DAI HOC QUOC GIA HA NOI TRITONG DAI HOC KHOA HOC T\S NHIEN Khao sat va phat trien quy trinh phan tich cac doc td huu ca kho phan huy thuoc nhom ankylphenol va bisphenol A 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 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 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 nu6c rac tai mot sd khu virc thuoc bai rac Ha Noi Ma sd: QT-04-34 Chu tri de tai: GS.TS Pham Hung Viet Cac can bo tham gia: ThS Tran Thi Lilu HVCH Tran Thi Tuyet Mai HVCH Trinh Thi Tham CN Le Thi Ngoc Ha 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 cac mSu nuac rac - Ung dung quy trinh khao sat vao viec phan tich cac din xuat phenol nghien cuu 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 miu nuac rac vai tin cay cao tren cac mSu gia - Tien hanh lay miu nudc rac tai vi trf mot sd bai rac khac 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 cac mdu thu thap - Xu ly, tdng ket cac ket qua phan tich va viet bao cao Tom tdt ket qua nghien cuii dat dugc - Da khao sat va hoan thien quy trinh xac dinh cac ankylphenol va bisphenol A 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 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 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 cac mSu phan tich Ham lugng cac mSu nudc rac n^m 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 mSu nudc rac tai khu virc bai rac khu vuc Nam San vin vugt qua tieu chuan Chau Au v6 ndng 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 moi trudng Cac sd lieu dugc chi nguy ca nhidm ti6m tang CLia cac hgp chat phan tich ddi vdi sinh vat huu sinh va de doa sue khoe ngudi Nhim kiem soat, danh gia su tdn tai, van chuyen ciia cac hgp chat cac hgp phan moi trudng khac can tiep tuc thuc hien nhiing nghien cuu sau han tuang lai 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: 9.720.000d6ng Quan ly phi: 720 000 ddng Dien nudc va xay dung ca sd vat chat: 720.000 ddng Hd trg dao lao va NCKH: 540.000 ddng Hoa chat, nguyen lieu, dung cu: 6.300.000 ddng KHOA QUAN LY GS.TS ^4^y^^^ Mi^ CHU NHIEM DE TAI ^ / GS.TS Pham Huna Viet TRUONG DAI HOC KHOA HOC TU NHIEN #H6 HI^U TRUONG BRIEF OF THE PROJECT 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 The Coordinator: Prof.Dr Pham Hung Viet 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 Purpose and contents of the research Purpose: ' Investigation and optimization for analytical procedure of alkylphenols (4nonylphenol, 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 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] 4-tertoctylphenol, 4-n-octylphenol and bisphenol A in leachates and groundwater samples at locations of selected dumping sites shown the presence of these compounds in analyzed samples Concentrations of nonylphenol and bisphenol A in leachates samples were ranged 447,5- 1856,3 ng/L and 767,9-7250,1 ng/L, respectively Concentration of nonylphenol in leachates samples at Namson dumping site exceeded United States and Europe standard regarding the predicted no-effect concentration in water (PNECy,a,er) although leachates treated - The results contributed assessment and monitoring spatial distribution and behavior of alkyl phenols and biphenyl A in the environment The measured data indicated potential risks of target compounds for wildlife and human health Further research need to be continued in the future to get an overview about these compound in the environment MUC LUC Trang I MO DAU II TONG QUAN 2.1 Gidi thieu vi bisphenol A (BPA) 2.7.7 Tinh chdt vat ly vd hod hoc 2.7.2 Ifng dung cua BPA 2.13 Nguon thdi BPA vao moi truang 2.1.4 Tdc dong cua BPA doi vai dong thuc vcit vd nguai 2.2 Gidi thieu chung v6 cac ankylphenol (AP) 2.2.1 Giai thieu veNP 2.2.2 Giai thieu ve OP 2.23 Ung dung cua AP 2.2.4 Nguon thdi AP vdo moi trudng 2.2.5 Tdc dong cua cdc AP ddi vdi dong thuc vat vd nguai 2.3 Nudc rac va cac van de sinh 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 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 m^u 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 \2 