Nghiên cứu chế tạo cột vi chiết mao quản hở để xác định một số chất cơ clo dễ bay hơi trong môi trường nước

I HC QUC GIA H NI TRNG I HC KHOA HC T NHIấN NG VN ON NGHIấN CU CH TO CT VI CHIT MAO QUN H XC NH MT S CHT C CLO D BAY HI TRONG MễI TRNG NC LUN N TIN S HO HC H NI - 2015 I HC QUC GIA H NI TRNG I HC KHOA HC T NHIấN NG VN ON NGHIấN CU CH TO CT VI CHIT MAO QUN H XC NH MT S CHT C CLO D BAY HI TRONG MễI TRNG NC Chuyờn ngnh: Hoỏ mụi trng Mó s: 62440120 LUN N TIN S HO HC NGI HNG DN KHOA HC: PGS.TS Quang Huy GS.TSKH Nguyn c Hu H NI - 2015 PH LC Ph lc 1: Tớnh cht vt lý ca mt s cht Cl-VOC Ph lc 2: Hỡnh nh v mụ hỡnh kim vi chit OT-SPME ch to v si vi chit SPME thng mi Ph lc 3: ng chun v phng trỡnh ng chun cỏc cht Cl-VOC Ph lc 4: Sc phõn tớch mu hn hp cht chun Cl-VOC bng thit b GC/MSD Phc lc 5: Sc phõn tớch mu trng, mu thờm chun àg/L v àg/L bng thit b GC/MSD Ph lc 6: Kt qu phõn tớch Cl-VOC cỏc mu nc mt ca mt s sụng, h thuc thnh ph H Ni Phc lc 7: Sc phõn tớch mt s cht Cl-VOC mu nc mt ca mt s sụng, h thuc thnh ph H Ni bng thit b GC/MSD M U Tớnh cp thit ca ti Cỏc hp cht d bay hi bao gm nhng cht nhúm dung mụi clo hu c, nhúm cht thnh phn ca nhiờn liu, Nhúm cht dung mụi clo hu c gm cú iclometan, tetraclometan, cloeten 1,1-icloeten, trans-1,2dicloeten, cis-1,2-icloeten, 1,2-icloetan, tetracloeten, 1,1,1-tricloetan, 1,1,2tricloetan, tricloeten, 1,1-icloetan, triclometan, Nhúm cht thnh phn ca nhiờn liu gm cú benzen, metyl tert-butyl ete, toluen, xylen Nh vy cỏc cht d bay hi l cỏc cht hu c cú ỏp sut hi ln hn 13,3 Pa 25oC hoc 10 Pa 20oC [32, 43] Cỏc cht d bay hi c tng hp vi lng ln s dng rng rói cụng nghip v sn xut, ch tỏc cỏc sn phm gia dng Cỏc húa cht ny c dựng ty ra, git khụ, lm sch kim loi, cht kt dớnh, cht hũa tan mc, cht lm sch ni tht, cht thnh phn nhiờu liu, Bờn cnh ngun húa cht tng hp, mt s cht bay hi cũn c t sinh mụi trng nh quỏ trỡnh x lý nc bng clo, quỏ trỡnh clo húa t nhiờn nc ngm, Cỏc nh khoa hc ó tỡm thy tt c cỏc cht d bay hi mụi trng nc v khụng khớ Nguyờn nhõn dn n s cú mt ca cỏc cht ny mụi trng l s dng chỳng khụng ỳng quy tc, thi b khụng x lý, lu gi khụng cn thn, s bay hi t nhiờn t cỏc vt dng, vt thi b v nc mt, un nc s dng n ung v tm git, Cỏc hp cht hu c d bay hi (VOCs) cú th gõy nh hng xu ti sc khe ngi v h sinh thỏi nng thp, chỳng tham gia vo nhiu phn ng to cỏc cht nguy hi mụi trng, lm gim lng ụzụn khụng khớ, Trong cỏc nghiờn cu gn õy, cỏc nh khoa hc ó ch nhiu cht c clo d bay hi (Cl-VOC) nng thp cú th gõy nh hng ti mt, gan, tim, phi v cú th dn ti ung th, gõy t bin gen, quỏi thai, Vi c tớnh d bay hi, hũa tan cao cỏc dung mụi, mc phõn tỏn cao v nng thp mụi trng, nờn vic tỏch chit, lm giu cỏc cht ny, ú cú nhúm cht Cl-VOC phõn tớch gp nhiu khú khn tng bc gii quyt nhng khú khn trờn, cỏc nh khoa hc ó nghiờn cu v phỏt trin nhiu phng phỏp tỏch chit v lm giu cht khỏc nh phng phỏp bm mu trc tip, phng phỏp chit lng - lng, phng phỏp sc khớ v by cht, phng phỏp sc khớ tun hon, phng phỏp khụng gian hi bm mu trc tip, Cỏc phng phỏp ny cũn cú mt s hn ch nh: cht cn phõn tớch cú th b nhim bn bi nn mu, chuyn cht vo h thng phõn tớch khụng n nh, cn cú thit b ph tr t tin, tn húa cht dung mụi, thi gian phõn tớch kộo di, khc phc nhng nhc im nờu trờn, nhng nm gn õy cỏc nh khoa hc ó trung phỏt trin mt cụng c tỏch chit v lm giu mu bng si vi chit pha rn (SPME) cú mng hp ph cht ph ngoi phõn tớch nhiu dng cht khỏc nc, ú cú cỏc cht Cl-VOC ó cú nhiu loi si SPME bỏn trờn th trng dn thay th cho cỏc phng phỏp tỏch chit v lm giu mu nờu trờn Tuy nhiờn, cỏc si SPME ang s dng ti cỏc phũng thớ nghim cũn cú nhng mt hn ch nh bn s dng thp, d h tn, d gy, giỏ thnh cao Nhm gúp phn phỏt trin v hon thin cỏc k thut tỏch chit v lm giu mu phõn tớch xỏc nh Cl-VOC nng thp, chỳng tụi nghiờn cu phỏt trin phng phỏp vi chit s dng ct vi chit pha rn mao qun h (OT-SPME) vi mng cht hp thu ph trong, trờn thnh ng mao qun phc v phõn tớch ụ nhim mụi trng