,1
2,9
3,07
4,84
3,78
2,94
3,97
Chemical Class
acidic structure
phenoxyalcanoic acid
pyridine herbicide
naphthoxyacetic herbicide
3,86
3,96
2
1,97
1,9
3,8
2,1
4,32
2,3
3,3
2,83
4
4
3,3
4,8
4,17
phenolic herbicide
pyridine herbicide
benzoic acid
imidazolinone herbicide
quinolinecarboxylic acid
pyridine herbicide
unclassified
amide herbicide
pyrimidinylsulfonylurea herbicides
triazinylsulfonylurea herbicides
sulfonanilide herbicide
cyclohexene oxime herbicide
special case
no acid
14
2
651
47
7
5
7
9
1
2
1
10
85
1
6
3283
421
314
146
94
81
49
31
25
24
18
18
16
9
7
6
3
2
2
1
1
1
1
1
4
18
16
1
10
2
1
1
1
2
Annex I 91/414
LEGUMES
CEREALS
FRUITING
VEGET.
LEAFY VEGET.
297
125
17
44
72
6
30
8
2
2
ALL COMMOD.
45
1
98
1
Fludioxonil
Fluazifop
2,4-D
Haloxyfop
Bentazone
MCPA
Clopyralid
Dicamba
2,4-DP
MCPP
4-CPA
Naphthoxyacetic acid, 2Bromoxynil
Triclopyr
Imazaquin
2,4,5-T
Quinmerac
Fluroxypyr
Ioxynil
2,4-DB
Cycloxydim
Metosulam
2,4,5-TP
Fenoxaprop-P
Formesafen
Imazapyr
Imazethapyr
Imazosulfuron
MCPB
Metsulfuron-Methyl
Picloram
Thifensulfuron-Methyl
Pesticide
2004 - 2007
Pending
Out
In
Out
In
In
In
Pending
In
Pending
Pending
pending
In
Pending
In
In
In
In
Pending
Pending
In
Pending
Out
Out
In
Out
Out
In
M
C
M
M
PP
et
N
e
su
to
ap
su
lfu
ht
la
ho
ro
m
n
xy
ac -Me
et
th
y
ic
ac l
id
,2
Pi
Th
cl
or
ife
Q
ns
ui am
nm
ul
fu
er
ro
ac
nM
et
hy
l
Tr
ic
lo
py
r
M
C
PB
2,
4D
2,
4D
B
2,
4D
P
4C
PA
Be
nt
az
on
Br
om e
ox
yn
C
il
lo
py
ra
C
l id
yc
lo
xy
di
m
D
Fe ica
m
no
xa ba
pr
op
-P
Fl
ua Flu
az
zi
i
fo
p- fop
PBu
ty
Fl
l
ud
io
xo
Fl
ni
ur
l
ox
y
Fo
py
r
m
es
af
en
H
al
ox
yf
Im o p
az
ap
Im
yr
az
Im aqu
az
in
Im eth
a
az
py
os
r
ul
fu
ro
n
Io
xy
ni
l
M
C
PA
2,
4,
5T
2,
4,
5TP
mean recovery in %
140
Spiking Level 0.01 mg/kg
120
100
80
60
40
20
Example 2,4-D
7
7
7
7
7
7
Add 10 mL Acetonitrile
alkaline hydrolysis:
Add NaOH and store for
30 min at RT,
then neutralize
Add ISTD-Solution
Shake
optionally:
Add NaOH to adjust pH
optionally:
Freeze-out of extracted
fat over night
8888883
!8"8#8
Alkaline Hydrolysis for the release of phenoxy-acid pesticides
" 8 "
wheat sample
At 70 C
At Room Temperature
1200
pH 12
30 min
1000
800
pH 10
30 min
pH 9
30 min
715
619
606
pH 10
60 min
600
336
400
275
135
200
100
dr
ol
in
w/
o
ER
S
Q
uE
Ch
pH
9/
3
hy
m
in
10
/
pH
pH
10
/
60
30
m
in
in
30
m
12
/
pH
30
10
/
pH
12
/
30
m
in
m
in
pH
Relativ concentration
1400
Alkaline Hydrolysis
Level of MCPA in berries
(%$
./
5#/
)8)8842* 8+,-
($$
'%$
'$$
&%$
&$$
%$
$
88
#88
Alkaline Hydrolysis
Level of 2,4-D in different citrus samples
12648
88
#88
12646
12345
08&1283 %12
1294
12949
12647
1284
12345
1294
12845
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