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 \'^ mSu nudc rac 4.5 K6't qua phan tich mSu nudc rac thirc te 19 4.5.1 Kei qud phdn tich cdc mau tai khu vuc bdi rdc Tay Mo 20 4.5.2 Ket qud phdn tich 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 Bang Mot sd tinh cha't ciia BPA Bang 2: D6c tinh ciia BPA ddi vdi mot sd dong thuc vat thuy sinh Bang Mot sd tinh chat vat ly cua nonylphenol Bang 4: Manh dac trung ciia cac hgp chat phan tich Bang 5: Ket qua phan tfch cac phan doan rtra giai Bang 6: Kd't qua hieu suat thu hoi ciia cac hgp chat phan tich mSu nudc rac tai ndng 50ng/L Bang : Ket qua phan tfch miu nudc tai bai rac Tay Md Bang 8: Ham lugng cac hgp chat phan tfch cac mSu tai bai rac Nam San Trang 17 17 19 20 21 DANH SACH CAC HINH Hinh Cong thuc phan tu cua BPA Hinh 2: Cong thuc c^'u tao ciia nonylphenol Hhih 3: Cong thuc c^'u tao ciia OP va NP Hinh 4: Cau true ciia hocmon nu tu nhien 17P-estradiol va hoocmon nu nhan tao 4-nonylphenol (mot dang ddng phan) Hinh 5: Cac budc tien hanh ciia phuang phap chiet pha rdn Hinh 6: Ca che phan ung dan xuat axetyl hda cacphenol Hinh 7: Dd thi bieu diSn ham lugng NP va BPA cac mau nudc tai khu vuc bai rac Tay Md Hinh 8: Do thi bieu di6n ket qua ndng NP,BPA cac mSu nudc tai khu vuc bai rac Nam Son Hinh 9: Do thi bieu diln su phan bd ciia NP va BPA cac mSu nudc rac va nudc ngam thu thap tai khu vuc bai rac Tay Md va Nam San Trang 10 16 21 22 23 L MO DAU G5n day, viec ph^n tfch cac hda chat tfch luy b^n mdi trudng va cd kha nang gay rdi loan noi tiet (EDCs) da thu hut dugc su quan tam cua nhieu nha khoa hoc nhirng anh hudng nguy hai cua chung den ngudi va dong vat nhu: anh hudng den he thdng sinh san, tap tfnh sinh hoat, tao cac u ac tfnh va gay hau qua nghiem 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 tijf lau da dugc ung dung rong rai cac hoat dong sdng ciia ngudi Ankylphenol (APs), san ph^m thoai bien ciia ankylphenoletoxilat, la loai hgp chat dugc dung bien 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 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 va ngoai phd Han nua, phan Idn cac bai rac chua dugc xay dung dung qui each, hgp ve sinh Vi vay, anh hudng su 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 phan cac chat thai tai cac khu chon lap rac Viec phan tfch cac hgp chat phenol miu nudc rac gap rat nhi6u khd khan khau xij ly mlu, su qua phuc tap v6 phan cac loai hgp chat gay anh hudng cd nen m^u Viec nghien cuu tim mot phuang phap hieu qua va thich hgp de tach chiet va lam sach cac hgp chat d^n xuat phenol ndi chung khdi mSu nudc rac la rat khd khan Nghien cuu dugc thuc hien vdi muc dich khao sat va hoan thien quy trinh xac dinh cac hgp chat ankylphenol va bisphenol A 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 nhilm cua cac hgp chat 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 moi phenol vdi moi axeton nhu mieu ta dudi day: HjC_ CHj Hinh 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\ tan nudc tha'p (120-300mg/l tai pH=7) Trong moi trudng kiem, BPA tan tdt hon cd hang sd phan ly pKa= 9,6-10,2 Bang Mot sd tinh chdt cua BPA Thong sd Khdi lugng phan tii Cong thuc phan tu Ty Nhiet soi Gia tri 228g/mol C15H16O2 l,195g/cm3 220^C(d4mmHg) 398"C(d760mmHg) Nhiet ndng chay pKa Do tan nudc 150-155"C 9,59—10,2 120 —300mg/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 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 nd cdn dugc six dung 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 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 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 rat cao BPA dich chiet tu nhirng nai phe lieu, chat thai Tai nai san xuat che ly, ham lugng nonylphenol mSu nuOc rac tai khu viic bai rac Nam San vin vugt qua tieu ch\xin Chau Au v6 ndng dd khdng gay ba^t ki anh hudng vdi sinh vat thiiy sinh Chiing tdi hy vgng nhirng k^t qua nghien cim se ddng gdp vao danh gia, quan trie sir phan bd cac hgp cha't hiru ca dgc hai ndi chung va cac hgp cha't ankylphenol, bisphenol A ndi rieng mdi trudng Va chiing tdi cung hy vgng nghien cihi se tiep tuc dugc