Khảo sát và phát triển quy trình phân tích các độc tố hữu cơ khó phân huỷ thuộc nhóm ankylphenol và bisphenol A trong nước rác tại một số khu vực bãi rác Hà Nội

DAI HOC QUOC GIA HA NOI
TRITONG
DAI HOC KHOA HOC
T\S
NHIEN
Khao sat va phat trien quy
trinh
phan
tich
cac doc
td
huu ca kho phan huy thuoc nhom
ankylphenol va bisphenol A trong
nu6c
rac
tai mot sd khu vuc bai rac Ha Noi.
MA SO: QT-04-34
CHU TRI DE TAI: GS.TS. Pham
Hiing
Viet
CAC CAN BO THAM GIA:
ThS.
Tran Thi
Liau
HVCH. Tran Thi Tuyet Mai
HVCH.Trinh Thi Thdm
CN. Le Thi Ngoc Ha
OAI HOC QUOC GlA
h-
.v'C
TRUNG TAM THONG TIN

THL'^"( -^^
DT/3
5G
Ha
Noi-
2005
BAO CAO TOM
TAT
KET QUA
THl/C
HIEN
De tai cap DHQG nam 2004
1.
Ten de tai:
Khao sat va phat trien quy
trinh
phan
tich
cac doc td hiru ca kho phan huy thuoc nhom
ankylphenol va bisphenol A trong
nu6c
rac tai mot sd khu vuc
thupc
bai rac Ha Noi.
Ma sd: QT-04-34
2.
Chu tri de tai: GS.TS. Pham Hung Viet
3.
Cac can bo tham gia: ThS. Tran Thi
Lilu

HVCH. Tran
Thi
Tuyet Mai
HVCH. Trinh Thi Tham
CN. Le Thi Ngoc Ha
4.
Muc tieu va noi dung nghien
cufu
Miic
tieu
ciia
de tdi:
- Nghien cuu khao sat va hoan thien quy trinh xac dinh cac hoa chat huu ca
tich
luy
b6n
thuoc
hg
ankylphenol
(4-nonylphenol,
4-t-octylphenol,
4-n-octylphenol)
va
bisphenol A trong cac
mSu
nuac rac.
- Ung dung quy trinh khao sat vao viec phan tich cac din xuat phenol nghien cuu trong
m^u
nuac rac va nuac ngam thuc te
dugc

thu thap tai
mpt
sd bai rac thuoc Ha
Npi
(bai
rac Nam San, Tay M6).
-
Kei
qua nghien cuu cua
d^
tai dugc
sir
dung lam khoa luan tdt nghiep ciia mpt sinh
vien khoa Hoa khoa K45 va mot bao cao khoa hoc tai Hoi nghi Khoa hoc cua truang
KHTN nam 2004.
Npi
dung nghien
cihi:
- Nghien cuu khao sat va hoan thien phuang phap
xir
ly
mSu
de xac dinh cac hgp chat
ankylphenol va bisphenol A trong miu nuac rac vai do tin cay cao tren cac miu gia.
- Tien hanh lay miu
nude
rac tai vi trf mpt sd bai rac khac nhau d Ha Npi la bai rac
Nam San, Tay M6 va lai vi tri cdng thai va nuac ngam xung quanh khu vuc bai chon
lap rac.
- Phan

tich
va xac dinh cac hgp chat nghien cuu trong cac miu thu thap.
- Xu ly, tdng ket cac ket qua phan tfch va viet bao cao.
5. Tom tdt ket qua nghien
cuii
dat duoc
- Da khao sat va hoan thien quy trinh xac dinh cac ankylphenol va bisphenol A trong
miu
nude
rac vai viec ap dung ky thuat chiet pha rin SPE (chat hap phu
CIS),
ket hgp
vdi ky thuat din xuat axetyl hoa vdi dp lap lai cao. Hieu suat thu hdi cua cac hgp chat
nghien cuu deu
>84%.
- Ket qua ap dung quy trinh khao sat thu dugc de xac dinh cac hgp chat 4-nonylphenol,
4-tert-octylphenol,
4-n-octylphenol, bisphenol A trong cac miu nuac ngam va
nude
rac
tai hai khu vuc bai rac lan
ciia
Ha Npi la Nam San va Tay
M6
cho thay su cd mat cua
cac hgp chat nay trong cac miu phan
tich.
Ham lugng trong cac miu
nude
rac nim

trong khoang 447,5-
1856,3ng/L
ddi vdi nonylphenol va
767,9-7250,
Ing/L
ddi vdi
bisphenol A. Mac du da qua xu ly, ham lugng nonylphenol trong miu
nude
rac tai khu
virc
bai rac khu vuc Nam San vin vugt qua tieu chuan Chau Au v6 ndng dp du doan
khong gay bat ki anh hudng vdi sinh vat thuy sinh.
- Ket qua ddng gdp vao viec danh gia, theo doi su phan bd, mdi quan he cua cac hgp
chat ankylphenol va bisphenol A trong moi trudng. Cac sd lieu do dugc chi ra nguy ca
6 nhidm ti6m
tang
CLia
cac hgp chat phan tfch ddi vdi sinh vat huu sinh va de doa sue
khoe con ngudi. Nhim kiem soat, danh gia su tdn tai, van chuyen ciia cac hgp chat nay
trong cac hgp phan moi trudng khac nhau can tiep tuc thuc hien nhiing nghien cuu sau
han trong tuang lai.
6. Kinh phi
ciia
de tai
6.1.
Kinh
phi
duoc cap:
18
trieu ddng

6.2. Giai trinh cac khoan chi:
- Thue khoan chuyen mon:
- Quan ly phf:
- Dien
nude
va xay dung ca sd vat chat:
- Hd trg dao lao va NCKH:
- Hoa chat,
nguyen
lieu, dung cu:
9.720.000d6ng
720.
000 ddng
720.000 ddng
540.000 ddng
6.300.000 ddng
KHOA QUAN LY
CHU NHIEM DE TAI
GS.TS.
^4^y^^^
Mi^
^/
GS.TS.
Pham
Huna Viet
TRUONG DAI HOC KHOA HOC TU NHIEN
#H6
HI^U
TRUONG
BRIEF OF THE PROJECT

1.
Name of project:
Investigation and development of analytical procedure for determintion of alkylphenol
and bisphenol A compounds among persistent organic pollutants in landfill leachate
samples from dumping sites in Hanoi.
The code number: QT-04-34
2.
The Coordinator: Prof.Dr. Pham Hung Viet
3.
The Participants of the project: M.Sc. Tran Thi Lieu
St. of M.Sc. Tran Thi Tuyet Mai
St. of M.Sc. Trinh Thi Tham
BcS.
Le Ngoc Ha
4.
Purpose and contents of the research
Purpose:
'
Investigation and optimization for analytical procedure of alkylphenols (4-
nonylphenol,
4-t-octylphenol, 4-n-octylphenol) and bisphenol A among persistent
organic chemicals in leachates samples.
- Application of obtained procedure on determination of target compounds in landfill
leachates and related ground water samples at some dumping sites in Hanoi (Nam Son
and Tay Mo).
- The results of this research was used for a graduated thesis of a chemistry student,
who studied at the course of K45 and a scientific report at scientific conference of
Hanoi University of Science in 2004.
Content:
- Study and development of preparation procedure to determine alkylphenols and

bisphenol A in leachates samples with significant reliability on spiked samples.
- Carry out collecting leachates samples, groundwater and surface samples around
some landfills in Hanoi (Namson, Taymo dumping sites).
- Analysis and determination target compounds in taken samples,
- Calculation, summarization the obtained results and writing the report.
5.
Actives and Results obtained
- Investigated and developed for analytical procedure of alkylphenols and bisphenol A
in leachates samples with application solid phase extraction (SPE) technique using
C18
cartridge and dramatization technique using anhidrite acetic derivative. The values of
recoveries for every target compounds achieved over 849c and high repeatability.
- The results of application researched procedure to
detennine
4-nonylphenol.
4-terl-
octylphenol, 4-n-octylphenol and bisphenol A in leachates and groundwater samples at
locations of selected dumping sites shown the presence of these compounds in
analyzed samples. Concentrations of nonylphenol and bisphenol A in leachates
samples were ranged 447,5- 1856,3 ng/L and 767,9-7250,1 ng/L, respectively.
Concentration of nonylphenol in leachates samples at Namson dumping site exceeded
United States and Europe standard regarding the predicted no-effect concentration in
water
(PNECy,a,er)
although leachates treated.
- The results contributed assessment and monitoring spatial distribution and behavior
of alkyl phenols and biphenyl A in the environment. The measured data indicated
potential risks of target compounds for wildlife and human health. Further research
need to be continued in the future to get an overview about these compound in the
environment.

