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

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

DAI HOC QUOC GIA HA NOI

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 T A T 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 m i u 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:

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 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

4-terl-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

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:

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

120 — 3 0 0 m g / 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 b l 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

Tom cam Mysidopsvbahia

Ca tue dau to Pimephales

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

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

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 tetrametylbutyOphenol

4-(l,l,3,3-OH 4-(l,l,3,3-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

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 d l 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

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 O O C H

C H X O O N a ,, ,

+ ( C H , C O ) , 0 '- ^ I + C H C O O H

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 d l 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- d l 4 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-d l 4 10 mg/l va tien hanh theo quy trinh phan tfch BPA-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

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

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

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

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

-196,3 0,7

-Tert-OP

-

-192,8

-

-n-OP

-

-189,5 1,4

-BPA

-

-193,6 2,2

-dl4

BPA -

-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

OAl HOC QUOC GIA n ^ TRUNG TAM THONG TIN TH-

or/ 33 6

H = ^^^ ^ 1 ! ^ ! ^ ^ 100 %

Trong dd, Cspi^g: ndng dd sau xir ly cua miu th6m chuin

Qiank- ndng dd sau xir ly ciia miu tring

Co : ndng dd ban diu khi them chuan Gia tri trung binh cua cac lin thf nghiem dugc tfnh nhu sau:

- 1 V

^^ = 7 2 ^

De kiem tra dd chfnh xac (dp lap lai) cua phuang phap, chiing ta lay gia tri trung binh ^ so sanh vdi gia tri xi tim dugc va gia tri thuc |i (gia tri dua vao) dl danh gia hieu suat thu hdi, dp lech chuin, he sd bien dpng

Bdng 6: Kdt qud hieu sudt thu hoi cua cdc hgp chdt phdn tich trong mdu nude

rac tgi nong do 50nglL

tert-OP

42,8 41,9 38,5 45,1 42,6 42,2 1,12 2,82 84,4

n-OP

41,8 46,5 42,6 44,5 39,6 43,0 1,37 3,19 86,0

BPA

47,9 49,1 42,7 47,2 41,8 45,7 1,54 3,37 91,4

BPA-dl4

92,5 89,4 91,6 86,8 87,3 89,5 1,26 1,41 89,5 Tat ca cac hieu suat thu hdi diu cao, dp lap lai tdt Hieu suat thu hdi eiia OP la thap nhat (84,4 va 86,0%) va cao nhat la 91,4% ciia BPA Nhu vay quy trinh dl ra dam

bao dugc dp chfnh xac va yeu ciu di ra ddi vdi viec phan tfch miu nude rac

4.5 Ket qua phan tich mau nude rac thirc te

Trong nghien ciru nay, chiing toi da tien hanh thu thap 9 mau nude rac va cac miu nude ngim xung quanh khu vuc 2 bai rac Nam San va Tay Md Thuc hien viec phan tfch cac hgp chat ankylphenol va bisphenol A theo diing quy trinh da dugc khao sat

Viec tfnh toan ndng dp chat phan tich do may tu dpng thuc hien theo chuang trinh lap san Sau dd, chiing toi tie'n hanh hieu chinh lai theo cong thiic sau:

^ H

1 C X F

v x l 0 0 %

Cx : Ndng dp cau tir trong miu phan tfch, ng/L

Cm : Ndng dp do may tfnh dua ra, |ag/L

Vc : Thi tfch mau co cudi ciing khi bam len may, ml

Vm : Thi tfch cua miu that dugc phan tfch, L

H : Hieu suat thu hdi, %

Ket qua phan tfch ham lirgng cac phenol phan tfch dugc trinh bay trong bang 7 vaS

4,5.1 Ket qud phdn tich trong cdc mdu tgi khu vuc bai rac Tay MS

Ham lugng cac hgp cha't phan tfch trong 3 miu nude rac va 2 miu nude ngam tai khu vuc bai rac Tay Md dugc trinh bay trong bang 7

Bdng 7 : Kdt qud phdn tich mdu nude tgi bdi rac Tay Md

4-tert-OP 8,3 -

281,3

-

-4-n-OP - -

137,2

-

-BPA

268,1 420,3 3162,4 3240,4 3913,0

Tong AP

98,4 93,5 1549,2 972,6

2026

Trong dd, TMNg: miu nude ngam TMR: miu nude rac

"-": nhd han gia tri phat hien cua phuang phap Tdng AP= NP4- 4-tert-0P+ n-OP

Ket qua phan tfch cho thay, hgp chat n-OP khong ed trong cac miu nude ngam phan tfch 4-t-OP do dugc vdi ham lugng kha thap trong 1 miu nude ngim dugc thu thap tai khu vuc nay (chi dat 8,3ng/L) Hgp chat NP dugc phat hien thay trong tat ca cac miu phan tfch vdi ham lugng kha cao, tren 90,1 ng/L va gia tri ham lugng trong cac miu nude rac cao han hin so vdi trong miu nude ngam Gia tri ham lugng NP cao nhat do dugc trong miu nude rac tai khu vuc bai rac nay la 2026ng/L Tir day cd thi tha'y su 6 nhilm cua NP trong nude rac, ciing nhu nguy ca tilm tang ddi vdi moi trudng xung quanh khu chon lap rac