Theo hng nghiờn cu ny, chỳng tụi la chn v thc hin ti lun ỏn: Nghiờn cu ch to ct vi chit mao qun h xỏc nh mt s cht c clo d bay hi mụi trng nc 2 Mc tiờu ca lun ỏn - Ch to ct vi chit OT-SPME vi mng pha tnh ph dựng vi chit mt s cht Cl-VOC khụng gian hi ca cỏc mu nc - S dng ct vi chit OT-SPME ch to c kt hp vi phng phỏp sc ký khớ etect ph (GC/MSD) phõn tớch xỏc nh mt s cht ClVOC cỏc mu nc thc t Ni dung nghiờn cu ca lun ỏn Lun ỏn trung nghiờn cu cỏc ni dung chớnh sau: - Nghiờn cu la chn cỏc cht v vt liu cú kh nng hp thu tt nht cỏc cht Cl-VOC lm cht to mng pha tnh ch to ct OT-SPME - Nghiờn cu to mng pha tnh cú bỏn dớnh cao trờn thnh bờn ng mao qun to thnh ct vi chit OT-SPME - Nghiờn cu la chn cỏc iu kin lm vic tt nht ca ct vi chit OT-SPME tỏch chit cỏc cht Cl-VOC mụi trng nc bng k thut khụng gian hi - ỏnh giỏ hiu qu lm vic ca ct OT-SPME tỏch chit Cl-VOC pha hi thụng qua cỏc giỏ tr khong tuyn tớnh, gii hn phỏt hin, gii hn nh lng, thu hi, chớnh xỏc - ỏnh giỏ bn, hiu qu s dng ca ct vi chit OT-SPME quỏ trỡnh tỏch chit cỏc cht Cl-VOC pha hi - S dng ct vi chit OT-SPME kt hp vi phng phỏp GC/MSD phõn tớch xỏc nh mt s cht Cl-VOC cỏc mu nc mt ly mt s sụng, h ti thnh ph H Ni v ỏnh giỏ mc ụ nhim cỏc cht ny i vi mụi trng nc mt ti cỏc khu vc nghiờn cu Nhng úng gúp mi ca lun ỏn - Ln u tiờn Vit Nam nghiờn cu v la chn than hot tớnh (GCB) v co-polyme polidimetylsiloxan (PDMS) to lp mng ph GCB v PDMS ca ct vi chit OT-SPME phõn tớch mt s cht Cl-VOC nc - Ln u tiờn ch to thnh cụng ct vi chit OT-SPME vi mng ph bờn thnh ct mao qun l thộp khụng g gm GCB v PDMS Ct vi chit OT-SPME cú chiu di 7,5 cm, ng kớnh ngoi 0,6 mm, ng kớnh 0,419 mm; lp mng ph GCB v PDMS cú dy 27,50 àm, chiu di lp ph 0,5 cm; phn ct khụng cú mng ph GCB v PDMS cú ng kớnh l 0,1 mm cho hiu qu vi chit Cl-VOC cao nht - Bc u úng gúp vo vic gii thớch quỏ trỡnh vi chit cỏc cht ClVOC khụng gian hi lờn trờn mng ph GCB/PDMS, ú cựng tn ti hai quỏ trỡnh hp ph v phõn b hũa tan cht - ó s dng ct vi chit OT-SPME ch to c kt hp vi phng phỏp khụng gian hi v sc ký khớ ờtect ph (GC/MSD) phõn tớch xỏc nh mt s cht Cl-VOC cỏc mu nc mt ly mt s sụng, h thuc thnh ph H Ni Kt qu phõn tớch 132 mu nc mt cho thy nng cỏc cht Cl-VOC xỏc nh c ti thi im ly mu u thp hn cỏc giỏ tr cho phộp tiờu chun nc mt ca Chõu u v Nht Bn; õy l nhng s liu ban u u tiờn v nng cỏc cht Cl-VOC nc mt mt s sụng, h H Ni c xỏc nh Chng TNG QUAN 1.1 Cỏc hp cht hu c bay hi v c tớnh ca chỳng Trờn thc t cú nhiu nh ngha v VOCs khỏc nhau; v c bn VOCs c nh ngha theo hai cỏch sau: Th nht, theo hng nh hng ca VOCs, nh ngha ca C quan bo v mụi trng Hoa K (US-EPA), VOCs l cỏc cht hu c phỏt tỏn vo mụi trng gõy nờn hin tng quang hoỏ ca tng ụzụn [46] Cỏch th hai, nh ngha da vo tớnh cht hoỏ lý, theo Kennes v Veiga [37], VOCs l cỏc hoỏ cht (bay hi) cú cha nguyờn t cacbon v cú ỏp sut bay hi thp hn 101 kPa 3730K (100oC) Tuy nhiờn, theo Hi th nghim v vt liu Hoa K, VOCs l cỏc hp cht hu c cú ỏp sut hi ln hn 13,3 Pa 25oC [32]; theo Vn bn 1999/13/EC ca Hi ng Chõu u, VOCs l cỏc hp cht hu c cú ỏp sut hi ln hn 10 Pa 20oC [43] VOCs c s dng nhiu ngnh cụng nghip khỏc nhau, v c tỡm thy sn, cht kt dớnh, dc phm, m phm, cht lm lnh, hoỏ cht to mựi, xng, VOCs thng l dung mụi cụng nghip nh triclometan, iclometan, benzen, toluen, xylen, VOCs cú thnh phn ca nhiờn liu xng du, cht lng thu lc, dung mụi pha sn, thuc tr sõu, VOCs cú nc mt, nc ngm l VOCs ụ nhim mụi trng t, nc, khụng khớ sinh VOCs cú th gõy tỏc hi trc mt hoc lõu di n sc kho ngi Tỏc hi tc thi tip xỳc vi cỏc VOCs cú th l gõy kớch ng mt, da v ng hụ hp, au u, chúng mt, ri lon th giỏc, mt mi, mt cõn i, bun nụn v suy gim trớ nh Khi tip xỳc lõu ngy vi cỏc cht VOCs cú th gõy nh hng n gan, thn v h thn kinh trung ng, VOCs cú th gõy ung th i vi ngi Vỡ vy, VOCs cn phi c phõn tớch, ỏnh giỏ, x lý v kim soỏt t cỏc ngun phỏt thi cỏc hp cht ny vo mụi trng sng nh nc, t v khụng khớ Vit Nam v cỏc nc trờn th gii ó v