Co 1. 2. 3. 4.
Med
Med
_______________ orresponding autho
Occupational and Medical Education Department of Oc University of Medi Research Center f University of Medi Institute for Envi Tehran, Iran
Optimiza
procedu
samples
Maryam Ram Seyed Jamale
Received: 11 M
Abstract
Background challenge for r simple, valid, a Methods: DL chlorpyrifos pe one factor at a Results: The with 1-500 µg concentration o different conce Conclusion: time, high extra
Keywords: Ch
Conflicts of Interes Funding: Tehran U
*This work has bee Copyright© Iran
Cite this artic microextraction https://doi.org/10
Introducti
Organopho found among spraying wor and equipmen
Most farme the lack of p
dical Journa
J Islam Repub Ir
________________ or: Dr Seyed Jamale Environmental Ce n, Tehran, Iran
ccupational Health ical Sciences, Tehra for Environmental ical Sciences, Kerma ironmental Resear
ation of
ure for de
s
min1, Monireh
eddin Shahtah
Mar 2018
d: Selecting an researchers. Thi and fast method LLME, coupled esticide in hum
time method. e limit of detect
g L-1 concent of 200 µg L-1 w entration levels
Compared to o action efficienc
hlorpyrifos, Dis
st: None declared University of Medica
en published under University of Medi
cle as: Ramin M
procedure for 0.34171/mjiri.33.
on
sphate pestic g toxin-produc rkers, and con nt (1, 2). ers who use pe proper knowl
al of the Islam
ran. 2019(20 Jul)
_
ddin Shahtaheri, sh enter, Health depu
Engineering, Scho an, Iran
Determinants of H anshah, Iran rch, Tehran Unive
dispersiv
etecting
Khadem2, Far
heri*2,4
Published
n effective sam is study aimed d with high effic d with high per man urine sampl
tion and enrichm tration range w
was less than 5 of 50, 200, and other extraction cy, and good en
spersive liquid-l
al Sciences r CC BY-NC-SA 1.0 li ical Sciences
M, Khadem M, detecting chl 71
cide poisonin cing workers nsumers of co
esticides daily edge about p
mic Republic
;33.71. https://do
[email protected]. uty, Ministry of He
ol of Public Health
ealth (RCEDH), Ker
ersity of Medical
ve liquid
chlorpyr
riborz Omidi3,
: 20 Jul 2019
mple preparation to optimize th ciency to detect rformance liqui les. Different a
ment factor of was used. The 5%. The relative d 1000 µg L-1, r techniques, the nrichment factor
liquid microext
icense.
Omidi F, Pourh lorpyrifos in h
ng is comm in factories, t ontaminated f
y are at risk d poisoning of t
c of Iran (MJ
oi.org/10.34171/m
c.ir ealth and
h, Tehran
rmanshah
Sciences,
↑W
Mo com sen use dev
→
Th det pre pre sam
d–liquid m
rifos in h
Mehran Pour
n method to m he dispersive liq t chlorpyrifos in id chromatogra affecting param
the method wa e relative stand
e recoveries of respectively. e optimized DL r for the extract
traction, Urine,
hosein M, Golb human urine s
monly toxin foods
due to these
chem Ther niqu logic
Co liqui
IRI)
mjiri.33.71
What is “already
ost sample pr mbination with nsitive detection ed widely for th veloping countr
→What this artic
e proposed m tector, is a sen eparation metho econcentration mples.
microext
uman ur
rhosein2, Farid
measure target p quid-liquid mic
n urine samples aphy equipped w meters on the eff
as 0.5 and 230 µ dard deviation f spiked urine s
LLME resulted tion of chlorpyr
HPLC
abaei F, Shahtah samples. Med
micals and co refore, it is ues to extra c
cal samples to onventional s id-liquid ext
y known” in th
reparation tech h gas chromato
n system, which he analysis of o ries.
cle adds:
method in this nsitive, simple, od and can be of chlorpyrif
traction
rine
deh Golbabae
pesticides in bi croextraction (D
s.
with ultra viole fficiency of the
µg L-1, respect (RSD) for 6 amples were 96
in some advant rifos from hum
heri SJ. Optimiz
J Islam Repub
orrect ways o necessary to t these hazard o evaluate the sample prepar
raction (LLE
his topic:
hniques have ography as a h ch are expensiv organophosphor
s study, witho rapid, and rep e used for the
fos residues ei2,
iological matri DLLME) techn
et detector, was method were o
tively. Linear c replicate expe 6.3%, 102.3%,
tages such as sh man urine sampl
zation of dispers
b Iran. 2019
of working w develop app dous compou exposure of w aration techniq E), solid-liqu
been used in igh selective o e and cannot b rus pesticides in
out any specia peatable sampl
extraction an from aqueou
ces is a seriou ique to obtain
s used to extrac optimized using
calibration curv eriments at th and 98.7% at 3
horter extraction es.
sive liquid–liqui (20 Jul);33:71
with them (3) propriate tech unds from bio
workers. ques, such a uid extraction
n or e n
al le d us
us a
ct g
e e 3
n
d 1.