MUC LUC
Trang
1.
MO DAU 1
II.
TONG QUAN 1
2.
L Gidi thieu
vi
bisphenol A (BPA) 1
2.7.7.
Tinh
chdt
vgt ly vd hod
hgc
2
2.7.2. ung dung cua BPA 2
2.1.3.
Nguon
thdi BPA vdo moi trucmg 2
2.7.4. Tdc
dgng
cua BPA doi vai dgng thuc vat vd con
ngi/ai
3
2.2.
Gidi thieu chung
v6
cac ankylphenol (AP) 4
2.2.1.Giai

thieu ve
MP 5
2.2.2. Giai
thieu ve
OP 5
2.23.
Ung dung
cita
AP 6
2.2.4.
Nguon
thdi AP vdo moi trudng 6
2.2.5. Tdc dgng
ciia
cdc AP ddi vdi dgng thuc
vgt
vd con nguai 7
2.3.
Nude
rac va cac van de nay sinh trong cac bai chon lap rac d Viet Nam
^
2.4. Phuang phap tach chiet pha rin vdi viec tach chiet cac hgp chat AP va
9
BPA
2.5.
Ky thuat din xuat hda
11
IIL
THUC NGHIEM 11
3.1.

Hda chat
11
3.2. Thiet bi
12
3.3.
Khao sat quy trinh phan tfch cac ankylphenol va bisphenol A trong miu
\2
nude
rac
3.3.1.
Thu thdp mdu
\2
3.3.2 Khao sdt giai dogn lam sach tren
cgtflorisil 12
3.3.2.1.
Chucfn
hi cot nhoi 12
3.3.2.2. Khao sdt luang dung moi
ri(a
gidi
I3
3.3.3. Khao sdt hieu sudt thu hoi
ciut
phuang phdp
I3
3.4. Phan tfch dinh tfnh va dinh lugng tren
GC/MS
13
3.5.
Hoan thien quy trinh phan tfch

I4
IV: KET QUA
VA
THAO LUAN
15
4.1.
Ket qua qua trinh din xuat hda
I5
4.2.
Xac dinh phan manh dac trung ciia cau ttr can phan
tich I5
4.3.
Khao sat quy trinh phan tfch
jy
4.4.
Khao sat hieu suat thu hdi
ciia
quy trinh phan tfch cac dan xuat phenol
\^
trong miu
nude
rac
4.5.
K6't
qua phan
tich
miu
nude
rac thuc te 19
4.5.1.

Ket qud phdn tich trong cdc mdu tgi khu vuc bdi rac Tay Mo 20
4.5.2. Ket qud phdn tich trong cdc mdu tai khu
vUc
bdi rac Nam San
21
4.5.3. So sanh ket qud phdn tich tgi hai khu
vUc bdi
rac nghien
cicu
22
V. KET LUAN 23
Tai lieu tham khao 24
Phu luc 26
DANH SACH CAC BANG
Trang
Bang 1. Mot sd
tinh
cha't
ctia
BPA 2
Bang 2:
D6c tinh
ciia BPA ddi vdi mot sd dong thuc vat thuy sinh 3
Bang 3. Mot sd
tinh
chat vat ly cua nonylphenol 5
Bang 4: Manh pho dac trung ciia cac hgp chat phan
tich
17
Bang 5: Ket qua phan tfch cac phan doan

rtra
giai 17
Bang 6: Kd't qua hieu suat thu hoi ciia cac hgp chat phan tfch trong miu 19
nude
rac tai ndng do
50ng/L
Bang 7 : Ket qua phan tfch miu nude tai bai rac Tay Md 20
Bang 8: Ham lugng cac hgp chat phan tfch trong cac miu tai bai rac Nam
21
San
DANH SACH CAC HINH
Trang
Hinh
I.
Cong thuc phan tu cua BPA 2
Hinh 2: Cong thuc
c^'u
tao ciia nonylphenol 5
Hinh 3: Cong thuc
c^'u
tao ciia OP va NP 6
Hinh 4: Cau
true
ciia hocmon nu tu nhien 17P-estradiol va hoocmon nu 7
nhan tao 4-nonylphenol (mpt dang ddng phan).
Hinh 5: Cac budc tien hanh cua phuang phap chiet pha rin 10
Hinh 6: Ca che phan ung din xuat axetyl hda cacphenol
16
Hinh 7: Dd thi bieu diSn ham lugng NP va BPA trong cac mau
nude

tai
21
khu vuc bai rac Tay Md
Hinh 8: Do thi bieu
di6n
ket qua ndng dp NP,BPA trong cac miu
nude
tai 22
khu vuc bai rac Nam San
Hinh 9: Do thi bieu diln su phan bd
ciia
NP va BPA trong cac miu
nude
23
rac va
nude
ngam thu thap tai khu vuc bai rac Tay Md va Nam San.
L
MODAU
Gin
day,
viec
ph^n tich
cac hda chat
tich
luy
b^n
trong mdi trudng va cd kha
nang gay rdi loan npi tiet (EDCs) da thu hut dugc su quan tam cua nhieu nha khoa hpc
do nhirng anh hudng nguy hai cua chung den con ngudi va dpng vat nhu: anh hudng

de'n he thdng sinh san, tap
tinh
sinh hoat, tao ra cac u ac
tinh
va gay hau qua nghiem
trpng cho cac the he tuang lai ma khd cd thi du bao trudc dugc. Trong dd, cac din xuat
phenol nhu ankylphenol va bisphenol A ndi trpi len do
tijf
lau da dugc ung dung rpng
rai trong cac hoat dpng sdng ciia con ngudi.
Ankylphenol
(APs),
san
ph^m
thoai bien
ciia
ankylphenoletoxilat, la loai hgp
chat dugc dung pho bien trong cac nganh cong nghiep, sinh hoat va cac ung dung
thuang mai (cong nghiep giay, vai sgi, san,
nhua,
san xuat chat tay
rii"a
sinh hoat va
cong nghiep); bisphenol A (BPA) dugc
diing
lam chat trung gian trong san xuat nhua
policaebonat va chat cham chay, chat ket
dinh,
chat bao phii bao ve, san, vat lieu xay
dung, giay nhiet, vat lieu bao ve dd dien, dien

