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 Muc tieu ciia de tai: - 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 C A N B O THAM GIA: ThS Tran Thi Lieu

HVCH Tran Thi Tuyet Mai HVCH.Trinh Thi Tham

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 virc thuoc 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

Muc tieu ciia de tai:

- 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 nirac ngam thuc te dugc thu thap tai mot sd bai rac thuoc Ha Noi (bai rac Nam San, Tay M6)

- Ket qua nghien cuu cua d^ tai dugc sir dung lam khoa luan tdt nghiep ciia mot sinh vien khoa Hoa khoa K45 va mot bao cao khoa hoc tai Hoi nghi Khoa hoc cua truang KHTN nam 2004

Noi 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 mSu gia

- Tien hanh lay m i u nudc rac tai vi trf mot sd bai rac khac nhau d Ha Noi la bai rac Nam San, Tay M6 va tai 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 mdu thu thap

- Xu ly, tdng ket cac ket qua phan tich va viet bao cao

5 Tom tdt ket qua nghien cuii dat dugc

- Da khao sat va hoan thien quy trinh xac dinh cac ankylphenol va bisphenol A trong

mfiu nudc rac vai viec ap dung ky thuat chiet pha vkn SPE (chat hap phu CI8), ket hgp

vdi ky thuat dfui xuat axetyl hoa vdi do 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 mau nuac ngam va nudc rac

tai hai khu vuc bai rac lan ciia Ha Noi la Nam San va Tay M6 cho thay su cd mat cua cac hgp chat nay trong cac mSu phan tich Ham lugng trong cac mSu nudc rac n^m 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 mSu nudc rac tai khu

virc bai rac khu vuc Nam San vin vugt qua tieu chuan Chau Au v6 ndng do du doan

khong gay bat ki anh hudng vdi sinh vat thiiy 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 tich 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 dugc cap: 18 trieu ddng

6.2 (liai trinh cac khoan chi:

- Thue khoan chuyen mon:

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 CI8 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-nonylpheno] 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-tert-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

I MO DAU 1

II TONG QUAN 1

2.1 Gidi thieu vi bisphenol A (BPA) 1

2.7.7 Tinh chdt vat ly vd hod hoc 2

2.7.2 Ifng dung cua BPA 2

2.13 Nguon thdi BPA vao moi truang 2

2.1.4 Tdc dong cua BPA doi vai dong thuc vcit vd con nguai 3

2.2 Gidi thieu chung v6 cac ankylphenol (AP) 4

2.2.1 Giai thieu veNP 5

2.2.2 Giai thieu ve OP 5

2.23 Ung dung cua AP 6

2.2.4 Nguon thdi AP vdo moi trudng 6

2.2.5 Tdc dong cua cdc AP ddi vdi dong thuc vat vd con nguai 7

2.3 Nudc rac va cac van de nay sinh trong cac bai chon lap rac d Viet Nam ^

2.4 Phuang phap tach chiet pha r^n vdi viec tach chiet cac hgp chat AP va 9

BPA

2.5 Ky thuat d&n xuat hoa 11

IIL THUC NGHIEM 11

3.1 Hda chat 11 3.2 Thiet bi 12

3.3 Khao sat quy trinh phan tich cac ankylphenol va bisphenol A trong m^u \2

nudc rac

3.3.1 Thu thap mau \2

3.3.2 Khao sat giai doan lam sach tren cotflorisil 12

3.3.2.1 Chuan hi cot nhoi 12

3.3.2.2 Khao sdt lU(yng dung moi rua gidi I3

3.3.3 Khao sdt hieu sudt thu hoi cua phucnigphdp I3

3.4 Phan tfch dinh tfnh va dinh lugng tren GC/MS 13

3.5 Hoan ihien quy trinh phan tfch I4

IV: KET QUA VA THAO LUAN 15

4.1 Ket qua qua trinh d3n xuat hda I5

4.2 Xac dinh phan manh dac trung ciia cau tir 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 mSu nudc rac

4.5 K6't qua phan tich mSu nudc rac thirc te 19

4.5.1 Kei qud phdn tich trong cdc mau tai khu vuc bdi rdc Tay Mo 20

4.5.2 Ket qud phdn tich trong cdc mau tai khu vUc hdi rdc Nam San 21

4.5.3 So sanh ket qud phdn tich tai hai khu vUc bdi rdc nghien cim 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 ciia 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 tich trong mSu 19

nudc rac tai ndng do 50ng/L

Bang 7 : Ket qua phan tfch miu nudc tai bai rac Tay Md 20

Bang 8: Ham lugng cac hgp chat phan tfch trong cac mSu tai bai rac Nam 21

San

DANH SACH CAC HINH

Trang Hinh 1 Cong thuc phan tu cua BPA 2 Hinh 2: Cong thuc c^'u tao ciia nonylphenol 5

Hhih 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 (mot dang ddng phan)

Hinh 5: Cac budc tien hanh ciia phuang phap chiet pha rdn 10

Hinh 6: Ca che phan ung dan xuat axetyl hda cacphenol 16

Hinh 7: Dd thi bieu diSn ham lugng NP va BPA trong cac mau nudc tai 21

khu vuc bai rac Tay Md

Hinh 8: Do thi bieu di6n ket qua ndng do NP,BPA trong cac mSu nudc tai 22

khu vuc bai rac Nam Son

Hinh 9: Do thi bieu diln su phan bd ciia NP va BPA trong cac mSu nudc 23

rac va nudc ngam thu thap tai khu vuc bai rac Tay Md va Nam San

trong cho cac the he tuang lai ma khd cd thi du bao trudc dugc Trong dd, cac dan xuat

phenol nhu ankylphenol va bisphenol A ndi trgi len do tijf lau da dugc ung dung rong rai trong cac hoat dong 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 policacbonat va chat cham chay, chat ket dinh, chat bao phii bao ve, son, vat lieu xay dung, giay nhiet, vat lieu bao ve dd dien, dien tir,