). h-
o-as n
DLLME for
(SLE), and s used for rout are being con ing faster an niques (4-7). for preparing liquid, gas, a less. The SM the volatile, n lic analytes f tural samples generally div solvent, and ( Dispersive low-fiber mic traction (SD (LLME) were the SME pro preparation m search (10-13
DLLME, w vents, is wide high extractio soluble in wa is rapidly inje ringe. The rap into the water rapidly in sm enriched orga by centrifugin instrument (1
Chlorpyrifo subgroup of phorothioic ac tural and dom temic, gastro The durabilit months, and i mals. The ab enzyme in th tion to contro The present effective, low termine the tr samples. In th od, with high the matrix, wa
Methods
Reagents a
Chlorpyrifo vided by Dr. solvents, incl chloroform, m chased from reagent grade sodium hydro ized water wa Iran). A stoc prepared by d
detection of c
soxhlet extrac tine applicati nducted in this nd stronger pr Solvent micr g samples by and solid sam ME is used to
nonvolatile, po from environm s. There are s
ided into 2 m (2) solvent wit liquid-liquid m croextraction DME), and
e the main an cedure in rec methods, SME 3).
which belongs ely used as a s on recovery ( ater, is dissolv ected into the pid injection o r causes the in mall microdrop anic phase is s
ng and it is di 8-21). os (trade nam
organic phos cid is used to mestic pests ( o-intestinal, an
ty of this co its toxicity is bility of this p he nervous sy ol and reduce w
t study aimed w-cost, and si race amounts his study, a u h extraction o as developed.
and solutions
os with purity Ehrenstorfer uding carbon methanol, acet Merck (Dar e sodium ch oxide were als as purchased ck solution of dissolving an a
chlorpyrifos in
ction, are wid ons. Furtherm s field with th reparation an roextraction (S
extraction an mples using 1 extract, purify olar, nonpolar mental, biolog several types major categori th membrane microextractio
(HFME), sin liquid-liquid nd most widely cent years. Un
E is still used
to the catego sample prepar (14-17). Extra
ed in dispersi e liquid sampl
of a mixture o nsoluble solve ps from the ta separated from irectly injecte
me of Dursban sphorus insec
control a wid 17). This pes nd respiratory mpound in t
very high for poison to inh ystem has attr workers’ expo d to optimize
imple extracti of chlorpyrif useful sample of very few pe
y of more tha Company (G tetrachloride tonitrile, and a rmstadt, Germ hloride, hydro
so obtained fro from Behan C f chlorpyrifos appropriate am
n urine
dely accepted more, new stu he aim of deve d extraction SME) is a me
d condensatio 00 μL solven y, and concen r, ionic, and m gical, and agr of SMEs tha es: (1) expose (7-9)
on (DLLME), gle-drop micr d microextra
y used metho nlike other sa d for scientifi
ory of exposed ration method acting solvent ve solvent, th le by a prope of organic solv
ent to be extra arget analyte. m the liquid sa ed to the analy
n EC40.8%), cticides and p de range of agr ticide has non y effects (22 he soil is 2 r humans and ibit cholinest acted much a osures (26-29) DLLME as a ion method to fos in human u preparation m esticide residu
an 98% were Germany). Org
, carbon disul acetone, were many). Analyt ochloric acid,
om Merck. De Company (Teh s (1000 ppm) mount of the p
d and udies elop- tech-ethod on of nt or ntrate
metal- ricul-at are
ed to
, hol- roex-action
ds of ample ic
re-d sol-d with
t, in-hen, it
er sy-vents acted . The ample yzing
as a phos- ricul- nsys-2-25).
to 4 d ani-terase
atten-). a fast,
o de-urine
meth-ue in
pro-ganic lfide, e pur- and eion-hran, ) was
pesti-cide pare wate
In
HP Kna dete perf mm, meth The 1.5 m resp cept Hett for c ated ic eq the e wate
Di
Fi trati trifu carb gal t 4000 cent sepa and Fina meth micr tion Ei fos e Thes solv disp tion, and quan ple o
Fig
e in acetonitril ed daily by di
er.