ang trung thc hin cụng vic trờn 1.2 Tớnh cht ca mt s cht c clo d bay hi Cỏc cht Cl-VOC mụi trng nc l nhúm cht cú c tớnh cao, c ỏnh giỏ cú nguy c gõy ung th, l mt nhng nguyờn nhõn gõy suy gim lng ụzụn tng bỡnh lu, hỡnh thnh khúi quang húa v cú mựi khú chu [72] Do tớnh cht c hi ca cỏc cht Cl-VOC, nờn c Vit Nam, cỏc nc v cỏc t chc trờn Th gii quy nh gii hn nng cho phộp cỏc cht ny nc ung v nc mt rt thp, Bng 1.1 Cỏc cht Cl-VOC cú nc ung v nc mt l cỏc hot ng cụng nghip, dõn dng cú s dng dung mụi v mt lng ớt hỡnh thnh t quỏ trỡnh clo húa nc ngm [1, 28, 40, 103] Bng 1.1 Quy nh gii hn nng cho phộp ca mt s cht Cl-VOC nc ung v nc mt TT Tờn cht 1,1-icloeten iclometan QCVN TC 01:2009/BYT US EPA (àg/L) (àg/L) [7] [22] TC WHO (àg/L) [56] - TC nc mt EU (àg/L) [41] - TC nc mt Nht Bn (àg/L) [91] 20 20 20 20 20 trans-1,2-icloeten - 100 - - - 1,1-icloetan - - - - - cis-1,2-icloeten - - - 40 Triclometan 200 80 300 2,5 60 Tetraclometan 12 Tricloeten 70 - 10 30 1,1,2-tricloetan - - - 10 Tetracloeten 40 40 10 10 Ghi chỳ: " - " Khụng cú s liu S cú mt ca cỏc cht Cl-VOC mụi trng khụng khớ, t v nc khụng ch nh hng ti sc khe ngi, m cũn cú tỏc ng trc tip ti h sinh thỏi trờn t lin v nc Cỏc cht Cl-VOC khụng ch c phỏt hin thy khụng khớ, m cũn c phỏt hin thy cỏc mch nc ngm nc r thi, rũ r t nhiờn t cỏc khu cụng nghip hoc cỏc kho húa cht, chụn ct di t khụng ỳng quy nh gõy ra; thng gp nht tng nc ngm l tricloetylen, tetracloeten v tetraclometan Quỏ trỡnh lu chuyn cỏc cht Cl-VOC mụi trng c ch trờn Hỡnh 1.1 Hỡnh 1.1 S lu chuyn cỏc cht Cl-VOC mụi trng 1.3 Cỏc phng phỏp xỏc nh Cl-VOC mu nc Cỏc cht Cl-VOC trng lng phõn t thp, hũa tan nc nh, vy nc t nhiờn Cl-VOC thng cú nng rt thp, t ppt - ppb phõn tớch xỏc nh Cl-VOC mụi trng nc thỡ vic chit v lm giu Cl-VOC gn nh bt buc Trc ht, Cl-VOC phi tỏch b nc lờn pha khớ hoc i vo dung mụi hu c, sau ú c lm giu phõn tớch nh tớnh v nh lng trờn h sc ký khớ s dng mt s cỏc loi etect thớch TI LIấU THAM KHO Ting Vit Dng Hng Anh (2003), Phõn tớch ỏnh giỏ mt s cht ụ nhim hu c nc ngm cung cp cho cỏc nh mỏy nc ti khu vc H Ni v kh nng hỡnh thnh nhng sn phm ph cú c tớnh cao nc mỏy quỏ trỡnh kh trựng bng clo, Lun ỏn tin s hoỏ hc, i hc Quc gia H Ni, H Ni Nguyn c Hu, Trn Mnh Trớ (2007), Nghiờn cu phng phỏp vi chit mng kim rng kt hp vi sc kớ khớ GC/FID v GC/MS xỏc nh cỏc hyrocacbon thm nhúm BTEX khụng khớ, Tp phõn tớch Hoỏ, Lý v Sinh hc, T12(4), tr 8-13 Nguyn c Hu (2005), Cỏc phng phỏp phõn tớch hu c, NXB i hc Quc gia H Ni, H Ni Nguyn c Hu, Nguyn Nh H (2003), "Nghiờn cu phng phỏp phõn tớch a d lng HCBVTV nc s dng ct chit pha rn than hot tớnh ụxi hoỏ kt hp vi sc ký khớ - ph (GC/MS)", Tp Phõn tớch Húa, Lý v Sinh hc, T8(1), tr 27-33 Nguyn c Hu, Phm Hựng Vit, Trn Th Thu Hin (2004), "Nghiờn cu phng phỏp phõn tớch a d lng HCBVTV nc s dng k thut chit pha rn than en graphit (carbonpack B) kt hp vi sc ký khớ - ph (GC/MS) v sc ký lng cao ỏp (HPLC)", Tp Phõn tớch Húa, Lý v Sinh hc, T9(1), tr 30-37 o Thanh Hựng (2003), Nghiờn cu mt s pha tnh tinh th lng s dng sc kớ khớ ct mao qun, Lun ỏn tin s hoỏ hc, Vin cụng ngh Hoỏ hc, Trung tõm Khoa hc T nhiờn v Cụng ngh Quc gia, H Ni 136 Quy chun Vit Nam QCVN 01:2009/BYT: Quy chun k thut quc gia v cht lng nc n ung Tiờu chun Vit Nam TCVN 6910-1:2001, chớnh xỏc ( ỳng v chm) ca phng phỏp o v kt qu o - Phn 1: Nguyờn tc v nh ngha chung Tiờu chun Vit Nam TCVN 6663-6:2008, Cht lng nc - Ly mu - Phn 6: Hng dn ly mu sụng v sui 10 Tiờu chun Vit Nam TCVN 5994:1995, Cht lng nc - Ly mu Hng dn ly mu h ao t nhiờn v nhõn to 11 Trn Mnh Trớ (2011), Nghiờn cu phỏt trin phng phỏp vi chit kt hp vi sc ký khớ phõn tớch hp cht hu c bay hi, Lun ỏn tin s hoỏ hc, i hc Quc gia H Ni, H Ni 12 Trn Mnh Trớ, o Thu Giang, ng Vn on, Quang Huy, Nguyn c Hu (2013), Phng phỏp ng lc hc vi chit pha rn khụng gian hi xỏc nh cỏc hp cht hu c bay hi, Tp Húa hc, 51(2C), tr 759-762 13 Ngụ Vn T, Nguyn Khoa Hin (2009), "S dng k thut