Ha N6i cd mot sd ft bai rac tip trung khdi lugng Idn rac thai sinh hoat tCr khdp 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 doc hai da, dang gay mdi quan tam Idn ddi vdi xa hoi Cac dgc 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 cac khu chon lap rac nay

Viec phan tfch cac hgp chat phenol trong miu nudc rac gap rat nhi6u khd khan trong khau xij ly mlu, do su qua phuc tap v6 thanh phan cac loai hgp chat gay anh hudng cd trong nen m^u Viec nghien cuu tim ra mot phuang phap hieu qua va thich hgp de tach chiet va lam sach cac hgp chat d^n xuat phenol ndi chung ra khdi mSu nudc rac la rat khd khan

Nghien cuu nay dugc thuc hien vdi muc dich khao sat va hoan thien quy trinh xac dinh cac hgp chat ankylphenol va bisphenol A trong mlu nudc rac sir dung ky thuat chiet pha rdn ket hgp vdi ky thuat dan xuat axetyl hoa Ben canh dd de gdp phan vao viec theo ddi, danh gia su phan bd, du doan nguy ca 6 nhilm cua cac hgp chat nay trong moi trudng, chiing tdi da ap dung quy trinh nghien cuu de phan tfch mot sd mSu nudc rac va nudc ngam thu thap tai hai bai rac Nam Son 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 cLia BPA thu dugc b^ng each ket hgp 2 moi phenol vdi 1 moi axeton nhu mieu ta dudi day:

Hinh 1 Cong thuc phdn tie cua BPA

2.LI Tinh chdt vat ly vd hod hoc

O di6u kien thudng, BPA tdn tai d trang thai r^n, cd cau triic tinh the\ do tan

trong nudc tha'p (120-300mg/l tai pH=7) Trong moi trudng kiem, BPA tan tdt hon do

cd hang sd phan ly pKa= 9,6-10,2

Bang 1 Mot sd tinh chdt cua BPA

Thong sd

Khdi lugng phan tii

Cong thuc phan tu

2 2 0 ^ C ( d 4 m m H g )

3 9 8 " C ( d 7 6 0 m m H g ) 150-155"C 9,59—10,2

120 — 3 0 0 m g / l

2.1.2 Ung dung ciia BPA

Gdn nhu toan bo (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 mot sd san pham chuyen dung khac BPA cdn cd mat trong nhung san pham nhu chat dfnh, chat Idt phu, bgt son, vat lieu xay dung, dia compact, vat lieu quang hoc, giay chiu nhiet, bao gdi Ngoai ra nd cdn dugc six dung trong cong nghiep nhugm 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 dong cong nghiep va thu cong nghiep

bdi day la mot loai hda chat tong hgp Mot lugng Idn BPA da di vao nudc 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 ran khac bdi ngudi ta da phat hien dugc ndng do rat cao BPA trong dich chiet tu nhirng nai do phe lieu, chat thai Tai nai san xuat che

bien, ham lugng thap cua BPA dugc thai tnJc tiep vao nudc be mat va khong khf qua he thdng nudc thai BPA cd mat trong khong khf 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

ung hoac BPA dugc sinh ra tai nhirng didu kien nhat dinh

2.1.4 Tdc dong cua BPA ddi v&i dong thuc vat vd con ngudi

BPA la mot trong nhiing hoa chat tong hgp kha b6n trong moi trudng Mot vai nghien cuu v6 doc tfnh cua BPA ddi vdi cac loai vi sinh vat, tao, dong vat khong xuong sdng, ca va con ngudi da chiing minh nd la mot chat cd ti6m nang gay 6 nhiem moi trudng nghiem trgng, de doa he sinh thai Tieu chuan ciia My va Lien minh chau Au v6 ndng do cua BPA trong moi trudng nudc la 1000 ng/1

Bang 2: Dgc tinh cua BPA ddi vai mot sd dong thuc vat 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 dong

M

4,6

3-3,5

15 9,4 7,5

Tham khao

Nhung anh hudng chu yeu ciia BPA la len he thdng noi tiet nhu kfch thfch hay kim ham hoat dong cua hoocmon gidi tfnh ddi vdi dong vat, cd the dan 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, dong vat cd vu hay lam tdc tu cung ciia cac loai dong vat bien +)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 chuc nang cua tuyen 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 trong,

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 nhi6u va dd la ngudn nguy hiem ddi vdi cac loai dong vat cung nhu con ngudi Su tiep nhiem BPA cd the khien cho ca the' cac dong vat dugc tiet ra hoocmon vitellogenin (mot loai protein noan hoang ciia cac dong vat cd xuang sdng gidng cai va khong cd trong cac ca th6 due cung nhu cac con non), anh hudng den viec tao tinh triing cung nhu su phat trien cua ca th^ d nhirng ca the nay ngudi ta da tim thay nhung te bao budng trung trong tinh hoan Mot vf du khac, tai Nhat Ban, khi nghien ciiu cac loai ca sdng trong moi trudng nudc cd chiia BPA (tai

ndng do 1820 |^g/l) da phat hien nhieu ca thi vira cd budng triing wita cd tinh hoan

