Cc phng php phn tch ho l

TRNG I HC CNG NGHIP THNH PH H CH MINH

KHOA CNG NGH HA HC

BI TIU LUN
MN: CC PHNG PHN TCH HA L
ti: TNG QUAN V THUC BO V THC VT H CHLOR
HU C
V PHNG PHP PHN TCH D LNG CA CHNG TRONG
NC V TRM TCH

GVHD: Ths.Nguyn Ngc Vinh

Nhm 8
LP: DHHO8ALT
Nm hc: 2013 - 2014

Cc phng php phn tch ho l

DANH SCH NHM 8

H v tn
1.
2.
3.
4.
5.
6.
7.

Nguyn Th Ngc Giu

Ng Th Ngc Bch
Nguyn Th Bch B
Nguyn Th Hin
Thnh Thy Dim
Trn Th Vn
Nguyn Th Hng

MSSV
12080551
12089201
12086161
12080041
12073921
12087511
12111761

Cc phng php phn tch ho l

Mc Lc
1

S LC V THUC BO V THC VT ...................................................................... 3

1.1

Thuc bo v thc vt ...................................................................................................... 3

1.2

Cc nhm thuc bo v thc vt ...................................................................................... 3

1.3

Cc dng thuc BVTV ..................................................................................................... 3

1.4

Phn loai: theo ngun gc ................................................................................................ 4

THUC TR SU H CHLOR HU C ............................................................................ 5

2.1

u im ........................................................................................................................... 5

2.2

Nhc im...................................................................................................................... 5

2.3

Mt s c im khc ...................................................................................................... 6

2.4

Phn loi .......................................................................................................................... 6

2.4.1

Mt s loi thuc chlor hu c thng dng trc y..7

2.4.1.1

DDT (Gesarol, Nexoid, zedan, polazotox)........................................................... 7

2.4.1.2

BHC ..................................................................................................................... 8

2.4.1.3

ANDRIN .............................................................................................................. 9

2.4.1.4

DIENDRIN .......................................................................................................... 9

2.4.1.5

ENDRIN .............................................................................................................. 9

2.4.1.6

THIODAN ......................................................................................................... 10

3 PHNG PHP PHN TCH D LNGCA CHNG TRONG NC V TRM

TCH. ............................................................................................................................................. 11

3.1

D lng ........................................................................................................................ 11

3.2

phng php phn tch d lng ca chng trong nc v tm tch. ............................ 11

3.2.1

S dng sc k kh vi u d bt gi in t (GC ECD)....11

3.2.2

Phng php Quechers v s dng sc k kh ghp khi ph(GC MS).15

Kt lun .................................................................................................................................. 16

Cc phng php phn tch ho l

THUC BO V THC VT H CHLOR HU C
1

S LC V THUC BO V THC VT

1.1

Thuc bo v thc vt
Thuc bo v thc vt (BVTV) hay nng dc l nhng cht c c ngun
gc t t nhin hay ha cht tng hp c dng bo v cy trng v
nng sn, chng li s ph hoi ca nhng sinh vt gy hi n ti nguyn
thc vt. Nhng sinh vt gy hi chnh gm su hi, bnh hi, c di, chut
v cc tc nhn khc.[1]

1.2

Cc nhm thuc bo v thc vt

Thuc bo v thc vt c chia thnh nhiu nhm da trn i tng sinh
vt hi.

1.3

- Thuc tr bnh

- Thuc tr nhn

- Thuc tr su

- Thuc tr tuyn trng

- Thuc tr c

- Thuc iu ha sinh trng

- Thuc tr c sn

- Thuc tr gm nhm

Cc dng thuc BVTV

Dng thuc
Nh du

Ch vit tt
ND, EC

Dung dch

DD, SL, L, AS

Bt ha nc

BTN, BHN, WP, DF,

WDG, SP
HP, FL, SC
H, G, GR
P
BR, D

Huyn ph
Ht
Vin
Thuc phun bt

Ghi ch
Thuc th lng, trong sut.
D bt la chy n
Ha tan u trong nc, khng cha cht
ha sa
Dng bt mn, phn tn trong nc thnh
dung dch huyn ph
Lc u trc khi s dng
Ch yu ri vo t
Ch yu ri vo t, lm b mi.
Dng bt mn, khng tan trong nc, rc
trc tip

