Hoàn thiện qui trình phân tích một số dẫn xuất Phenol thuộc nhóm Ankylphenol và Bisphenol A trong mẫu nước rác tại các bãi rác khu vực Hà Nội

HOAN THEN QUY
TRINH
PHAN
TICH
MOT SO
DAN XUAT
PHENOL
THUOC
NHOM
ANKYLPHENOL
vA BISPHENOL A
TRONG
MAU
NUOC
RAC
TAi
cAc
BAI
RAC
KHU
vac HA
NOI
IRAN
THI
Llfiu,
HOANG
TUE
MINH,
BUI THU HA, PHAM HUNG VIET
Trung tdm Nghien
aim

Cong nghe Moi trudng
vd Phdt trien ben
vitng,
Trudng Dai hoc
KHTN,
DHQGHN
Tom tat
Mot so cac dan xuat phenol thudc hg ankylphenol nhu
nonylphenol, octylphenol va bisphenol dugc
ling
dung rdng rai trong
cdng nghiep, sinh boat va cd kha nang gay rdi loan tuyen ndi tiet dd'i
vdi ddng vat hiiu sinh ciing nhu con ngudi. Cac ankylphenol, san pham
thoai bie'n ciia ankylphenoletoxylat cd tinh doe va tich
luy
ben trong
mdi trudng cung nhu xam nhap vao chudi
thiic
an. Viec nghien
ciiu,
danh gia va quan trac cac hgp cha't nay trong cac hgp
ph^n
khac nhau
cua mdi trudng tai Viet Nam da budc dau dugc quan tam trong vai
nam gSn
day. Va'n de d
nhilm
mdi trudng tai cac khu vuc xung quanh
bai chdn
la'p

rac, nha't la cac bai rac thai sinh boat
tir
cac do thi
Idn
nhu
Ha Ndi gay khdng it nhiing birc
xiic
dd'i vdi cac nha quan
ly
va anh
hudng nguy hai tdi
siic
khoe cua ngudi dan trong khu vuc va cdng
ddng. Chung tdi da tie'n hanh khao sat, hoan thien quy trinh phan tich
cac ankylphenol va bisphenol trong
miu nude
rac (trudc va sau xtr ly)
va ap dung de xac dinh ham
lugng
cac hgp cha't nay trong mot so
mlu
nude
va
nude
rac thu thap tai 2 bai rac Nam San, Tay Md. Hieu sua't
thu hdi ciia cac hgp chat phan tich la
4-nonylphenoI
(4-NP), 4-tert-
oetylphenol (4-t-OP) va
4-n-octylphenol

(4-n-OP) va bisphenol A
813
(BPA) deu dat tir 84,4- 91,4%. Ket qua phan tich cho thay, ham lugng
cac ankylphenol va BPA trong cac
mSu
tai khu vuc bai rac Tay Md
cao
ban so vdi khu vuc bai rac Nam San. Cac NP va nha't la BPA deu
cd mat vdi ham lugng kha cao trong cac
mSu nude
rac. Ham lugng sau
xir ly cua BPA do dugc tdi 3913,0 ng/L va cua NP do dugc 2026,0
ng/1.
Mac du, ham lugng NP va BPA sau
xic
ly tai bai rac Nam Son
deu thap ban so vdi bai rac Tay Md do he thd'ng xir ly tuang dd'i hien
dai va thdi gian di vao boat ddng chua
lau,
nhung cac gia tri ham
lugng nay deu cao ban tieu chuan ve gia tri ham lugng khdng gay bat
ky anh hudng vdi ddng vat thuy sinh
ciia
Chau Au. Cd the ndi bai rac
la ngudn d nhiem tiem tang cac ankylphenol va bisphenol A tdi moi
trudng va nguy ea de dga
su:c
khde con ngudi.
Chiing
tdi hi vgng se c6