md rong tuong lai TAI LIEU THAM KHAO Reitzel L.A and Ledin A., (2002) Determination of phenols in landfill leachate-contaminated groundwaters by solid-phase extraction Journal of Chromatography 972, 175-183 Ribeiro A., Neves M.H., Almeida M.F., Alves A and Santos L (2002) Direct determination of chlorophenols in landfill leachates by solid-phase micro-extraction-gas chromatography-mass spectrometry Journal of Chromatography A, 975, 267-274 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 Nguyen Dire Hue (2001) Cdc phuang phdp phdn tich hilu co truang DHKHTN-DHQG Hd Noi Pham Hiing Viet (2003) Co so ly thuyet cua phuong phdp sdc ky khi, NXB Khoa hoc va Ky thuat Ha Ndi 76 Tap chi Phan tich Hoa, Ly va Sinh hoc, 2005 ANALYTICAL DETERMINATION OF REVELANT ALKYLPHENOLS AND BISPHENOL A OF LANDFILL LEACHATES SAMPLES COLLECTED IN HANOIS • * DUMPING SITES Tran Thi Tuyet Mai, Tran Thi Lieu, Pham Hung Viet Research Center for Environmental Technology and Sustainable Development Hanoi University of Science, VNU ABSTRACT Some derivative phenols of the alkylphenol group such as nonylphenol, octylphenol and bisphenol A are widely present in the environment from industrial and domestic used from the use of medical, diethylstibeltrol, herbisides, pesticides, fungisides These compound are thought to disrupt endocrine products of alkylphenolethocylates are toxic, persistent in the environment and have the potential to be present in the food chain This study was focussed on the refinement of an existing technique for the anlysis of alkylphenols and bisphenol A in leachate and ground water samples The samples were collected from landfill areas in NamSon and TayMo, Hanoi The recovered values of 4-nonylphenol (4-NP), 4-tert-octylphenol (4-t-OP), 4-n-octyophenoI (4-n-OP) and bisphenol A (BPA) were ranged from 84.4 to 91.4% The results indicated that the concentration of target alkylphenols and bisphenol A in TayMo samples was higher than that of samples from NamSon The concentrations of 4-NP and BPA in Tay Mo samples was significantly high value in leachates samples, with the concentrations of treated ones were 3913r|g/l and 2026rig/l for BPA and NP, respectively And these values were still exceeding the European values of Predicted Non-Effect Concentration for water environment [3] It is seemed that in Viet Nam dumping sites are potential pollution sources of alkylphenols and BPA and they have the potential to effect human health and the environment INTRODUCTION Nowadays, the identified ECDs can be classified into more than 50 types of groups of chemical such as insecticides, pesticides, fungicides, products of incineration, industrial and domestic waste The analytic procedure of AP and BPA in waste samples is still very difficult because of the complexity of sample matrix Therefore, to determine AP and BPA efficiently, the solid-phase micro extraction method (SPME) and Gas chromatograph mass spectrometer (GC-MS) method were applied The SPME column with CI8 has been chosen in order to separate analysed compounds from the raw sample with high efficiency [3] Acetic anhydrite is a cost effective solvent to use for the acethyhsation reaction of phenol derivatives The purpose of this paper is to optimize the analytical procedure of some APs and BPAs in the groundwater, leachate based on the combination of two tecliniques: SPE and derivitisation ones EXPERIMENTAL ANALYSIS This research include two phases: (1) screenning and optimizing the analytical procedure for APs and BPAs in rubbish water samples, (2) applying this procedure in the measurement o{ these 1- compounds in ruooiisira •wmv-i Son and Tay Mo landfill areas ^^^H^^A^^^ ,^ re-treated and treated) and surface water samples in Nam Sampling Nine leachate samples were collected in amber glass bottles in TayMo and NamSon regions, then filtered through the glass paper in the lab(GF/F, whatman, England) The filtered solution was acidified with HCl 4M to achieve the pH that prevent samples from degrading by microbial organisms, and then stored at 4*^C in