Nhu vay tai ndng do nay, xu hudng bien ddi gidng la lam tang gidng cai Di6u nay cd anh hudng Idn den sd lugng ciia loai

Nhung dong vat Ihiiy sinh khong xuong sdng ciing td ra nhay cam vdi BPA Dong vat than m6m phan iing vdi chat nay d ndng do rat thap Thf nghiem tren loai

than m6m Potamopyrgus antipodarum cho thay ngay ca khi d dang hdn hgp vdi nhidu

chat khac trong nudc thai ga cdng da qua xii ly, BPA cung cd kha nang gay tac dong ddng thdi len triing va phoi d ndng do thap va kim ham su phat tri6n d ndng do cao han

Vao nam 2000, mot sd nha khoa hgc da cong bd nhung ket qua nghien ciiu thay rang ngay tai ndng do thap, BPA cung cd th6 gay anh hudng len he sinh san cua dc sen

cai nudc nggt Marisa cornuariettis va Nucelle lapillus, lam sung tay tuyen sinh due va

diit dng din triing

Ca che tac dong cua BPA hien vSn chua dugc khing dinh ro rang Nhung mdi day, mot phep thu trong ca the' da dua ra ca che phan tu trong dd BPA cd the viia anh hudng den hoat tfnh va chiic nang cua ca quan thu nhan hoocmon andogen Tuy vay, nhij*ng tac dong cua BPA d lieu lugng nhd vSn tiep tuc dugc ban luan

2.2 Gioi thieu chung ve cac ankylphenol (AP)

Ciic AP dudi dang ankylphenol etoxylat (APE) la nhdm cac chat hoat dong be 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 mot chat hoat ddng

be mat khong phan ly trong cac thude trii sau vdi mot lugng nhd trong tdng san luang lieu 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 lan Day la mot hoa chat long

hgp rat dgc hai Nd cd kha nang tfch tu sinh hoc, trong cac mo cua ca \hi sdng va tfch

tu trong mdi trudng NP da dugc xac dinh trong cac mSu moi trudng d My, Canada va Chau 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 tiep vdi vdng tham ciia phan tit phenol 4-NP, cha't cd gdc nonyl nam d vi trf ddi dien vdi nhdm hidroxy la hgp chat phd bien nhat, ehiem khoang 90% NP thuang mai

HO X ^ C , H , 3

Hinh 2: Cong thuc cdu tao cua nonylphenol

4-NP la chat long, sanh, cd mau vang nhat, trong sudt, cd mui phenol nhe Cac hang sd vat ly ciia NP dugc trinh bay trong bang 3

Bang 3 Mot sdtinh chdt vat ly cua nonylphenol

Thong sd

Khdi lugng phan tir

Cong thiic phan tu

NP la chat rat ft tan trong nudc (do 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 CLia cac dong 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 thuic cdu tao cua OP vd NP

4-OP tdn tai d dang tinh th^ trang hoac bui vdi mot sd hang sd vat ly sau

Cong thiic phan tu: C14H22O

Nhiet do ndng chay: 81-84°C, nhiet do soi: 150°C (d 4 mmHg) Ty trgng 0,961 g/cm\ Diem chop chay: >230"C

4-OP ben va de bat chay, cd kha nang pha huy cac mang nhay Dgc tfnh ciia nd hien nay van chua dugc nghien ciiu day du LD50 vdi chuot (qua mieng) 4600 mg kg"' LD50 vdi thd (qua da) 1880 mg kg '

2.2.3 ling dung cua AP

Oclyl- va nonylphenol dugc iing dung rong rai lam nguyen lieu dau cua cac chat lay riia, chat nhu hoa, tac nhan lam udt hoac phan tan trong san, nhua chdng oxi hoa, thude trii sau (trii nam) hay chat tao bgt, chat lam ben sir dung trong cong nghiep san xuat nhua PVC AP ciing dugc diing nhu chat phu gia trong dau ma boi Iron

Nonyl- va octylphenol la nhirng san pham ben ciia qua trinh phan huy sinh hgc cac APE, chiing dugc san xuat khoang 10 000-50 000 tan/nam trong dd udc tfnh san lugng CLia loan chau Au la 6800 lan

2.2.4 Nguon thdiAP vdo moi tru&ng

Hau het cac AP dugc thai ra moi trudng dudi dang APEO, chat nay tiep luc thoai bien thanh ankylphenol mono hay dietoxylat rdi hap thu trong biin va tram tfch Ahel va cong su (1994) da udc tfnh trong mot chu trinh xu ly nudc thai khoang 40%

NP dugc xir ly, 20% hap thu vao biin, cdn lai 40-45% khong xu ly dugc va di vao cac ddng chay

Ngudn thai chfnh ciia AP vao moi trudng la {\X cac san pham lay riia, mgl sd san

pham cong nghiep khac nhu scm, thuoc diet cd, hda my pham, nhua phenolic, dich chiet tir cac bai chon lap rac thai Ngoai ra NP cdn thoai ra moi trudng tir cac san pham

lam bang 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 dong cua cdc AP ddi vdi dong thuc vat vd con ngudi

Nhirng nghien ciiu tac ddng cua cac AP ddi vdi dong vat dua vao nhirng thf nghiem sinh hgc trong hay ngoai ca the Tren thuc te, nhung ap luc v6 mat dao diic khong cho phep chiing ta nghien ciiu true tiep tren ca the con ngudi Vi vay, chiing ta phai dua tren nhiing tai lieu dich t6 dang tin cay ve nhiing thir nghiem d dong 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 the' tranh khdi nhiing han che va sai sdt

