BO
GIAO
DUG VA DAO TAO
TRirdNG Dm HOC
T6NG HOP
HA
Ndl
Phung Thi Thanli
Tu
NGHIEN
CtrtJ PIIAN
TICH,
DANH
GIA
TON
LlTdNG
HOA CHAT BAO VE
THlTC
VAT
VA
TINH TRANG 6 NHIEM MOI TRlTdNG
6
MOT SO TINH MIEN TRUNG
Chuyen
nganh
: Hoa
hCru
ccf
Ma
so 01.04.02
LUAN

chimg
ve HCBVTV 3
1.2. Phan
loai
HCBVTV 3
1.3. Tmh hinh san xuat va
sik
dung HCBVTV 5
1.4. Tac hai cua HCBVTV 7
1.5. Ton
lifdng
HCBVTV trong moi
tnl6ng
24
1.5.1.
Su
di chuyen cua HCBVTV trong moi
trifdng
24
1.5.2.
Van de ton
lifdug
HCBVTV trong nong san
28
1.5.3.
Phildng
phap phan tich ton
lUdng
HCBVTV
trong moi

phiidng
phap xac dinh warfarin trong phan rom 54
2.2.1.
Thiet
bi,
dung cu, hoa chat 55
2.2.2.
PhUdng
phap sinh hoc 55
2.2.3.
Phiidng
phap phan
tich
hoa hoc. 57
2.3.
Lap dung phUdng phap GC/ECD xac dinh HCTS. 62
.
2.3.1.
Thiet bi, dung cu, hoa chat 62
2.3.2. Phiidng phap phan tich 62
2.4.
LTng
dung 65
2.4.1.
Doi
tUdng
nghien
ciiu
66
2.4.2. Nghien

Su
lam dung HCBVTV 88
2.4.8.
Xii ly
HCTS trong
nvfdc
89
2.4.9. Tac tai cua HCBVTV den
sufc
khoe
ngUcii
tiep xuc 90
ni.
Phan thao luan ket qua nghien
ciiu
95
3.1.
PhUdng phap phan tich. 95
3.2. Ton
lUdng
HCTS bi cam va han che sU dung d mien
Trxmg
102
3.3.
Danh gia
mtic
do 6 nhiem moi
trudng
d mien Trung 106
3.4.

lUdng
thUc. So'
lUdng
nay c6 the nuoi
song 150 trieu
nguM
trong mot nam [ 38, 53 ].
6
nU6c ta HCBVTV
dUdc
diing
rong rai. Hang nam
lUdng
HCBVTV
svL
dung binh quan la
0,5 - 0,7 kg hoat chat / ha [24].
Nhd
diet dUdc con trung sau benh nen
san
lUdng lua
tang
10%,b6ng,
day, do tUdng, cam, che tang tii 17,6 - 70
% [ 5, 53 ]. Nam mUdi nam qua, viec dung HCBVTV mot
each
than
trong va c6 kiem soat la dieu can thiet de phat trien nen nong nghiep
hien dai va sit dung trong viec khong
che

the he nay sang the he khac [76, 81 ]. Hien nay sU quan ly
HCBVTV d
nUdc
ta chUa that chat che.
O
mien Trung, dat dai can coi,
sau benh
luon
de doa mua mang.
Dae
trUng cua khi hau mien Trung
la : nhiet do cao,
lUdng
mUa
Idn
va gio bao nhieu. Dieu do de dang cho
viec di dong nhanh cac ton
lUdng
HCBVTV vao khong khi, dat,
nU6c,
gay 6 nhiem moi
trU5ng
tren mot dien rong. Mac du nha
nU6c
da c6
lenh
cam dung diclodiphenyl tricloetan (DDT), hexacioxiclohexan
(HCH) va han che sU dung wofatox, monitor [75] nhUng cho den nay
nhan dan van quen dung wofatox va monitor. Su quan ly HCBVTV d
mien Trung cung con long

