M

EVALUMETHO

B

UATIODS OF

BY LC-

www.

N OF DF PESTIToF-M

1 eurl-pestici

DIFFERCIDE R

MS and

des.eu

RENT ERESIDU

d GC-T

XTRACUES INToF-M

CTIONN SPICEMS

 

N ES

 

 

Con 

1.  A

2.  S

3. 

4. 

5. 

6. 

7. 

7.1

8. 

8.1

8

8

8

9. 

ntent

Aim and sc

Short desc

Consumab

Chemicals

Instrument

Instrument

Procedure

1.  Sampl

7.1.1.  Cl

7.1.2.  Fre

7.1.3.  Di

Results .......

1.  LC-ToF

8.1.1. Sorb

8.1.2. Freez

8.1.3. Spice

GC-ToF r

cope .........

cription .......

bles ............

s ..................

tation and

tation and

e ..................

le extractio

lean-up so

eezing-out

lution stud

....................

F backgrou

ent effect

zing out an

e matrices

results ........

www.

....................

....................

....................

....................

analytical

analytical

....................

on ................

orbent stud

t study ........

y .................

....................

und distribu

on cayenn

nd dilution

backgrou

....................

2 eurl-pestici

....................

....................

....................

....................

l condition

l condition

....................

....................

dy .................

....................

....................

....................

ution ..........

ne and bla

effect.......

und differe

....................

des.eu

....................

....................

....................

....................

ns for the LC

ns for the G

....................

....................

....................

....................

....................

....................

....................

ack peppe

....................

nces. .........

....................

....................

....................

....................

....................

C-ToF-MS ..

GC-ToF-MS .

....................

....................

....................

....................

....................

....................

....................

er .................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

....................

 

....... 3 

....... 3 

....... 3 

....... 4 

....... 4 

....... 5 

....... 6 

....... 6 

....... 6 

....... 7 

....... 8 

....... 8 

....... 8 

....... 8 

..... 14 

..... 18 

..... 18 

 

 

1.

Thi

an

of

rem

ob

2.

Ho

ex

Se

76

ex

co

Ext

MF

rep

ma

ob

co

ma

3.

Aim an

is study is

nalysis of p

this matrix

moval of

btain the c

Short de

omogenou

xtracted w

p, and EM

°C) was

xtracts we

ompounds

tractor (M

FE create

present re

ass, reten

btained. T

omplexity

atrix comp

Consum

Automa

and 1 t

50 ml P

15 ml P

Vortex

Automa

nd scope

aimed to

pesticide r

x and the

volatile o

cleanest e

escription

us sample

with modif

MR. The n

evaluated

ere analy

s were re

MFE) algor

es a com

eal molec

ntion time

The resultin

of the ma

ponents.

mables

atic pipet

to 5 mL.

TFE centri

TFE centri

atic axial

www.

o develop

residues in

e high bac

oils, piperin

extract.

n

es of bla

fied QuEC

necessity o

d. Dilution

yzed by b

trieved a

rithm in th

pound lis

ules. At th

e, and in

ng data w

atrices thr

ttes, suitab

fuge tube

fuge tube

extractor

3 eurl-pestici

p a multire

n spices, t

ckground

ne and lip

ck peppe

ChERS, tes

of a freez

n factor w

both GC

nd count

he MassH

st of all t

he end of

ntensity o

was evalu

rough the

ble for ha

es with scr

es with scr

r

des.eu

esidue ext

taking into

effect ge

pid prese

er, cayen

sting 3 dif

zing out st

was also

-ToF-MS a

ted using

unter Wo

the peaks

f the data

of all ma

uated to

e number

ndling vo

rew caps

rew caps

raction m

o accoun

enerated.

nt in spic

nne and

ferent sor

tep in dry

studied. T

and LC-To

the Mole

orkstation

s in the d

a process,

atrix com

get inform

and distr

lumes of 1

method fo

nt the diffic

The aim is

ce matrice

curcuma

rbents: PS

ice (CO2

The obta

oF-MS. M

ecular Fea

Software.

data file

a list with

mponents

mation of

ribution of

10 to 200

 

r the

culty

s the

es to

are

A, Z-

2 at -

ined

Matrix

ature

. The

that

h the

was

f the

f the

µL

 

 

4.