nhiing nghien
cu:u sau
rdng ban de ddng gdp vao viec quan trac, danh
gia su ton
luu,
phan bd va van chuyen
ciia
cac
bcTp
chat ankylphenol
va bisphenol A trong mdi trudng.
OPTIMIZATION OF ANALYTICAL PROCEDURE FOR SOME
DERIVATIVE PHENOLS AMONG ALKYLPHENOL AND BISPHENOL A
FROM LANDFILL LEACHATES SAMPLES IN HANOI'S DUMPING SITES
Pham Hung Viet, Tran Thi Lieu, Hoang Tue Minh
Research Centre for Environmental Technology and Sustainable
Development (CETASD), Hanoi University of Science, VNU
Abstract
Some derivative phenols of alkylphenol group as nonylphenol,
octylphenol and bisphenol A are widely applied in industry, domestic
activities and cause disrupting endocrine system for wildlife and
human. The alkylphenols, degradation products of
alkylphenolethoxylates, are toxic, persistent in the environment and
potential penetration into food chain. Recently, studying and
monitoring of these compounds in different environmental
components in Vietnam have been concerned remarkably. The
environmental pollution problems around the dumping sites, specially
industrial and municipal ones like Hanoi, caused difficulties for the
local authorities and hazardous risks for health of wildlife and human.
We carried out studying and completing the analytical procedure for

some derivative phenols of alkylphenol group and bisphenol A in
groundwater, landfill waste water samples (pre-treated and treated)
814
ana
appiiea
mat to samples
laKen
in Nam Son and Tay Mo landfill
areas,
Hanoi. The recovery values of
4-nonylphenol
(4-NP), 4-tert-
octylphenol (4-t-OP), 4-n-octylphenol (4-n-OP) and bisphenol A
(BPA) were ranged from 84.4 to 91.4%. According to the researched
results, the concentrations of target alkylphenols and bisphenol A in
Tay Mo samples is higher than that in Nam Son. The concentrations of
nonylphenol and bisphenol A are significantly high in leachates
samples, with concentrations of treated ones were
3913ng/l
and
2026ng/l for BPA and NP, respectively. Although, the concentrations
of target alkylphenols and bisphenol A in leachates samples at Nam
Son (modern waste water treatment system and short time operation)
is lower comparision to that one at Tay Mo but these values are higher
the European values of Predicted Non-Effect Concentration for water
environment. It is seemed that dumpingsites are potential pollution
sources of alkylphenols and bisphenol A for the environment, health
of wildlife and human. We hope that we will have further researches
about these compounds, contribute to assessing and monitoring its
accumulation, spatial distribution as well as its fate in the

environment.
Gidi thieu
Su tha'm
Igc
cac cha't gay d
nhilm
tir cac ngudn
chii
ye'u nhu bai
chdn
la'p
rac cd the dan tdi su nhiem ban cua mdi trudng
nude,
bao
gdm ca ngudn cung ca'p nude udng. Qua trinh phan tich cac chat d
nhiem hiiu ca nhu ankylphenol hay bisphenol A trong
nude
rac gap rat
nhieu khd khan, trd ngai. Nen
mfiu
rat
phiic
tap, bao gdm ham lugng
cao cua cac axit humic va
fulvic
cung nhu cac mud'i
ciia
chiing, gay
can trd den viec phat hien hay lam giam kha nang thu hdi
ciia

cac chat
phan tich
[1,2].
Ngoai ra, cac hgp chat quan tam thi cd mat trong cac
mlu
vdi ham lugng ra't khac nhau, tao thach
thiic Idn
cho viec tim ra
mot phuang phap cd the xac dinh trong mot khoang ndng do
mlu
rdng. Vi vay, viec chiet tach, lam sach
mau
rdi
lira
chgn phuang phap
xac dinh dugc dat ra trong nghien
ciiu
nay. Ky thuat chie't pha
ran
ket
hgp vdi dan xuat hoa, xac dinh tren thiet bi sac ky khi-khdi phd dua
lai
hieu sua't thu hdi cao, tiet kiem dung mdi da dugc
lua
chgn de phan
tich cac ankylphenol va bisphenol A trong mau
nude
rac.
815
Cot chie't pha