- Danh gia ton
lUdng
hoa chat
tri^
sau bi cam
sii
dung va han che
sii dung
ci
mot so' tinh mien Trung.
- Danh gia tinh trang 6 nhiem moi
trU6ng
do HCBVTV gay ra tai
cac cd
scl
san xuat, bao quan, sU dung va sau cac ddt bao
lut
d mien
Trung.
- De xuat mot so' bien phap giai quyet tinh trang 6 nhiem moi
trudng.
I.
PHAN TONG QUAN
TAI LIEU
1.1. Khai niem chung ve HCBVTV
HCBVTV la ten goi chung de chi cac hoa chat dung trong nong
nghiep, lam nghiep,
nh^m
muc dich diet sau benh, c6 dai, con trung va
dong vat gam nham de bao ve cay trong, cac

chiia
dong
- Cac hdp chat
chiia lUu
huynh
- Cac hdp chat chiia thuy ngan
- Mot
so'loai
khac
*
Nhom cac chat trii
c6
dai, lam rung la, kich
thich
sinh
trUdng
:
- Cac hdp chat cua phenol
- Cac hdp chat
ciia
phenoxi [2,4 diciophenoxyaxetic axit -2,4 - D]
- Cac dan xuat cua axit
alofic
[dalapon]
- Cac dan xuat cua cacbamat
[satxm,
eptam]]
- Triazin [simazin, atrazin, evik ]
* Nhom cac chat diet chuot va dong vat gam nham : phoszin va
warfarin

cd,ceresau,
granosan, felizan [114]
- Cac dan xuat cua hdp chat nitro [41]
- Cac dan xuat
ciia
ure [41]
- Cac dan xuat ciia axit cacbamic [61]
- Cac dan xuat cua axit propionic [41]
- Cac dan xuat cua axit xianhidric [41]
1.2.2.2. Cac chat
trvtsau
v6
ca:
[41, 61]
- Cac hdp chat ciia asen [131]
- Cac hdp chat ciia dong [61]
- Cac hdp chat cua
lUu
huynh [138]
- Cac hdp chat
v6
cd khac [114]
1.2.2.3. Cac chat trii sau nguon gob thiic vat la : cac
ancaloit,
thUc vat
CO
chiia nicotin, anabazin, piretroit [41, 121, 140]
1.2.3. Pban
loainbom
doe tbeo TCYTTG

Qua da
The ran
10
10 - 100
100 1000
1000
The long
40
40-400
400-4000
4000
1.3. Tinh hinh san xuat va sik dung HCBVTV :
L3.1.
Tlnb
binb sin xuat va
svt
dung HCBVTV tren
tbegioi
Tii lau con
ngUdi
da biet
dtmg
mot so' san pham tU nhien
de
diet
truf
sau benh
nhu
cac hdp chat cua asen, cac hdp chat ciia flo, cac chat
CO

Tuy vay, hien nay HCBVTV van dUdc
sii
dung vdi khoi
lUdng
16n tren
the gidi.
U*6c
tinh hang nam cac
nU6c
tren the gidi diing khoang 1,25
ti tan nguyen chat HCBVTV [23]. Hien nay cd khoang 100.000 hdp
chat hoa hoc dUdc tong hdp va dUdc thi nghiem de lam HCBVTV [38].
Trong dd cd khoang 1.500 hdp chat dUdc xac dinh tinh nang, 500 hdp
chat dat tieu chuan quoc te, dUdc
dua
vao
sii
dung [56]. Rieng d My
cdl.200
HCTS da dUdc dang ky, 35.000 san pham thUdng mai dUdc ban
dudi
dang cac thUdng pham khac nhau [5]. Tuy cd
nhUng
y kien khac
nhau ve viec sii dung HCBVTV nhUng miic sU dung HCBVTV hang
nam tren the gidi van tang tren 10% [53]-
Nam 1985 My sU dung 486 trieu tan HCBVTV, rieng nganh
nong nghiep sU dung 464,22 trieu tan [38].
Indonexia
nam 1982

