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NHNG THCH THC TRONG PHN

TCH KIM NGHIM THC PHM


HIN NAY, MI QUAN TM LN
CA CC PHNG KIM NGHIM
Nguyn Hng Tho, Nguyn Phng Phi, V Trng Duy, Nguyn S Hong Lin,
V Phng Tho, inh th H Long, Phm th nh, Chu Phm Ngc Sn
Hi Ha hc TP H Ch Minh
Cng ty Dch v KHCN Sc K Hi ng

PHN TRNH BY
I. NHNG S KIN V AN TON THC PHM
II. CC HA CHT C HI
III. NHNG THCH THC TRONG PHN TCH
KIM NGHIM M BO AN TON THC PHM

I. NHNG S KIN
1.Cung cp thc phm (TP) hin nay mang tnh ton cu i hi phi
tng cng gim st m bo an ton thc phm (ATTP)
2. Thc phm hin rt nhiu v phc tp, ph gia thc phm rt a dng,
an xen vi ha cht c kh nng gy c c tnh hay do thiu hiu bit c
cho thm vo to c mt c trng nhm t li nhun bt chnh
3. Mc nguy him c th rt ln i vi nhng thc phm sn xut ti cc
nc c h tng cha tht pht trin v c cu gim st cha tht hiu qu
Cc mi nguy him: vi sinh, vt l, ha hc, hng nhi
4 Mt chuyn ngnh gi l Foodomics
chuyn nghin cu thc phm
(dinh dng, thc phm bin i gen, protein hc, c cht hc lin quan)

TNH TON CU CA S LY NHIM MELAMINE

Trong nhng nm gn y, hng ho Vit Nam xut khu nhn chung c cht
lng tt hn nh cc bin php qun l cht ch, h thng phng kim nghim
ngy cng c tng cng v hot ng c hiu qu
H THNG THNG BO V CNH BO CA CHU U V CHT LNG
THC PHM CHO NGI V THC N CHN NUI
Nm

S l hng khng t
yu cu

Th
hng

Nm

S l hng khng t
yu cu

Th hng

2002

67

2007

45

18

2003

19

35

2008

56

15

2004

59

13

2009

100

11

2005

124

2010

71

13

2006

68

13

2011

109

*Trong nc, v sinh an ton thc phm (VSATTP) vn cn b e da v hin


ang l mt vn bc xc\ca x hi.
*Qun l VSATTP vn cn phn no lng lo, cha tht m bo TP an ton.

Vic nhim vi khun c hi vn cn chim t l kh cao.


*Vi tc th ha v cng nghip ha, tng dn s kh nhanh hin nay,
nu qun l khng cht, nhim cho t c cht mi trng nh hng khng
nh n VSATTP

*Vic gi nhn hiu, vic s dng nhng ha cht nhi ph gia TP c th nguy
hi cho sc khe ngi tiu dng, v mc ch li nhun phi php, to nhiu vi
phm v ATTP:
-melamine trong sa v sn phm t sa, ng cho vo mt ong
-DEHP dng lm cht to c, phm mu cng nghip b cm dng trong TP,
-nc tng nhim 3-chloro-1,2-propandiol (3-MCPD)
- phm mu cng nghip rhodamine B nhum ht da, 2,4-diaminoazobenzene
dng nhum g vt cho c mu vng ti, orange II nhum tht quay v tht x xu
cho c mu cam ti bt mt .
-khng sinh, cht dit nm mc trong nui trng thy sn,
-ha cht tng trng b cm: clenbuterol v salbutamol, ractopamine , to tht siu
nc trong chn nui gia sc gia cm
-trifluralin trong thy sn v ethoxyquin trong tm do b nhim t thc n.

VSATTP ca thc n ng ph: vn rt ng lo

CAC S KIEN VE NGO OC THC PHAM


SO VU NGO OC SO NGI B NGO
THC PHAM
OC THC PHAM

SO NGI
CHET

1997-2000

1391

25 509

217

2001

245

3 901

63

2002
2005
2006
2007
2008
2009
2010
2011
2012 (n 12/2012)

208
144
165
248
205
152
175
148
164

4 894
4 300
7135
7329
7828
5200
5664
4700
5400

71
53
57
55
61
35
51
27
33

CHI PH/NM

Trung bnh 200 triu USD theo WHO (10/2007)

Nhng kh khn trong gim st, kim nghim ATTP


*Trong tnh hnh sn xut hin nay, kh d on ht tt c nhng
cht nguy hi c th c trong thc phm v thc n chn nui v do
rt him khi kim sot chng trn vn.
Vic nhp khu phi php qua bin gii nhng ha cht, sn phm
khng r ngun gc, vic qun l cn lng lo cc ph gia thc phm
trong nc cng lm trm trng thm s mt VSATTP.