Tuang tu nhu NP, hgp chat BPA cung tim thay trong tat ca cac miu phan tfch Ham lugng do dugc trong miu nude ngam cQng dat tdi vai tram ng/L va vin nhd han gin 10 lin so vdi trong miu nude rac Gia tri ham lugng BPA cao nhat do dugc trong nude ngam va nude rac tucmg iing la 420,3 va 3913ng/L

D6 thi hinh 7 bilu diln sir phan bd ham lugng ciia NP va BPA trong cac miu phan tfch

tai khu vuc bai rac Tay Mo

Hinh 7: Do thi bieu dien ham luang NP vd BPA trong cdc mdu nitdc tgi khu vi/c

bdi rac Tdy Mo

4.5.2 Ket qud phdn tich trong cdc mdu tgi khu vuc bdi rac Nam San

Ham lugng cac hgp chat phan tfch cd trong cac miu nude rac va nude ngim trong cac miu thu thap tai khu vuc bai rac Nam San dugc trinh bay trong bang 8

Bdng 8: Ham luang cdc hgjy chdt phdn tich trong cdc mdu tai bdi rac Nam San

4-tert-OP

-6,0 194,0

-4-n-OP

- - -

-BPA

108,8 156,2 7250,1 767,9

Tong AP

51,7 60,6 2050,3 447,5 Trong dd: NSNg: miu nude ngam; NSRTr: miu nude rac trudc xir ly; NSRSau: miu nude rac sau xir ly

"-": nhd han gia tri phat hien cua phuang phap Tdng AP= NP-h 4-tert-0P+ n-OP

Ket qua phan tfch cho thay, n-OP khong cd trong tat ca cac mau nude ngim va nuac rac

Hgp chat 4-tert-OP cung tim thay trong nude ngam, nhung vdi ham lugng rat tha'p (chi cd 6ng/L) va trong nude rac trudc xir ly vdi ndng dp kha cao la 194ng/L

NP do dugc trong tat ca 2 loai miu vdi gia tri ham lugng trong nude ngim tir 51,7-54,6ng/L; ham lugng trong nude rac cao han rat nhilu, k l ca nirdc rac da qua xir

ly ham lugng cung cao han 8 lan so vdi trong nude ngim Ben canh dd, ta cung thay dugc cd su giam dang k l ham lugng NP trudc va sau xir ly.(tii 1856,3ng/L giam xudng cdn 447,5ng/L) Tuy nhien, gia tri ham lugng NP sau xir ly nay vin cao han so vdi gia tri ham lugng du doan khdng gay anh hudng tdi moi trudng nude cua Chau Au (330ng/L) Dilu nay the hien nguy ca tilm tang ngudn gay 6 nhilm cua NP ddi vdi moi trudng xung quanh khu vuc bai rac nay, mac du day la bai chon lap rac kha quy each va mdi di vao hoat dpng tir 1999 de'n nay

Tuang tu nhu NP, BPA ciing cd mat trong cac miu phan tfch tai dia diem nay Ndi chung, ham lugng BPA nim trong khoang 108,8-156ng/L ddi vdi miu nude ngim Ket qua ciing chi ra cd su ch6nh lech ro ret vl ham lugng BPA trudc va sau xu ly Gia tri BPA do dugc sau xir ly giam di gin 10 lin so vdi trudc khi xir ly Tuy nhien gia tri ham lugng nay vin d miic kha cao (767,9ng/L)

Ham lugng ciia NP va BPA trong cac miu nude rac va nude ngim phan tfch tai khu vuc bai rac Tay Md dugc mo ta trong hinh 8

Hinh 8: Do thi hieu dien kdt qud nong do NP, BPA trong cdc mdu nude tai khu

vi/c bdi rac Nam San 4.5.3 So sanh ket qud phdn tich tgi hai khu vice bdi rac nghien ciiu

Qua ket qua qua phan tfch cac miu nude rac va nude ngim tai 2 khu vuc bai rac Tay Md va Nam San cho thay n-OP hiu nhu khong phat hien thay trong tat ca cac miu thu thap Hgp chat nay chi tim thay trong 1 miu nude rac tai khu vuc Tay Md vdi ham lugng la 137,2 ng/1