khụng gian hi kt hp GC-ECD (HS/GC/ECD) xỏc nh trihalomethanes nc mỏy ti Tha Thiờn Hu", Tp Khoa hc, i hc Hu, 50, tr 165-174 14 Nguyn Anh Tun, Nguyn c Hu, Trn Mnh Trớ (2004), Nghiờn cu ch to kim bm mu dựng vi chit pha rn phõn tớch mt s hoỏ cht Pyrethoid, Tp phũng chng st rột v cỏc bnh ký sinh trựng, 4, tr 59-65 15 Phm Hựng Vit (2005), Sc ký khớ - C s lý thuyt v kh nng ng dng, NXB i hc Quc gia H Ni, H Ni 137 Ting Anh 16 A Kot-Wasik, J Debska, J Namiesnik (2004), Monitoring of organic pollutants in coastal waters of the Gulf of Gdask, Southern Baltic, Mar Pollut Bull, 49, pp 264-276 17 A Kumar, A.K Malik, D.K Tewary, B Singh (2008), A review on development of solid phase microextraction fibers by sol-gel methods and their applications, Anal Chim Acta 610, pp 1-14 18 A Sarafraz-Yazdi, F Ghaemi, A Amiri (2012), Comparative study of the sol-gel based solid phase microextraction fibers in extraction of naphthalene, fluorene, anthracene and phenanthrene from saffron samples extractants, Microchim Acta 176, pp 317-325 19 A Sarafraz-Yazdi, H Piri Moghadam, Z Eshaghi, S Sepehr (2010), Comparative study of the three sol-gel based solid phase microextraction fibers in extraction of BTFEX from water samples using gas chromatography-flame ionization detection, Anal Methods 2, pp.746752 20 A Sarafraz-Yazdi, M Abbasian, A Amiri (2012), Determination of furan in food samples using two solid phase microextraction fibers based on sol-gel technique with gas chromatography-flame ionization detector, Food Chem 131, pp.698-704 21 A Sarafraz-Yazdi, M Mosadegh, A Amiri (2011), Determination of volatile organic compounds in environmental water samples using three solid-phase microextraction fibers based on sol-gel technique with gas chromatography- flame ionization detector, Anal Methods 3, pp.18771886 22 A Sarafraz-Yazdi, M Sayyar Ardaki, A Amiri (2013), Determination of monocyclic aromatic amines using headspace solid-phase microextraction based on sol-gel technique prior to GC, J Sep Sci 36, pp.1629-1635 138 23 A Sarafraz-Yazdi, S Sepehr, Z Eshaghi, H.P Moghadam (2010), Application of sol-gel based poly (ethylene glycol)/multiwalled carbon nanotubes coated fiber for SPME of methyl tert-butyl ether in environmental water samples, Chromatographia 72, pp.923-931 24 A Sarafraz-Yazdi, Z.R Dizavandi, A Amiri (2012), Determination of phenolic compounds in water and urine samples using solid-phase microextraction based on sol-gel technique prior to GC-FID, Anal Methods 4, pp 4316-4325 25 A Tor (2006), Determination of chlorobenzenes in water by drop-based liquid-phase microextraction and gas chromatography-electron capture detection, J Chromatogr A 1125, pp 129-132 26 A Tor, M.E Aydin (2006), Application of liquid-phase microextraction to the analysis of trihalomethanes in water, Anal Chem Acta 575, pp 138-143 27 A.A Matin, P Biparva, M Gheshlaghi, K Farhadi, A Gheshlaghi (2013), Environmentalmonitoring of complex hydrocarbon mixtures in water and soil samples after solid phase microextraction using PVC/MWCNTs nanocomposite fiber, Chemosphere 93, pp.1920-1926 28 Aaron W Browna, Paul S Simone Jr.a, b, J.C Yorkc, Gary L Emmert (2015), A device for fully automated on-site process monitoring and control of trihalomethane concentrations in drinking water, Analytica Chimica Acta 853, pp 351-359 29 Abua Ikem (2010), Measurement of volatile organic compounds in bottled and tap waters by purge and trap GC-MS: Are drinking water types different, Journal of Food Composition and Analysis 23, pp 7077 139 30 Alankar Shrivastava, Vipin B Gupta (2011), Methods for the determination of limit of detection and limit of quantitation of the analytical methods, Chronicles of young scientists 2(1), pp 21-25 31 Anastasia D Nikolaou, Spyros K Golfinopoulos, Maria N Kostopoulou, George A Kolokythas, Themistokles D Lekkas (2002), Determination of