Cc phng php phn tch ho l

1.4

Phn loai: theo ngun gc

Thuc BVTV ho hc:
V c
Hn hp Bordeaux: thuc tr bnh thnh phn gc Cu bao gm tetracupric
sulfate v pentacupric. c s dng c ch cc enzyme khc nhau ca
nm, dit nm cho tri cy v rau mu.
Hp cht Arsen: thuc tr su cha thch tn (As) bao gm trioxitarsenic,
natri arsenat, canxi arsenat.
Hu c
Clo hu c: Cc Clo hu c l nhng hp cht hydrocacbon clo ho trong
phn t c gc aryl, carbocylic, heterocylic.
Phosphate hu c: ln hu c l nhng cht t nht mt nguyn t
phosphate 4 ho tr. C th chia lm 3 nhm dn xut chnh:
+ Aliphatic ( mch thng)
+ Phenyl (mch vng)
+ Heterocylic (d vng)

Carbamate: l dn xut ca carbamic, tc dng ln ln hu c c ch

cholinesterase. Nhn chung, nhm ny c thp, ngoi l cc nitrosomethyl
carbamate l cht gy c t bin.
Pyrethroid: nhm thuc tng t pyrethrum. c chia lm 2 loi tu
thuc vo nhit thp hay cao. Pyrethroid c 4 th h thuc:
+ Allethrin
+ Tetramethrin
+ Fenvalerate
+ Th h 4 c nhiu tnh vt tri.
Cc loi khc: Lu hunh hu c c vng phenyl, cc loi thycyanates
cha gc SCN ngn tr h hp v bin dng t bo
Thuc BVTV sinh hc: c ngun gc sinh hc l cc loi thuc chit xut t
nhng nguyn liu t nhin nh ng vt, thc vt, vi khun v mt s
khong cht nht nh.
Thuc vi sinh: bao gm cc vi sinh vt ( to, vi khun, virus,..) l thnh
phn ho hc. Mi loi thnh phn c kh nng kim sot mt loi gy hi
tng ng.

Cc phng php phn tch ho l

Cht bo v thc vt kt hp: l hp cht thc vt sinh ra t vt liu di

truyn c them vo cy trc . Ngoi ra cn c cc loi chit sut
thun tho mc.
Thuc sinh ho: l hp cht trong t nhin tiu dit cn trng theo c ch
khng c.

THUC TR SU H CHLOR HU C
Thuc bo v thc vt h clor c xp vo loi cht hu c kh phn hu
(POPs). Hu ht nhng cht ny iu b cm s dung do nh hng tnh c
hai ca chng ti con ngi v ng vt.

2.1

u im
Qui trnh sn xut tng i n gin, gi thnh ca ch phm thp, d ch
bin hot cht thnh nhiu dng ch phm khc nhau (BTN, ND, BR, H...).
Do d s dng trn nhiu loi cy trng v nhng iu kin ng rung
khc nhau.
Cc thuc ny thng c ph tc ng rng, hiu lc kh cao, thi gian
hiu lc di thch hp cho vic phng tr ngoi ng, nht l i vi cc loi
cy cng nghip. bn ha hc ln trong nhng iu kin thng thng
nn d bo qun tn tr.