the refrigerator until samples are analysed Chemicals The target compounds APs (4-NP, 4-t-OP, 4-n-OP), bis phenol A, internal standard solution naphthlene-d8, bisphenol A-dl4 (surrogate) by Chem Service Stock standard solutions of the target compounds were prepared in the acetone(Meck analytical grade) Then the standard curves of these substance concentrations are established The samples were denvitised by acetic anhydric Distilled water used in the laboratory was twice flllered by Millipore Florisil (90-100 mesh) by Supelco and Na2S04 anhydrous of Merck were baked at 450^^C for 12 hours Solid-phase extraction column with the absorbent RP-18500mg by Merck was used Equipment SPME (Supelco) 2.GC/MS-QP2010 by Shimazu with spUtless system and detector temperature: 280 C, injection volume is 2|il Capillary column DB-5 (30m in length, 0.25 mm in diameter and coved by 0.25 ^m of thickness of 100% dimethylpolysiloxane) Optimization of analytical procedure lOml volume of sample was taken, then filtered solution of samples was extracted by the SPE 200ml of the fillered acid preserved solution was extracted by SPE The SPE carridge was twice washed with 20ml hexane, 20nil MeOH and 10ml ion-free water The sample was pumped into the SPE column with speed of lOml/min (The SPE column was fushed with MeOH to desorb the analytes) The target substances were also desorbed by 20ml MeOH lOpl surrogate BPA-dl4 were added into the desorbed soUition as accompanying substance, then the yield of recovery was calculated The desorbed solution was concentrated by the Rotary, condensed by Nitrogen The 20ml solution was then dissolved in a mixture Dichloromethane(DCM):hexan (1:3).This mixture is placed on a florisil column(with 5g florisil) This mixture was eluted with 20ml hexan:DCM (2:3) to remove some affector And a final cultion -ith 100ml (5% MeOH/DCM) to elute AP and BPA The extract The acetylisation reaction was carried by adding 50pl Pyrol and 50 pi acetic anhydrite into the gas chromaticaly vial The vial is shaken with the pyrol and acetic anhydride and is left overnight to ensure complete reaction The internal standard Naphtalen-d8 10 ppm was added into the vial The solution was brought to ml with hexan and put into the chromatographic vial 1.5 ml, then identified in GC-MS with following program: The column temperature starts at 50^C for minutes, increases to lOO^C with speed 20"C.min"', then confinously to 120°C with the speed lO^C.min"', and finally to 280^^^ with the speed 20°C.min'' for mins The total time for analysis is 19.5 mins RESULTS AND DISCUSSION Optimization of analytical procedure The analytical procedure was opfimised using CI8 column with SPE due to the case of application, the cost benefit and high efficiency of sepration of compounds The technique was further optimised by the acetylisation of phenol by acetic anhydride in pyrol solvent at room temperature This two-staged process allows for the accurate and economic analysis oi^ alkylphenol and bisphenol A in leachate sampless Using this analytical procedure the result indicates that the recovered efficiency of ankylphenol and BPA is good value The recover efficiency illustrated in table Table I The recover efficiency of compounds in samples with concentration at 50ng/L Experiment 4-NP tert-OP n-OP BPA BPA-dl4 39,2 42,8 41,8 47,9 92.5 41,6 41,9 46,5 49,1 89.4 42,7 38,5 42,6 42,7 91,6 47,5 45,1 44,5 47.2 86,8 46,1 42,6 39,6 41,8 87.3 Average 43,4 42,2 43,0 45,7 89.5 Standard deviation 1,69 1,12 1,37 1,54 1,26 Coefficient variation(%) 3,88 2,82 3.19 3.37 1.41 Efficiency (%) 86,8 84,4 86,0 91.4 89.5 These efficiency values are relatively high Hence, this anal>'tical procedure ensure the accurancy and the requirement for analysis Obtained results -3- W P :ra5;ii(S'0 ::nis ;;ii;rxon=£^ ;:!;ii;;„uirv,;,;, lure for groundwater and leachate samples from NamSon and TayMo land fill region and repeated times The recovered values of analysed compounds ranged from 84.4 to 91.4% meaning the accuracy is high The obtained results of concentration of