tir,
Ha
N6i
cd mpt sd ft bai rac
tip
trung khdi lugng
Idn
rac thai sinh hoat
tCr
khip
cac khu dan cu dd thi trong va ngoai thanh phd. Han nua, phan
Idn
cac bai rac chua
dugc xay dung dung qui each, hgp ve sinh. Vi vay, anh hudng su
6
nhilm
v6
miii, cung
nhu cac chat thai dpc hai da, dang gay mdi quan tam
Idn
ddi vdi xa hoi. Cac dpc td hiru
ca khd phan huy ndi chung va cac hgp chat ankylphenol va bisphenol A ndi rieng cd
mat kha phd bien trong thanh phan cac chat thai tai eac khu chon lap rac nay.
Viec phan tfch cac hgp chat phenol trong miu nude rac gap rat nhilu khd khan
trong khau xtr ly miu, do su qua phuc tap vl thanh phan cac loai hgp chat gay anh
hudng cd trong
nin
miu. Viec nghien cuu tim ra mpt phuang phap hieu qua va thfch
hgp de tach chiet va lam sach cac hgp chat din xuat phenol ndi chung ra khdi miu
nude

rac la rat khd khan.
Nghien cuu nay dugc thuc hien vdi muc dfch khao sat va hoan thien quy trinh
xac dinh cac hgp chat ankylphenol va bisphenol A trong miu
nude
rac
sir
dung ky
thuat chiet pha rin ket hgp vdi ky thuat din xuat axetyl hoa. Ben canh dd de gdp phan
vao viec theo ddi, danh gia su phan bd, du doan nguy ca 6 nhilm
ciia
cac hgp chat nay
trong moi trudng, chiing toi da ap dung quy trinh nghien cuu de phan tfch mot sd miu
nude
rac va
nude
ngam thu thap tai hai bai rac Nam San va Tay
M6.
H.
TONG QUAN
2.1.
Gidi thieu ve Bisphenol A (BPA)
Bisphenol A (BPA) la ten thong dung cua 2,2-(4,4-dihidroxydiphenyl)propan.
Cong thuc
ciia
BPA thu dugc bing each ket hgp 2
moi
phenol vdi 1
moi
axeton nhu
mieu ta dudi day:

HjC_
CHj
Hinh
1.
Cong thuc phdn
tii
cua BPA
2JJ.
Tinh chdt vgt ly vd hod hoc
O dilu kien thudng, BPA tdn tai d trang thai rin, cd cau true tinh
thi,
dp tan
trong
nude
tha'p (120-300mg/l tai
pH=7).
Trong moi trudng kilm, BPA tan tdt han do
cd hing sd phan ly pKa= 9,6-10,2.
Bdng 7. Mot sd tinh chdt cua BPA
Thong sd
Khdi lugng phan tii
Cong thuc phan tu
Ty trpng
Nhiet dp soi
Nhiet dp ndng chay
pKa
Dp tan trong nude
Gia tri
228g/mol
C15H16O2

l,195g/cm3
220^C(d4mmHg)
398"C(d760mmHg)
150-155"C
9,59—10,2
120
—300mg/l
2.1.2. Ung dung
ciia
BPA
Gin nhu toan bp (99,9%) san pham ciia BPA dugc
sir
dung nhu mot chat trung
gian ciia qua trinh san xuat nhua polycacbonat, chat deo tong hgp epoxy, chat lam
cham chay hay mpt sd san phim chuyen dung khac. BPA cdn cd mat trong nhung san
pham nhu chat dfnh, chat
Idt
phu, bpt san, vat lieu xay dung,
dia
compact, vat lieu
quang hpc, giay chiu nhiet, bao gdi. Ngoai ra nd cdn dugc six dung trong cong nghiep
nhupm hoac san xuat vd nhua ciia cac thiet bi dien. BPA ciing dugc diing la chat uc che
phan ung hoac chat chdng oxi hoa trong qua
trinh
san xuat PVC.
2.13.
Nguon thdi BPA vdo moi tru&ng
Ngudn thai BPA
chii
yeu la

X\s
cac hoat dpng cong nghiep va thu cong nghiep
bdi day la mot loai hda chat tong hgp. Mpt lugng
Idn
BPA da di vao
nude
thai cong
nghiep va do thi (da hoac chua qua
xir
ly). Ngoai ra, nd cdn dugc dua vao moi trudng
thong qua cac phe lieu, chat thai rin khac bdi ngudi ta da phat hien dugc ndng dp rat
cao BPA trong dich chiet tu nhirng nai do phe lieu, chat thai. Tai nai san xuat che
bie'n, ham lugng thap cua BPA dugc thai
true
tiep vao
nude
bl mat va khong
khi
qua he
thdng
nude
thai. BPA cd mat trong khong
khi
trong qua trinh san xuat va
sir
dung.
Ngoai ra, BPA ciing cd the thoat ra
tijf
cac san pham c6 chua lugng nhd BPA chua phan
ling hoac BPA dugc sinh ra tai nhirng dilu kien nhat dinh.

2J.4.
Tdc
dpng ciia
BPA ddi voi dong thuc vgt vd con ngudi
BPA la mpt trong nhiing hoa chat tong hgp kha
bin
trong moi trudng. Mot vai
nghien
ciiu
vl dpc tfnh cua BPA ddi vdi cac loai vi sinh vat, tao, dpng vat khong xuang
sdng, ca va con ngudi da chiing minh nd la mpt chat cd tilm nang gay
6
nhiem moi
trudng nghiem trpng, de doa he sinh thai. Tieu chuan ciia My va Lien minh chau Au vl
ndng dp cua BPA trong moi trudng nude la 1000
ng/1.
Bdng 2: Dgc tinh
ciia
BPA ddi vdi mot sd dgng thuc vgt thuy sinh
Loai
Vi sinh vat
nude
ngot
Pseudomonas putida
Pseudomonas flourcscens
Bp chet nude Daphnia
magna
Tom cam Mysidopsvbahia
Ca tue dau to Pimephales
promcias

Ca hdi ddm den
Oncorhynchus mykiss
Ca sdc
Oiyzias
latipes
Ca sudt Menidia menidia
Ca chep Cyprinodon
variegatus
Chi
sd
EClO 18
gid
IC50
EC50 48 gid
LC50 96 gid
LC50 96 gid
LC50 96gid
LC50 48gid
LC50 48 gid
LC50 96 gid
Tac dong
Giam 10%
sinh trudng
Bat dpng
Tu vong
Tir
vong
Tu vong
Tu vong
Tii

vong
Tu vong
Gia tri
(mg/l)
>320
54,5
3,9
M
4,6
3-3,5
15
9,4
7,5
Tham
khao
17]
|13|
[13]
151
[51
[8]
[9]
[13]
[12]
Nhung anh hudng chu yeu
ciia
BPA la len he thdng npi tiet nhu kfch thfch hay
kim ham hoat dpng cua hoocmon gidi tfnh ddi vdi dpng vat, cd the din den nhung hau
qua nhu: +)anh hudng den
sir

sinh san; lam mat kha nang sinh san d cac loai chim, gay
phat tnen gidi tfnh khong binh thudng d chim, ca, bd sat, dpng vat cd vu hay lam tic tu
cung
cLia
cac loai dpng vat biln. +)Suy yeu kha nang sinh
due
nhu doi gidng cai (gay
ra d ca), bien dang phoi cac loai chim hoac lam chet triing cac loai ca.
+jGiam
sd
lugng ca thi loai do su rdi loan sinh
due.
+) Gay rdi loan chiic nang cua tuye'n yen va
tuy6'n
sinh
due
ciia con ngudi, Ngoai ra nd cdn ngan can, pha huy qua trinh san xuat
hoocmon tuyen yen va tinh hoan. Do vay viec thu tinh va tao triing bi anh hudng
nghiem trpng,
Ngay nay, do su phat trien manh me ciia
nin
cong nghiep, lugng BPA dugc su
dung va thai loai vao moi trudng ngay cang nhilu va dd la ngudn nguy hiem ddi vdi
cac loai dpng vat cung nhu con ngudi. Su tiep nhiem BPA cd the khien cho ca
thi
cac
dgng vat dugc tiet ra hoocmon vitellogenin (mpt loai protein noan hoang ciia cac dpng
vat cd xuang sdng gidng cai va khong cd trong cac ca
thi
due cung nhu cac con