2.2

Nhc im
Do bn ha hc ln nn thuc d lu b trong t ai, cy trng, nng
sn, thc phm. Chng lm cho mi trng b nhim trong mt thi gian
lu di. Thi gian phn hy 95 % hot cht trong iu kin t nhin ca
DDT l 10 nm; BHC l 6,5 nm; Dieldrin l 8 nm; Chlordane l 3,5 nm.
B thuc lu tn khng nhng lm cho phm cht, hnh thc ca nng sn
b xu i m cn gy c cho ngi hay gia sc s dng nng sn , nh
BHC thng li mi kh chu trn nng sn nh khoai ty, rau, u...
C kh nng gy trng c tch ly mnh. Qua s tip xc vi thuc nhiu
ln hay qua chui thc n hm lng thuc trong c th, ch yu trong m
m tng ln rt nhiu; n mt lng no n biu hin cc triu chng
ng c rt him ngho nh ung th, qui thai... [2]
c i vi c v thin ch ln.
Khi s dng mt loi thuc Clo hu c ti mt a phng trong nhiu
nm d gy ra hin tng cn trng khng thuc. Do nhng nhc im
5

Cc phng php phn tch ho l

trn, ngy nay nhiu thuc tr su gc Clo hu c b cm hoc hn ch
s dng nhiu nc.
2.3

Mt s c im khc
Cu to ha hc: trong phn t ca cc hp cht ny u c cha nguyn t
Clo v cc vng benzene hay d vng.
Tnh cht vt l: thuc k ngh u dng rn, khng tan hoc t tan trong
nc, tan nhiu trong dung mi hu c, v thng c mi hi kh chu.
Dng ch phm thng gp l ND, BTN, H, bt phun cc hm lng khc
nhau.
Tnh cht ha hc: cc thuc Clo hu c thng c bn ha hc ln, tn
ti lu di ngay c iu kin ngoi ng, phn ln u b phn hy trong
mi trng kim
Tnh c: c thuc i vi ng vt mu nng u t trung bnh n
cao, trong cc hp cht nhm DDT, BHC, nhm Cyclodien c kh nng
tch ly trong c th ngi v ng vt (tr Thiodan). Cc thuc Clo hu c
thng c tc dng v c v tip xc ln cn trng, mt s cn c c tnh
xng hi. Cc thuc ny thng tc ng ln h thn kinh bng cch c ch
men cholinesterase v tc ng ln mt s c quan khc lm ri lon hot
ng ca c th cn trng dn n cht.

2.4

Phn loi
Thuc bo v thc vt h clor c chia lm 3 nhm:
+ Dichlorodiphenyl ethane ( DDT, DDD,DDE)
+ Cyclodiene ( aldrin, dieldrin, heptachlor, endosulfan)
+ Chlorocyclohexane (, , , HCH).

Cc phng php phn tch ho l

2.4.1

Mt s loi thuc chlor hu c thng dng trc y

2.4.1.1 DDT (Gesarol, Nexoid, zedan, polazotox)

Dng ch phm thng gp: 30ND, 75BHN, 10BR, 5H,
Cng thc phn t: C14H9Cl5
Tn ho hc: 1,1,1- trichloro- 2,2 bis (p-chlorophenyl) ethane
Cng thc ho hc:
7

Cc phng php phn tch ho l

Tnh cht vt l:
DDT l mt hn hp nhiu ng phn, trong ng phn para c c
cao nht vi cn trng. Sn phm cng nghip th rn, mu trng ng c
mi hi.
Tnh cht ho hc:
Thuc rt bn iu kin thng nhng d b kim thu phn thnh DDE,
nht l khi c s hin din cc mui st
c tnh:
Thuc c kh nng tch lu trong c th ngi v ng vt, nht l cc m
m, m sa, n khi lng gy c th thuc s gy ra cc bnh him
ngho nh ung th, sinh qui thai. DDT c hi vi c v ong, DDT an ton
vi cy trng, tr thuc h bu b. Thuc cm s dng. Thuc c nhm II
2.4.1.2 BHC
Tn gi: lindafor90, lindane, BHC, HCH,
Tn ho hc: Benzenhexachlorit
Cng thc ho hc: C6H6Cl6