strumentatio
PLC (HPLC auer, Japan), e ermine and se formed on Ag , ID = 4.6 mm hanol–water
pump flowra mL/min and 2 ponse for the
table under th tich zentrifuge centrifugation d in water bath quipment (Son
experiments w er and dried in
ispersive liqui
irst, 10 mL sp on of analyte ugal tube; then bon tetrachlori tube. The clou 0 rpm and the trifugal tube. arated by a sy
its solvent e ally, the rem hanol and 20 rosyringe and
(Fig. 1). ight factors th extraction wer se factors inc vent, volume o perser solvent,
, and sample p 1 varied in d ntity. Figure 2
of 1 ppm chlo
g. 1.The principle
le. Working st iluting the sto
on
pump k-10 quipped with eparate chlorp gilent Eclipse m; Reprosil-PU
solution (60:4 ate and colum 25°С, respecti
analyte and m he detection w en Rotofix 32 n. The samples h at 150 W and noSwiss SW 6 were washed w n an oven at 5
id–liquid micr
piked urine sa e (1 ppm) was n, 1.5 mL of m
ide was quick udy solution w e extractant w The phase co yringe and pou vaporated un aining settled
µL of it was d injected into
hat could pote re examined to cluded the ex of the extract
centrifugatio pH. In each st ifferent levels
2 shows chrom orpyrifos befo
e of DLLME meth
standard soluti ock solution w
001, UV det a UV detecto pyrifos. The s Plus C18 co UR C-18 AQ 40, v/v) as m mn temperatur
ively. The chr matrix interfe
wavelength o (Baoding, Ch s were ultraso d 40 kHz usin 6 H). All glas with acetone 0°С temperat
roextraction p
ample with de s poured into methanol cont kly injected to was centrifuge was settled to ontaining chl oured into ano nder the gentl d phase was withdrawn u o the HPLC f
entially affect to find their op xtraction solv tion solvent, v on time and sp
tep, 7 factors s to determine matograms of ore (A) and a
thod
ions were pre with deionized
ector k-2600 or, was used to separation wa
lumn (L= 250 10 µm) using mobile phase re were set a romatographic erence was ac
of 203 nm. A hina) was used onically irradi ng an ultrason ssware used in
and deionized ure.
procedure
efined concen o a 15mL cen taining 150 µL
o the centrifu ed for 5 min a the bottom o lorpyrifos wa other test tube le flow of N2 dissolved in sing a 100 µL for quantifica
the chlorpyri ptimum levels vent, disperse volume of the peed, salt addi
were constan e the optimum f aqueous sam
fter (B) of ap
e-d
0; o as 0 g e. at c c-A
d i- n-n d
n-L
u-at of as e, 2. n L
a- i-s. er e i-nt m
m-
j
plying DLLM
Urine samp
Urine samp and stored in were placed double-distill sodium hydro pared specim preparation m
Enrichment
To develop chlorpyrifos, efficiency we the analyte c traction effici recovery (ER lowing equati
EF = Csed /
Where, Csed in the settled extraction, res Csed was ob jection of stan
ER= CsedVsed
Where, Vsed and the aque replicate extra
Results
Effect of ex
An extracti to extract the graphic behav chloride (CC
(A)
Fig. 2.Chromat
ME procedure.
ple preparatio
ples were co n a freezer at− in centrifuge ed water. PH oxide solution men was analy
method.
t factor and e
p DLLME m some parame ere investigate oncentration iency, enrichm R) of the analy
ions:
C0
d and C0 are th d phase and i
spectively. btained from th
ndard solution
d/C0Vaq×100%
d and Vaq are t eous sample,
actions was re
xtraction solve
ion solvent w analyte as w vior. Three so Cl4), carbon d
tograms of aqueo
on
ollected from −18°C. Urine tubes and di H was adjuste ns to the samp yzed accordin
extraction reco
method for pr eters controll ed using sam of 1 ppm. To ment factor (E yte were calc
he concentrati in the aqueou
he calibration ns.
%= EF×(Vsed/V
the volumes o respectively. eported for all
ent
was selected ba well as its appr
olvents, inclu isulfide (CS2)
ous sample of chl
exposed wo samples (5.0 iluted with 50 ed at 6 by ad ples. Next, the ng to the prop
overy
reconcentratio ing the extra ple solutions o evaluate the EF) and extra culated by the
ions of the an us samples be
curve of direc
Vaq)×100%
of the settled p The average l experiments.
ased on capab ropriate chrom ding carbon t ), and chloro
orpyrifos before (
orkers mL) 0 mL dding e pre-posed
on of action with e ex-action
e
fol-(1)
nalyte efore
ct
(2)
phase of 3 .
bility
mato- tetra-oform
(CH DLL such effic aque optim resu and coul lutio with effic the men
Eff
Th taini vent solv tinct vent tone tract tione was
Eff
Th men eval volu crea chlo of th crea 150µ to th cons the o
(B)
(A) and after (B)
HCL3), were LME. The im h as density a ciency of the eous solutions
mize the extra ults, no distinc CHCL3 as e ld not effectiv on because o h CS2, CHCL3 ciency for ch optimum ext nts.