Nam
Tii xa xUa, nhan dan ta da biet dung nicotin lay tii cay thudc la,
thudc lao va rotenon che tU mot sd' cay ho dau de
trii
sau hai rau va
cay an qua. Nhan dan Nam bo da diing dau
gasol
de phong trii ray nau
hai
Ilia d
cac tinh mien Tay. Tii nam 1957, DDT va
nhUng
hdp chat
tUdng tu dUdc diing rong rai
d
nUdc ta [41]. Tii nam 1963
d
mien
B^c
da diing nhieu wofatox, dipterex, malathion, Bi58 [61]. O mien Nam
nhan dan diing nhieu diazinon , monitor, orthene, azodrin [41]. Nudc
ta la mot nUdc ndng nghiep, khoang 13 trieu ho gia dinh gom 52 trieu
ngUdi lam viec trong
linh
vUc ndng nghiep [18, 43], do dd viec
sii
dung
HCBVTV ngay cang tang [51, 57]. Trong tong so HCBVTV dUdc
sii
dung, HCTS chiem 68%, HCTN chiem 24% va HCTC chiem 8% [43].

hinh nbiem doc
HCBVTV.
1.4.1.1. Tinh hinh nhiSm doc HCBVTV tren
the
gidi.
So'
ngUdi bi
nhilm
doc HCBVTV ngay cang tang tren the gidi
[38].
Nam 1977, dUa vao bao cao cua 9 nUdc, TCYTTG [24] da Udc tinh
hang nam tren the gidi cd 20640 ngUdi chet vi HCBVTV. Nam 1981
TCYTTG Udc tinh rang toan cau cd 750000 ngUdi bi nhiem doc. Gan
day Uy ban
Idnh
te va xa hoi chau A va Thai Binh DUdng da cho biet
so'
ngUdi bi nhiem doc
len
den 2 trieu, trong dd sd'
tii
vong la 40000
ngudi [24]. Theo Rosenstock [36] d My cd khoang 3000 cdng
nhan bi nhiem doc hang nam. Nam 1987 cac tac gia dieu tra tai phong
kham cap
ciiu
va nhap vien d Nebraska thay ty le nhiem doc HCBVTV
la
1,35/1000
dan, trong dd

vong [84]. Theo Bary [76] va
Fest [83] khoang 10% cac trUdng hdp bi nhiem doc cap ciiu la do
HCBVTV, trong dd cd 50% la do nhdm cd photpho.
1.41.2
Tinh hinh nhiSm doc
HCBVTVd Viet
Nam
- Theo Le Dinh Cdng,
ci
Ben Tre tU nam 1986-1992 cd 1102 ngUdi
bi nhiem doc, cd 208 ngUdi chet [5].
6
Tien Giang tii nam 1986-1992 cd
3.167 ngudi bi
nhigm
doc HCBVTV, trong dd cd 333 ngUdi chet [60].
8
Theo Le Trung, tu: nam 1986-1991 sd ngUdi vao dieu tri d mot so benh
vien tinh thanh va benh vien Bach Mai la 3.019 ngUdi, trong dd sd'
ngitdi
tu tu
cliie'm
89,5%,
do nham
lin
la 3,8% va do nghe nghiep la
6,6%. Ty le
tii
vong do nhiem doc HCBVTV kha cao, trong dd HCTS cd
photpho chiem 10,4% [58].

xiic
mdi trUdng
chii
yeu qua dUdng tieu hoa (vdi thiic an, nUdc udng bi
nhiem HCBVTV) [76, 78].
Mdi loai, mdi nhdm HCBVTV cd cd
che
tac hai
Ichac
nhau . Cd
the
tong quat cd
che
chung d hinh 1 va 2 [5]
^
''
Dat
-* 1
Khong khi
Sinh thai
s^
^ '
Nude
tl
lUc
a
n
^ '
Ngudi
Hinh 1 : Su

^•
Doc
bao
thai
V
Doc
sinh
hoc
>•
Dot
bien
gien
Hinh 2 : Tac hai cua HCBVTV
i.
4.3.
Tac hai cua HCTS nhom cd clo.
HCTS nhdm cd clo la dan xuat clo ciia cac hidrocacbon da nhan,
cac
xicloparafin
cac tecpen va benzen : cacbon tetraclorua, DDT, HCH,
cloperin,
pentaclonitrobenzen
Cac chat nay cd clo trong phan
tii
nen
nen tac dung ciia chiing dd'i vdi cd
the
nhieu
liic
gid'ng nhau, chi khac