non),
anh hudng den viec tao tinh triing cung nhu su phat trien cua ca
thi.
d nhirng ca the
nay ngudi ta da tim thay nhung te bao budng triing trong tinh hoan. Mpt vf du khac, tai
Nhat Ban, khi nghien
ciiu
eac loai ca sdng trong moi trudng nude ed chiia BPA (tai
ndng dp 1820
|^g/l)
da phat hien nhilu ca
thi vira
cd budng triing
vira
cd tinh hoan.
Nhu vay tai ndng dp nay, xu hudng bien ddi gidng la lam tang gidng cai. Dilu nay cd
anh hudng
Idn
den sd lugng ciia loai.
Nhung dpng vat thiiy sinh khong xuang sdng
cijng
td ra nhay cam vdi BPA.
Dpng vat than
mIm
phan
iing
vdi chat nay d ndng dp rat thap. Thf nghiem tren loai
ihfm mIm
Potamopyrgus
antipodanmi

cho thay ngay ca khi d dang hdn hgp vdi nhilu
chat khac trong
nude
thai ga cdng da qua
xii
ly, BPA cung cd kha nang gay tac dpng
ddng thdi len triing va phoi d ndng dp thap va kim ham su phat triln d ndng dp cao
han.
Vao nam 2000, mpt sd nha khoa hpc da cong bd nhung ke't qua nghien
ciiu
thay
ring ngay tai ndng dp thap, BPA cung cd
thi
gay anh hudng len he sinh san cua dc sen
cai nude ngpt Marisa cornuariettis va Nucelle
lapillus,
lam sung tay tuyen sinh due va
diit
dng din triing.
Ca che tac dpng cua BPA hien vin chua dugc khing dinh ro rang. Nhung mdi
day, mpt phep thu trong ca
thi
da dua ra ca che phan tu trong dd BPA cd the viia anh
hirdng den hoat tfnh va chiic nang cua ca quan thu nhan hoocmon andogen. Tuy vay,
nhij*ng
tac dpng cua BPA d
lilu
lugng nhd vin tiep tuc dugc ban luan.
2.2.
Gioi thieu chung ve cac ankylphenol (AP)

Cac AP dudi dang ankylphenol etoxylat (APE) la nhdm cac chat hoat dpng bl
mat dugc phd bien nhat hien nay. Trong dd khoang 80% la cac nonylphenol etoxylat
(NPEs). Cac
octylphenol
etoxylat (OPEs) cung dugc su dung nhu mpt chat hoat dong
bl mat khong phan ly trong cac thudc trii sau vdi mot lugng nhd trong tdng san luang
tieu thu.
Trong 40 nam gan day, 450 trieu tan nonylphenol (NP) dugc san xual tren loan
the gidi, chi rieng tai Hoa Ky, con sd nay la 150 000 tan. Day la mpl hoa chat long
hgp rat dpc hai. Nd cd kha nang tfch tu sinh hpc, trong cac mo
ciia
ca
thi
sdng va
ifch
tu trong mdi trudng. NP da dugc xac dinh trong cac miu moi trudng d My, Canada va
(Thau Au, dan tdi nguy ca gay 6 nhiem tai cac hd va cac ddng song.
22J,
Gi&i thieu veNP
NP bao gdm nhieu ddng phan vdi chudi
nonyl lien
ken
true
tie'p vdi vdng tham
cua phan tit phenol. 4-NP, cha't cd gdc nonyl nim d vi trf ddi dien vdi nhdm hidroxy la
hgp chat phd bien nhat, chie'm khoang 90% NP thuang mai.
HO
X ^C,H,3
Hinh 2: Cong thuc cdu tgo cua nonylphenol
4-NP la chat long, sanh, cd mau vang nhat, trong sudt, cd mui phenol nhe. Cac

hing sd vat ly
ciia
NP dugc trinh bay trong bang 3.
Bdng 3. Mot
sdtinh
chdt vgt ly
ciia
nonylphenol
Thong sd
Khdi lugng phan tir
Cong thiic phan tir
Ty trpng
Nhiet dp soi
Nhiet dp ndng chay
pKa
Dp tan trong
nude
Gia tri
222,36g/mol
Ci.H.aO
0,937g/cm3
293-297^C
2^C
9,59—10,2
5,34
mg/l (20'^C)
NP la chat rat ft tan trong
nude
(dp tan d
20''C

la 5,34 mg/l), tan tdt trong
benzen, anilin, heptan, etylenglycol.
NP cd tfnh
ua
ma nen nd cd kha nang tfch tu trong cac mo ma hay trong ca the
ciia
cac dpng vat.
2.2.2. Gioi thieu ve OP
Cong thiic phd bien nhat
ciia
4-OP la
para-tertoctylphenol
hay 4-(l,l,3,3-
tetrametylbutyOphenol
OH OH
n - octylphenol tert - octylphenol
Hinh 3: Cong
thitc
cdu tgo cua OP vd NP
4-OP tdn tai d dang tinh
thi
tring hoac bui vdi mot sd hing sd vat ly sau
Cong thiic phan tir:
C14H22O
Nhiet dp ndng ehay:
81-84°C,
nhiet dp soi:
150°C
(d 4 mmHg). Ty trpng 0,961
g/cm\

Diim
chop chay:
>230"C
4-OP
bin
va de bat chay, cd kha nang pha huy eac mang nhay. Dpc tfnh
ciia
nd
hien nay vin chua dugc nghien
ciiu
day
dii.
LD50 vdi chupt (qua mieng) 4600 mg kg"'.
LD50 vdi thd (qua da)
1880
mg kg
'.
2.2.3.
ling
dung cua AP
Octyl-
va nonylphenol dugc
iing
dung rpng rai lam nguyen lieu dau
ciia
cae chat
tay rira, chat nhu hoa, tac nhan lam udt hoac phan tan trong son, nhua chdng oxi hoa,
thudc trir sau (trir nam) hay chat tao bpt, chat lam
bin
sir dung trong cong nghiep san

xuat nhua PVC. AP ciing dugc dung nhu chat phu gia trong dau ma boi tran
Nonyl- va octylphenol la nhiing sin phim
bin ciia
qua trinh phan huy sinh hpc
cac APE, chiing dugc san xuat khoang 10 000-50 000 tan/nam trong dd udc tfnh san
lugng
ciia
toan chau Au la 6800 tan.
2.2.4. Nguon
thdiAP
vdo moi tru&ng
Hiu het
Ctic
AP dugc thai ra moi trudng dudi dang APEO, chat nay tiep tuc
thoai bien thanh ankylphenol mono hay dietoxylat rdi hap thu trong
biin
va tram tfch.
Ahel
va cpng su (1994) da udc tfnh trong mpt chu trinh xir ly
nude
thai khoang 40%
NP dugc xir ly, 20% hap thu vao
biin,
cdn lai 40-45% khong
xii
ly dugc va di vao cac
ddng chay.
Ngudn thai chfnh
ciia
AP vao moi trudng la tir cac sin pham tay rira, mpt sd san