ffect of disper
he type of dis ing preconcen ts must be ap vent and samp t cloudy solut ts, including m e, were exam
tion recovery ed solvents. T
selected for l
ffect of volum
he effect of e nt factor and luated by usin umes of CCl4 ase of the CC orpyrifos incre he sediment p ased by eleva µL. According he highest ex stant. Therefo optimal volum
preconcentration
examined a mportant prope
nd solubility, target analyte s of chlorpyr action solvent ct cloudy solu extraction solv vely disperse
f low extract , CCl4 resulte lorpyrifos. He traction solve
rser solvent
sperser solven ntration of th ppropriately m ple solution, s
tion. Therefor methanol, eth ined. Methan for the analy Taking into a ater experime
me of extractio
extraction solv extraction re ng 2 mL met
(50, 100, 150 Cl4 volume, th eased. It was a phase at the b ating the vol
g to the result xtraction reco re, the volum me of CCl4.
n
as extraction erties of sele , could affect e. For this pu rifos (1 ppm) t. According t ution was form
vents, indicat among aqueo ction capabilit ed in the high ence, CCl4 w ent for subse
nt is very imp he analyte. Th miscible in b so that they ca
re, 4 possible hanol, acetoni nol showed th yte compared account the d ents.
on solvent
vent volume ecovery of th ethanol contai 0, and 200µL) he extraction also found th bottom of the lume of CCl ts, more volum overy and aft me of 150µL w
n solvents in ected solvents
the extraction urpose, 10 mL were used to to the obtained med using CS
ting that they ous sample so
ty. Contrasted hest extraction was selected a
equent experi
portant for ob he chosen sol oth extraction an form a dis
disperser sol itrile, and ace he highest ex to other men data, methano
on the enrich e analyte wa ining differen ). With the in recoveries o at, the volume e test tube in
4 from 50 to me of CCl4 led er that it wa was selected a n s, n L o d S2 y
o-d n as
i- b- l-n s- l- e- x- n-ol
h-as nt n-of
e
n-o d as as
DLLME for
Effect of vo
The other p covery and en solvent. Diffe mL) containin volume. The at first and th anol. At low was not form recovery of t increased to enrichment fa ubility of CC tion recovery more than 1. the increase i extraction sol solvent.
According to obtain high
Effect of ce
To separate DLLME is ce cloudy solutio the bottom of and rate on t optimized in respectively. minutes and t optimum leve
Effect of sa
To prove th efficiency, di 2, 4, and 6% crease the so and increase the obtained r to the lower aqueous phas cient of the performed wi
Effect of sa
Sample pH extraction eff hydrochloric samples, the
Table 1.Quantit
LR (µg L-1)
5-500
Table 2.Relative
Spiked
a Mean of three det
detection of c
olume of dispe
parameter that nrichment fac erent methano ng 150 µL CC
extraction rec hen decreased w volumes of med completely
the analyte. W 1.5 mL, the h actor was obta Cl4 in aqueous
decreased wh 5 mL. This d in the ratio o lvent and prev
to the results h enrichment f
entrifugation
e the extractan entrifugation on and helps t f the tube. Th the extraction the ranges of According t the speed of els of centrifug
alt addition
he effect of i fferent concen w/v) were in lubility of the extraction int results, increa extraction eff se viscosity d analyte. The ith no salt add
ample pH
is also anothe ficiency. By ad acid or sodiu stability of ch
tative features of r2
0.9931
e recovery (RR) a d levels (µg L-1)
50 200 1000
terminations ± stand
chlorpyrifos in
erser solvent
t could affect tor was the vo ol volumes (0 Cl4 were used
coveries of the by raising the methanol, th y, leading to When the vol highest extrac ained due to d s solution. Ho hen the volum decrease can b of the dispers vention in sett
s, 1.5 mL met factor and ext
time and spee
nt phase, an i process. This the extraction he effects of c efficiency w f 5–20 min an to the results
4000 rpm we gation for nex
ionic strength ntrations of so nvestigated. S
e analyte in t to the organic asing the NaCl fficiency, as th
decreased the erefore, next dition.
er important f dding the appr um hydroxide
hlorpyrifos un
the proposed met MDL (µg
L-1)
0.5
and RSD values o
dard deviation
n urine
t the extractio olume of disp 0.5, 1, 1.5, 2 to find the opt e analyte incre e volume of m he cloudy solu the low extra lume of meth ction recovery decreasing the wever, the ex me of methanol be explained ive solvent to tling the extra
thanol was ch raction recove
ed
mportant fact s step destroy solvent to set centrifugation were examined nd 2500-4000 s, the time ere selected a xt experiments
on the extra odium chlorid Salting out can
the aqueous p c phase. Base l concentratio he increase o e diffusion co
experiments
factor affectin ropriate amou solutions to w nder the pH r
thod for chlorpyri LOQ (µg L-1)
5
of chlorpyrifos in RR ( 96.3 ± 102.3
98.7 ±
on re-perser 2, 2.5 timal eased
meth-ution action hanol y and e sol- xtrac-l was
with o the action
hosen ery.