volatile organic compounds in surface waters and treated wastewater in Greece, Water Research 36, pp 2883-2890 32 ASTM D3960-05 (2013), Standard Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related Coatings, ASTM International, West Conshohocken, PA, 2013 33 Berg Fohn R (1997), Method and device for solid phase microextraction, United States Patent 6164144 34 Bernhard Rothweiler (2014), Analysis of volatile organic compounds in environmental waters using the agilent 7697A headspace and 7890B/5977A GC/MS, Solution Note, Agilent Technologies 35 Biziuk., Przyjany A (1996), Review: Methods of isolation and determination of valatile organohalogen compounds in natural and treated waters Journal of Chromatography A 733, pp 417-448 36 Bruno Kolb,Leslie S Ettre (2006), Static Headspace-Gas Chromatography: Theory and Practice 2nd Edition, Wiley-Interscienc 37 C Kennes, M.C Veiga, in: C Kennes, M.C Veiga (Eds.) (2001), Bioreactors for Waste Gas Treatment, Kluwer Academic Publishers, Dordrecht, p.3 38 Cancho B., Ventura F., Galcaran M., Diaz A., Ricart S (2000), Determination, sythesis and survey of iodinated trihalomethanes in water treatment processes, Wat Res 34 (13), pp 3380-3390 140 39 Chai M., Arthur L C., Pawliszyn , Belardi P R., and Pratt F K., (1993), Determination of volatile chlorinated hydrocarbons in air and water with solid-phase microextraction, Analyst, 118, pp.1501-1505 40 Chonghua Xuea, Qi Wangb, Wenhai Chua, Michael R Templeton (2014), The impact of changes in source water quality on trihalomethane and haloacetonitrile formation in chlorinated drinking water, Chemosphere 117, pp 251-255 41 EC (2008), Council Directive 2008/105/EC of the european parliament and of the council of 16 December 2008 on environmental quality standards in the field of water policy 42 E Adomaviciute, K Jonusaite, J Barkauskas, V Vickackaite (2008), In-groove carbon nanotubes device for SPME of aromatic hydrocarbons, Chromatographia 67, pp 599-605 43 EC (2006), Council Directive 1999/13/EC of 11 March 1999 on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and installations 44 Eduardo J Bottani and Juan M.D Tascún (2008), Adsorption by Carbons, Elsevier Publishers 45 EPA 5021A (2003), Volatile organic compounds in various sample matrices using equilibrium headspace analysis 46 EPA (2006), Code of Federal Regulations Title 40: Protection of Environment Chapter I: Environmental Protection Agency Subchapter C: Air Programs Part 51, Subpart F, Section 51.100 47 EPA (2009), National Primary Drinking Water Regulations 48 EPA 8000c, Rev.3 (2003), Determinative chromatographic separations, US Environmental Protection Agency 141 49 EPA 8260C (2006), Volatile organic compounds by gas chromatography/mass spectrometry (GC/MS) 50 F Wu, W Lu, J Chen, W Liu, L Zhang (2010), Single-walled carbon nanotubes coated fibers for solid-phase microextraction and gas chromatography-mass spectrometric determination of pesticides in Tea samples, Talanta 82, pp.1038-1043 51 F.J Santos, M.T Galceran, D Fraisse (1996), Application of solidphase microextraction to the analysis of volatile organic compounds in water, Journal of Chromatography A, 742, pp 181-189 52 Frộdộric Delage, Pascaline Prộ v Pierre Le Cloirec (1999), Effects of moisture on warming of activated carbon bed during voc adsorption, Journal of environmental engineering, pp.1160 - 1167 53 Fu H., Guan J., and Bao J J., (2006), A Hollow Fiber Solvent Microextraction Approach to Measure Drug- Protein Binding, The Japan Society for Analytical Chemistry vol-22, p.1565-1569 54 Gomes B R., Nogueira R., Oliveira M J., Peixoto J., Brito G A., (2009), Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM, Environ Sci Pollut Res, 16, pp.671-678 55 Greg Johnson, Determination of VOCs in water using static headspace GC/MS with simultaneous full scan and selective ion recording, Field