Tnh cht vt l: BHC nguyn cht dng kt tinh mu trng , gm nhiu

ng phn khng gian, trong ng phn gammar c kh nng thng hoa
nhit c cao.
8

Cc phng php phn tch ho l

Tnh cht ho hc: BHC bn vng iu kin thng, bn vi tc ng ca
nh sang, cht oxy ho, mi trng axit nhng b phn hu trong mi
truong2 kim, nht l cc dung mi ca BHC.
2.4.1.3 ANDRIN
Tn ho hc: 1,2,3,3,10,10-hexaclo-1,4,4a,5,8-hexahydroexo-1,4 endo5,8
dimethylennaptalin
bn ho hc ln, khng b nh sng, kim v axit phn hu. Tc dng
tip xc, v c v xong hi. trong t v trong cy thuc chuyn ho
thnh diendrin.
Tnh c: thuc c kh nng tch lu trong c th ng vt. Rt c vi c
2.4.1.4 DIENDRIN
Tn ho hc: 1,2,3,3,10,10- hexaclo- 6,7-epoxi-1,4,4a,5,6,7,8,8aoctahydro- 1,4 endo 5,8 ddimethylen naptalin.

c im ho hc: tng t nh andrin

c tnh cp cao hn andrin
Thuc c tc ng tip xc v v c.
2.4.1.5 ENDRIN
Endrin l ng phn khng gian ca diendrin. C cc c tnh ho, k tng
t nh endrin.
Tnh c ca endrin kh cao
Cng thc ho hc ca endrin:

Cc phng php phn tch ho l

2.4.1.6 THIODAN
Tn ho hc: 1,2,3,7,7- hexaclo- bicycle- (2,2,1)-2-hepten-5,6-bisoximetylensunfat
Cng thc ho hc:

Sn phm cng nghip l nhng tinh th nh, mu nung d thu phn

thnh nhng cht khng c.
t c vi ong v mt s loi cn trng c ch khc, n tht hoc k sinh
trn su hi.
C c cp tnh cao nhng khng c tnh tch lu. Trong c th ng vt
hot cht nhanh chng b phn hu thnh nhng cht khng c v c
thi ra ngoi.

10

Cc phng php phn tch ho l

3

3.1

PHNG PHP PHN TCH D LNGCA CHNG TRONG

NC V TRM TCH.
D lng
L lng cht c cn lu li trong nng sn hoc mi trng sau g
(microgram) hocmkhi phun thuc BVTV. D lng c tnh bng mg
(miligram) lng cht c trong 1 kg nng sn hoc th tch khng kh,
nc t Trng hp d lng qu nh, n v cn c tnh bng ppm
(phn triu) hoc ppb (phn t).
- MRL (Maximum Residue Limit): mc d lng ti a cho php lu tn
trong nng sn m khng nh hng n sc khe con ngi, vt nui.
- ADI (Acceptable Daily Intake): lng cht c chp nhn hp thu vo c
th, khng gy hi cho ngi hoc vt nui trong 1 ngy, g hp cht c
cho n v th trng.mc tnh bng mg hp cht c cho n v th
trng.
- D lng biu hin hai kha cnh :
+ Trong t v nc
+ Trong sn phm nng nghip

3.2
3.2.1

phng php phn tch d lng ca chng trong nc v tm tch.