Trong nhiing nam gan day, nhu'ng tai lieu nghien ciiu tren loan the gidi da dua

ra nhirng canh bao v6 tinh trang 6 nhidm moi trudng, va nhiing tac dong cd hai gay ra bdi cac hoa chat lam rdi loan tuyen noi tiet Mot vai nha khoa hgc da chiing minh rang nhiing hgp chat nay cd anh hudng den he sinh san, tap tfnh hoat dong ciia con ngudi cung nhu cac loai khac, gay ra nhirng u ac tfnh va nhiing hau qua nghiem trgng khac cho the he tuang lai

Dgc tfnh ciia APs tang theo chidu dai ciia chuoi ky nudc va dugc thi hien khi

chiing phan bd vao cac mang md cua ca the nhu mang cua bg may gongi gay gian doan viec tdng hgp ra nang lugng Nhiing tac dong ciia AP bat dau d ndng do khoang l,5mg/l Tuy nhien NP the hien tfnh dgc d ndng do thap han nhieu, khoang 0,112 mg/l ddi vdi ran nudc Nhin chung cac AP dgc hon APEO, vf du NP dgc hon NPEO khoang

10 lan

Estrogen la loai hoocmon di6u chinh sir phat tri6n, quy dinh dac tfnh cua gidng

cai Hien nay da c6 nhiing bang chiing chu'ng id rang mot sd hda chat tu nhien ciing

nhu tdng hgp cd the' bat chudc hoat dong ciia hoocmon nay

dao cua chudt gidng nhu hien tugng dien ra vao chu ky dong due, Su sirng hda ciing xay ra khi thir nghifm vdi 4-tert-pentylphenol nhung khong xay ra vdi 2-n-pentylphenol Di6u nay dugc giai thfch do su khac nhau cua 2 nhdm the d vdng benzen

Bang chiing tiep theo dugc cong bd vao nam 1978 khi Mueller va Kim nghien

cihi thay rat nhidu AP cd thi thay the cac estradiol lien ket vdi ca quan thu nhan

Nhiing tac dong nay xay ra manh tai nhiet do thap (0-4^^)

Tuy nhien, nhiing ket qua nghien ciiu tren khong gay dugc su quan tam rong rai

cho 6€n nam 1991, khi Soto va cac cdng sir tinh cd phat hien 4-NP trong khi thf

nghiem tr6n cac te bao ung thu via MCF7, nhay cam vdi estrogen Hg phat hien thay mot hgp chat tach ra khdi dng ly tam va khien cho cac te bao phat trien manh me, mot hien tugng thudng thay dudi tac dong cua estrogen Hgp chat nay da dugc xac dinh la

NP, chat dugc dua vao thanh phan dng nghiem vdi muc dfch lam tang do b6n 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 lie

che \\tc tdng hgp va chuyen hda cac enzym cua hoocmon, lam gia tang cac te bao ung

thu va la nguyen nhan gia tang ty le ngudi bi mac benh ung thu tinh hoan va ung thu vii lai cac nudc phuang Tay trong han 40 nam gan day Do miic do nghiem trgng cua nd

ma hien nay nhieu nudc tren the gidi da cd nhirng bien phap giam thi6u va ngan chan viec sir dung cac APEO trong cac chat lay rira gia dung

2.3 Nudc rac va cac van de nay sinh trong cac bai chon lap rac 6 Viet Nam [4,51

Nudc rac cd the' dinh nghia nhu mgl chat ldng tham qua chat thai ran, mang theo cac chat hoa tan va chat ran la lirng Trong phan Idn trudng hgp, nudc rac dugc sinh ra

do qua trinh xam nhap ciia cac ngudn nudc lir ben ngoai vao nhu he thdng thoai nudc

bt mat, nudc mua, nudc ngam va nudc dugc sinh ra do qua trinh phan huy chat thai

trong bai chon lap

Lugng nudc rac hinh thanh trong cac bai chon lap dugc udc tfnh dua tren su can bang nudc trong bai chon lap Sir can bang nudc bao gdm long lugng nudc di vao bai chon lap trir di lugng nudc tieu thu cho phan iing hoa hgc va lugng nudc bi bay hai Lugng nudc rac tdi da cd kha nang sinh ra la lugng nudc khong vugt qua kha nang giii

am cua cac vat lieu trong bai chon lap Ket qua thf nghiem chi ra rang lugng nudc rac sinh ra Idn nhat sau 25 ngay chon lap Ngudn nudc chii yeu bao gdm nudc di vao cac 6 chon lap tir phfa tren, lugng am cd san 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 didu kien cho rudi mudi phat tridn, miii hoi thdi bdc len do qua trinh phan huy yem khf trong bai rac Vi vay, da gay ra 6 nhi^m khong khf va ngudn nudc ngam ca mot viing rong Idn

Cac bai chdn lap rac d thanh phd Idn deu trong tinh trang qua tai, khong dugc thid't ke va quy hoach ngay tir dau, cong vdi viec quan ly van hanh yeu kem nen da gay

ra hang loat cac van di het siic nan giai

Nudc rac sinh ra tir cac bai chon lap (chu yeu la tir cac hd tfch trii nudc rac bd trf xung quanh bai rac) chay tran ra ngoai he thdng bd bao gay thiet hai nang n^ cho ddi sdng san xuat va sinh hoat ciia dan cu Nudc rac sinh ra khong dugc xir ly kip thdi

hoac chua dat tieu chuan dang c6 nguy ca gay 6 nhiem nudc ngam va viing nong

nghiep xung quanh

Viec giam thieu va phan loai chat thai ran tai ngudn hau nhu chua dugc quan tam va thuc hi6n, nhi^u cha't thai nguy hai trong y te va cong nghiep dugc thu gom va chdn chung vdi chat thai sinh hoat