Lugng 4-tert-OP cd mat trong cac miu nude ngam ciing khong Idn (khoang vai ng/1 den han hai tram ng/L)

Ham lugng cac chat phan ti'ch trong cac miu nude ngam do dugc tai Tay Md nhin chung cao han d Nam San Dilu nay cd the giai thfch vi bai rac Nam San mdi

dugc dua vao sir dung sau khi bai rac Tay Md ddng cira Vi vay su tfch tu eiia cac AP

va BPA trong nude ngim tai bai rac nay tha'p han

Cac hgp chat NP va BPA cd mat ra't nhilu trong nude rac Ham lugng cua chiing (sau khi xir ly) dat tdi 3913,0 vdi BPA va 2026,0 ngA vdi NP (TMR3) Day la ngudn 6 nhilm tilm tang tdi mdi trudng, de dpa siic khde con ngudi Nhiing ngudn nude nay cin dugc tap trung thu gom va tai xir ly

So sanh cac miu nude rac tai hai bai rac nhan thay he thdng xir ly nude rac d Nam San tuang ddi tdt han so vdi tai bai rac Tay Mo Ham lugng cac chat nghien ciiu sau khi xir ly la 447,5 ng/1 vdi NP va 767,9 ng/1 vdi BPA, bdi day la bai rac mdi va hien dai nha't Ha Npi Tuy nhien ham lugng nay vin cdn cao (nhat la vdi 4-NP, vugt qua tieu chuan Chau Au vl ndng dp khdng gay bat ki anh hudng vdi sinh vat thuy sinh- 330 ng/1)

Hinh 9 thi hien su phan bd cua NP, BPA va tdng AP trong cac miu thuc te tai 2 khu vuc bai rac nghien ciiu

D N P

• BPA

• T6ng AP

T M N g l TMNg2 T M R l TMR2 TMR3 NSNgl NSNg2 NSRTr NSRSnu

Hinh 9: Do thi bieu dien suphdn bd cua NP vd BPA trong cdc mdu nude rac

vd nUdc ngam thu thdp tgi khu vuc bdi rac Tdy MS va Nam San

V KET LUAN

Qua qua trinh nghien ciiu, chiing toi da thu dugc nhiing ket qua sau:

- Da tien hanh din xuat hda thanh cong cac APs va BPA nghien ciiu bing anhydrit axetic trong mdi trudng natriaxetat Day la phuang phap din xuat dan gian, phan irng din xuat xay ra nhanh chdng, dinh lugng va tac nhan din xuat re tiln Phuang phap din xuat axetyl hda cac phenol cd nhilu hii'a hen thay the cho ky thuat silyl hda vin dimg hien nay

- Xay dung va khao sat quy trinh phan ti'ch dinh tfnh va dinh lugng cac AP va BPA trong nude rac vdi dp tin cay cao

- Ap dung quy trinh khao sat thu dugc de phan tfch cae hgp chat 4-NP, 4-OP, BPA trong cac miu nude va nude rac tai hai khu vuc bai rac Idn cua Ha Npi la Nam San va Tay M6

Ket qua cho tha'y su cd mat cua cac hgp cha't nay trong cac miu phan tfch 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 xir ly, ham lugng nonylphenol trong miu nude rac tai khu vuc bai rac Nam San vin vugt qua tieu chuan Chau Au ve nong dp khong gay bat ki anh huang vdi sinh vat thuy sinh

Chiing tdi hy vpng nhiing ke't qua nghidn ciiu nay se ddng gdp vao viec danh gia, quan trie su phan bd cac hgp chat hiiu ca dpc hai ndi chung va cae hgp chat ankylphenol, bisphenol A ndi rieng trong moi trudng Va chiing toi ciing hy vpng nghien ciiu nay se tiep tuc dugc md rong trong tuang lai

TAI LIEU THAM KHAO

1 Nguyln Diic Hue (2001), Cac phuuong phap phan tfch hiiu ca, trudng

5 10 Alexander H.C., Dill D.C., Smith I.W., Guiney P.D and Dorn P.B (1988), "Bisphenol A: A cute Aquatic Toxicity", Environ Toxicol And Chemistry, 7,

pp 19-26

6 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

7 Fabig W (1988), ''Determination of the Acute Bacterial Toxicity of Bisphenol A Dow Europe SA study report", Fraunhofer - Institute for Environmental Chemistry and Ecotoxicology, Horgen, Switzerland

8 Lysat A and Marcinek J (1972), "Multiple Toxic Effect of Simulta neous action of some chemical substances on Fish", Rocz nank Roln Sr H rybactwo.,

94 (3), pp 53-63