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 KIN1.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
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 7 2007 45 18
2003 19 35 2008 56 15
2004 59 13 2009 100 11
2005 124 7 2010 71 13
2006 68 13 2011 109 9
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
*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 PHAMSO VU NGO OC
THC PHAMSO NGI B NGO 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 phmkhng 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 phii 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, bisphenol 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 MELAMINEBIS PHENOL A
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).
Acrylamide
Loi thc phm N
Hm lng
[g/kg]
Trung
bnh
[g/kg]
Hm lng
Thng gpSo mau
nhiem
min. max.
Khoai chin lt
mng192 140 3640 819 1000 76
Khoai cng chin 98 < 10 2779 151 570 11
Bnh biscuit, bnh
nng38 < 10 1090 190 660 4
C ph bt 30 115 1685 343 370 14
Bnh m nng ming nh
32 15 1714 133 610 8
Ng cc n sng 32 < 10 846 65 260 4
HAM LNG ACRYLAMIDE
Asparagine Acrylamide
Nhit, ng(glucose, fructose)
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
Acid elaidic (trans) Acid oleic (cis)
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
nhit
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.
CO
O CH2 CH
CH2
(CH2)3 CH3
CH3
C O CH2 CH
CH2 CH3
(CH2)3 CH3
O
C
O
O
C O
O
(CH2)3
(CH2)3
CH3
CH3
DEHP : trong cac loai bao b, tham trainha, ao i ma bang PVC
DBP : my pham
DEHP DBP
Environment Health Perspect, 108,895-900 (2000)
QUI NH NAY CUNG C VIET NAM AP DUNG (QUYET NH 3339/2001/Q-BYT 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.
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
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).
C
C
O
O
OCH2CH(CH2)3CH3
OCH2CH(CH2)3CH3
CH2CH3
CH2CH3
Di(2-ethylhexyl) phthalate (DEHP)
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.
Gan ay, mot so mau cong nghiep a c tm thay trong thc pham va a c chau Au xep vaoloai doi tng kiem tra:
Orange II Rhodamine B Para Red
Phm mu cng nghip
N N
H2N
NH2
2,4-diaminoazobenzene
Tht heo quay, x xu g, vt ti sng ht da 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 (NON-
TARGETS, UNKNOWNS) NGOI CC CHT NHM N
(TARGETS)
PHT HIN V INH LNG
THERMO TSQ
8000 GC-MSMS
*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
Chit cht phn tch Lm m c v tinh ch nh lng
(Extraction) loi tp (Clean- up) GC-MS; GC-MS/MS
LC-MS, LC-MS/MS
Mc ich: Xc nhn ng cht phn tch, tng nhy caphng php, bo v thit b phn tch
III.1. CHUN BI MU
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 cnhng 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 Phn tch pha hi Headspace H Combi-Pal
Vi ly trch trn pha rn Hot ha Np mu Ra loi tp Ra gii
Ly trch trn pha rn SPE
HEADSPACE GC, HEADSPACE- GC/MS
Gn nh khng chun b mu
V mu
ml
Vncl
VMeOH std l
Cstdppm
Vtng ml
Cchunthm ppm
Cng
mi sc k
Ct ng chun(ppm)
0.5 80 0 30400 0.58 0.00 1254132
795.91
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
y = 1629.6403x + 1297053.7546
R2 = 0.9986
0
1000000
2000000
3000000
4000000
5000000
-1000 0 1000 2000 3000
C (ppm)
Area
Phng php thm chun
nh lng Metanol trong mu ngi say ru
PHN TCH PHA HI T I HI CHUN BI MU