application report, Perkin elmer 56 Guidelines for drinking-water quality, fourth edition, WHO, 2011 57 H Asadollahzadeh, E Noroozian, S Maghsoudi (2010), Solid-phase microextraction of phthalate esters from aqueous media by electrochemically deposited carbon nanotube/polypyrrole composite on a stainless steel fiber, Anal Chim Acta 669, pp 32-38 142 58 H Bagheri, Z Ayazi, H Sistani (2011), Chemically bonded carbon nanotubes on modified gold substrate as novel unbreakable solid phase microextraction fiber, Microchim Acta 174, pp 295-301 59 H Liu, J Li, X Liu, S Jiang (2009), A novel multiwalled carbon nanotubes bonded fused-silica fiber for solid phase microextraction-gas chromatographic analysis of phenols in water samples, Talanta 78, pp 929-935 60 H Liu, L Ji, J Li, S Liu, X Liu, S Jiang (2011), Magnetron sputtering Si interlayer: a protocol to prepare solid phase microextraction coatings on metal-based fiber, J Chromatogr A 1218, pp 2835-2840 61 Harris C Daniel (2003), Quantitative chemical analysis, W H Freeman and Co., 744 pages 62 Howard, P H., Sage, G W., Jarvis, W F & Gray, D A (1990) Handbook of Environmental Fate and Exposure Data for Organic Chemicals Vol II Solvent Lewis, Chelsea, MI, USA 63 I Minet, L Hevesi, M Azenha, J Delhalle, Z Mekhalif (2010), Preparation of apolyacrylonitrile/multi-walled carbon nanotubes composite by surface-initiated atom transfer radical polymerization on a stainless steel wire for solid-phase microextraction, J Chromatogr A 1217, pp 2758-2767 64 J Dewulf, H Van Langenhove (1997), Chlorinated C1- and C2hydrocarbons and monocyclic aromatic hydrocarbons in marine waters: An overview on fate processes, sampling, analysis and measurements, Water Research, Volume 31, Issue 8, August 1997, Pages 18251838 65 J Dewulf, H Van Langenhove (1997), Simultaneous Determination of C1 and C2-Halocarbons and Monocyclic Aromatic Hydrocarbons in Marine Water Samples at ng/L Concentration Levels, Intern J Environ Anal Chem 61, pp 35-46 143 66 J Feng, M Sun, L Xu, J Li, X Liu, S Jiang (2011), Preparation of metal wire supported solid phase microextraction fiber coated with multi-walled carbon nanotubes, J Sep Sci 34, pp 2482-2488 67 J Lỹ, J Liu, Y Wei, K Jiang, S Fan, J Liu, G Jiang (2007), Preparation of single-walled carbon nanotube fiber coating to solidphase microextraction of organochlorinepesticides in lake water and wastewater, J Sep Sci 30, pp 2136 - 2143 68 J Pettersson, J Roeraade (2005), Method for Analysis of Polar Volatile Trace Components in Aqueous Samples by Gas Chromatography, Anal Chem 77, pp 3365-3371 69 J Wu, J Pawliszyn (2001), Preparation and applications of polypyrrole films in solid-phase microextraction, J Chromatogr A 909, pp 37-52 70 J Wu, J Pawliszyn (2004), Solid-phase microextraction based on polypyrrole films with different counter ions, Anal Chim Acta 520, pp 257-264 71 J.C Flúrez Menộndez, M.L Fernỏndez Sỏnchez, J.E Sỏnchez Urớa, E Fernỏndez Martớnez, A Sanz-Medel (2000), Static headspace, solidphase microextraction and headspace solid-phase microextraction for BTEX determination in aqueous samples by gas chromatography, Analytica Chimica Acta 415, pp 9-20 72 J.G Calvert (1994), Chemistry for the 21st Century The Chemistry of the Atmosphere: Its Impact on Global Change, Blackwell Scientific Publications, Oxford 73 J.H You, H.L Chiang, P.C Chiang (1994), Comparison of adsorption characteristics for VOCs on activated carbon and oxidized activated carbon, Environmental Progress, Vol.13, No.1, p.31 144 74 J.-X Wang, D.-Q Jiang, Z.-Y Gu, X.