Cac van d6 tren chfnh la mdt sd nguyen nhan gay ra su cd nhieu nai nhu trudng hgp va bd bao d bai rac Dong Thach va nhieu trudng hgp hoa mau ciia nong dan d gdn khu chon lap bi chet De han che den miic thap nhat hau qua, chfnh quyen cac cap dang tim mgi bien phap xir ly va cai tao bai chon lap Dien hinh la du an xay dung khu xir ly nudc rac tai bai chon lap Nam San- Sdc San- Ha Noi, bai chon lap Dong Thach Thanh Phd Hd Chf Minh va mot vai bai chon lap khac bat dau chuan bi trien khai

2.4 Phuong phap tach chiet pha rdn vdi viec tach chiet cac hgp chat AP va BPA

[1,21

Nguyen tac ciia chiet pha ran la sir dung chat chiet d dang hat nhd, xdp nhdi trong cot chiet cac chat can phan tfch ra khdi dung dich rdi diing mot 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 mot lugng nhd dung moi

Cot sac ky dugc nhdi bang nhiing vat lieu xdp, hat nhd cd chiia nhiing nhdm chu:c khac nhau Chat ldng dugc dua qua cot dudi tac dung ciia ap suat hoac chan khong

-^A^

i A

w

chat phan tfch

Hinh 5: Cdc budc tien hdnh cua phuang phdp chiet pha ran

Phuang phap chiet pha ran gdm 4 budc, dugc mo tii 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 trong giiia cac hat val lieu hap phu

Budc 2: Dung dich mau dugc chay qua cot Chat phan tfch va mot vai thanh phan 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 the sir dung chfnh dung moi hoa lan mSu 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 de' 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 hap phu pha thudng: cac silica trung tfnh, oxil 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 Igc phan tir theo do Idn, kfch thude

Chat hap phu pha khf- rdn

Hidn nay, phucmg phap chiet pha ran ngay cang dugc sir dung rong rai va phd

bid'n do nhiing uu di^m vugt trgi sau:

Hi6u suat 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 sac ky khf

An toan, dan gian, d6 sir dung, cd th^ tien hanh hang loat

2.5 Ky thuat d^n xuat hda

Viec phan tfch cac AP va BPA bang phuang phap sac ky thudng gap khd khan

Pic thu dugc thudng thap, nhiSu va khd nhan dang do cd nhdm OH phan cue cd kha

nang luu giii lau vdi pha tinh cua c6t sac ky gay ra hien tugng keo chan pic, can trd

viec dinh tfnh, dinh lugng mot each chinh xac

Dc khac phuc hien tugng tren ngudi ta thudng sir dung ky thuat dan xuat hda,

thay the nhdm OH phan cue bang cac nhdm chiic khac ft phan cue han Cac ky thuat

thudng diing d^ dan xuat hda hgp chat phenol la silyl hda, axetyl hda, metyl hda

Trong nghien ciiu nay, chiing toi lua chgn phuang phap axetyl hda cac phenol

bang anhydrit axetic Phan iing nay dien ra nhanh, dinh lugng tai nhiet do 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

III THirC NGHIEM

Nghien ciiu bao gdm 2 phan: khao sal va hoan thien quy trinh phan tfch cac

ankylphenol va bisphenol A trong mSu nudc rac, va ap dung quy trinh khao sal dugc

vao xac djnh cac ankylphenol va bisphenol A trong mot sd mau nudc rac (trudc va sau

xir ly) va mau nudc ngam lai 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 noi chuan naphtlen-d8 va chat ddng hanh bisphenol

A-dl4 (surrogate) dugc dat tir Chem Service Dung dich chuan gdc ndng do 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 chuan

Anhydrit axetic, axit HCl dac, loai tinh khiet phan tfch ciia hang Merck dugc sir dung lam tac nhan axit hoa va dSn xuat hoa

Cac dung moi diclometan, hexan, axeton va metanol loai tinh khiet phan tfch cua Merck

Nudc cat 2 ISn dugc loc qua thiet bi khir ion hoa Millipore (Nhat Ban)

Cha't hap 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, lii hot, bg cat dudi dung moi bang khf N2

Tliiet bi quay cat chan khong ciia hang Buchi (Nhat Ban)

Cot lach sac kf : cot mao quan DB-1, dai 30m, dudng kfnh trong 0,32mm, hi

day pha tinh 0,25|am

Thiet bi sdc ky khf khdi phd GCMS- QP2010 ciia hang Shimadzu

Thiet bi chiet pha ran ciia hang Supelco

3.3 Khao sat quy trinh phan tich cac ankylphenol va bisphenol A trong mau nudc rac

33.1 Thu thap mau

9 mau nudc rac va nudc ngam quanh khu vuc 2 bai rac Tay Md va Nam San

dugc thu thap vao trong cac chai thuy tinh 4L sSm mau va dugc loc qua giay loc thuy

linh (GF/F, Whatman, Anh) Dich loc dugc axit hoa vdi HCl 4M vi 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 doan lam sach tren cotflorisil