phim cong nghiep khac nhu scm, thudc diet cd, hda my pham, nhua phenolic, dich
chiet tir cac bai chon lap rac thai. Ngoai ra NP cdn thoat ra moi trudng tir cac san pham
lam bing nhua polystyren va PVC.
iTdc
tfnh lugng AP dugc san xuat tren toan the gidi
Ik
khoang 10 000- 50 000 tan/ nam
(1995).
2.2.5. Tdc dgng cua
cdc
AP ddi
v&i
dong thuc vgt vd con nguoi
Nhiing nghien
ciiu
tac ddng eua cac AP ddi vdi dpng vat dua vao nhirng thf
nghiem sinh hpc trong hay ngoai ca the. Tren thuc te, nhung ap luc vl mat dao
diic
khong cho phep chiing ta nghien
ciiu true
tiep tren ca the con ngudi. Vi vay, chiing ta
phai dua tren nhung tai lieu dich tl dang tin cay vl nhiing thir nghiem d dpng vat, ca
hay chim,
tir
dd danh gia nhiing anh hudng cd the cd ddi vdi con ngudi. Tuy nhien, do
su khac biet giira cac loai trong tu nhien nen phuang phap nay khong
thi
tranh khdi
nhiing han che va sai sdt,
Trong nhiing nam gin day, nhirng tai lieu nghien

ciiu
tren toan the gidi da dua
ra nhirng canh bao vl tinh trang
6
nhilm moi trudng, va nhiing tac dpng cd hai gay ra
bdi cac hoa chat lam rdi loan tuyen npi tiet. Mpt vai nha khoa hpc da chiing minh rang
nhirng hgp chat nay cd anh hudng den he sinh san,
tap
tfnh hoat dpng
ciia
con ngudi
cung nhu cac loai khac, gay ra nhirng u ac tfnh va nhiing hau qua nghiem trpng khac
cho the he tuang lai.
Dpc tfnh
ciia
APs tang theo chilu dai
ciia
chuoi ky nude va dugc
thi
hien khi
chiing phan bd vao cac mang ma eua ca the nhu mang cua bp may gongi gay gian
doan viec tdng hgp ra nang lugng. Nhirng tac dpng
ciia
AP bit dau d ndng dp khoang
l,5mg/l.
Tuy nhien NP the hien tfnh dpc d ndng dp thap han nhieu, khoang
0,112
mg/l
ddi vdi ran nude. Nhin chung cac AP dpc han APEO, vf du NP dpc han NPEO khoang
10 lin.

Estrogen la loai hoocmon dilu chinh
sir
phat triln, quy dinh dac tfnh
ciia
gidng
cai.
Hien nay da c6 nhirng bing chiing
chu'ng
td ring mpt sd hda chat tu nhien ciing
nhu tdng hgp cd
thi
bat
chude
hoat dpng
ciia
hoocmon nay.
Me OH
OH
Hinh 4: Cdu
true
cua hocmon ml tu nhien
17fi-estradiol
vd hoocmon ml nhdn
tgo 4-nonylphenol (mot dang dong phdn).
Bing chiing diu tien chirng td ring cac para-AP cd the hoat dpng nhu estrogen
dugc xuat ban vao nam 1938 khi Dodds va Lawson cong bd ket qua cho chuot da cit
budng triing an
lOOmg
4-propylphenol.
Hp nhan thay hda chat nay gay sirng hda am

dao cua
chudt
gidng nhu hien tugng dien ra vao chu ky dpng
due,
Su sirng hda ciing
xay ra khi thir
nghifm
vdi
4-tert-pentylphenol
nhung khong xay ra vdi 2-n-
pentylphenol. Dilu nay dugc giai thfch do su khac nhau
ciia
2 nhdm the d vdng
benzen.
Bang chiing tie'p theo dugc cong bd vao nam 1978 khi Mueller va Kim nghien
ciiu
thay rat nhilu AP cd
thi
thay the cac estradiol lien ket vdi ca quan thu nhan.
Nhung tac dpng nay xay ra manh tai nhiet dp thap
(0-4^^).
Tuy nhien, nhiing ket qua nghien cuu tren khong
gay
dugc su quan tam rpng rai
cho
6€n
nam 1991, khi Soto va cac cdng su tinh cd phat hien 4-NP trong khi thf
nghiem
tr6n
cac te bao ung thu vu MCF7, nhay cam vdi estrogen. Hp phat hien thay

mpt hgp chat tach ra khdi dng ly tam va khien cho cac te bao phat trien manh me, mpt
hien tugng thudng thay dudi tac dpng
ciia
estrogen. Hgp chat nay da dugc xac dinh la
NP,
chat dugc dua vao thanh phan dng nghiem vdi muc dfch lam tang dp
bin.
Ket qua
tuang tu Cling thu dugc khi thir nghiem vdi NP thuang mai.
Vi nhirng ly do tren, cac APEO bi nghi ngd da
gay
nen nhiing anh hudng nhu
ire
che
\\tc
tdng hgp va chuyin hda cac enzym
ciia
hoocmon, lam gia tang cac te bao ung
thu va la nguyen nhan gia tang ty le ngudi bi mic benh ung thu tinh hoan va ung thu
vii
lai cac nude phuang Tay trong han 40 nam gin day. Do
miic
dp nghiem trpng eua nd
ma hien nay nhilu
nude
tren the gidi da cd nhirng bien phap giam thilu va ngan chan
viec sir dung cac APEO trong cac chat tay rira gia dung.
2,3.
Nude
rac va cac van de nay sinh trong cac bai chon lap rac

6
Viet Nam
[4,51
Nude
rac cd
thi
dinh nghia nhu mpt chat
Idng
tham qua chat thai rin, mang theo
cac chat hoa tan va chat rin la
lirng.
Trong phan
Idn
trudng hgp, nude rac dugc sinh ra
do qua trinh xam nhap
ciia
cac ngudn nude tir ben ngoai vao nhu he thdng thoat
nude
bl mat,
nude
mua,
nude
ngim va nude dugc sinh ra do qua trinh phan huy chat thai
trong bai chon lap .
Lugng nude rac hinh thanh trong cac bai chon lap dugc udc tfnh dua tren su can
bing nude trong bai chon lap.
Sir can
bing
nude
bao gdm tong lugng nude di vao bai

chon lap trir di lugng nude tieu thu cho phan
iing
hoa hpc va lugng nude bi bay hai.
Lugng
nude
rac tdi da cd kha nang sinh ra la lugng nude khong vugt qua kha nang giii
am cua cac vat lieu trong bai chon lap. Ket qua thf nghiem chi ra ring lugng nude rac
sinh ra
Idn
nhat sau 25 ngay chon lap. Ngudn
nude chii
yeu bao gdm
nude
di vao cac 6
chdn lap ttr phfa tren, lugng am cd sin trong rac thai, lugng am
ciia
vat lieu bao
phii
va
lugng
a'm
trong
biin.
Do phan
Idn
cac bai chon lap d Viet Nam chua hgp ve sinh,
chii
yeu la chon lap
16 thien nen da tao dilu kien cho rudi mudi phat triln,
miii

hoi thdi bdc len do qua trinh
phan huy yem khf trong bai rac. Vi vay, da gay ra
6
nhilm khong khf va ngudn
nude
ngam ca mpt viing rpng
Idn.
Cac bai chdn
la'p
rac d thanh phd
Idn diu
trong tinh trang qua tai, khong dugc
thid't
ke va quy hoach ngay tir dau, cpng vdi vice quan ly van hanh yeu kem nen da gay
ra hang loat cac van dl het
siic
nan giai.
Nude
rac sinh ra tir cac bai chon la'p (chu yeu la tir cac hd tfch trir
nude
rac bd trf
xung quanh bai rac) chay tran ra ngoai he thdng bd bao
gay
thiet hai nang nl cho ddi
sdng san xuat va sinh hoat cua dan cu. Nude rac sinh ra khong dugc xir ly kip thdi
hoac chua dat tieu chuin dang ed nguy ca
gay 6
nhiem nude ngam va viing nong
nghiep xung quanh.
Viec giam thieu va phan loai chat thai rin tai ngudn hau nhu chua dugc quan