rdn
vdi chat ha'p phu
Cuj
dugc lua chgn
d^
tach
chi^t
cac hap cha't phan tich ra khdi nen mau cho hieu qua cao [3]. Tac nhan
dan xua't boa anhydrit axetic de kiem, re tien dugc dung cho phan ling
dan xua't axetyl hoa cac dan xuat phenol.
Muc
dich ciia
nghien
ciiu
la khao sat quy trinh phan tich ddng thdi
mot so ankylphenol va bisphenol A trong mau
nude
rac va nude
ng&n
bi d nhiem xung quanh ling dung ky thuat chie't pha ran, ke't hgp vdi
ky thuat dan xuat hoa. Phuong phap
loai
bd dugc nhiing anh hudng
cua nen
mSu
va hieu qua trong viec xac dinh lugng ve't mdi trudng.
Thi/c
nghiem
Nghien
ciiu

bao gdm 2 phan: khao sat va hoan thien quy trinh
phan tich cac ankylphenol va bisphenol A trong mau
nude
rac, va ap
dung quy trinh khao sat dugc vao xac dinh cac ankylphenol va
bisphenol A trong mot so
mlu nude
rac (trudc va sau xir ly) va mSu
nude
mat tai 2 khu vuc bai rac Nam San va Tay Md.
Thu thap mau
9
mau
nude rac va
nude
ngam quanh khu vuc 2 bai rac Tay M6 va
Nam San dugc thu thap vao trong cac chai thuy tinh 4L sam mau va
dugc
Igc
qua giay
Igc
thuy tinh (GF/F, Whatman, Anh). Dich
Igc
dugc
axit hoa vdi
HCl
4M ve pH 2 de ngan can su phan buy
ciia
cac vi sinh
vat va dugc bao quan tai

4"C
cho de'n khi chie't phan tich.
Hoa chat
Cac chat chuan ankylphenol
(4-t-octylphenol,
4-nonylphenol, 4-n-
octylphenol) va bisphenol A, dung dich chat ndi chuan
naphtlen-dS
va
chat ddng hanh bisphenol
A-dl4
(surrogate) dugc dat tii
Chem
Service. Dung dich chuan gdc ndng do
lOOOmg/L ciia
mdi cha't dugc
chuan bi trong dung mdi axeton va dugc pha
loang diing
lam
ch^t
chuan them vao va lap dudng
chu^n.
Anhydrit axetic, axit HCl dac, loai tinh khie't phan tich cua hang
Merck dugc sir dung lam tac nhan axit boa va dan xua't hoa.
Cac dung mdi diclometan, hexan, axeton va metanol loai tinh
khie't phan tich
ciia
Merck.
816
iNuoc

cat z
lan ouge igc
qua thie't bi
khuf
ion hoa Millipore
(Nhat Ban).
Chat ha'p phu florisil (90-100 mesh) sieu tinh khiet
ciia
Supelco va
Na2S04 khan dang tinh khiet phan tich
ciia
Merck dugc nung trong
Id
qua dem tai
450°C.
Sir dung cot chiet pha ran vdi chat ha'p phu
RP-18
500mg cua hang
Merck.
Thiet bj
Thie't bi chie't pha
ran
cua hang Supelco.
Viec xac dinh tren thie't bi dugc thuc hien tren thiet bi
sdc
ky khi-
khdi phd
GC/M8-QP2010
cua hang Shimadzu. Thie't bi dugc chay d che
do khdng chia ddng va nhiet do cdng bam