* Ph gia TP vn by bn chung vi ho cht dng cho mc ch

khc, qun l Nh nc cha quy nh rch ri, to iu kin cho


ngi sn xut, v li nhun bt chnh, lm dng trong ch bin
TP.
* Lu

cng mt ha cht nhng s dng cho thc phm


th kht khe hn nhiu so vi nhiu mc tiu cng
nghip khc.

*Cc quy nh v tiu chun VSATTP nhiu nc trn th gii ngy

cng kht khe, thng xuyn c duyt li, cc n v kim nghim


phi lin tc ci tin cc phng php kim nghim ph hp hn v nu
khng th c xut khu cng b e da.
Cc phng th nghim cung cp dch v kim nghim thc phm phi
i mt vi nhng gii hn lin tc c h thp v mc nhim ha
cht c th gy nguy him.
*Nhng hot ng kim nghim cng lc cng tng cng c th to nh
hng xu n sc khe con ngi v mi trng vi vic s dng
nhng lng ln ha cht v dung mi c hi c thi b thiu kim
sot sau .
*Vic

ci tin cc phng php kim nghim lm


gim thiu ti a nguy hi cho sc khe v mi
trng sng l rt cn thit.

*Nhiu phng tin kim nghim hin c trong nc ch yu

kim sot c cc i tng nhm n ch cha cho php


nhn din thm cc cht l khc khng nm trong tm nhm.
Ngun nhn lc c trnh chuyn mn cao, kinh nghim cn
mng.
*khng c nhng phng tin kim nghim ph hp qun l tt cht
lng thc phm th xut khu sang EU, Bc M, Nht s b e da.
*Ngay c trong nc, ngi tiu dng ngy nay cng ngy cng thc r
cht lng thc phm khng phi ch l ngon ming, bt mt m cn phi
an ton, khng gy hi n sc khe.

Bo co ny xin c gii hn vo nhng phc tp trong kim


nghim ha cht hu c c hi trong thc phm bng cc
phng php sc k nhm gp phn vo m bo VSATTP
trong tnh hnh thc t hin nay ca Vit Nam

Agilent GC-MS/MS

II.CC LOI HA CHT HU C C HI


C TH PHT HIN TRONG THC PHM
1. Ha cht c gc t nhin:
* Cyanogenic glycosides trong mng, khoai m
* Tetrodotoxin trong c nc v trong mt s
hi sn khc
* c cht sinh hc bin trong cc loi nhuyn
th hai mnh v (ASP, DSP,PSP)
* Mycotoxins (aflatoxin, ochratoxin)
* Histamine v cc biogenic amines khc

2. Cc loi thuc bo v thc vt


b cm hoc dng qu gii hn
cho php:
* organochlorides,
* organophosphates,
* carbamates, pyrethroids,
triazines, trifluralin

3. Cc loi thuc th y, dc liu b cm hoc dng qu gii hn cho


php ( tetracyclines, sulfonamides, aminoglycosides, chloramphenicol, malachite
green, crystal violet, nitrofurans, fluoroquinolones, nitroimidazoles, beta-agonists
nh clenbuterol, salbutamol, ractopamine)
4. Ph gia b cm hoc dng qu gii hn cho php (cht bo qun,
phm mu)

5. Ha cht c sinh ra trong qu trnh ch bin thc phm


(acrylamide, 3-chloro-1,2-propandiol, 1,3-dichloro-2-propanol)

KHNG SINH

ACRYLAMIDE

3-MCPD

6. Ha cht c gc mi trng ( kim loi nng, alkylphenols, PAH,


PCB, dioxins..)

7. Ha cht c thi ra t bao b (styrene, dialkyl phthalates, bis


phenol A)

8. Ha cht nhi (Adulterants) nhm to mt c trng cho thc


phm (melamine gi tng m, ng saccharose gi glucose,
fructose tng ngt mt ong, sa pha long vi nc, phm mu
Sudan trong bt t, bt cary, DEHP to c)

DEHP

MELAMINE

BIS PHENOL A

Acrylamide
OC CHAT DE SINH RA T CACH CHIEN, XAO NNG LAM THC AN CUA
TA.
HAM LNG ACRYLAMIDE AC BIET CAO TRONG KHOAI TAY CHIEN.
IARC SAP ACRYLAMIDE VAO LOAI CO KHA NANG GAY UNG TH CHO NGI (Class
2A, LD50 chuot 107/mg/kg the trong).

HAM LNG ACRYLAMIDE


Hm lng
Loi thc phm

[g/kg]
min.

max.