tor in ys the ttle at time d and rpm, of 5 as the
s.
action de (0, n de-phase ed on on led of the
oeffi-were
ng the unt of water range
of 2– tion fore men
An
An acte limit (LO viati reco ditio obta was with LOQ and were indic meth 95.7 and of th Ur plied chlo accu with of 5 ing show reco cove in co firm RSD conc matr for p
Di
Th taine ed m samp pose for t LOQ
rifos
RSD 200 µg L-1 sp
Intra-day 1.9
n urine sample (%) ± 2.1a
± 4.2 ± 3.1
–10 was teste recovery of t , doubled-dist nt in the study.
nalysis
nalytical featu ristics of the t of detection OQ), correlatio
ion (RSD%), overy (ER), w ons to evalua ained results over a broad h correlation c Q, calculated b 10, were 0.5 e less than 5 cating an acc hod. The EF 7%, respectiv ER, and low he proposed m Urine sample a d to the pr orpyrifos in th uracy of the D h the target an 0, 200, and 1 the recommen wn in Table 2
overies ranged eries of the an
oncentration l ming the validi Ds for the rea
centrations. T rix has no sig preconcentrati
iscussion
he comparison ed for the pres methods for a
ples is summ ed method is c
the other met Q compared to
(%) piked (n=6)
Inter-day 4.69
d. It was indic the analyte wa tilled water w .
ures of the me e method, inc n (LOD or MD
on coefficient enrichment f ere determine te the perform were summar d concentratio coefficient (r2 based on sign 5 and 5, resp % for interda ceptable repea and ER for t ely. Satisfact MDL and LO method.
analysis: The
reconcentratio he spiked urin DLLME proce nalyte at 3 dif 000 µg L-1 an nded method. . According to d from 96.3% nalyte indicate
levels of 50, 2 ty of the prop al samples w hese results in gnificant effec ion of chlorpy
n of LR, RSD sented method analysis of the marized in Tab
comparable o hods. This stu o most reporte
EF
230
RSD (%) (n=3) 2.2 4.07
3.1
cated that the as obtained at was used witho
ethod: The an
cluding linear DL), limit of t (r2), relative factor (EF), a ed under the o mance of the arized in Tab
on range for 2) of 0.993. T
nal to noise ra pectively. The ay and intrad
atability for t the pesticide tory repeatabi OQ are the ma
e proposed me on and dete ne samples. T edure, sample fferent concen nd analyzed in The analyte o obtained da %-102.3%. Th
ed no significa 200, and 100 posed method were fairly low
ndicate that th ct on the pro yrifos from ur
D, MDL, LO d with those o e target analy
ble 3. The RS or better than
udy found low ted methods. T
ER (%)
95.7
higher extrac t pH 6. There out pH adjust
nalytical char r range (LR) quantification e standard de
and efficiency optimized con e method. The
le 1. linearity the pesticide The MDL and atio (S/N) of 3 e RSD value day precisions the developed
were 230 and ility, high EF ain advantage
ethod was ap ermination o To validate the
es were spiked ntration level n triplicate us recoveries are ata, the relative he relative re ant difference 0 µg L-1, con . The obtained w at differen he real sample
posed method ine sample.
Q and EF ob of other report yte in differen SD of the pro those reported wer MDL and The MDL wa
c- e-
t- r-), n
e-y
n-e y e, d 3 s s, d d F s
p-of
e d s
s-e e
e-s
n-d nt e d
b- t-nt
o-d d as
Table
Pestic
Diazin Chlor Malat Diazin Chlor Malat Diazin Chlor
Diazin Chlor Malat Chlor
lower or com niques even detectors. Mo high selective photometric (FID), or MS with gas chro be widely use developing co does not need simple, rapid, traction and from aqueous In a study d nebulization s to determine tography–mas MDL and R However, in µg L-1 and 4.0 conducted by that are lighte and achieved sent study.