5.

Centrifu

proced

Conce

Injectio

Chemic

Aceton

Trisodiu

Disodiu

Sodium

Anhydr

Primary

Bondes

SupelTN

EMR-lip

EMR-lip

Ultra-pu

Pesticid

Instrum

Agilent

uge, suita

dure and c

ntration w

on vials, 2

cals

nitrile ultra

um citrate

um hydrog

m chloride

rous magn

y seconda

sil-C18 N QuE Z-sep

pid d-SPE

pid polish m

ure water

des standa

mentation a

t 1290 HPL

Column: mm x 50 mMobile pwater, 5mMobile pmethanoFlow rateInjection v

www.

able for the

capable o

workstatio

ml, suitab

a-gradient

dihydrate

gencitrate

nesium su

ary amine

p, bulk ma

material

r

ards

and analy

C

Agilent Emm x1.8 µhase A: M

mM ammohase B: 0l, 5mM am: 0.3 mL/mvolume: 4

4 eurl-pestici

e centrifu

of achiev

n

ble for GC

t grade

e

e sesquihy

ulphate

e bonded

aterial

ytical con

Eclipse Pluµm Methanol onium form0.1% Formmmoniummin 4 µL

des.eu

ge tubes

ing at lea

and LC a

ydrate

silica (PSA

nditions for

us Rapid R

0.1% Formmate

mic acid m formate

employed

ast 3700 rp

auto-samp

A), bulk m

r the LC-To

Resolution

mic Acid,

in ultrapu

d in the

pm

pler.

aterial

oF-MS

n HD C18

, 2% ultra

ure water

 

8, 2.1

pure

r, 2%

 

 

6.

MoTi0 2 151

Agilent

Instrum

Agilent

Ra

(°C

40

5

obile phasme [min] 5 7

t 6550 LC-

4GHz HigESI sourceGas flow:Nebuliser Nebuliser Sheath gaSheath gaIonisationCapillary OctapoleFragment

mentation a

t 7890 A

Column: 2Column mL/min inCarrier gaInjection Ultra InertInjection vInjection Oven tem

ate

C/min)

Backfluhs

www.

se gradien Mobile

20% 20% 100% 100%

QTOF-MS

gh Resolute gas tem 14 L/min gas and gas pressas flow: 12as tempe

n mode: p voltage: 4e RF Peak:tor 360 V

and analy

2 columnsflows: 1.0

n the secoas: heliummode: spt liner withvolume: 2temperat

mperature

Value

60

120

310

sing: at 31

5 eurl-pestici

nt e phase A

tion Modemperature:

collision gsure: 30 ps2 L/min rature: 35

positive 4000 V : 750V

ytical con

s of HP-5M0 mL/minond colum

m (99.999 %litless

h a glass w2 µL ture: 280 °e program

e (°C) H

(m

1

0

0

0°C for 2

des.eu

A Mobile80% 80% 0% 0%

e : 160°C

gas: nitrogsi

50 °C

nditions for

MSUI, 15 mn in the mn %) at cons

wool frit

°C m:

Hold time

min)

0

0

min

e phase B

gen

r the GC-T

m x 0.25 mmfirst colum

stant press

Runtim

(min)

1

2.5

40.5

ToF-MS

m x 0.25 µmn and

sure 14.1 p

me

 

µm 1.20

psi

 

 

7.

7

Agile

Proced

7.1. Sam

7.1.1.

ent 7200 G

EI ion sou4 GHz HigIon sourceQuadrupAcquisitiom/z range

ure

mple extra

Clean-up

2g portio

centrifuge

7 mL of

(soaking t

10 mL of a

The sam

(AGYTAX®

4 g of ma

trisodium

hydrogen

samples w

for 7 min.

The extra

9 mL su

centrifuge

with dry ic

5 mL of

precipitat

The extra

stabilized

www.