3.3.2.1 Chuan hi cot nhoi

Col lam sach tu nhdi florisil dugc chuan bi nhu sau: Chuan bi cot sac 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 bi mat florisil Qua trinh nhdi cot udt

dugc tien hanh lan lugt nhu sau: col dugc nhdi dau lien la lap bong thuy linh, tiep den

la lap Na2S04 khan rdi 5g florisil Tren ciing la 1 lap Na^SOj khan Go nhe phfa thanh ngoai cot de' chat hap phu dugc nen chat Chii y trong khi nhdi col khong dugc de col kho

3.3.2.2 Khao sdt luang dung moi rUa gidi

- Them true tiep 10 jil surrogate BPA- dl4 ndng do 10 mg/l, 2 jil hdn hgp chu^n 10 mgA vao c6t

- Khao sat phan doan F l : dung 20 ml hdn hgp n-hexan : diclometan (1:3 vi thi

tich) di loai bd cac chat anh hudng

- Khao sat phan doan F2; diing 20 ml hdn hgp n-hexan : diclometan (2:3 ve the tfch) d^ loai bd cac chat anh hudng

- Khao sat phan doan F3: diing hdn hgp diclometan : metanol (95 : 5 vi thi tfch)

de rira giai cac cha't 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 vi khoang 0,5 ml, ddi dung moi bang each them liep 8

ml axeton va chuyen sang dng nghiem cd vach Tiep tuc c6 dung moi bang ddng khf

nita vi 0,5 ml Axetyl hda hdn hgp bang anhidrit axetic Them \0\i\ noi chuan naphtalen- d8 10 mg/l, dinh miic vi 1ml Lac manh trong vai giay bang thiet bi lac rdi

lien hanh bam len GC/MS de phan tfch tu dong theo chuang trinh dat sSn

3.3.3 Khao sdt hieu sudt thu hoi cua phuang phdp

Quy trinh kiem tra hieu suat thu hdi dugc tien hanh nhu sau:

- Chuan bi mSu them chuan bang each lay 10 ml mSu nudc 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 mSu trang bang each lay 10 ml nudc ca't 2 lan, them vao 10 \JL\

BPA-d l 4 10 mg/l va lien 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 bang each can chfnh xac lOmg cac chuan don rdn va dinh miic trong binh 10ml va dinh miic tdi vach chuan vdi dung moi axeton Ndng do chuan gdc la lOOOmg/1

Sau dd tir cac dung dich gdc nay pha loang de dugc day chuan cd ndng do tir 5 den 200ppb

Tat ca cac dung dich chuan diu dugc dan xuat axetyl hoa trudc khi bam len

may

-I-) Dinh luang:

Cac hgp chat AP va BPA nghien ciiu dugc dinh lugng theo phuang phap noi chuan vdi chat noi chuan la naphtalen-d8

Ndng do thuc ciia mdi chat phan tfch trong mSu dugc tfnh theo cong thiifc sau:

Cs = (a xAS/AIS -^b) x HS/S Trong dd:

CS la ndng dd cua cha't c^n phan tfch trong mSu

a la do ddc ciia dudng chu£n

b la doan chan cua dudng chuan

AS la di6n tfch ciia cha't chu^n phan tfch do dugc tren GC/MS

AIS la dien tfch ciia chat noi chuan do dugc tren GC/MS

IIS la lugng chat noi chuan dugc them vao mSu

S la lugng mau phan tfch ban dau

+) Dieu kien Idm viec cua thiet hi 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 (do dai cot la 30m, dudng kfnh trong 0,32mm, do day Idp pha tinh 0,25^m)

- Khf mang He (do tinh khiet 99,999%) dugc sir dung la khf mang vdi tdc do 2ml/phut

- Mau dugc bam vao qua thiet bi bam mSu tu dong AOC-20i vdi che do khong chia ddng

3.5 Hoan thien quy trinh phan tich

Dich loc ciia mSu dugc chiet bdi ky thuat chiet pha ran vdi col SPE RP-18, da dugc rira lan lugt ciing vdi 20ml n-hexan, 20ml DCM, 20ml MeOH va 10ml nudc cat khir ion Cho 200ml dich Igc mau di qua cot SPE vdi tdc do lOml/phiil 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 chal ddng hanh, tfnh gia tri hieu suat thu hdi

Dich rira giai dugc c6 cat quay chan khong va c6 bang nita tdi gan kho, rdi hoa tan lai trong 1ml hdn hgp DCM/hexan (l:3,v/v) Diing pipel Paster dua qua cot sdc ky

dugc nhdi 5g cha't ha'p phu florisil (da hoat hoa 12 gid tai 130°C) de tien 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 vi 1ml Chuyen vao lo nhd sdc ky 1,5ml Cd bang nita vi gan kho

Thuc hi6n phan iing ddn xuat axetyl hoa bdng each cho them 50|il natriaxetic va

50|il anhydrit axetic vao Ig sdc ky Ldc manh Ig, de yen tai nhiet do phdng qua dem di

phan ling ddn xuat hoa xay ra hoan toan

Cho 0,5ml hexan vao Ig nhd, ldc manh va ly tam (tdc do 1000 vdng/phiit) Tach lay Idp n-hexan Thuc hien qua trinh them 0,5ml hexan 2 lan niia Lap hexan thu thap dugc lam khan qua Na2S04 Cd dac Idp hexan v6 the tfch <lml Them 10|il chat noi chuan naphtalen-d8 lOppm Dinh miic ve 1ml bdng hexan Chuyen sang Ig sdc 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 ddn xuat hoa