In this stud veloped from chlorpyrifos. extraction of The proposed son with othe traction time ment factor. broad dynam were attained
Conclusion
In the prese ly optimized man urine sa tion of the an proposed opt other extracti shorter extrac enrichment fa
e 3.Comparison o cide
non rpyrifos thion
non rpyrifos thion
A
non rpyrifos
S
non rpyrifos thion
Fr
rpyrifos
mparable than those emplo ost of the men e or sensitive
detection (FP S; and all of omatography ed to analyze ountries. The d any special
, and repeatab preconcentra s samples.
done by Wan single-drop m organophosph ss spectrome SD were 1.6 the present s 07, which we y Farajzadeh e er than water w
favorable and
dy, DLLME p m aqueous s
The most imp the analyte w d procedure ha er extraction , better repro
Also, good mic linear rang
d using the DL
n
ent work, DLL for the extra amples. Differ nalyte were in timized proce ion technique ction time, be actor. The wo
of the presented m Sample
Water sample
1. 1. 1. Aqueous
sample 0.60.7 1. Summer
crops 2 4
ruit juice 0. 1 1
Urine 0.
n most of the oying mass sp
ntioned techn detection syst PD), flame io
these detecto (GC) are exp organophosph
proposed me detector, but ble and can b ation of chlo
ng et al in 201 microextraction horus pesticid etry. The res 6 µg L-1 and tudy, MDL a ere much lowe et al in 2016 were used as e d very similar
procedure wa samples for
portant effect were investigat ad some advan
techniques su oducibility, an precision, su ge, and low LLME method
LME procedu action of chlo rent effecting nvestigated an edure in com s had more a etter reproduc orthy analytica
method with other MDL
.4 µg L-1
.6 µg L-1
.6 µg L-1
65 µg L-1
74 µg L-1
.3 µg L-1
2 2 4 2 µg kg-1
4 µg kg-1 116
5 µg kg-1
µg kg-1
µg kg-1
.5 µg L-1
e mentioned pectrometry ( niques have us tem, such as f onization det ors in combin ensive and ca horus pesticid ethod in this s it still is sens be used for the
orpyrifos resi
11 (30), pneum n method was des by gas chr
sults showed 8.3, respecti and RSD were
er. Also, in stu (31), ionic liq extraction solv r results in the
as successfully the extractio tive factors fo ted and optim ntages in com uch as shorte nd higher en uitable recove
limit of dete d.
ure was succes orpyrifos from factors in ex nd developed. mparison with dvantages suc ibility, and hi al figures, suc
r methods used in
LOQ R
- - - 2.2 µg L-1
2.5 µg L-1
4.5 µg L-1
6.3 µg kg-1
1.8 µg kg-1
- - -
1 2 1 5 µg L-1 4
tech-(MS) sed a flame tector nation annot des in study sitive, e ex-idues
matic used
roma-that ively. e 0.5 udies quids vents e
pre-y de-on of
or the mized.
mpari-er ex- nrich-eries, ection
ssful-m hu- xtrac-. The h the ch as igher ch as
suita wide were ing as a effic
Ac
Th first 9223 Univ ing t Univ
Co
The
Re 1.Pa
ry. pre 2.Wa
tion ass by 201 3.Ko Go mo 200 4.Am cro fam 5.Xi
act sph 6.An IS bas 82. 7.Ra tion 8.Ko An 9.Gj asp bra n the analysis of t RSD
(%)
L
9.4 8.3 7
5-500 5-500 5-500 6
4 4
3-4000 3-4000 3-4000 5.5
9.1
5-500 10-800
1.51 2.27 1.88
4-200 4-200 4-200 4.07 5-500
able recoverie e dynamic lin e attained by
to obtained re a simple proc ciency to deter
cknowledge
his work has author, M 3491001). Th versity of Me this project. T versity of Med
onflict of Inter
authors decla
eferences wliszyn J. Sampl
Fundamentals a ehensive Analytic ang H, Li G, Zha n of triazine he sisted extraction w high-performan 12;1233(1):36-43 oohpaei AR, Sh olbabaei F. Appli olecularly imprin
08;75(4): 978–98 melin V, Lavrukh oextraction for th mily in natural wa ao Y, Zhang H. tive constituents f henanthera. Anal ndruch V, Acebal et al. Automate sed on a sequenti .
amos L. Critical o n techniques. J C okosa JM. Advan nal Chem. 2013;4 elstad A, Jensen pects of hollow f ane extraction. An
the target analyte
LR Ex
0 µg L-1
0 µg L-1
0 µg L-1
00 µg L-1
00 µg L-1
00 µg L-1
0 µg kg-1
0 µg kg-1
0 µg kg-1
0 µg kg-1
0 µg kg-1
0 µg L-1
es, good preci near range, a DLLME meth esults, the pro cedure to prov rmine chlorpy
ments
been extracte Maryam Ram
he authors wo edical Science This study rec dical Sciences
rests
are that they h
ling and Sample P and New Directio cal Chemistry); 20 ang Y, Chen H, Z erbicides in cer with solidification nce liquid chro 3.
ahtaheri SJ, Ga cation of multiva nted polymers 86.
hin D, Tret yako he determination aters by HPLC. J Homogeneous io from fruits of Sch Chim Acta. 2012 l CC, Skrlikova J d on-line dispers ial injection syste
overview of selec hromatogr A. 201 nces in solvent-m
3(1):2-13. H, Rasmussen K fiber liquid-phase
nal Chim Acta. 20 xtraction
Factor Ex tim -
-
50
50
230
ision and enric and low limit
hod. In concl oposed metho vide high pre yrifos in comp
ed from Ph.D min (researc would like to es for funding ceived funding
s.
have no compe
Preparation in Fi ons in Sample P 002.