Trung
bnh
[g/kg]

Hm lng
Thng gp

So mau
nhiem

Khoai chin lt
mng

192

140

3640

819

1000

76

Khoai cng chin

98

< 10

2779

151

570

11

Bnh biscuit, bnh


nng

38

< 10

1090

190

660

C ph bt

30

115

1685

343

370

14

Bnh m nng
ming nh

32

15

1714

133

610

Ng cc n sng

32

< 10

846

65

260

Asparagine

Nhit, ng
(glucose, fructose)

Acrylamide

Cht beo trans (Trans fat) trong thc phm chin vi


du thc vt
*T

phn ng hydrogen ha cc cht bo c nhiu ni kp trn


dy triglycerid
*T s dng phn ha cht bo dng cis thnh trans trong qu
trnh chin nng lin tc thng qua s hnh thnh gc t do
nhit
Acid elaidic (trans)

Canada: nh hn 0,2 mg/ phn n


M
: nh hn 0,5 mg/ phn n
Trng hp ny c th ghi:
TRANS FAT = 0

Acid oleic (cis)

Nguy c thc phm b nhim cht c thi ra t bao bi


Mt s loi bao b cho thc phm cha nhng ph gia c th
thi ra v i vo thc phm v gy nhim thc phm:

-Cht ha do DEHP (thng gi l DOP) trong cc bao b


PVC d dng thi vo thc phm, nht l cc thc phm nhiu
bo.
-Nhiu cun loi nha trong dng bc thc phm a vo l
nng hay l vi sng thc cht l nha PVC vi cht ha do
DOP, d dng thi DOP vo thc phm nhit cao.
-Formaldehyde t chn a bng nha melamine formaldehyde
c th thi vo thc phm khi s dng nhit cao.

DEHP
O

DBP
CH2 CH3

C O CH CH (CH ) CH
2
23
3

C O (CH ) CH
23
3

C O CH2 CH (CH2)3 CH3


CH2 CH3
O

C O (CH2)3 CH3

DEHP : trong cac loai bao b, tham trai


nha, ao i ma
bang PVC

DBP : my pham

Environment Health Perspect, 108,895-900 (2000)

QUI NH CHAU AU 90/128/EEC:


-SO LNG TOI A CHAT THNG T BAO B I VAO 1KG THC PHAM
LA 60 MG HOAC 10MG/DM2 DIEN TCH BAO B
-VI CHAT OC CO QUI NH RIENG

QUI NH NAY CUNG C VIET NAM AP DUNG (QUYET NH 3339/2001/QBYT NGAY 30/7/2001).
TUY NHIEN, TRONG DANH SACH CAC HOA CHAT CO THE THOI RA TH
OI VI ESTE PHTALAT, VIET NAM CH LIET KE DIETHYL PHTALAT.

Pht hin c cht phthalate trong nc gii kht


50 loi nc gii kht cha c dc gy hi c pht
hin Trung Quc. i Loan va pht hin mt cng ty sn
xut cht to c dng trong thc phm v ung c s
dng ha cht DEHP rt c hi cho sc khe
(26/5/2011).

O
C

Di(2-ethylhexyl)
phthalate (DEHP)

C
O

CH2CH3
OCH2CH(CH2)3CH3
OCH2CH(CH2)3CH3
CH2CH3

Bisphenol A, ha cht c c th
thi ra t cc binh sa

Vit Nam c quy nh mc BPA cho php l 2,5 mg/kg (Quyt


nh 46/2007/Q-BYT).
Kt qu cc mu kim nghim BPA thi nhim t bnh sa tr
em do Vin Kim nghim An ton v sinh thc phm Quc gia
tin hnh u thp so vi quy nh hin hnh (ti cng ty Sc

K Hi ng:0,7 ppm trn mt s chai sn xut ti


Nht).
Theo cc nghin cu ti M, BPA c
th gy tn thng no, nh hng
ti kh nng sinh sn, thay i chc
nng h min dch, v lu di c
nguy c gy ung th.

Phm mu cng nghip


Gan ay, mot so mau cong nghiep a c tm thay trong thc pham va a c chau Au xep vao
loai doi tng kiem tra:

N N

NH2

H2N

Orange II
Tht heo quay, x xu

2,4-diaminoazo
benzene
g, vt ti sng

Rhodamine B
ht da

Para Red
gia v, mt s loi ht

III.NHNG THCH THC C TRNG


TRONG PHN TCH KIM NGHIM
M BO AN TON THC PHM

III.1. CHUN BI MU: chit ra c cht phn tch t nhng nn


mu thng rt phc tp: tht , c, sa, mt ong, thc n a dng
III.2. PHNG PHP O:
* pht hin va o c chnh xc nhng lng cht tht nh, nht
l i vi nhng cht c b cm hn, khng c c trong thc
phm, phng php khng to m tnh gi hay dng tnh gi
* c th pht hin v nh lng c nhiu cht c trong mt
ln x l mu
* phng php phi n nh, p dng c cho nhiu nn mu
tng t, nhanh, t tn ha cht, dung mi nht l ha cht dung
mi c hi, bo m an ton cho sc khe, khng gy hi mi
trng
III.3. PHT HIN C NHNG CHT KHC (NONTARGETS, UNKNOWNS) NGOI CC CHT NHM N
(TARGETS)