S dng sc k kh vi u d bt gi in t (GC ECD).
Vt liu v phng php

11

Cc phng php phn tch ho l

K thut ly mu:
Mu nc:Thu thp nhiu mu nc mt ngu nhin, ng nht to
thnh mt mu trn mi sng . c lp li ba ln vo mt ma . Acid
sulfuric m c c thm vo mi mu ngay sau khi thu thp ngn
chn s thay i ca vi sinh vt c trong mu . Cc mu ny c gi lnh
trong qu trnh vn chuyn n phng th nghim v sau c lu tr 4
C trong t lnh cho n khi phn tch.[3]
Mu trm tch: c thu thp bng cch o xung t 0-10 cm di b mt
cng ni ly mu nc. Mu trm tch c bc trong l nhm mng v sau
t trong mt ti nha . Mu c gi lnh trong qu trnh vn chuyn
n phng th nghim. Ti phng th nghim , mu c ng kh trc khi
chun b v tin hnh phn tch. Mu trm tch sau c gii ng v sy
bng khng kh kh nhit mi trng. Cc mu trm tch kh ny c
sng qua li thp khng g 2,0 mm .
Chit cc chlor hu c trong thuc tr su( OCPs) trong mu trm tch v
mu nc.
Mu nc: Mu nc c em chit vi n-hexan: dichloromethane (1:1)
trong bnh chit, lp li nhiu ln. Sau , gp cc mu chit li v lm
khan bng Na2SO4. Cho mu bay hi hon ton 50oC v sau ho tan
mu li bng n-hexan chun b cho phn tch sc k kh.[4]
Mu trm tch: Mu c chit bng cch s dng ht thng chit Soxhlet.
Sau mu c cho vo mt becher cha sn Na2SO4 lc u. Sau hn
hp c a vo ni chit h thng Soxhlet. Hn hp c chit vi
acetone:n-hexane (20:80) 50oC. Hn hp chit c lc v c cn cn
1ml.
Ct sc k dng phn tch cc muchit t nc v trm tch
1 l cho mi ln phn tch mu bng ct sc k, c tim vo trong h
thng GC ECD XL PerkinElmer s dng thit b phn tch v u d
Ct: Zebron ZB35 fused silica v c tnh bn, tr v mt ho hc. S dng
ct mao qun khng chia dng dng phn tch 30cm 0.25mm 0.25m
(ct mao qun phim mng).
Nhit ban u ca l cha ct tch l 50oC( gi khong 1 pht), sau
tng nhanh ln 200oC( 40oC/ pht) gi 2 pht, tng nhanh ln 240oC ( 4oC/1
pht) gi 1 pht, tip tc tng ln 270oC ( 4oC/1 pht), gi khong 5 pht.
Nhit ca thit b u v bung kim tim tng ng l 300oC v
250oC.

12

Cc phng php phn tch ho l

Kh mang thng s dng l heli, argon, nit v hydro. Kh hydro c kt

qu tt nht, nhng v l do an ton nn t s dng nn kh mang thng
c s dng l 99,99% l kh nit .Hiu qu ca vic tch chit nhng
nhit khc nhau c xc nh bng cch so snh pic ca cc mu chit
vi pic ca cc mu chun.[5]
u d
S dng u d bt in t 63Ni-ECD

Mu sau khi i qua khi ct tch c a thng vo bung cng vi kh

mang. Tu theo i lc ca chng m cc e s cp s b bt gi v to ra cc
phn t ion m. Cc ion m ny s kt hp vi ion dng ca kh mang
to ra phn t trung ho. Do in t b ly mt khi h v dng in nn b
gim i so vi lc ch c kh mang i qua nn mc suy gim ca dng
in nn khi c cht i qua c biu hin bng pic sc k cht .[6]
Tt c cc hp cht ny u c ho tan v gii ra trong khong thi gian
l 30 pht , s dng sc k GC ECD. Vic nhn dng cc mu chit chlor
hu c trong thuc bo v thc vt (OCPs) bng cch xc nh cc pic v
thi gian lu ca chng vi cc cht tiu chun v nng c tnh ton
trn my tnh thng qua cc yu t phn hi ca cc hp cht chlor hu c.

13

Cc phng php phn tch ho l

Bng tiu chun ca cc hp cht chlor hu c c phn tch bng GC
ECD .

18 OCPs:
p,p'- DDT

Endrin

p,p'- DDE

Endrin aldehyde

p,p'- DDD

Endrin ketone

-HCH

Heptachlor

-HCH

Heptachlor epoxide

-HCH

Endosulfan I

-HCH

Endosulfan II

Aldrin

Endosulfan sulfate

Dieldrin

Methoxychlor
14

Cc phng php phn tch ho l

3.2.2

Phng php Quechers v s dng sc k kh ghp khi ph (GC MS).