tam
va thuc
hi6n,
nhilu chit thai nguy hai trong y te va cong nghiep dugc thu gom va
chdn chung vdi chat thai sinh hoat.
Cac van dt tren chfnh la mdt sd nguyen nhan
gay
ra su cd nhilu nai nhu trudng
hgp va bd bao d bai rac Dong Thach va nhilu trudng hgp hoa mau
ciia
nong dan d gin
khu chdn lap bi chet. De han che den
miic
thap nhat hau qua, chfnh
quyIn
cac cap dang
tim mgi bien phap xir ly va cai tao bai chon lap. Diln hinh la du an
xay
dung khu xir ly
nude
rac tai bai chon lap Nam San- Sdc San- Ha Npi, bai chon lap Dong Thach Thanh
Phd Hd Chf Minh va mpt vai bai chon lap khac bat diu chuan bi triln khai.
2.4. Phuong phap tach chiet pha rdn vdi viec tach chiet cac hpp chat AP va BPA
[1,2]
Nguyen tac cua chiet pha ran la sir dung chat chiet d dang hat nhd, xdp nhdi
trong cot chiet cac chat cin phan tfch ra khdi dung dich rdi dung mpt dung moi thfch
hgp rira giai chiing ra khdi cot. Day la qua trinh lam sach kem vdi lam giau Chat phan
tfch dugc tach ra khdi cac chat ban va dugc hda tan lai trong mpt lugng nhd dung moi.
Cot sic ky dugc nhdi bing nhirng vat lieu xdp, hat nhd cd chiia nhiing nhdm
chu:c

khac nhau. Chat long dugc dua qua cot dudi tac dung
ciia
ap suat hoac chan
khong.
w
2.
DDC
M
3.
^A^
fi
A
u
Rira giai
cac chat anh hudng
fi
A
w
chat phan tfch
Hinh 5: Cdc budc tien hdnh
ciia
phuang phdp chiet pha rdn
Phuang phap chiet pha rin gdm 4 budc, dugc mo ta nhu hinh 5.
Budc 1: Vat lieu nhdi cot dugc lam udt va solvat hda cac nhdm chiic. Budc nay
cdn cd nhiem vu loai bd khdng khf d cac khoang trdng giira cac hat vat lieu hap phu.
Budc 2: Dung dich miu dugc chay qua cot. Chat phan tfch va mot vai thanh
phin anh hudng dugc
giir
lai, cac thanh phan khac khong bi hap phu dugc loai ra ngoai.
Budc 3: Loai bd cac chat anh hudng ra khdi cot, chi giii lai chat phan tfch. Cd

thi
sir dung chfnh dung moi hoa tan miu de rira giai.
Budc 4: Giai hap chat phan tfch ra khdi chat hap phu bang dung moi thfch hgp.
Dung moi nay phai dac trung dl pha va tuang tac giiia chat phan tfch va chat hap phu
va rira giai cang ft chat anh hudng cang tdt.
Chat hap phu chiet pha ran thudng dugc sir dung gdm cac loai:
Chat ha'p phu pha thudng: cac silica trung tfnh, oxit nhom
Chat hap phu pha ngugc: cac silica da dugc
ankyl
hda nhdm OH
Chat cd kha nang trao ddi ion
Chat ray hay sang lpc phan tir theo dp
Idn,
kfch thudc
Chat hap phu pha khf- rin
Hidn nay, phucmg phap chiet pha rin ngay cang dugc sir dung rpng rai va phd
bidn do nhirng uu
diim
vugt trpi sau:
Hi6u
sua't thu hdi cao.
Kha nang lam sach, lam giau chat phan tfch
Idn.
Giam lugng dung moi sir dung.
Cd kha nang ket hgp vdi sic ky
khf.
An toan, dan gian, dl sir dung, cd
thi
tie'n hanh hang loat.
2.5. Ky thuat

d^n
xuat hda
Viec phan tfch cac AP va BPA bing phuang phap sic ky thudng gap khd khan.
Pic thu dugc thudng thap, nhilu va khd nhan dang do cd nhdm OH phan cue cd kha
nang luu giir lau vdi pha
tinh
cua
c6t
sic ky
gay
ra hien tugng keo chan pic, can trd
viec dinh tfnh, dinh lugng mpt each chfnh xac.
Dc khac phuc hien tugng tren ngudi ta thudng sir dung ky thuat din xuat hda,
thay the nhdm OH phan cue bing cac nhdm chiic khac ft phan
cue
han. Cac ky thuat
thudng diing dl dan xuat hda hgp chat phenol la
silyl
hda, axetyl hda, metyl hda
Trong nghien
ciiu
nay, chiing toi lua chpn phuang phap axetyl hda cac phenol
bing anhydrit axetic. Phan
iing
nay dien ra nhanh, dinh lugng tai nhiet dp phdng. Phan
ling dugc mo ta nhu sau:
OH OOCH
C
H X O O N
a ,, ,

+
(CH,CO),0 '- ^ I
+
CH.COOH
HI.
THirC
NGHIEM
Nghien
ciiu
bao gdm 2 phan: khao sat va hoan thien quy trinh phan tfch cac
ankylphenol va bisphenol A trong miu
nude
rac, va ap dung quy trinh khao sat dugc
vao xac djnh cac ankylphenol va bisphenol A trong mpt sd mau nude rac (trudc va sau
xir ly) va mau
nude
ngam tai 2 khu vuc bai rac Nam Son va Tay Mo.
3.1.
Hda
chat
Cac chat chuan ankylphenol (4-t-octylphenol, 4-nonylphenol, 4-n-octylphenol)
va bisphenol A, dung dich chat npi chuan naphtlen-d8 va chat ddng hanh bisphenol A-
dl4
(surrogate) dugc dat tir Chem Service. Dung dich chuan gdc ndng dp
lOOOmg/L
ciia
mdi chat dugc chuan bi trong dung moi axeton va dugc pha loang diing lam chat
chuan them vao va lap dudng chuin.
Anhydrit axetic, axft HCl dac, loai tinh khiet phan tfch
ciia

hang Merck dugc sir
dung lam tac nhan axit hoa va din xuat hoa.
Cac dung moi diclometan, hexan, axeton va metanol loai tinh khiet phan tfch
cua Merck.
Nude cat 2 lin dugc lpc qua thie't bi khir ion hoa Millipore (Nhat Ban).
Cha't ha'p phu florisil (90-100 mesh) sieu tinh khiet
ciia
Supelco va
Na2S04
khan
dang tinh khiet phan tfch
ciia
Merck dugc nung trong
Id
qua dem tai
450*'C.
Sir dung
c6t
chiet pha ran vdi cha't hap phu
RP-18
500mg cua hang Merck.
3.2.
Thiet bj
can
phan tfch Metier cd dd chfnh xac
lO'^g.
Til say,
tii
hot, bp cat duoi dung moi bing khf
N2