541.
Klii
chat doc xam nhap vao cd the
dii lUdng nhd
cung
gay nhiem doc man tinh vi nd tich luy trong cd the, dac biet la d to
chiic md [ 92, 104]. Da sd' HCTS - cd clo deu dao thai qua
sUa
va gay
doc dd'i vdi noi gid'ng [36, 118, 109]. Cac hdp chat DDT, diendrin,
andrin cd thdi gian ban huy sinh hoc dai [22, 28]. Chiing phai dUdc
xii
ly nghiem ngat vi chiing hen quan den mat can
hkng
sinh thai va
anh hudng tram trong den
siic
khoe con ngUdi [102, 103]. Tat ca cac
chat nay deu dUdc chiing minh la cac chat gay ung thU tren dong vat
[36,
137, 139, 144, 145, 147]
1.4.4.
Gidi
tliieu
mot so HCTS -
ccf
clo
tbiidng
dung
1.4.4.1. DDT,

- DDT [21]
11
- DDT cd dang tinh
thd
khong man, bay hdi d ap
lUc
1,5.10'^
mmHg tai
20^C,ndng chaydl09^GDDT
dd tan trong cac dung mdi hiiu
cd (hidrocacbon thdm va cac dan xuat halogen cua chiing, cac xeton,
cac este cua axit cacboxylic). DDT tan kem trong cac hidrocacbon mach
th^ng
va vong no.
6
nhiet do
27^C
DDT hoa tan trong nUdc vdi nong
do 0,001
mg/1
[38]. DDT ben
vttng
vdi tac dong cua nhiet do, dun sdi
vai gid van khdng bi phan huy. Trong mdi trUdng
Idem
bi phan huy
thanh DDE it doc hdn. O dieu kien tU nhien, tinh doc ciia DDT duy tri
dUdcl2nam[41,
144]
- DDT ky thuat, san pham thUdng mai, chiia khoang 70% dong

dong
hdn
[106].
H * Diclodiphenyl dicloetan
^^~\^~^—
C^"
^^
* Tetraclodiphenyletan
CHCl2^—
*
TDF
*
Rotan
c) DMC la chat ket tinh cd mau, ndng chay d 70
^C,
DMC it ben
trong mdi trUdng hdn DDT va DDE [81, 106]
12
—
?^
—
CI—
^
/)~^^—C
y)~*^^
"^
4,4'-cUclometyLbenzhidrol
^^ CH3 ^-^ ^^
DCPC
^=

doc vdi tat ca cac loai cdn triing, la chat ket tinh mau vang, ndng chay
d37OC[105]
*^^~'4 //~" ^-^""v y — ^'^ * Etyl
4,4'-diclobenzylat
c
O
^
OCH2CH3
D
San pham cudi
ciing
la metoxiclo. Metoxiclo it ben trong mdi
trUdng hdn DDT, nd chiu tac dung khii clo nhanh hdn
[106].
H
''l,l,l-triclo-2,2-bis(P-metoxiphenyl)etan
CH30-{^^H(^
*
DMDT
CCI3 '-''•
Metoxi - DDT
- DDT thudc nhdm doc loai II,
LD50
: 113 mg/kg [131, 132] ADI :
0,02 mg/kg
[131].
Nong do td'i da trong mdi trUdng lao dong la 1
mg/m^
trong khi quyen la
0_,05mg/m'^

ngay nay DDT da bi cam diing
[133].
Nudc ta van cdn mot sd ndi
sii
dung DDT do cac nguon budn lau dUa vao. Ndng dan
sii
dung DDT
trong khau
khii
trung dat, bao quan hat gidng [24, 61].
- DDT tich luy trong to chiic md cua ngUdi va dong vat, luan
chuyen trong cac ddi tUdng tU nhien
ciia
mdi trUdng (dat, nUdc, khdng
khi,
cay cd ) Vi vay mac du da cam sU dung, ngUdi ta van tim thay
DDT va cac san pham chuyen hoa ciia nd trong cac cd quan
phii
tang
cua con ngudi va dong vat [101,
106],
DDT va cac san pham chuyen
hoa cua nd dUdc thai qua
stfa
va nUdc tieu khoang 1% trong ngay. Khi
phan tich DDT d tre sd sinh nhan thay cd khoang 0,24 mg DDT trong 1
kg can nang
ciia
tre sd sinh do
bii sUa