mSu
dugc dua tdi
280°C.
The tich bam la
2|LI1.
Cot mao quan DB5, dai 30m, dudng kinh trong
0,25mm, do day lap phim
0,25fim.
Chuang trinh nhiet do
ciia
may:
nhiet do ban dau
50°C
giu trong 2 phut. Tang de'n
lOO^C
vdi tdc do
20>hut.
Tie'p tue tang nhiet do
len 20"C
vdi tdc do
10°C/phut.
Cudi
cung tang nhiet do len
280°C
vdi tdc do
20°C/phut,
giii trong 5 phut.
Cac cha't nghien ciru dugc dinh tinh dua vao cac manh phd khdi
ciia
cac dan xuat axetyl boa tuang

ling
xac dinh
trdn
thiet bi phd khdi.
Sir
dinh lugng cac chat theo phuang phap ndi chuan, vdi cha't ndi
chu^n
naphtalen-d8.
Hoan thien quy trinh phan tich
Dich
Igc ciia mSu
dugc chiet bdi ky thuat chiet pha ran vdi cot
SPE
RP-18,
da dugc rira lan
lugt
ciing vdi 20ml n-hexan, 20ml DCM,
20ml
MeOH va 10ml
nude
cat
khii
ion. Cho 200ml dich
Igc miu
di
qua cot SPE vdi tdc do
lOml/phiit.
Cac chat can tach chie't dugc rira
giai ra vdi 20ml MeOH.
Dua them

lOjul
chat surrogate
BPA-dl4
vao dich rira giai dugc de
lam chat ddng hanh, tinh gia tri hieu suat thu hdi.
Dich rira giai dugc cd ca't quay chan khdng va cd bang nita tdi gan
khd, rdi hoa tan lai trong 1ml hdn hgp
DCM/hexan
(l:3,v/v). Dung
pipet Paster dua qua cot sac ky dugc nhdi 5g cha't ha'p phu florisil (da
817
boat hoa 12 gid tai
130"C)
d^
tie'n hanh budc lam sach. Thuc
hiSn cdc
phan doan rira giai vdi
lin
lugt cac hdn hgp dung mdi sau: 20ml
hexan/DCM
(l:3,v/v), 20ml hexan/DCM (2:3.v/v),
lOOml
5%
MeOH/DCM. Phan doan 3
chiia
cac hgp cha't ankylphenol va
bisphenol A quan tam. Cd ca't quay chan khdng dich
rura
giai phan
doan thu thap

v6
1ml. Chuyen vao
Ig
nhd
sdc
ky
1,5ml.
Cd bang
nito
ve
gSn
khd.
Thuc hien phan
ling
dan xuat axetyl boa bang each cho them
50^1
pyrol
va
50|al
anhydrit axetic vao
Ig
sac ky. Lac manh
Ig,
de
yen
tai
nhiet do phdng qua dem de phan
ling
dan xuat boa xay ra hoan toan.
Cho 0,5ml hexan vao

Ig
nhd, lac manh va ly tam (tdc do 1000
vdng/phiit).
Tach lay
Idp
n-hexan. Thuc hien cho trinh them 0,5ml
hexan them 2 lan niia. Ldp hexan thu thap dugc lam khan qua
Na2S04.
Cd dac ldp hexan ve the tich
<lml.
Them
10|a,l
chat ndi chuan
naphtalen-d8
lOppm.
Dinh
miic
ve 1ml bang hexan. Chuyen sang
Ig sac
ky 1,5ml va tie'n hanh xac dinh tren GC/MS theo chuang trinh da dinh.
Ket qua va thao
luan
Hoan thien quy trinh
Ky thuat SPE vdi cha't ha'p phu
CI8
dugc lua chgn de chie't tach
cac hgp chat nghien
ciiu
ra khdi nen
mSu