PHT HIN V INH LNG


*c

cht trong thc phm ch yu dng vi lng rt kh pht


hin v phn tch, c bit trong nn mu phc tp
* Phng php phn tch lun ci tin:
-p ng tiu chun ngy cng kht khe
-nhanh, ng, lp li tt, khng lm nhim mi trng, khng
gy hi n sc khe
THERMO TSQ
8000 GC-MSMS

III.1. CHUN BI MU
Chit cht phn tch
(Extraction)

Mc ich:

Lm m c v tinh ch
loi tp (Clean- up)

nh lng
GC-MS; GC-MS/MS
LC-MS, LC-MS/MS

Xc nhn ng cht phn tch, tng nhy ca


phng php, bo v thit b phn tch

KH KHN TRONG CHUN BI MU:


Nn mu phc tp
* Cht phn tch dng vt
* S cht phn tch c th nhiu v kh khc bn cht
* Cht phn tch c th to phn ng vi nn mu
*Tp ng chit vi cht phn tch (co-extractants) gy kh trong
clean-up
*Thi gian dnh cho chun b mu c th chim n trn 70% ton
thi gian hon tt phn tch

Khu ny c th gy hi cho sc khe ngi v cho mi


trng sng nu s dng nhiu ha cht c hi
Cn p dng nhng nguyn tc ca ha hc xanh trong chun
b mu

Trong khu ny, xu hng chung hin nay l phi t c


nhng mc tiu sau y:
- chit c cng lc nhiu cht,
- hiu sut chit phi t gn 100%,
- gii hn pht hin phi thp,
- t tp cht i km theo gim ti a nh hng ca nn mu v
tng chn lc,
- lp li tt, n nh ca phng php chit t tt,
- p dng c cho nhiu nn mu khc nhau,
- s dng cng t mu cng tt nhm gim hiu ng nn, nhng
phi m bo c tnh i din ca mu phn tch,
- s dng t ha cht trong tch chit, an ton cho ngi
thao tc, t gy nhim mi trng,
-nhanh, d thao tc, gi thnh thp.
-Trong mt s trng hp, phng php nh lng trc tip
trn my, nu c, rt c khuyn khch.

Nhng vn cn ch trng khu ny:


* bn cht ca nn mu, bn cht ca cht phn tch

*mc hp ph ca cht phn tch trn nn mu, thm ch c


th phn ng vi mu
* bn cht ca tp:
hm lng tp i km khng nhng gy kh khn trong tch
chit cht phn tch, to m tnh gi hay dng tnh gi m
cn c th to tr ngi trong khu nh lng.

H QU
* Sc km cht lng
* Kh khn trong nhn danh cht phn tch
* Gim nhy khin khng phn tch c lng nh cht
* Gim kh nng to ion t cht phn tch, nht l u to
ion ESI, dn n nh lng sai nu khng c bin php ph
hp
* lm bn h my phn tch, gy nght ct.

Cc k thut tch chit v clean-up thng dng:


k thut chit lng siu ti hn (Supercritical Fluid Extraction SFE),
k thut chit nhanh vi dung mi (Accelerated Solvent Extraction ASE),
k thut sc k gel (Gel Permeation Chromatography GPC),

k thut chun b mu trc tuyn,


k thut clean-up bng ly trch trn pha rn c ci tin (Solid Phase Extraction
SPE) nh:
- ct Mixed Mode SPE,
- ct c hiu MIPSPE,
- ct i lc min dch (Immunoaffinity column),
- b kit QuEChERS p dng cho phn tch thuc bo v thc vt, dc
m rng ra thm cho mt s i tng khc nh, khng sinh, thuc th y,
k thut phn tch trc tip trn my (HS-GC, SPME- HS-GCvi u d khi
ph nu c

Chit nhanh ASE

Vi ly trch trn pha rn

Phn tch pha hi Headspace

Hot ha

Np mu

H Combi-Pal

Ra loi tp Ra gii

Ly trch trn pha rn SPE

HEADSPACE GC, HEADSPACE- GC/MS

Gn nh khng chun b mu

PHN TCH PHA HI T I HI CHUN BI MU


Phng php thm chun
V mu
ml

Vtng
ml

Cchunthm
ppm

Cng
mi sc k

Vnc
l

VMeOH std
l

Cstd
ppm

0.5

80

30400

0.58

0.00

1254132

0.5

70

10

30400

0.58

524.16

2230763

0.5

60

20

30400

0.58

946.71

2809327

0.5

40

40

30400

0.58

2096.55

4707576

Ct ng chun
(ppm)