Ky thuat dan xuat cd nhieu uu diem cho viec phat hien ddng thdi cac hgp chat phenol vdi do nhay va do chgn loc cao Trong dd cac ky thuat silyl hda dugc iing dung rong rai do cd kha nang cai thien do chfnh xac, do nhay, do lap lai va kha nang phan giai vi nd lam triet tieu dudi pic, tang tfnh b6n nhiet ciia cac phenol Tuy nhien gia thanh ciia chiing lai rat ddt, khdng phii hgp vdi di6u kien nghien cuu tai Viet Nam Chfnh vi vay, viec khao sat de tim tac nhan ddn xuat hda khac hieu qua, re lien han rat

dugc quan tam Trong khudn khd nghien ciiu ciia di tai nay, chung toi khao sal phuang

phap ddn xuat axetyl hda cac phenol bdng tac nhan ddn xuat hoa anhidrit axetic

Khi tien hanh phan iing este hda true tiep bdng axit cacboxylic, trong phan iing nay cac phenol ddng vai trd cung cap proton va axit cacboxylic cung cap nhdm hidroxy cho phan tir nudc tach ra Tuy nhien, hieu suat dat dugc thudng rat thap Vi vay de thu dugc cac phenolesle, thudng phai tien hanh theo phuang phap Solten-Baoman (1884-1886) lire la cho cac phenol lac dung vdi clorua axit hoac anhydrit axit Irong moi trudng baza Chiing toi da tien hanh phan iifng bdng anhidrit axetic trong moi Irudng nalriaxetat 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 dieu kien nhiet do phdng Han nira, cac tac nhan dan xuat lai rat re Nhugc diem duy nhat ciia phuang phap la axil axetic (san pham ciia phan iing) va anhidrite axetic du cd kha nang an mdn cac thiet bi kim loai cua he thdng sdc ky nen cdn lien hanh loai bd chiing trudc khi bam len may

Hinh 6: Ca che phdn I'ing ddn xiid't 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: Manh pho ddc trung ciia cdc hop chat phdn tich

4.3 Khao sat quy trinh phan tich

Do phan cue cua dung moi rira giai cd the anh hudng tdi hieu suat thu hdi cua chat phan tfch trong mdu moi trudng Vdi cac mau nudc, diclometan dugc chgn la dung mdi chiet bod chiing cd kha nang tuang tac manh vdi dang phenoxi tuang ddi phan cue trong moi trudng pH= 2 Tuy nhien, nudc rac la moi Irudng 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 do cac phenol dugc tfnh theo cong thiic:

C = Cspike - Cblank Trong dd: Cspike : ndng do cac phenol trong mdu them chudn

Cblank: ndng do cac phenol trong mdu trdng Ket qua khao sat hieu suat thu hdi trung binh qua cot florisil tai ndng do cac phenol la 200ng/L sau 5 Idn lap lai dugc trinh bay trong bang 5

Bdng 5: Ket qud phdn tich cdc phdn doan rua gidi

-dl4

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 ciia mdu th6m chudn

Qiank- ndng dd sau xir ly ciia mdu trdng

Co : ndng dd ban dau khi them chuan Gia tri trung binh ciia cac lan thf nghiem dugc tfnh nhu sau:

- 1 V

^^ = 7 2 ^

De kiem tra dd chfnh xac (do 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) di danh gia

hieu suat thu hdi, do lech chudn, he sd bien dong

khi su sai khac giiia gia tri trung binh va gia tri thuc khong dang ki Phep so sanh nay

dugc lien hanh nhd chuan Student

Bdng 6: Ket qud hieu sudt thu hoi cua cdc hap chdt phdn tich trong mdu nudc

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 deu cao, do lap lai lot Hieu suat thu hdi ciia OP la thap nhat (84,4 va 86,0%) va cao nhat la 91,4% ciia BPA Nhu vay quy trinh de ra dam

bao dugc do chfnh xac va yeu cdu di ra ddi vdi viec phan tfch mdu nude rac

4.5 Ket qua phan tich mdu nudc rac thirc te

Trong nghien ciru nay, chiing toi da tien hanh thu thap 9 mau nudc rac va cac mdu nudc ngdm 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 loan ndng do chat phan tfch do may tu dong thuc hien theo chuang trinh lap san Sau dd, chiing toi tien hanh hieu chinh lai theo cong thiic sau:

^ H

1 C X F

v x l 0 0 %

Cx : Ndng do cau tir trong mdu phan tfch, ng/L

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

Vc : The' tfch mdu c6 cudi ciing khi bom len may, ml

Vm : Th6 tfch cua mdu that dugc phan tfch, L

H : Hieu suat thu hdi, %

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

4,5.1 Ket qud phdn tich trong cdc mdu tai khu vuc bai rdc Tay MS

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

Bdng 7 : Ket qud phdn tich mdu nudc tai bdi rdc Tdy Mo

4-tert-OP 8,3

Tong AP

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

2026

Trong dd, TMNg: mdu nude ngam TMR: mdu nudc rac

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

Kel qua phan lich cho thay, hgp chat n-OP khong cd trong cac mdu nudc ngam phan tfch 4-l-OP do dugc vdi ham lugng kha thap trong 1 mdu nudc ngdm dugc thu thap tai khu vuc nay (chi dat 8,3ng/L) Hgp chat NP dugc phat hien thay trong tat ca cac mdu phan tfch vdi ham lugng kha cao, tren 90,1 ng/L va gia tri ham lugng trong cac mdu nudc rac cao han hdn so vdi trong mdu nudc ngam Gia tri ham lugng NP cao nha't do dugc trong mdu nudc rac tai khu vuc bai rac nay la 2026ng/L Tu day cd the tha'y su 6 nhifim cua NP trong nudc rac, ciing nhu nguy ca tiem 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 mdu phan tfch Ham lugng do dugc trong mdu nudc ngam cQng dat tdi vai tram ng/L va vdn nhd han gan 10 lan so vdi trong mdu nudc rac Gia tri ham lugng BPA cao nhat do dugc trong nudc ngam va nudc rac tucrng iing la 420,3 va 3913ng/L