-P Yan (2006), Multiwalled carbon nanotubes coated fibers for solid-phase microextraction of polybrominateddiphenyl ethers in water and milk samples before gas chromatography with electron-capture detection, J Chromatogr A 1137, pp 8-14 75 Janusz Pawliszyn (2012), Handbook of Solid Phase Microextraction, Elsevier Inc 76 Karine Jacq, Frank David, Pat Sandra (2008), Analysis of volatile organic compounds in water using static headspace-GC/MS, Application note, Agilent technologies 77 Ketola A.R., Kotiaho T., Cisper E.M., Allen M.T (2002), Enviromental application of membrane introduction mass spectrometry, Journal of mass spectrometry 37, pp.457-476 78 Kohji Yamamoto, Mionoru Fukushima, Naoya Kakutani, Kouichi Kuroda (1997), Volatile organic compounds in urban rivers and their estuaries in osaka, Japan, Environmental Pollution 95, No.1, pp 135143 79 L Chen, W Chen, C Ma, D Dud, X Chen (2011), Electropolymerized multiwalled carbon nanotubes/polypyrrole fiber for solid-phase microextraction and its applications in the determination of pyrethroids, Talanta 84, pp.104-108 80 Louch D Motlagl S Pawliszyn J (1992), Dynamics of organic compound extraction from water using liquid-coated fused silica fiber, Anal Chem., 84, No10, pp 1187-1199 81 M Rezaee, Y Assadi, M.-R Milani Hosseini, E Aghaee, F Ahmadi, S.Berijani (2006), Determination of organic compounds in water using dispersive liquid-liquid microextraction, J Chromatogr A 1116 (1-2), pp 1-9 145 82 Maeda T., Hisamoto., Ando M (1997), Relative certification of the water quality standard solution VOC-23 compounds sold in Japan, Bunseki Kagaku J 46 (1), pp 63-68 83 Mark van Lieshout, Shimadzu Benelux, Determination of Organic Volatiles in Water by Headspace GC/MS, Application Note, Shimadzu Europa GmbH 84 Mc Nally M.E., Grob R.L (1985), Review: current applications of static and dynamic headspace analysis Part one: Environmental application, Journal of American Laboratory 95, pp.20-33 85 Meier C Peter, Richard E Zỹnd (2000), Statistical methods in analytical chemistry (153), John Wiley and Sons 86 N Rastkari, R Ahmadkhaniha, M Yunesian, L.J Baleh, A Mesdaghinia (2010), Sensitive determination of bisphenol A and bisphenol F in canned food using a solidphase microextractionfibre coated with single-walled carbon nanotubes before GC/MS, Food Addit Contam Part A Chem Anal Control Expo Risk Assess 27, pp.1460-1468 87 N Rastkari, R Ahmadkhaniha, N Samadi, A Shafiee, M Yunesian (2010), Single-walled carbon nanotubes as solid-phase microextraction adsorbent for the determination of low-level concentrations of butyltin compounds in seawater, Anal Chim Acta 662, pp 90-96 88 N Rastkari, R Ahmadkhaniha, M Yunesian (2009), Single-walled carbon nanotubes as an effective adsorbent in solid-phase microextraction of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether from human urine, J Chromatogr B 877, pp.1568-1574 89 NIOSH Pocket Guide to Chemical Hazards, CDC, USA (2010) 146 90 P Kueseng, J Pawliszyn (2013), Carboxylated multiwalled carbon nanotubes/polydimethylsiloxane, a new coating for 96-blade solid-phase microextraction for determination of phenolic compounds in water, J Chromatogr A 1317, pp.199- 202 91 POMRAC, Vladivostok, Russian Federation (2009), Region overview on River and Direct inputs of Contaminants into the Marine and Coastal Environmentin NOWPAP regionwith special focus on the land based sources of Pollution, POMRAC Technical report No.7, pp.27-30 92 Q Li, X Ma, D Yuan, J Chen (2010), Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes for the determination of benzene, toluene, ethylbenzene, xylenes in aqueous samples, J Chromatogr A 1217, pp 2191-2196 93 R Jiang, F Zhu, T Luan, Y Tong, H Liu, G Ouyang, J Pawliszyn (2009), Carbon nanotube coated solid-phase microextraction metal fiber based on sol-gel technique, J Chromatogr A 1216, pp 4641-4647 94 R Kubinec, J Adamuscin, H Jurdakovỏ, M Foltin, I Ostrovský, A.Kraus, L Sojỏk (2005), Gas chromatographic determination of benzene, toluene, ethylbenzene and xylenes using flame ionization detector in water samples with direct aqueous injection up to 250 microl, J Chromatogr A 1084, pp 