Zhao Q, Song W, reals using dyna n of floating orga omatography. J
anjali MR, Rahi ariate analysis to (MIPs) for a
ov A. Dispersive of herbicides of Anal Chem. 201 onic liquid micro chisandra chinens
2;712(1):78-84. J, Sklenarova H, sive liquid–liqui em. Microchem J
cted contemporar 12;1221(1):84-98 microextraction te
KE, Petersen-Bje e microextraction 012;742(1):6-10. xtraction me (min)
M
20 PN
G
15 M
D G
35 U
D
HP
40 CP
4 D
HP
chment factor t of detection usion, accord od can be used
econcentration plex matrices.
D. thesis of the ch code: o
thank Tehran g and support
g from Tehran
eting interests
ield and Laborato Preparation (Com
, et al. Determina amic microwave anic drop followe Chromatogr A
mi Forushani A o the screening o ametryn. Talanta
e liquid-liquid mi f urea derivative 3;68(9):822-830. oextraction of th sis and Schisandr
Solich P, Balog d microextractio J. 2012;100(1):77
ry sample prepara 8.
echniques. Trend
ergaard S. Kineti n and electromem Method Ref
–SDME– GC–MS
(
MWA– LLME– GC–FID
(
UASE– LLME– SFO– PLC– UV
(
PE–GC– FPD
(
LLME– PLC–UV
Thi
r, n,
d-d n
e of n
t-n
.
o-
m- a- e-d A.
A, of a.
i-es
. he
ra
h n
7-
a-ds
ic
m-ference
(30)
(31)
(32)
(33)
is work
DLLME for
10.Breadmore M direct injection 1218(10):1347 11.Anastassiade easy multi-resi ing and disper ticide residues 12.Fritz JS, Mac matographic o 902(1):137–16 13.Behbahani M
zadkia M et al extraction as trace detection Food Chem. 20 14.Rezaee M, A Berijani S. Det sive liquid-liqu 15.Jamali MR,
solid- phase ex 16.Zhang YF, L factant-enhanc bined with gas mination of ph 1274(1):28-35 17.Barata C, Sol
ty of organoph bofuran) pestic 18.Omidi F, Be traction and tra and food samp Magn Magn M 19.Cruz-Vera M ments based o 1(8):1719–172 20.Pourhossein A, Seyed Som uid microextra nin using high 2017;14(4):85-21.Ho YM, Tsoi ophosphate scr herbal medicin Chim Acta. 20 22.Yan H, Du J, dispersive liqu chromatograph mestic wastew 23.Cinelli G, A assisted disper chromatograph and rapid dete in wine. Anal M 24.Sanagi MMM of organophos traction couple Malays J Anal 25.Sousa R, Ho tion and appli simultaneous d ticides in water 26.Wu C, Liu H organophospho persive liquid– ganic droplet Anal Bioanal C 27.Mukdasai S,
combined with pyrethroids in 120(1):289-29 28.Boonchiangm
pyrethroid inse liquid microex matography. T 29.Shan H. Simu
detection of c
MC. Ionic liquid-b n for capillary e 7-1352. es M, Lehotay SJ
idue method emp sive solid-phase in produce. J AO cka M. Solid-pha or electrophoreti 66.
M, Hassanlou PG l. Application of a new, fast, sim n of lead and cad 015; 187(1):82-8 Assadi Y, Milani termination of org uid microextractio Firouzjah A, Ra xtraction. Talanta Lee HK. Low-den ced-emulsification s chromatography hthalate esters in
.
layan A, Porte C. hosphorus (chlorp cides to Daphnia ehbahani M, Bojd
ace monitoring o ples based on m Mater. 2015;395(1 M, Lucena R, Ca on dispersive (m 28.
M, Shahtaheri SJ meah M, Divani R action method for performance liqu -94.
i YK, Leung KSY reening in twelve nes by dispersiv 013;775(2):58-66. , Zhang X, Yang uid–liquid micro hy for simultaneo waters. J Sep Sci. 2 Avino P, Notardo
rsive liquid–liqu hy with a nitrogen ermination of org
Methods. 2014;3 M, Miskam SU, sphorus pesticide ed with gas chro Sci. 2011;15(2): omem V, Moreira ication of disper determination of
rs. Anal Methods H, Liu W, Wu Q orus pesticides in –liquid microextra followed by hig Chem. 2010;397( , Thomas C, Sr h high performan n water and 6.
ma S, Ngeontae ecticides in fruit xtraction combine Talanta. 2012;88(1 ultaneous determ
chlorpyrifos in
based liquid phas lectrophoresis. J
J, Stajnbaher D, ploying acetonitri
extraction for the OAC Int. 2003;86 ase trapping of so
ic analysis. J C
G, Amini M, Om solvent-assisted mple and reliable dmium ions in fr
8.