Phng php Quechers thng kt hp vi GC MS , LC - MS/MS m rng
phm vi phn tch cc loi thuc tr su.
a phn vic phn tch d lng ca thuc tr su u da vo sc k xc nh,
c sc k kh (GC) v sc k lng cao p (HPLC) v thng s dng sc k khi
ph xc nh cc cht c phn tch tch ra bng cng ngh sc k. Sc k khi
ph (GC MS) tr thnh mt cng c tiu chun trong cc phng lab v n c th
cung cp cc thng tin c bn nh ng tnh, nh lng cho mi ln tim mu. Hu
ht nhng cng ngh khi ph ny c thit k theo kiu t cc cho kt qu chc
chn v thc tin, ion ho bi s va chm electron (EI).
Mc ch ca phng php Quechers kt hp vi GC MS l xc nh atrazine,
fipronil, endosulfan c trong mu trm tch v mu nc.[7]
Vt liu v phng php
Gm cc bc:
+ Cho mu nc v mu trm tch vo cc ng trong my ly tm
+ Cho MeCN, MGSO4, NaCl vo mi ng v tin hnh ly tm trong vng 1 pht
+ Cho MeCN vo ct tch SPE c sng PSA v C18 v 1 lp MgSO4 hot tnh
+ Thu dung dich chit
+ Ly 1ml dung dch mu a vo thit b ly mu t ng phn tch GC MS.
Th tch dung phn tch l 1 l.
Nng cc cht phn tch ny c xc nh bng sc k kh kt hp vi khi
ph QP 2010 cng vi u d chn lc khi lng (MSD), ct mao qun 30m
DB 5, ng knh 0.25mm, chiu dy lp phim l 0.1 m
Nhit bung tim : 250oC
Nhit b kt ni : 250oC
Tc ca dng kh mang: 0.75ml/pht
Thit b tim lm vic ch khng phn tch vi nhit khi ng 120oC gi
3 pht, 220oC (18oC/pht) , 270oC (20oC/pht) gi 5 pht.
15

Cc phng php phn tch ho l

Sau khi tim mu vo ct, mu s c tch ra v c dng kh tr y. Mu sau
khi bin thnh dng kh i qua bung ion ho qua b phn kt ni v dc ion ha.
Sau khi ion hnh thnh v tch nhau theo s khi , nhim v detector l pht hin v
ghi nhn. Sau qua h thng x l d liu s thu thp v tnh ton.

Kt lun
Chit xut siu lng ti hn ( SFE) v chit sut lng lng ( LLE) c s dng
kh tt trong vic lm sch mu nc.Chit bng h thng Soxhlet cng cho kt
qu tt i vi mu trm tch. Nng cht gy nhim trong nc thp hn
trong nng cht gy nhim c trong mu trm tch. Kt qu ny chng minh
rng nhng hp cht k nc v c khuynh hng tch lu trong trm tch v m
m [8].
Phng php Quechers, GC - MS : t s dng, t tiu tn dung mi, chnh xc
cao, recoveries cao, lng mu i qua nhiu, kh nng thu hi cao. Bn cnh
ngi lm khng cn nhiu kinh nghim, ho cht khng t v t tiu tn. C kh
nng nh tnh v nh lng cc cht c trong mi ln tim mu

16

Cc phng php phn tch ho l

Ti liu tham kho
[1] http://vietpat.com.vn/chung-nhan-hop-quy/thuoc-bao-ve-thuc-vat/145-thuocbao-ve-thuc-vat--thuoc-bao-ve-thuc-vat.html
[2] http://trangvangnongnghiep.com/bao-ve-thuc-vat/11009-thuoc-nhom-clo-huuco.html#.UyFcPs5oH1U
[3]http://www.labtechgroup.com/English/ziliao/Determination%20of%20Organoch
lorine%20Pesticides%20Residue%20in%20Tap%20Water%20by%20Sepaths6.pdf
[4] http://www.jeb.co.in/journal_issues/201303_mar13/paper_05.pdf
[5] http://downloads.hindawi.com/journals/isrn.soil.science/2013/131647.pdf
[6] Cc phng php phn tch ho l, TS. Nguyn Ngc Vinh, khoa cng ngh
ho hc, H cng nghip TP. HCM
[7] http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3017303/#!po=50.0000
[8] A.Aydin and T. Yurdun, Residues of organochlorine pesticides in water
sources of istanbul , Water, Air, and Soil Pollution, vol 111, no.1 4, pp 385
389,1999

17