795.91

5000000

Area

4000000
3000000
2000000

y = 1629.6403x + 1297053.7546
R2 = 0.9986

1000000
0
-1000

1000

2000

3000

C (ppm)

nh lng Metanol trong mu ngi say ru

Phn tch tp cht trong du bo bng k thut


HS-SPME-GC-MS
Du thc phm olein c gi n cng ty Sc K
Hi ng tm cht l to mi v khc thng so
vi mu nhp trc y

Mu C, i chng

Mu B

Dy hydrocarbon chun

C13

C14

C15

C16

C17

Mu B

C13

C14

C15

C16

C17

C18

Mu D
C12

C13

C14

C15 C16 C17

C14

C15 C16

Mu E
C12

C13

C17

B KIT EZ:Faast CA PHENOMENEX

Nguyn tc
Phng php EZ:faast nguyn thy c p dng cho phn tch aminoacid.
Aminoacid trong mi trng acid c cho qua v gi li trong mt u lc
cha nha trao i cation, sau c n vo mt vial thy tinh v c
chuyn ha nhanh bng n-propyl chloroformate trong chloroform. Sn
phm chuyn ha c chit khi mi trng phn ng bng isooctan . Mt
lng dung dch c em thi kh di N2 v nh mc li bng pha ng
, lc v tim vo my LC-MS/MS.

SO3 H

+ R

CH

NH3

COOH

u lc SCX

SO3

H3N

CH

COOH
Ra vi nc kh ion

SO3

H3N

NaOH
CH

Ra gii

COOH

SO3 Na

CH

COO

NH2

RCH
NH2

COO

Cl

CH2CH2CH3
Chuyn ha

O
Cl

CH2CH2CH3

GC/MS; LC/MS, LC/MSMS

CH COOCH2CH2CH3
NHCOOCH2CH2CH3
Isooctane

Sn phm chuyn ha

PHN TCH AMIN BIOGEN (Biogenic amines)


Sinh ra t s decarboxyl ha aminoacid di tc dng enzim

ng chun cho amin biogen


Intensities of Ions for Quantitation

Conc. of A
(mg/L)

A/512

A/128

A/64

A/16

A/8

A/2

Phenethylamine

23.776

11137

43830

98330

356097

721678

2843597

Tryptamine

24.057

161497

665310

1239572

4729615

9534987

35716484

Putresceine

24.746

220446

883123

1633455

6632519

13265038

52943154

Cadaverine

47.134

569946

2263573

4533683

18881438

38013484

140317910

Histamine

10.094

91637

365599

770881

2681246

5406498

20467821

Tyramine

18 334

346657

1373636

2910502

12072790

24975146

98137104

Spermidine

12.375

20349

81682

184494

644621

1304684

5097514

Serotonine

15.741

94037

372146

683018

2948357

5913565

21551005

Spermine

28.906

22219

90016

194243

786734

1590137

6005443

BA

-2-phenethylamine: y = 568351 x + 3563


-Tryptamine:
y = 7 133 502 x +170484
-Putresceine:
y = 10 586 246 x + 15625
-Cadaverine:
y = 28 060 272 x + 648712
-Histamine
y = 4 086 002 x + 93564
-Tyramine:
y = 19 652 779 x + 40998
-Spermidine
y = 1 018 489 x + 10374
-Serotonine
y = 4 308 694 x + 120835
-Spermine:
y = 1 201 369 x +17 763

R2 = 0.9999
R2 = 0.9997
R2 = 1.000
R2 = 0.9995
R2 = 0.9998
R2 = 1.000 .
R2 = 0.9999
R2 = 0,9993
R2 = 0.9998

Sc khi ca mu nc mm M4

Phenethylamine

Histamine

Tyramine
Putresceine

Spermidine
Tryptamine
Serotonin

Cadaverine

Spermine

Kt qu phn tch amin biogen trong mt s mu

1.Mu + dung mi+ m


+ IS + Mg SO4 , lc 1 pht

2. Ly tm 2 3 pht

5. Cho vo LC-MSMS

4.Ly tm 2 3 pht

5. Cho vo GC-MS

3.Ly lp trn cho


vo C18, PSA,
MgSO4 clean-up

K THUT QuEChERS

K thut QuEChERS
*Lm n gin ha khu chun b mu so vi truyn thng
*Rt it tn thi gian
*Ph hp vi ha phn tch xanh
-khng i hi thy tinh th nghim phc tp
-it tn dung mi, ha cht
-t cht thi
-t gy nhim mi trng