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
C13 C14 C15 C16 C17 C18
C13 C14 C15 C16 C17
Dy hydrocarbon chun
Mu B
Mu D
Mu E
C12 C13 C14 C15 C16 C17
C12 C13 C14 C15 C16 C17
B KIT EZ:Faast CA PHENOMENEX
Nguyn tcPhng 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
COOH
NH3+
SO3- H3N
+CH
COOH
R
CH
COOH
RSO3- H3N
+NaOH
SO3- Na
++ R CH
NH2
COO-
RCH COO-
NH2+ Cl C
O
O CH2CH2CH3
Cl C
O
O CH2CH2CH3
R CH COOCH2CH2CH3
NHCOOCH2CH2CH3
u lc SCX
Ra vi nc kh ion
Ra gii
Chuyn ha
Isooctane
Sn phm chuyn haGC/MS; LC/MS, LC/MSMS
PHN TCH AMIN BIOGEN (Biogenic amines)
Sinh ra t s decarboxyl ha aminoacid di tc dng enzim
BAConc. of A
(mg/L)
Intensities of Ions for Quantitation
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
-2-phenethylamine: y = 568351 x + 3563 R2 = 0.9999-Tryptamine: y = 7 133 502 x +170484 R2 = 0.9997-Putresceine: y = 10 586 246 x + 15625 R2 = 1.000-Cadaverine: y = 28 060 272 x + 648712 R2 = 0.9995-Histamine y = 4 086 002 x + 93564 R2 = 0.9998-Tyramine: y = 19 652 779 x + 40998 R2 = 1.000 .-Spermidine y = 1 018 489 x + 10374 R2 = 0.9999-Serotonine y = 4 308 694 x + 120835 R2 = 0,9993-Spermine: y = 1 201 369 x +17 763 R2 = 0.9998
ng chun cho amin biogen
Sc khi ca mu nc mm M4
Phenethylamine
Putresceine
Tryptamine
CadaverineSpermine
Serotonin
Spermidine
Tyramine
Histamine
Kt qu phn tch amin biogen trong mt s mu
2. Ly tm 2 3 pht
4.Ly tm 2 3 pht
3.Ly lp trn cho
vo C18, PSA,
MgSO4 clean-up
5. Cho vo LC-MSMS
5. Cho vo GC-MSK THUT QuEChERS
1.Mu + dung mi+ m
+ IS + Mg SO4 , lc 1 pht
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
PHNG PHP INHLNG
TRIFLURALIN
TRN NN C
NH LUNG TRIFLURALIN TRN NN C BASA BNG GCMS
Chun b mu theo phng php QuEChERS
Giai on 1: Chit
1,25 ml ni chuntrifluralin d14 10
ppb
Mu xay nhuyncn 5 gram
Vortex13.75 ml AcOH 1%
/ACN
Lc u6 g MgSO4 v 1,5
g NaOAc
Chitlp trn
Ly tm 4000 vng/pht, 5 pht
1 g MgSO4 + 300 mg C18
Lc u, ly tm 4000 vng/pht, 5 pht
Rt 12 ml lp trn, thikh bng kh N2
nh mc 1 ml bnghexane, lc tim vo
my GCMS
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
Giai on 2: Clean-up
MT S KT QU PHN TCH THC NGHIM
Bng 10. Mt s kt qu phn tch thc nghim
IV. MT S KT QU PHN TCH THC NGHIM
Loi muC basa
filletCh c Hi sn
S lng mu 99 11 22
S mu nhim
trifluralin29 11 10
Hm lng
trifluralin
0,3 n 44,7
g/kg
1,9 n 158,5
g/kg
0,3 n 59,1
g/kg
Tng s mu phn tch t thng 04-2010 n thng 10-2010 l 132 mu. Smu nhim trifluralin 50 mu
THEO MT TI LIU, CC PHNG PHP CHUN
BI MU C S DNG NHIU LABO TRN TH
GiI GM:
1. SPE 50 %
2. QuEChERS 37,5 %
3. CHIT LNG LNG HAY CHIT RN LNG 31,2%
4. LC QUA A 62,5%
5. KHC 18,2%
III.2. CI TIN THIT BI PHN TCH
III.2.1. Thit b sc k1.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 .
Mi thon:* phn gii tng
* nhy tng, LOD h thp
*o a d lng c hiu qu
nhy tng
phn gii tng
CT LI RN POROSHELL, KINETEX, ACCUCORE
NEXERA ACCELAFLEXAR FX 15
AGILENT 1290
HPLC UPLC
III.2.2. Ci tin u d khi ph1.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 thchhp.
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 phctp
L vo rng-ion vo nhiu
L ra hp hn-tptrung ion vo Q3
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)
Metabolit (suberic acid) trong nc tiu chut
Hexa BDE trong bn
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.
.