ciia
HCH. NgUdi ta thUdng
sit
dung dong phan
a
14
than kinh. Nd bit cac
Id
tren mang te bao than kinh, ngan chan qua
trinh tham
hiit
Na"*"
va lam mat tinh phan cUc cua
te
bao than kinh
d^n
den khdng
dAn
truyen dUdc xung
lUdng.
Vi vay DDT
dUdc
xem nhu
la mot trong cac HCTS quan trong nhat va dUdc
sii
dung rong rai
trong ndng nghiep [41]. Do sU ton
lUu
lau dai trong mdi trUdng nen
ngay nay DDT da bi cam diing

[41].
1.4.4.2.2.
HCH - Hexacioxiclohexan,
CQHQCAQ,
M =
290,8
- HCH cd
ttin
goi : 1, 2, 3, 4, 5, 6 hexacioxiclohexan
- Cac ten khac : hexaclo, hexacloran, lindan, gamakan, 666
[124,
147].
H.Faraday tong hdp HCH tit nam 1925, Vander Linden tim ra
cac dang dong phan cua HCH va chiing dUdc dimg lam
tlCBVTV
tit nam
1935.
Cd 8 dong phan cua HCH. Ngudi ta thUdng
sii
dung dong phan a
14
p,
Y,
5-HCH
nhUng chi cd dong phan
y-HCH
lacd
dac tinh
trii"
sau rd ret.

- HCH ben vdi anh sang, nhiet do, khdng khi va vdi cac axit
manh, phan huy thanh triclobenzen va
HCl
trong mdi trUdng kiem,
- Doc tinh hoa hoc :
LDQQ
qua mieng 88 mg/kg,
LD50
qua da 300
mg/kg, thudc nhdm doc loai II [124, 131].
- HCH la thudc trii sau cd hoat tinh cao, cd pho tac dung rong,
dUdc sii dung cho nhieu loai cay trong vi nd cd kha nang diet trit nhieu
loai sau hai : sau
due
than, bo canh
ciing
hai
liia,
ray nau. HCH ton
lUu
lau dai trong mdi trUdng nen da bi cam sU dung [133,
1471.
Lieu
cho phep trong mdi trUdng lao dong la 0,2
mg/m'^
khdng khi
[41|.
Tieu
chuan cua My gidi han 0,2-0,5 mg/kg dat. Mudn trong cac loai cay an
cu trong dat da xU

nhitng
ngitdi khdng tiep
xiic
vdi HCH, trong
sUa ciing
cd HCH
vi
nd
ton
lUu
trong thitc an va nUdc udng [25, 35]. Theo Le Trung [54],
Biii
Thanh Tam
[41]
Linda Rosens [37], bieu
liien lam
sang
ciia
nhiem doc
HCH giong nhu nhiem doc DDT, chi khac la bieu hien rd ret hdn. HCH
Cling gay nhiem doc cap tinh va man tinh, lam rdi loan mau va cd quan
tao man. HCH cdn cd tac hai tdi cac qua trinh chuyen hoa tao enzim d
gan va gay thoai hoa
tebao
gan [76, 92].
1.4.5. Tac hai chung cua HCBVTV nhom
cd
photpho
1.4.5.1. Dac tinh chung cua HCBVTV
nliom

16
Thiophotphat
A
RO
OX
R'
^
//
s
Pv
RO'^
0-{^
V02
Dithiophophat
RQ .S
A
RO SX
^=
Metylparathion : R la CH3
^=
Parathion :R la
(^2^5
CHoO
S
^ \
II
P
/ !
CH3O S-CHCOOC2H5
CH2COOC2H5

cda
HCBVTV nhdm cd photpho [39, 92, 136]
f>(ft!
-^or
^
/
• — "-•'
";\.7"
"'.,.,:,
\.'l!i
17
••M*r
».^ '-
'
*•
- Cac hdp chat cd photpho deu cd ap suat hdi cao, de bay hdi, la
nhfing
chat doc dUdng ho hap. Chiing de hoa tan trong cac dung mdi
hiiu cd va dau md,
dl
bi phan huy nen
„
khd thu hdi dUdc chinh
pham ban dau.
*•
- Dac diem chung ve hoa hoc ciia cac hdp chat cd photpho la de
bi thuy phan.
RO.
RO
P(S)