PHM VI P DNG
*Thc

phm:

d lng ha cht s dng trong nui trng c kh nng gy hi


cho ngi thng qua dy chuyn thc phm
*thuc tr su, dit c, dit nm mc, cht bo qun
*khng sinh
*cht tng trng
*ph gia s dng qu mc cho php

Mi trng

*Cht thi c hi t nh my
* Kim loi nng
*PCB, PAH, dioxins
*Mycotoxins

NH LUNG TRIFLURALIN TRN NN C BASA BNG GCMS

PHNG PHP INHLNG

TRIFLURALIN
TRN NN C

Chun b mu theo phng php QuEChERS


Giai on 1: Chit
Mu xay nhuyn
cn 5 gram
1,25 ml ni chun
trifluralin d14 10
ppb

Vortex

13.75 ml AcOH 1%
/ACN

Lc u

6 g MgSO4 v 1,5
g NaOAc

Giai on 2: Clean-up
Ly tm 4000
vng/pht, 5 pht

Hiu sut thu hi trn 91%


(0,25-1,25 g/kg trong c)
LOD : 0,02 g/kg trong c
Gii hn ti a cho php:
1 g/kg c
nh hng nn: khng c

Chit
lp trn
Lc u, ly tm 4000
vng/pht, 5 pht
Rt 12 ml lp trn, thi
kh bng kh N2

nh mc 1 ml bng
hexane, lc tim vo
my GCMS

1 g MgSO4 + 300
mg C18

MT S KT QU PHN TCH THC NGHIM

IV. MT S KT QU PHN TCH THC NGHIM

Bng 10. Mt s kt qu phn tch thc nghim


Tng s mu phn tch t thng 04-2010 n thng 10-2010 l 132 mu. S
mu nhim trifluralin 50 mu

Loi mu

C basa
fillet

Ch c

Hi sn

S lng mu

99

11

22

S mu nhim
29
11
10
trifluralin
Hm lng 0,3 n 44,7 1,9 n 158,5 0,3 n 59,1
trifluralin
g/kg
g/kg
g/kg

THEO MT TI LIU, CC PHNG PHP CHUN


BI MU C S DNG NHIU LABO TRN TH
GiI GM:
1.
2.
3.
4.
5.

SPE
QuEChERS
CHIT LNG LNG HAY CHIT RN LNG
LC QUA A
KHC

50 %
37,5 %
31,2%
62,5%
18,2%

III.2. CI TIN THIT BI PHN TCH


III.2.1. Thit b sc k
1.K thut sc k lng siu nhanh (UPLC) gim ng k thi gian
phn tch tng nhy v phn gii.
2.Nhng loi ct sc k lng c bit nh ct Poroshell, ct a c
ch Mixed Mode, ct Hilic gp phn nng cao kh nng phn tch
ca thit b.
3.Sc k kh nhanh vi ct ngn, ng knh nh v pha tnh
mng rt ngn bt thi gian phn tch.
4.K thut backflush gip bo v ct phn tch t b d
m bo tt hn kt qu phn tch,
5.K thut GCxGC vi phn mm deconvolution tch mi
nhn din chnh xc cc cu t c thi gian lu rt gn nhau trong
hn hp a cu t phc tp .

CT LI RN POROSHELL, KINETEX, ACCUCORE


nhy tng

phn gii tng

Mi thon:
* phn gii tng
* nhy tng, LOD h thp
*o a d lng c hiu qu

HPLC

NEXERA

ACCELA

FLEXAR FX
15

UPLC

AGILENT 1290

III.2.2. Ci tin u d khi ph


1.Li th:
*xc nhn tt ha cht bng thi gian lu v ph (GC-MS) hoc nh
nhng mnh ion c trng (GC-MSMS, LC-MS, LC-MSMS)
nh lng tt nh nng cao nhy bng cch kh nhiu nn thch
hp.
2.GC-MS, LC-MS: s dng nhiu trong nc phn tch vt hu c
trong thc phm
3. LC-MSMS v gn y GC-MSMS: s dng phn tch d lng trong
nhng nn mu phc tp
4.Cc u d khi ph lin tc c ci tin bn khu:
*hiu sut to ion b phn to ion,
*hiu sut chuyn ion ca b phn chuyn ion t b to ion n b phn
tch khi,
*cch kh cc tp trung ha trong qu trnh to ion hay phn mnh ion,
*cch pht hin ion detecto

Mc tiu cui cng:


tng nhy v phn gii,
cho php phn tch nhng hm lng cht rt nh trong nn thc phm rt phc
tp

L ra hp hn-tp
trung ion vo Q3

L vo rngion vo nhiu

LC-MSMS ca Thermo Fisher vi k thut H-SRM cho


php ci t Q1=0,1 Da, loi c cc ion c phn t khi rt
gn ion phn tch , do tng phn gii v chn lc