GC-Q-ToF

rce operagh Resolute temoeraole analyz

on mode: e: 45-550

action

p sorbent

on of sa

e tube.

milli-Q wa

time: 30 m

acetonitri

ple is sh

®,Cirta La

agnesium

citrate

ncitrate s

were aga

ct was the

upernatan

e tube an

ce (CO2 a

the extra

te using a

act was

with 5 mL

6 eurl-pestici

ating at 70tion Modeature: 280

yzers temp Full scan

study

mple wa

ater were

min)

le were a

aken by

ab. S.L., Sp

m sulphate

dihydrat

sesquihyd

in shaken

en centrif

nt were

nd were p

at -76°C) f

act was th

a Pasteur P

transferre

L water.

des.eu

0 eV e 0 °C perature: 1MS

as weight

e added

dded.

an auto

pain) for 7

e, 1 g of s

te and

drate we

n in the au

uged at 3

transferre

placed in

for 6 min.

hen sepa

Pipette.

ed to EM

150 °C

ted in a

to hydra

omatic ax

min.

sodium ch

0.5 g

ere adde

utomatic a

3700 rpm f

ed to a

a polystyr

arated fro

MR-lipid t

50 mL

ate the sp

xial extra

hloride, 1

of disod

ed and

axial extra

for 5 min.

15 mL

rene box

om the fro

tube alre

 

PTFE

pices

actor

g of

dium

the

actor

PTFE

filled

ozen

eady

 

 

The

free

pol

PSA

The

free

pol

Z-se

7.1.2.

The

free

ext

PSA

sorb

lipid

The extra

centrifuge

transferre

chloride a

After vor

supernata

For LC a

mixture o

times is ob

For GC a

reconstitu

e same p

ezing out

ystyrene

A.

e same pr

ezing out

ystyrene

ep.

Freezing

ese 3 ex

ezing out

ract were

A and Mg

bent, 5 m

d tubes al

www.

act was s

ed at 37

ed to an E

and 4g of

rtex and

ant was c

analysis, t

of methan

btained (

analysis, 50

uted with

rocedure

t step, t

tube con

rocedure

t step, t

tube con

-out study

xtraction

step. Aft

e added

gSO4, Z-Se

mL of supe

lready sta

7 eurl-pestici

shaken in

700 rpm f

EMR-polish

f magnesi

centrifug

collected.

he extrac

nol/water

160 pg in

0 µL of th

50 µL of e

e was rep

the extra

taining 75

was repe

the extra

taining 75

y

methods

ter the fir

directly t

ep and M

ernatant w

abilized wi

des.eu

n a vorte

for 5 min

h tube co

um sulfate

ge at 370

ct was d

r (50/50).

column).

he extract

ethyl aceta

peated us

act was

50 mg of

eated usin

act was

50 mg of

were re

rst centrif

to polysty

MgSO4. In

were trans

ith 5 mL w

x for 1 m

. A 5 mL

ontaining

e.

00 rom fo

diluted 5

A final d

t was eva

ate.

ing PSA.

transferre

MgSO4 a

ng Z-sep.

transferre

MgSO4 a

epeated

ugation s

yrene tube

the case

sferred dir

water.

min and

L extract

1g of sod

or 5 min,

times wi

dilution o

aporated

Following

ed to 15

nd 125 m

Following

ed to 15

nd 125 m

without

step, 5 m

es contai

e of EMR-

rectly to E

 

then

was

dium

the

th a

of 25

and

g the

mL

mg of

g the

mL

mg of

any

mL of

ining

-lipid

EMR-

 

 

8.

8

7.1.3.

For

bac

dilu

(16

100

Results

8.1. LC-T

8.1.1. S

a)

Dilution s

the an

ckground

ution facto

x107 pg i

0 time tota

ToF backg

Sorbent eff

Number

compone

freezing o

www.

study

alysis of

signal,

ors. The fi

n column

al dilution

ground dis

fect on ca

and

ents of C

out and w

8 eurl-pestici

spices o

2 injectio

rst injectio

n) and the

(4 x107 pg

stribution

yenne and

distributio

Cayenne

with 25 tim

des.eu

on LC, a

ons were

on consist

e second

g in colum

d black pe

on of

using EM

es dilution

and for r

made w

ted of 25

d injection

mn).