Tliiet
bi quay eat chan khong
ciia
hang Buchi (Nhat Ban).
Cot tach sic kf : cot mao quan
DB-1,
dai 30m, dudng kfnh trong 0,32mm, bl
day pha
tinh
0,25|am.
Thiet bi sic ky khf khdi phd GCMS-
QP2010 ciia
hang Shimadzu.
Thiet bi chiet pha rin
ciia
hang Supelco.
3.3.
Khao sat quy trinh phan
tich
cac ankylphenol va bisphenol A trong mau
nude
rac
33.1.
Thu thap mdu
9 miu
nude
rac va nude ngim quanh khu vuc 2 bai rac Tay Md va Nam San
dugc thu thap vao trong cac chai thuy tinh 4L sim mau va dugc lpc qua giay loc thuy
tinh (GF/F, Whatman, Anh). Dich lpc dugc axit hoa vdi HCl 4M vl pH 2 de ngan can
sir

phan huy
ciia
cac vi sinh vat va dugc bao quan tai 40C cho den khi chiet phan tfch.
33.2 Khao sdt giai dogn lam sach tren cgtflorisil
3.3.2.1.
Chuan bi cot nhoi
Cot lam sach tu nhdi florisil dugc chuin bi nhu sau: Chuan bi cot sic ky thuy
tinh dai 50cm, dudng kfnh trong 1cm da dugc lam sach, say kho. Can chfnh xac 5g
chat hap phu florisil da dugc say trong
Id
nung qua dem tai
200^C
vao trong cdc thuy
tinh nhd. Them dung moi n-hexan den ngap bl mat florisil. Qua trinh nhdi cot udt
dugc tie'n hanh lan lugt nhu sau; cot dugc nhdi dau tien la ldp bong thuy tinh, tiep den
la ldp
Na2S04
khan rdi 5g florisil. Tren ciing la 1 ldp
Na^SOj
khan. Go nhe phfa thanh
ngoai cot dl chat hap phu dugc nen chat.
Chii
y trong khi nhdi cot khong dugc de cot
kho.
3.3.2.2. Khao sdt luang dung moi nh gidi
- Them
true
tiep 10
jil
surrogate BPA- dl4 ndng dp 10 mg/l, 2

jil
hdn hgp
chuin 10
mgA
vao
c6t.
- Khao sat phan doan
FI:
dung 20 ml hdn hgp n-hexan : diclometan
(1:3
vl
thi
tfch) dl loai bd cac chat anh hudng.
- Khao sat phan doan
F2;
diing 20 ml hdn hgp n-hexan : diclometan (2:3 vl
thi
tfch) dl loai bd cac chat anh hudng.
- Khao sat phan doan F3: diing hdn hgp diclometan : metanol (95 : 5 vl
thi
tfch)
de rira giai cac chit phan tfch. Phan doan F3-1: 0-100 ml; phan doan F3-2:
100-110ml;
phan doan
F3-3:
110-130
ml.
Co ta't ca cac phan doan vl khoang 0,5 ml, ddi dung moi bing
each
them tiep 8

ml axeton va chuyen sang dng nghiem cd vach. Tiep tuc co dung moi bing ddng khf
nita vl 0,5 ml. Axetyl hda hdn hgp bing anhidrit axetic. Them
\0\i\
npi chuin
naphtalen- d8 10 mg/l, dinh
miic
vl 1ml. Lie manh trong vai giay bing thie't bi lie rdi
tien hanh bam len GC/MS dl phan tfch tu dpng theo chuang trinh dat sin.
3.3.3. Khao sdt hieu sudt thu hoi cua phuang phdp
Quy trinh kilm tra hieu suat thu hdi dugc tien hanh nhu sau;
- Chuan bi miu them chuan bing
each
lay 10 ml miu nude rac them vao dd 100
jil hdn hgp chuan 500
|ag/l,
10 |il BPA- dl4 10 mg/l rdi thuc hien quy trinh phan tfch
nhu tren.
- Lam them miu tring bing
each
lay 10 ml nude ca't 2 lan, them vao 10
\JL\
BPA-
dl4
10 mg/l va tien hanh theo quy trinh phan tfch d tren
3.4.
Phan
tich
dinh tinh va dinh luong tren GC/MS
+j
Pha dung dich chuan:

Dung dich gdc cua cac dan xuat phenol dugc chuan bi bing each
can
chfnh xac
lOmg
cac chuan dan rin va dinh
miic
trong binh 10ml va dinh
miic
tdi vach chuan vdi
dung moi axeton. Ndng dp chuin gdc la
lOOOmg/1.
Sau dd tir cac dung dich gdc nay pha loang dl dugc day chuin cd ndng do tir 5
den 200ppb.
Tat ca cac dung dich chuin
diu
dugc din xuat axetyl hoa trudc khi bam len
may.
4-)
Dinh luang:
Cac hgp chat AP va BPA nghien ciiu dugc dinh lugng theo phuang phap npi
chuan vdi chat npi chuan la naphtalen-d8.
Ndng dp thuc
ciia
mdi chat phan tfch trong miu dugc tfnh theo cong
thiifc
sau:
Cs = (a
xAS/AIS -^b)
x
HS/S

Trong dd:
CS la ndng dd cua cha't cin phan tfch trong miu.
a la dp ddc
ciia
dudng chuin.
b la doan chin cua dudng chuan.
AS la
di6n
tfch cua cha't
chu^n
phan tfch do dugc tren GC/MS.
AIS
la dien tfch cua chat npi chuan do dugc tren GC/MS.
IIS la lugng chat npi chuan dugc them vao miu.
S la lugng miu phan tfch ban dau.
+j
Dieu kien lam viec
ciia
thiet bi GC/MS:
Cac hgp chat nghien
ciiu
dugc phan tach bang viec sir dung thiet bi sac kf khf
GC/MS-
QP2010
cua hang Shimadzu nhirng thong sd sau:
-
Cot mao quan DB-1 (dp dai cot la 30m, dudng kfnh trong 0,32mm, dp day ldp pha
tinh
0,25^m).
- Khf mang He (dp tinh khiet 99,999%) dugc sir dung la khf mang vdi tdc dp 2ml/phiit.

- Miu dugc bam vao qua thiet bi bam miu tu dpng AOC-20i vdi che dp khong chia
ddng.
- Nhiet dd cot :
50T
-
Nhiet dp cdng bam miu;
230''C
- Nhiet dp detecta:
280T
- Chuang trinh nhiet dp
ciia
may: nhiet dp ban dau
50'^C
giir trong 2 phut. Tang den
lOOT
vdi tdc dp
20T/phut.
Tie'p tuc tang nhiet dp len
20''C
vdi tdc dp
lOT/phiit.
Cudi
ciing tang nhiet dp len
280°C
vdi tdc dp
20'^C/phut,
giii trong 5 phiit. Tdng thdi gian
phan tfch la 23,5 phut.
3.5.
Hoan thien quy trinh phan tich

Dich lpc
ciia
miu dugc chiet bdi ky thuat chiet pha rin vdi cot SPE
RP-18,
da
dugc rira lin lugt ciing vdi 20ml n-hexan, 20ml DCM, 20ml MeOH va 10ml
nude
cat
khir ion. Cho 200ml dich lpc miu di qua cot SPE vdi tdc dp
lOml/phiit.
Cac chat can
tach chiet dugc rira giai ra vdi 20ml MeOH.
Dua them
10)^1
chat surrogate
BPA-dl4
vao dich rira giai dugc de lam chat ddng
hanh, tfnh gia tri hieu suat thu hdi.
Dich rira giai dugc co cat quay chan khong va co bing nita tdi gin kho, rdi hoa
tan lai trong 1ml hdn hgp
DCM/hexan
(l:3,v/v). Diing pipet Paster dua qua cot sic ky
dugc nhdi 5g cha't ha'p phu florisil (da hoat hoa 12 gid tai
130°C)
de tie'n hanh budc lam
sach. Thuc hien cac phan doan rira giai vdi lan lugt cac hon hgp dung mdi sau: 20ml
hexan/DCM
(l:3,v/v), 20ml hexan/DCM (2:3.v/v), 100ml 5% MeOH/ DCM. Phan
doan 3 chiia cac hgp chat ankylphenol va bisphenol A quan tam. Co cat quay chan
khong dich rira giai phan doan thu thap vl 1ml. Chuyin vao