Thc phm

Mi trng

Khoa hc ca s sng

Ch SIM (mt t cc)

Ch MRM ( ba t cc)

Isoprothiolane trong gng (1ppb)

Hexa BDE trong bn

Metabolit (suberic acid) trong nc tiu chut

III.3. Phn tch a d lng hp cht nhm n


v nhng hp cht khng nhm n (Target,
Non-target, Unknown analytes)
Thit b hin i GC-MSMS ba t cc QqQ v UPLC-MSMS ba
t cc QqQ:
-s dng nhiu hin nay trong nc do c nhy v phn gii tng, thch
hp cho phn tch vt hu c.
-gii hn ca u d khi ph 3 t cc
khng th nhn danh c
ha cht hon ton khng bit.

-khc phc: ngoi cht phn tch nhm n, phn no c th nhn din c
thm nhng cht khc bit nu c c s d liu (non-target known
analytes) ci sn trong my (tin ion + 2 mnh ion con + khong thi gian lu
+ t l ion) thng qua phn mm thch hp. S cht nhn din c c th
n vi trm cht.
.

Target:
-cht cn phn tch thng qua GC-MS, LC-MS tt nht l qua
GC-MS/MS hay LC-MS/MS
-i hi c chun v ni chun so snh thm thi gian lu

Non-Target:
-i hi c d liu, ion phn t, ion phn mnh, 2 mnh
ion con, thi gian lu, t l ion
-gii hn bi s d liu trong c s d liu database

Cht khng bit (unknown) : cht mi khng c trong c


s d liu

Yu cu khch hng: nh lng carbaryl trong nho


iu kin vn hnh my
Column
Mobile phase A
Mobile phase B
Gradient program

: GL InertSustain C18 ( 150 mm x 2.1 mm., 3 m)


: 0.1 % formic acid in Water
: 0.1 % formic acid in Methanol
: Time (min)
1.00
2.00
4.00
5.00
7.00
10.00
10.50
14.00

Flow rate
Injection volume
Column temperature

: 0.2 mL / min
: 5L
: 40

MS
Nebulizing gas flow
Drying gas pressure
DL temperature
BH temperature
Interface
CID Gas

: SHIMADZU LCMS-8030
: 1.5 L / min
: 10 L / min
: 250
: 400
: ESI
: 230 kPa

B Conc.
B Conc.
B Conc.
B Conc.
B Conc.
B Conc.
B Conc.
Stop

40
60
60
80
100
100
20

Compounds
Methomyl
Methomyl
Acephate
Acephate
Carbendazim
Carbendazim
Isoprocarb
Isoprocarb
Carbaryl
Carbaryl
Fenobucarb
Fenobucarb
Propoxur
Propoxur
Aldicarb
Aldicarb
2,4 D
2,4 D
Carbofurane
Carbofurane
Aldicarb-sulfone
Aldicarb-sulfone
Methiocarb
Methiocarb
Oxamyl
Oxamyl

m/z
CE (V)
163.00>87.90
10
163.00>106.00
12
184.10>124.60
20
184.10>143.00
10
191.90>132.00
31
191.90>160.05
19
194.20>77.00
35
194.20>95.10
16
202.00>127.00
28
202.00>145.10
15
208.10>77.10
30
208.10>95.10
16
210.20>152.90
10
210.20>168.00
10
213.00>70.00
25
213.00>89.00
25
218.85>125.00
30
218.85>161.00
15
222.10>123.10
22
222.10>165.20
12
223.10>123.00
24
223.10>166.20
12
226.10>121.20
12
226.10>168.60
20
237.10>72.10
30
237.10>108.90
30

Compounds
Carbofurane-3OH
Pirimicarb
Pirimicarb
Imidacloprid
Imidacloprid
Thiamethoxam
Thiamethoxam
Tebuconazole
Tebuconazole
Tebuconazole
Flusilazole
Flusilazole
Propiconazole
Propiconazole
Thiodicarb
Thiodicarb
Difenoconazole
Difenoconazole
Chlorantraniliprole
Chlorantraniliprole
Indoxacarb
Indoxacarb
Emamectine benzoate
Emamectine benzoate
Abamectine
Abamectine

m/z
CE (V)
238.50>181.30
10
239.00>72.00
35
239.00>182.00
35
256.00>175.00
15
256.00>209.10
19
291.90>181.00
15
291.90>211.20
25
308.10>57.10
30
308.10>70.00
50
308.10>125.10
40
316.00>165.10
30
316.00>247.15
20
342.00>69.10
20
342.00>158.95
20
355.00>88.10
20
355.00>108.10
20
406.00>187.00
30
406.00>250.95
30
484.00>285.80
15
484.00>453.05
15
528.00>150.00
30
528.00>218.00
30
886.50>81.90
50
886.50>158.25
45
896.00>448.80
45
896.00>751.10
50