Hosseini MR, A ganic compounds on. J Chromatogr ahnama R. Solv a. 2013;116(1):45 nsity solvent-bas n liquid–liquid y–mass spectrom n bottled water. J
. Role of B-estera pyrifos, malathio magna. Toxicol. di MK, Shahtahe f cadmium ions i modified magneti
1):213-220. ardenas S, Valca micro) extraction
J, Maleck Khani R. Optimization o r determination of uid chromatograp
Y. Highly sensitiv e commodities of ve liquid–liquid
.
G, Row KH, Lv oextraction coupl ous analysis of n 2010;33(12):1829 onato I, Russo M uid microextracti n–phosphorus de ganophosphorus p
:782-790. Ibrahim MA, Wa es by dispersive l omatography-elec
232-239. a JL, Madeira LM
rsive liquid–liqu carbamates and o s. 2013;11:2736-2 Q, Wang C, Wan n environmental action with solidi gh-performance l (6):2543-2549.
rijaranai S. Two nce liquid chrom vegetable samp
W, Srijaranai S. juice samples u ed with high per 1):209-215. mination of six ne
n urine
se microextraction Chromatogr A.
Schenck FJ. Fa le extraction/ par e determination o 6(2):412–431.
olutes for further Chromatogr A.
midi F, Esrafili A dispersive solid-e prsolid-econcsolid-entratio uit and water sam
Aghaee E, Ahma s in water using d r A. 2006;1116(2 vent-assisted disp
4-459. ed vortex-assiste
microextraction metry for the fast J Chromatogr A.
ases in assessing t n) and carbamate 2004;66(2):125– eri SJ. Solid pha in environmental c nanoporous si
arcel M. Sample . Anal Method.
H, Rahimi Forou of dispersive liqu
f trace salivary m phy. Iran Occup H
ve and selective o f fruits, vegetable microextraction.
Y. Ultrasound-as led with capillar nine pyrethroids
9-1835. MV. Ultrasound-v
ion coupled wit tector for simulta pesticides and tri
an WA. Determi liquid-liquid mic tron capture dete
M, Alves A. Opt id microextractio organophosphoru 2745.
ng Z. Determinat water samples b ification of floati iquid chromatog
o-step microextr matographic analy ples. Talanta.
. Determination sing dispersive li rformance liquid
eonicotinoid resid n with
2011;
ast and rtition-of
pes-r chpes-ro- chro-2000;
A, Far-phase on and mples.
adia F, disper-2):1-9. persive
ed sur- com- deter-2013;
toxici-e (car-–139. ase
ex-l water ilica. J
treat-2011;
ushani uid liq- melato-Heal J.
organ-es and . Anal
ssisted ry gas in
do- vortex-th gas aneous iazines
ination cro
ex-ection.
timisa-on for us
pes-tion of by dis-ing or-graphy.
raction ysis of 2014;
of six iquid– d
chro-dues in soi 33( 30.P pho ext on 34( 31.Z poi the fru Foo 32.W tion term ma 33.F cro for cid 48(
l using DLLME (9):2553-2557. Pirsaheb M, Fattah
orous pesticides traction followed the solidificatio (2):378-385. Zhao WJ, Sun XK
int extraction co e determination o uit juice by gas
od Chem. 2011;1 Wang Y, Wang Z n of pneumatic n mination of Orga ass spectrometry. Farajzadeh MA, A owave-accelerated r extraction and p de residues from
(1):73-80.
E-HPLC and UV
hi N, Shamsipur in summer crops d by dispersive li n of floating or
K, Deng XN, Huan upled with ultra of organophosph chromatography
27(2):683-688. , Zhang H, Shi Y nebulization singl anophosphorous p J Sep Sci. 2011;3 Asghari A, Feridu d dispersive liqu pre-concentration
aqueous sample
V. Spectrosc Sp
M. Determinatio s using ultrasoun iquid-liquid micr rganic drop. Foo
ang L, Yang MM, asonic-assisted ba
horous pesticides with flam photo
Y, Ren R, Zhang le-drop microextr pesticides by gas 34(15):1880-1885 uni B. An efficie uid–liquid microe n of some organo
les. J Food Com
pect Anal. 2013
on of organophos nd-assisted solven roextraction base od Control. 2013
, Zhou ZM. Clou ack-extraction fo s in concentrate ometric detection
g H et al. Applica raction for the de chromatography– 5.
ent, rapid and mi extraction metho ophosphorus pesti mpos Anal. 2016 3;
s-nt d 3;
d or d n.
a- e-–
i-d i-6;
