HOAN THEN QUY TRINH PHAN TICH MOT SO DAN XUAT PHENOL THUOC NHOM ANKYLPHENOL vA BISPHENOL A TRONG MAU NUOC RAC TAi c A c BAI RAC KHU v a c HA NOI IRAN THI Llfiu, HOANG TUE MINH, BUI TH
Trang 1HOAN THEN QUY TRINH PHAN TICH MOT SO DAN XUAT PHENOL THUOC NHOM ANKYLPHENOL
vA BISPHENOL A TRONG MAU NUOC RAC
TAi c A c BAI RAC KHU v a c HA NOI
IRAN THI Llfiu, HOANG TUE MINH, BUI THU H A , P H A M 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
Trang 2(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)
Trang 3ana 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-4-tert-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
Trang 4Cot 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
Trang 5iNuoc 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
Trang 6boat 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
Trang 7^^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
: H N P
'•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
Trang 8ngam 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
Trang 9^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