do su thuan tien, tie't kiem
dung mdi, tinh tu ddng boa cao ma hieu qua phan tich
vSn
cao.
Viec phan tich cac ankylphenol va bisphenol A bang phuang phap
sac ky thudng gap khd khan. Pic thu dugc thudng tha'p, nhieu va khd
nhan dang do cd nhdm OH phan
cue
cd kha nang luu giii lau vdi pha
tinh ciia
cot
sdc
ky gay ra hien tugng keo chan pic, can trd viec dinh
tinh, dinh lugng mot each chinh xac. De khac phuc hien tugng tren
ngudi ta thudng sir dung ky thuat
dSn
xua't hda, thay the' nhdm OH
phan cue bang cac nhdm
chiic
khac it phan cue ban. Cac ky thuat
thudng diing de dan xua't hda hgp chat phenol la
silyl
hda, axetyl hoa,
metyl
hda [4] Trong nghien
ciiu
nay, chiing tdi lua chgn phuang
phap axetyl hda cac phenol bang anhydrit axetic, mot tac nhan
din
xua't hoa de kiem, re tien trong mdi trudng dung mdi pyrol. Phan ling

nay dien ra kha nhanh, dinh lugng tai nhiet do phdng.
818
^^a^
anKyipacaui vet uispacnui
A dugc phat hien va xac dinh tren
thie't bi GC/MS vdi nhieu uu diem dac trung nhu vdi viec sir dung cac
hgp
cbSit
ddng vi danh dau lam chat chuan de lam tang do chinh xac
ciia
phep phan tich, xac dinh thanh
pb^n
nguyen to cua hgp
ch§[t
neu
sijf
dung thie't bi cd do phan giai cao va cd the phan tach dugc cac pic sac
ky khdng phan tach tren ca sd su khac nhau ve phd khdi ciia chiing [5].
Gia tri hieu sua't thu hdi cua cac ankylphenol va bisphenol A
nghien
ciiu
theo quy trinh deu cao, do lap lai tdt. Hieu sua't thu hdi
ciia
4-tert-OP la thap nhat (84,4%) va cao nhat la 91,4% cua BPA.
Ket qua phan
tich
cac
m^u
thiic te
Chiing tdi da ap dung quy trinh tren de phan tich 9

mSu
nude rac
va
nude
ngam dugc thu thap quanh khu vuc 2 bai rac Tay Md va Nam
San. Hinh 1 md ta ndng do 2 hgp cha't
chii
ye'u la 4-nonylphenol (NP)
va bisphenol A (BPA) trong cac mau phan tich.
8000
7000
6000
5000
N6ng do (ng/L) 4000
3000
2000
\om
oJ
yll
:HNP
'•BPA
F^
TMNgl TMNs2 TMRl
TMR2
TMR.I NSNgl
NSNg2 NSRTr NSRS
Hinh L Nong do cua (NP) vd bisphenol A (BPA) trong cac mdu
nude
rac vd
nude

ngam thu thap tai khu
vUc
bai rac
Tay MS vd
Nam
San.
Trong do TMNg:
nude ngdm
Tay M6 NSNg:
nude nglm
Nam Son
TMR:
nude
rac Tay M6 NSRTr:
nude
rac trudc khi xir ly
NSRS:
nude
rac sau khi xir ly
Ke't qua cho thay n-OP
chi
cd mat trong 1
mau nude
rac khu vuc
Tay Md (TMR -
137,2
ng/1), khdng thay su cd mat cua no trong
nude
819
ngam. Lugng tert-OP cd mat trong cac

mSu
nude
ngSm
ciing khdng
Idn
(khoang vai
ng/I).
Ham lugng cac cha't phan tich trong cac
mSu
nude ngam lay tai Tay Md cao ban d Nam San. Dieu nay cd the giai
thich vi bai rac Nam San mdi dugc dua vao sir dung vao nam 1999, sau
khi bai rac Tay Md ddng cira vi vay su tich tu cua cac ankylphenol,
bisphenol A trong nude ngam cdn tha'p.
Cac nonylphenol va nha't la bisphenol A cd mat trong
nude
rac vdi
ndng do kha cao. Ham lugng ciia chiing (sau khi xir ly) dat tdi 3913,0
vdi bisphenol A va 2026,0 ng/1 vdi nonylphenol (TMR3). Day
la
ngudn d nhiem tiem tang tdi mdi trudng, de dga
siic
khde con ngudi.
8o sanh cac mau nude rac tai hai bai rac nhan tha'y he thd'ng xu
ly nude rac d Nam San tuang dd'i tdt, ham lugng cac chat nghien
ciiu
sau khi xir ly la 47,5 ng/1 vdi nonylphenol, va 767,9 ng/1 vdi
bisphenol A bdi day la bai rac mdi va hien dai nhat Ha Ndi. Tuy
nhien ham lugng nay
vSn
cdn cao (nha't la vdi 4- nonylphenol, vugt