D6 Ihi hinh 7 bieu diln sir phan bd ham lugng ciia NP va BPA trong cac mdu phan tfch

lai khu vuc bai rac Tay Mo

4000

3000 Ham luong (ng/L) 2000

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

Bdng 8: Hdm luang cdc hajy chdt phdn tich trong cdc mdu tai bdi rdc 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: mdu nudc ngam; NSRTr: mdu nudc rac trudc xir ly; NSRSau: mdu nudc rac sau xir ly

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

Ket qua phan tfch cho thay, n-OP khong cd trong tat ca cac mdu nudc ngdm va nuac rac

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

NP do dugc trong lat ca 2 loai mdu vdi gia tri ham lugng trong nudc ngdm tir 51,7-54,6ng/L; ham lugng trong nudc rac cao han rat nhi6u, ke ca nudc rac da qua xu

ly ham lugng cung cao hon 8 lan so vdi trong nudc ngdm Ben canh dd, ta cung thay

dugc cd su giam dang ki 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 vdn cao han so vdi gia tri ham lugng du doan khdng gay anh hudng tdi moi trudng nudc cua Chau Au (330ng/L) Di6u nay the hien nguy ca tiem tang ngudn gay 6 nhiSm 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 dong tir 1999 den nay

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

Ham lugng ciia NP va BPA trong cac mdu nudc rac va nudc ngdm phan tfch tai khu vuc bai rac Tay Md dugc mo ta trong hinh 8

8000

6000 Ham Iircfng (ng/L) 4000

2000

D N P

• BPA

NSNgl NSNg2 NSRTr NSRSau

Hinh 8: Do thi bieu dien ket qud nong do NP, BPA trong cdc mdu nudc tai khu

vUc bdi rdc Nam San 4.5.3 So sdnh ket qud phdn tich tai hai khu vuc bdi rdc nghien ciiu

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

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

Ham lugng cac chat phan tich trong cac mdu nudc ngam do dugc tai Tay Md nhin chung cao hon d Nam Son Di^u 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 ciia cac AP

va BPA trong nudc ngdm tai bai rac nay tha'p hon

Cac hgp chat NP va BPA cd mat ra't nhieu trong nudc 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 nhi6m ti6m tang tdi mdi trudng, de doa siic khde con ngudi Nhiing ngudn nudc nay cdn dugc tap trung thu gom va tai xir ly

So sanh cac mdu nudc rac tai hai bai rac nhan thay he thdng xir ly nudc 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 Noi Tuy nhien ham lugng nay vdn cdn cao (nhat la vdi 4-NP, vugt qua lieu chuan Chau Au ve ndng do khdng gay bat ki anh hudng vdi sinh vat thuy sinh- 330 ng/1)

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

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 nudc rdc

vd nudc ngdm thu thap tai khu vuc hdi rdc Tdy MS vd Nam San

V KET LUAN

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

- Da tien hanh ddn xuat hda thanh cong cac APs va BPA nghien ciiu bdng anhydrit axetic Irong mdi trudng nalriaxetat Day la phuang phap ddn xua't dan gian, phan irng ddn xuat xay ra nhanh chdng, dinh lugng va tac nhan ddn xuat re ti6n Phuang phap ddn xuat axetyl hda cac phenol cd nhi6u hira hen thay the cho ky thuat silyl hda van dimg hien nay

- Xay dung va khao sat quy trinh phan lich dinh linh va dinh lugng cac AP va BPA trong nudc rac vdi do tin cay cao

- Ap dung quy trinh khao sat thu dugc de phan tfch cac hgp chat 4-NP, 4-OP, BPA trong cac mdu nudc va nudc rac tai hai khu vuc bai rac Idn ciia Ha Noi la Nam San va Tay M6

Ket qua cho thdy su cd mat cua cac hgp cha't nay trong cac mdu phan tfch Ham lugng trong cac mdu nudc rac ndm 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 mdu nudc rac tai khu vuc bai rac Nam Son vdn vugt qua tieu chuan Chau Au ve nong do khong gay bat ki anh huong vdi sinh vat thuy sinh

Chiing tdi hy vgng nhiing ket qua nghien ciiu nay se ddng gdp vao viec danh gia, quan trde su phan bd cac hgp chat hiiu ca dgc hai ndi chung va cac hgp chat ankylphenol, bisphenol A ndi rieng trong moi trudng Va chiing toi ciing hy vgng nghien curu nay se tiep tuc dugc md rong trong luong lai

TAI LIEU THAM KHAO

1 NguySn Diic Hue (2001), Cac phuuong phap phan tfch hiiu ca, Irudng

5 10 Alexander H.C., Dill D.C., Smith I.W., Guiney RD 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-ethinyleslradiol 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 Simulla neous action of some chemical substances on Fish", Rocz nank Roln Sr H rybaclwo.,

94 (3), pp 53-63