analysed subtances illustrated at table and table Table 2: The analysed result at TayMo Concentration (rig/l) NP tert-OP n-OP BPA Total TMSl 90.1 8.3 - 268.1 366.5 TMS2 93.5 - - 420.3 513.8 TMRl 1130.7 281.3 137.2 3162.4 4711.6 TMR2 972.6 - - 3240.4 4213.0 TMR3 2026.0 - - 3913.0 5939.0 TMS: groundwater samples TMR: leachate samples Table 3: The analysed result at NamSon Concentration (rig/l) NP Tert-OP n-OP BPA Total NSR 51,7 - - 108,8 160.5 NSS 54,6 6,0 - 156,2 216,8 NSTl 1856,3 194,0 - 7250,1 9300,4 NST2 447,5 - - 767,9 1215.4 NSR: surface water sample NSS: groundwater sample NSTl: pre-treated leachate sample NST2: treated leachate sample Figures and also illustrate the concentration reported of two main compounds: 4-nonylphenol (NP) and bisphenol A (BPA) in these samples Con centra I ion TMRl TMR3 FigL The graph dcscrible the concentration of Fig The graph de.scnhle the conceniraimn of NP and BPA in samples at TaxMo ^P ^"^^ ^^A m samples at NamSon In all of analysed samples, n-OP only occurs in leachate sample TMR at 137.2 ng !• The n-OP is not present in surface and ground water samples The concentration of tcrt-OP m groundwater is 4- The presence of NP, expecially BPA, in rubbish water is higher than the other The samples from TayMo recorded concentration of BPA at 3913.0 ng/l and NP at 2026.0 rig/l (TMR3) Comparing the rubbish water samples at NamSon to these at TayMo, the results indicate that treatment is having some impact on target analyse concentration The concentration of treated substances are 447.5r|g/l and 767.9r|g/l with NP and BPA, respectively, because NamSon is the newest and the most modem rubbish dumping in HaNoi However, this concentration is relative high (this value is higher than the European values of Predicted Non-Effect Concentration for water environment- 330r|g/l) CONCLUSION Application of SPE with the CI and acetylisation is very efficient for the analytical procedure for AP and BPA in rubbish water samples The derivatization technique is very simple, fast and cheap The results of 4-nonylphenol (4-NP), 4-tert-octylphenol (4-t-OP), 4-n-octylphenol (4-n-OP) and bisphenol A (BPA) show the presence of these compounds in both groundwater and leachate samples Concentration ranged from 447.5 to 1856.3 r\g/\ for 4-NP and ranged from 767.9 to 7250.1 r[g/\ for BPA in both the TayMo and NamSon landfills Compare to American criteria, the concentration of AP and BPA are more higher than that of American criteria (330r|g/l) and these compounds are very toxic hence there is a requirement for guidelines protective of both human health and the environment to be derived which are based on the local condition, climate and ecology Futher work needs to also undertaken in the treatment mechanisms of landfill leachate and the prevention of waste materials in the groundwater environment in VietNam The treatment occuring at NamSon has shown that it is effective but not completely at reducing the iexels of the target analyses researched in this paper namely AP and BPA Although the number of analysed samples is not very high (9 samples) but this analytical procedure has been repeated times and the recovery efficiency of researched compounds is above 84% in all samples, consequently, the accuracy is high and reliable We also hope that in the future, there will be more research about this analytical procedure to determine the presence and fateofEDC in VietNam ACKNOWLEDGMENT The author would like to thank Dr Takada (Tokyo University of Agriculture and Technology) for his advise and cooperation during the research The financial support for this study was pro\ided by Hanoi University of Science in frame of the Research Grant No QT-04-34, REFERENCES: Reitzel L.A and Ledin A., (2002) Determination of phenols in laudfill Icachalc-coniaminaicd groundwaters hv solid-phase extraction Journal of Chromatography, 972, 175-1 S3 Ribeiro A., Neves M.H., Almeida M.F., Alves A and Santos L., (2002) Direct determination of chlorophenols in landfdl leachates hy solid-phase micro-extraction-^^as chromaio