III.3. Phn tch a d lng hp cht nhm n
v nhng hp cht khng nhm n (Target,
Non-target, Unknown analytes)
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 cs d liu
Yu cu khch hng: nh lng carbaryl trong nho
Column : GL InertSustain C18 ( 150 mm x 2.1 mm., 3 m)Mobile phase A : 0.1 % formic acid in WaterMobile phase B : 0.1 % formic acid in MethanolGradient program : Time (min)
Flow rate : 0.2 mL / minInjection volume : 5LColumn temperature : 40
MS : SHIMADZU LCMS-8030Nebulizing gas flow : 1.5 L / minDrying gas pressure : 10 L / minDL temperature : 250BH temperature : 400Interface : ESICID Gas : 230 kPa
iu kin vn hnh my
1.00 B Conc. 402.00 B Conc. 604.00 B Conc. 605.00 B Conc. 807.00 B Conc. 10010.00 B Conc. 10010.50 B Conc. 2014.00 Stop
Compounds m/z CE (V) Compounds m/z CE (V)
Methomyl 163.00>87.90 10 Carbofurane-3OH 238.50>181.30 10
Methomyl 163.00>106.00 12 Pirimicarb 239.00>72.00 35
Acephate 184.10>124.60 20 Pirimicarb 239.00>182.00 35
Acephate 184.10>143.00 10 Imidacloprid 256.00>175.00 15
Carbendazim 191.90>132.00 31 Imidacloprid 256.00>209.10 19
Carbendazim 191.90>160.05 19 Thiamethoxam 291.90>181.00 15
Isoprocarb 194.20>77.00 35 Thiamethoxam 291.90>211.20 25
Isoprocarb 194.20>95.10 16 Tebuconazole 308.10>57.10 30
Carbaryl 202.00>127.00 28 Tebuconazole 308.10>70.00 50
Carbaryl 202.00>145.10 15 Tebuconazole 308.10>125.10 40
Fenobucarb 208.10>77.10 30 Flusilazole 316.00>165.10 30
Fenobucarb 208.10>95.10 16 Flusilazole 316.00>247.15 20
Propoxur 210.20>152.90 10 Propiconazole 342.00>69.10 20
Propoxur 210.20>168.00 10 Propiconazole 342.00>158.95 20
Aldicarb 213.00>70.00 25 Thiodicarb 355.00>88.10 20
Aldicarb 213.00>89.00 25 Thiodicarb 355.00>108.10 20
2,4 D 218.85>125.00 30 Difenoconazole 406.00>187.00 30
2,4 D 218.85>161.00 15 Difenoconazole 406.00>250.95 30
Carbofurane 222.10>123.10 22 Chlorantraniliprole 484.00>285.80 15
Carbofurane 222.10>165.20 12 Chlorantraniliprole 484.00>453.05 15
Aldicarb-sulfone 223.10>123.00 24 Indoxacarb 528.00>150.00 30
Aldicarb-sulfone 223.10>166.20 12 Indoxacarb 528.00>218.00 30
Methiocarb 226.10>121.20 12 Emamectine benzoate 886.50>81.90 50
Methiocarb 226.10>168.60 20 Emamectine benzoate 886.50>158.25 45
Oxamyl 237.10>72.10 30 Abamectine 896.00>448.80 45
Oxamyl 237.10>108.90 30 Abamectine 896.00>751.10 50
Chromatogram of Grape sample detected some kinds of pesticide
CARBARYL NOT DETECTED
TEBUCONAZOLEDETECTED
DIFENOCONAZOLEDETECTED
EMAECTIN BENZOATEDETECTED
CARBENDAZIMDETECTED
Compounds m/z Re. Time Area Result (g/kg) Compounds m/z Re. Time Area Result (g/kg)
Methomyl --- 0 0 NDCarbofurane-3OH --- 0 0 ND
Methomyl --- 0 0 NDPirimicarb --- 0 0 ND
Acephate --- 0 0 NDPirimicarb --- 0 0 ND
Acephate --- 0 0 NDImidacloprid 256.00>175.00 5.232 5738 ND
Carbendazim 191.90>132.00 4.56 253980 5.22Imidacloprid 256.00>209.10 5.254 6193 ND
Carbendazim 191.90>160.05 4.563 1378045 5.22Thiamethoxam 291.90>181.00 4.762 661776 ND
Isoprocarb --- 0 0 NDThiamethoxam --- 0 0 ND
Isoprocarb --- 0 0 NDTebuconazole 308.10>57.10 9.177 539979 15.21
Carbaryl --- 0 0 NDTebuconazole 308.10>70.00 9.203 2195189 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 --- 0 0 NDPropiconazole 342.00>69.10 9.31 254589 4.97
Propoxur 210.20>168.00 7.523 7555 NDPropiconazole 342.00>158.95 9.31 161899 4.97
Aldicarb 213.00>70.00 6.766 16463 NDThiodicarb --- 0 0 ND
Aldicarb 213.00>89.00 6.808 5283 NDThiodicarb 355.00>108.10 8.024 24423 ND
2,4 D --- 0 0 NDDifenoconazole 406.00>187.00 9.471 4567308 83.58
2,4 D --- 0 0 NDDifenoconazole 406.00>250.95 9.48 138018832 83.58
Carbofurane --- 0 0 NDChlorantraniliprole --- 0 0 ND
Carbofurane --- 0 0 NDChlorantraniliprole --- 0 0 ND
Aldicarb-sulfone --- 0 0 NDIndoxacarb --- 0 0 ND
Aldicarb-sulfone --- 0 0 NDIndoxacarb --- 0 0 ND
Methiocarb --- 0 0 ND
Emamectine
benzoate 886.50>81.90 8.809 326320 6.44
Methiocarb --- 0 0 ND
Emamectine
benzoate 886.50>158.25 8.809 2235497 6.44
Oxamyl --- 0 0 NDAbamectine 896.00>448.80 10.193 379 ND
Oxamyl --- 0 0 NDAbamectine --- 0 0 ND
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
SPIROXAMINE
MS
MS/MS
CO
ON
H
C O + N
+
CH3CHO
C
O
O
N
H H
C O + N
O
H
m/z = 100,11262
m/z = 144,13883
ION PHN T V CC NG V
V. KT LUNMt 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