qua tieu chuan Chau Au ve ndng do khdng gay ba't ky anh hudng vdi
sinh vat
thiiy
sinh (330 ng/1).
Ket luan
Viec ap dung ky thuat chie't pha ran SPE cha't hap phu
0,^,
ket hgp
vdi ky thuat dan xua't axetyl boa rat hieu qua dd'i vdi quy trinh phan
tich cac hgp chat ankylphenol va bisphenol A trong
mlu
nude rac. Ky
thuat dan xuat hoa dan gian, phan
ling
xay ra nhanh, dinh lugng va tac
nhan dan xuat anhydrit axetic re tien. Hieu sua't thu hdi cua cac hgp
chat nghien
ciiu
deu >84%, vdi do lap lai cao.
Ket qua ap dung quy trinh khao sat thu dugc de xac dinh cac hgp
cha't 4-nonylphenol,
4-tert-octylpbenol,
4-n-octylphenol, bisphenol A
trong cac
mSu nude
ngam va nude rac tai hai khu vuc bai rac
Idn
ciia
Ha Ndi la Nam San va Tay Md cho tha'y su cd mat cua cac hgp chit
nay trong cac

mSu
phan tich. Ham lugng trong cac
mlu
nude rac nam
trong khoang 447,5-
1856,3ng/L
dd'i vdi nonylphenol va 767,9-
7250,1
ng/L dd'i vdi bisphenol A. Mac
dii
da qua xir ly, ham lugng
nonylphenol trong
mSu
nude rac tai khu vuc bai rac Nam San
vln
vugt
qua tieu chuan Chau Au ve ndng do khdng
gay
bat ky anh hudng vdi
sinh vat thuy sinh.
820
^auag lui
11^
vviig
i.iiu"6
.v^.
vjua
nghien
cuii
nay se ddng gdp vao

danh gia, quan trac su phan bd cac hgp chat hiiu ca doc hai ndi chung
va cac hgp chat ankylphenol, bisphenol A ndi rieng trong mdi trudng.
Va chiing tdi cung by vgng nghien ciru nay se tie'p tue dugc md rdng
trong tuang lai.
Tai lieu tham khao
1.
Reitzel L.A. and Ledin A., (2002). Determination of phenols in
landfill leachate-contaminated groundwaters by solid-phase
extraction. Journal of Chromatography, 972,
175-183.
2.
Ribeiro A., Neves M.H., Almeida M.F.,
Alves
A. and Santos
L.,
(2002).
Direct determination of chlorophenols in landfill
leachates by solid-phase micro-extraction-gas chromatography-
mass
spectrometry.
Journal of Chromatography A,
975,261-21
A.
3.
Braun p., Moeder M.,
Schrader
St., Popp K., Kuschk P.,
Engewald W. (2003). Trace analysis of technical nonylphenol,
bisphenol A and
17a-ethinylestradiol

in wastewater using
solid-phase microextraction and gas chromatography-mass
spectrometry. Journal of Chromatography A, 988,
41-51.
4.
Nguyen
Diie
Hue (2001). Cdc phuang phap phdn tich
hm
ca,
Trudng DHKHTN-DHQG Ha Ngi.
5. Pham Hiing Viet (2003). Ca sd ly thuyet cua phuang phdp sac
ky khi, Nxb. Khoa hgc va Ky thuat Ha Ndi.
821