epper

co-extrac

R-lipid sor

n (16x107 p

reducing

with diffe

times dilu

n consiste

cted m

rbent wit

pg in colu

 

the

erent

ution

ed of

matrix

hout

umn)

 

 

b) Number

compone

out and w

www.

and

ents of Ca

with 25 tim

9 eurl-pestici

distributio

ayenne us

mes dilutio

des.eu

on of

sing PSA s

on (16x107

co-extrac

orbent wi

pg in colu

cted m

thout free

umn)

 

matrix

ezing

 

 

c) Number

compone

freezing o

www.

and

ents of C

out and w

10 eurl-pestici

distributio

Cayenne

with 25 tim

des.eu

on of

using Z

es dilution

co-extrac

Z-sep sor

n (16x107 p

cted m

rbent wit

pg in colu

 

matrix

hout

umn)

 

 

d) Number

compone

without fr

column)

www.

and

ents of b

reezing ou

11 eurl-pestici

distributio

black pe

ut and wi

des.eu

on of

epper us

th 25 time

co-extrac

ing EMR-

es dilution

cted m

-lipid sor

n (16x107 p

 

matrix

bent

pg in

 

 

e) Number

compone

freezing

column).

www.

and

ents of b

out and

12 eurl-pestici

distributio

black pep

with 25

des.eu

on of

pper using

5 times d

co-extrac

g PSA sor

dilution (

cted m

rbent wit

16x107 p

 

matrix

hout

g in

 

 

f)

Number

compone

freezing o

www.

and

ents of bl

out and w

13 eurl-pestici

distributio

ack pepp

with 25 tim

des.eu

on of

per using

es dilution

co-extrac

Z-sep so

n (16x107 p

cted m

orbent wit

pg in colu

 

matrix

hout

umn)

 

 

8.1.2.

a)

Freezing

Number

compone

out and w

www.

out and d

and

ents of C

with 25 tim

14 eurl-pestici

dilution eff

distributio

urcuma u

mes dilutio

des.eu

fect

on of

using EMR

on (16x107

co-extrac

R sorbent

pg in colu

cted m

with free

umn)

 

matrix

ezing

 

 

b)

Number

compone

out and w

www.

and

ents of C

with 100 ti

15 eurl-pestici

distributio

urcuma u

mes diluti

des.eu

on of

using EMR

on (4x107

co-extrac

R sorbent

pg in colu

cted m

with free

umn)

 

matrix

ezing

 

 

c) Number

compone

freezing o

www.

and

ents of b

out and w

16 eurl-pestici

distributio

black pe

with 25 tim

des.eu

on of

epper usin

es dilution

co-extrac

ng EMR

n (16x107 p

cted m

sorbent

pg in colu

 

matrix

with

umn)

 

 

d)

Number

compone

freezing o

www.

and

ents of b

out and w

17 eurl-pestici

distributio

black pe

with 100 tim

des.eu

on of

epper usin

mes dilutio

co-extrac

ng EMR

on (4x107 p

cted m

sorbent

pg in colu

 

matrix

with

umn)

 

 

9.

a

8.1.3.

TIC o

sorbe

colum

GC-ToF r

a) TIC of

and PS

pg in c

EMR

PSAZ‐sep

Spice ma

of black

ent with f

mn).

results

black pe

A without

olumn)

p

www.

atrices ba

pepper,

reezing o

epper with

t freezing

18 eurl-pestici

ckground

cayenne

out and 2

h the 3 c

out and w

des.eu

d differenc

and cur

25 times

clean-up s

with 25 tim

ces.

rcuma us

dilution (

sorbents o

mes total

sing EMR-

(16x107 p

of EMR, Z

dilution (8

 

-lipid

pg in

Z-sep

8x107

 

 

b

b) TIC of b

in colum

W

W

black pep

mn) and w

With freez

Without f

www.

pper using

with and w

zing out reezing ou

19 eurl-pestici

g EMR with

without fre

ut

des.eu

h 25 times

eezing ou

total dilu

t.

ution (8x10

 

07 pg