hoat hoa nhan
photpho. Phan
ling
xay
ra
thUdng tao thanh chat
lic
che enzim
cholinesteraza manh hdn, phan
Idn
chuyen nhdm
y
P=S thanh nhdm
\
p=o.
(C2H50)2 -
P
-
o/
\N02
+ O2 + H2O ^ (C2H50)2
-P
-0-(^
^ NO2 + H2SO4
Parathion
-a
Paraoxon
- Di ddi vdi phan
ling
hoat hoa la phan

Axit 0,0 - dimetyl dithiphotphoryl axetic kem doc hdn dimetoat den
3.400 lan.
1.4.5.2. Dxidng xam nhap cua HCBVTV nhom
ca
photpho vao
ccf
the:
'^'
HCBVTV nhdm cd photpho xam nhap vao cd the qua dudng hd
hap,
tieu hoa, da. Su hap thu cac hdp chat cd photpho d niem mac
dudng tieu hoa dien ra rat nhanh, chi sau vai
phiit
da xuat hien cac
dau hieu nhiem doc [76, 81]. Qua trinh hap thu qua da cham hdn,
khoang sau 2 gid mdi bat dau cd cac dau hieu ciia sU iic
che
enzim
cholinesteraza,nhttng
dau hieu nay keo dai 2 ngay [38].
1.4.5.3. Chuyen hoa cua HCBVTV nhom
cd
photpho trong
ccf
the.
- HCBVTV nhdm cd photpho de tan trong
lipit.
Chiing dUdc hap
thu nhanh chdng vao man, cac dich the cua to chiic va dat dUdc ndng
do cao trong cac

cholinesteraza, gay tinh trang tich luy nhieu chat axetylcholin dan
den nhiing rdi loan nghiem trong qua trinh dan truyen d cac synap
than kinh va
hitng
phan qua
miic
do he thdng than kinh trung Udng.
Vi vay chiing dUdc goi la nhiing chat doc than
Idnh
[81, 106].
- Binh thudng enzim
chohnesteraza
tac dung vdi axetylcholin
Sau khi tac dung, enzim cholinesteraza dUdc hoi phuc nhd phan
ling
thuy phan ciia hdp chat cholinesteraza-axetyl hoa.
- Trong trUdng hdp nhiem doc HCBVTV- cd photpho thi enzim
cholinesteraza ket hdp vdi phan tii HCTS cd photpho tao thanh hdp
chat ben viing, khd thuy phan, ket qua la enzim cholinesteraza bi
iic
che
[1,41].
- HCBVTV-cd photpho dUdc dung de : chdng sau benh cho cac
loai cay cdng nghiep, cay an qua, rau,
liia
mau, diet cd dai, chdng nam,
lam rung la, diet trii rudi, mudi, bo chet [12, 22, 28].
L
4.6.
Gidi tbieu mot so

nUdc[117].
- Cung nhu cac HCTS-cd phopho, parathion de bi thuy phan.
Tinh chat quan trong
thii
hai la phan
ling
hoat hoa nhan photpho,
phan ling xay ra thUdng tao thanh chat
tie che
enzim cholinestaraza
manh hdn. Trong cd
the
parathion chuyen hoa thanh paraoxon doc hdn
parathionlOOO lan [39, 56].
- Parathion thudc nhdm doc loai I. Hdp chat nay cUc ky doc vdi
dong vat cd
vii
[76], Parathion nhiem doc qua dUdng hd hap, da, tieu
hoa. Nd dUdc chiing minh cd tac hai man tinh nhU gay cac khoi u trong
thUdng than, chiing teo va thoai hoa vong mac va sU thoai hoa ciia day
than
Idnh
hdng. Cac tac gia da ket luan rang parathion la chat gay
khoi u loai C, cd kha nang gay ung thu tren ngUdi [98, 117]. LD50 la
13 mg/kg,
ADI:
0,005 mg/kg the trong [114, 132].
- Cac dac diem ve sinh ly va sinh hoa : Parathion la chat diet cdn
triing. Parathion tac dong len ngudi bang
each