Ip
nhd sic ky
1,5ml.
Cd
bang nita vl gan kho.
Thuc
hi6n
phan
iing
din xuat axetyl hoa bing each cho them
50|il
natriaxetic va
50|il
anhydrit axetic vao
Ip
sic ky. Lie manh
Ip,
dl yen tai nhiet dp phdng qua dem dl
phan ling din xua't hoa xay ra hoan toan.
Cho 0,5ml hexan vao
Ip
nhd,
lie
manh va ly tam (tdc dp 1000
vdng/phiit).
Tach
lay ldp n-hexan. Thuc hien qua trinh them 0,5ml hexan 2 lin nira. Ldp hexan thu thap
dugc lam khan qua Na2S04. Cd dac ldp hexan vl
thi
tfch

<lml.
Them
10|il
chat npi
chuan naphtalen-d8
lOppm.
Dinh
miic
vl 1ml bing hexan. Chuyin sang
Ip
sic ky
1,5ml va tien hanh xac dinh tren GC/MS theo chuang trinh da dinh.
IV: KET QUA VA THAO LUAN
4.1.
Ket qua qua trinh din xuat hoa
Ky thuat dan xuat cd nhilu uu
diim
cho viec phat hien ddng thdi cac hgp chat
phenol vdi dp nhay va dp chpn Ipc cao. Trong dd cac ky thuat silyl hda dugc
iing
dung
rpng rai do cd kha nang cai thien dp chfnh xac, dp nhay, dp lap lai va kha nang phan
giai vi nd lam triet tieu duoi pic, tang tfnh
bin
nhiet
ciia
cac phenol. Tuy nhien gia
thanh cua chiing lai rat dit, khdng phu hgp vdi dilu kien nghien
ciiu
tai Viet Nam.

Chfnh vi vay, viec khao sat de tim tac nhan din xuat hda khac hieu qua, re tiln han rat
dugc quan tam. Trong khudn khd nghien
ciiu ciia
dl tai nay, chiing toi khao sat phuang
phap din xuat axetyl hda cac phenol bing tac nhan din xuat hoa anhidrit axetic.
Khi tie'n hanh phan
iing
este hda true tiep bing axit cacboxylic, trong phan
iing
nay cac phenol ddng vai trd cung cap proton va axit cacboxylic cung cap nhdm hidroxy
cho phan tir nude tach ra. Tuy nhien, hieu suat dat dugc thudng rat thap. Vi vay dl thu
dugc cac phenoleste, thudng phai tien hanh theo phuang phap Sotten-Baoman
(1884-
1886)
tiic
la cho cac phenol tac dung vdi elorua axit hoac anhydrit axit trong moi
trudng baza. Chiing toi da tien hanh phan
u:ng
bing anhidrit axetic trong moi trudng
natriaxetat. Phuang phap nay td ra thfch hgp vdi cac chat cd phan tir lugng
Idn
nhu
BPA, NP Phan
irng
xay ra nhanh, dinh lugng tai dilu kien nhiet dp phdng. Han nira,
eac tac nhan dan xuat lai rat re. Nhugc
diim
duy nhat
ciia
phuang phap la axit axetic

(san pham
ciia
phan
iing)
va anhidrite axetic du cd kha nang an mdn cac thiet bi kim
loai cua he thdng sic ky nen cin tien hanh loai bd chiing trudc khi bam len may.
H,C
C=0
o
CH3C00 +
H3C
H3C
o
R
C
I
o
c—o
0—(x
R
Hinh
6: Ca che phdn
I'ing
ddn
xudt axetyl hoa cacphenol.
4.2.
Xac dinh phan manh dac trung cua cau tu can phan
tich
Tien hanh bam
l|al

dung dich
chuSn ciia
phenol da duac chuan bi len thiet bi
GC/MS de xac djnh cac manh pho dac trung ciia chiing. NP the hien 7 pic cua 7 dong
phan khac nhau. Ngoai ra, mot so pic ciia NP la cua nhidu dong phan
chii
khong phai
cua mot ca'u
true
duy nhat. Con lai OP va BPA chi
th6
hien mot pic duy nhat.
Bdng 4: Mdnh pho ddc trung cua cdc hop chat phdn tich
Chat
Naphthalene- d8
NP
n-OP,
tert-OP
BPA,
BPA-dl4
Phan manh dac trung (m/z)
136
107,
121, 135, 149, 163, 177, 191, 220, 262
135,
107,206, 139, 140
213,224,326,312
4.3.
Khao sat quy trinh phan
tich

Dp phan
cue
cua dung moi rira giai cd
thi
anh hudng tdi hieu suat thu hdi
ciia
chat phan tfch trong miu moi trudng. Vdi cac mau
nude,
diclometan dugc chpn la dung
mdi chiet
bdd
chiing cd kha nang tuang tac manh vdi dang phenoxi tuang ddi phan
cue
trong moi trudng
pH=
2. Tuy nhien,
nude
rac la moi trudng rat phuc tap, chiia nhieu
cha't anh hudng nhu cha't mau, rugu, amin, axit hiiu ca. Bdi vay chiing toi da tien hanh
rira giai 3 phan doan nham muc dfch loai bd tdi da cac chat ban.
Ndng dp cac phenol dugc tfnh theo cong thiic:
C = Cspike - Cblank
Trong dd: Cspike : ndng dp cac phenol trong miu them chuin
Cblank: ndng dp cac phenol trong miu tring
Ket qua khao sat hieu suit thu hdi trung binh qua cot florisil tai ndng dp cac
phenol la 200ng/L sau 5 lin lap lai dugc trinh bay trong bang 5
Bdng 5: Ket qud phdn tich cdc phdn dogn rua gidi
Phan doan
FI
F2

F3-1
F3-2
F3-3
The
tich
(ml)
20
20
90
10
20
NP
-
-
196,3
0,7
-
Tert-OP
-
-
192,8
-
-
n-OP
-
-
189,5
1,4
-
BPA

-
-
193,6
2,2
-
BPA-
dl4
-
-
195,0
-
-
FI
n-hexane: DCM (1:3)
F2 n-hexane: DCM (2:3)
F3
DCM:
MeOH (95:5)
Qua khao sat nhan thay, vdi
thi
tfch cua 2 phan doan
FI,
F2 sir dung cac hdn
hgp dung moi n-hexane: DCM (1:3) va n-hexane: DCM (2:3) dl loai bd cae hgp chat
gay anh hudng ft phan cue han so vdi cac phenol ta thay cac hgp chat can phan tfch
chua bi rira giai ra. Va vdi
thi
tfch 100ml hdn hgp DCM: MeOH (95:5), cac phenol
dugc rira giai het. Vi vay, chiing toi chpn:
4-

Phan doan
FI:
20 ml
4-
Phan doan
F2: 20 ml
4^
Phan doan
F3: 100 ml
4.4.
Khao sat hieu suat thu hoi
ciia
quy trinh phan tich cac din xuat phenol trong
mau nude rac
Chiing toi tien hanh khao sat hieu suat thu hdi cua cac dan xuat phenol nghien
ciiu
vdi 5 miu them chuan ndng dp 50 ng/1. Hieu suat thu hdi cua cac hgp chat phan
tfch dugc tfnh theo cong thiic:
OAl
HOC QUOC GIA
n^
TRUNG TAM THONG TIN TH-
or/
33 6