Chromatogram of Grape sample detected some kinds of pesticide

CARBENDAZIM
DETECTED

EMAECTIN BENZOATE
DETECTED
DIFENOCONAZOLE
DETECTED

CARBARYL NOT
DETECTED

TEBUCONAZOLE
DETECTED

Compounds

m/z

Re. Time

Area

Result (g/kg)

Compounds

m/z

Re. Time

Area

Result (g/kg)

Methomyl

---

NDCarbofurane-3OH

---

ND

Methomyl

---

NDPirimicarb

---

ND

Acephate

---

NDPirimicarb

---

ND

Acephate

---

NDImidacloprid

256.00>175.00

5.232

5738

ND

4.56
4.563

253980
1378045

5.22 Imidacloprid
5.22 Thiamethoxam

256.00>209.10

5.254

6193

ND

291.90>181.00

4.762

661776

ND

ND

Carbendazim 191.90>132.00
Carbendazim 191.90>160.05
Isoprocarb

---

NDThiamethoxam

---

Isoprocarb

---

ND Tebuconazole

Carbaryl

---

NDTebuconazole

308.10>57.10
308.10>70.00

9.177
9.203

539979
2195189

15.21
15.21

Carbaryl

202.00>145.10

7.925

11669

NDTebuconazole

308.10>125.10

9.203

389237

15.21

Fenobucarb

208.10>77.10

8.59

62695

NDFlusilazole

316.00>165.10

8.997

14170

ND

Fenobucarb

208.10>95.10

8.59

516093

NDFlusilazole

316.00>247.15

9.022

18907

ND

Propoxur

---

ND Propiconazole

342.00>69.10

9.31

254589

4.97

Propoxur

210.20>168.00

7.523

7555

ND Propiconazole

342.00>158.95

9.31

161899

4.97

Aldicarb

213.00>70.00

6.766

16463

NDThiodicarb

---

ND

Aldicarb

213.00>89.00

6.808

5283

NDThiodicarb

355.00>108.10

8.024

24423

ND

2,4 D

---

ND Difenoconazole

406.00>187.00

9.471

4567308

83.58

2,4 D

---

ND Difenoconazole

406.00>250.95

9.48 138018832

83.58

Carbofurane

---

NDChlorantraniliprole

---

ND

Carbofurane

---

NDChlorantraniliprole

---

ND

Aldicarb-sulfone ---

NDIndoxacarb

---

ND

Aldicarb-sulfone ---

NDIndoxacarb

---

ND

886.50>81.90

8.809

326320

6.44

886.50>158.25

8.809

2235497

6.44

10.193

379

ND

ND

Methiocarb

---

Methiocarb

---

Emamectine
ND benzoate
Emamectine
ND benzoate

Oxamyl

---

NDAbamectine

896.00>448.80

Oxamyl

---

NDAbamectine

---

TM C V KHNG BI GII HN CC CHT


KHC TRONG MU K C UNKNOWNS NGOI
CHT CN PHN TCH: GC-QTOF V LC-QTOF, VI
PHN GiI CAO (10000 40000), ORBITRAP VI
PHN GII CAO HN (10 000- TRN 50 000)
*Full scan MS: tm cc cht c cng mi sc k trn
ngng ci t
*Vi mi cht , phn mnh tip cho Full MSMS
*C cc phn t khi chnh xc (sai s c ppm) ca
precursor ion , cc ion ng v, cc mnh ion con
*C cng thc nguyn tng ng vi cc ion
T , QUA MERCK INDEX HAY TH ViN C
CUNG CP HOC QUA CHEMSPIDER, XC NHN
CHT.

SC D FULL MS CA DICH CHIT T NHO

MS

SPIROXAMINE

MS/MS

O
C
N

O
+

m/z = 100,11262

CH3CHO
O
C
O
H H

O
H

m/z = 144,13883

ION PHN T V CC NG V

V. KT LUN
Mt h thng qun l c hiu qu, bt chng cho, d dng qui trch
nhim, hng mnh v xy dng chui thc phm an ton t trang tri
n bn n, cng thm mt h thng labo kim nghim c t chc rt
khoa hc vi trang b hin i chuyn dng v i ng giu kinh nghim,
nng n nhit tnh, c qun l theo mt h thng cht lng c quc
t cng nhn, c m rng thc s theo hng x hi ha, huy ng
c tng lc l cha kha gp phn m bo VSATTP trong nc trong
thc t nui trng v sn xut hin nay.

V MT NGY MAI AN TON, HNH PHC

THNH THT CM N

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