90-94 95 Rene P Schwarzenbach, Philip M Gschwend and Dieter M Imboden (2003), Environmental Organic Chemistry 2nd Edition, John Wiley & Sons, Inc 96 Rouessac F., Rouessas A., (2007), Chemical analysis: Modern insstrumentation methods and technique, John Wiley and Sons, 574 pages 147 97 S.A.S Wercinski, J Pawliszyn (Eds.) (2009), Solid-phase microextraction - A practical guide, Marcel Dekker, New York 98 S.L Chong, D Wang, J.D Hayes, B.W Wilhite, A Malik (1997), Solgel coating technology for the preparation of solid-phase microextraction fibers of enhanced thermal stability, Anal Chem 69, pp.3889-3898 99 Sadao Nakamura., Shigeki Daishima., (2005), Simultaneous determination of 22 volatile organic compounds, methyl-tert-butyl ether, 1,4-dioxane, 2-methylisoborneol and geosmin in water by headspace solid phase microextraction-gas chromatography-mass spectrometry, Analytica Chimica Acta, 548, pp.79-85 100 W Chen, J Zeng, J Chen, X Huang, Y Jiang, Y Wang, X Chen (2009), High extraction efficiency for polar aromatic compounds in natural water samples using multiwalled carbon nanotubes/Nafion solidphase microextraction coating, J Chromatogr A 1216, pp 9143-9148 101 W Du, F Zhao, B Zeng (2009), Novelmultiwalled carbon nanotubespolyaniline composite film coated platinum wire for headspace solidphase microextraction and gas chromatographic determination of phenolic compounds, J Chromatogr A 1216, pp 3751-3757 102 W Zhang, Y Sun, C Wu, J Xing, J Li (2009), Polymer-functionalized single-walled carbon nanotubes as a novel sol-gel solid-phase microextraction coated fiber for determination of poly-brominated diphenyl ethers in water samples with gas chromatography-electron capture detection, Anal Chem 81, pp 2912-2920 103 Wenhai Chu, Dongmei Li, Naiyun Gao, Daqiang Yin, Yanshen Zhang, Yanping Zhu, Comparison of free amino acids and short oligopeptides for the formation of trihalomethanes and haloacetonitriles during chlorination: Effect of peptide bond and pre-oxidation, Chemical Engineering Journal, Available online July 2015, Accepted Manuscript 148 104 X Liu, Y Ji, Y Zhang, H Zhang, M Liu (2007), Oxidized multiwalled carbon nanotubes as a novel solid-phase microextraction fiber for determination of phenols in aqueous samples, J Chromatogr A 1165, pp.10-17 105 Xichao Chen, Qian Luo, Donghong Wang, Jijun Gao, Zi Wei, Zijian Wang, Huaidong Zhou, Asit Mazumder (2015), Simultaneous assessmen ts of occurrence, ecological, human health, and organoleptic hazards for 77 VOCs in typớcal drinking water sources from major river basins, China, Environmental Pollution 206, pp 64-72 106 Z Polkowska (2004), Determination of volatile organohalogen compounds in urban precipitation in Tricity area (Gdask, Gdynia, Sopot), Chemosphere 57, pp 1265-1274 149 [...]... trong vi chiết pha rắn không gian hơi xác định các hợp chất hữu cơ bay hơi , Tạp chí Hóa học, 51(2C), tr 759-762 13 Ngô Văn Tứ, Nguyễn Khoa Hiền (2009), "Sử dụng kỹ thuật không gian hơi kết hợp GC-ECD (HS/GC/ECD) để xác định trihalomethanes trong nước máy tại Thừa Thiên Huế", Tạp chí Khoa học, Đại học Huế, 50, tr 165-174 14 Nguyễn Anh Tuấn, Nguyễn Đức Huệ, Trần Mạnh Trí (2004), Nghiên cứu chế tạo kim... THAM KHẢO 1 Tiếng Vi t 1 Dương Hồng Anh (2003), Phân tích đánh giá một số chất ô nhiễm hữu cơ trong nước ngầm cung cấp cho các nhà máy nước tại khu vực Hà Nội và khả năng hình thành những sản phẩm phụ có độc tính cao trong nước máy do quá trình khử trùng bằng clo, Luận án tiến sĩ hoá học, Đại học Quốc gia Hà Nội, Hà Nội 2 Nguyễn Đức Huệ, Trần Mạnh Trí (2007), Nghiên cứu phương pháp vi chiết màng kim... chuẩn Vi t Nam TCVN 5994:1995, Chất lượng nước - Lấy mẫu Hướng dẫn lấy mẫu ở hồ ao tự nhiên và nhân tạo 11 Trần Mạnh Trí (2011), Nghiên cứu phát triển phương pháp vi chiết kết hợp với sắc ký khí phân tích hợp chất hữu cơ bay hơi, Luận án tiến sĩ hoá học, Đại học Quốc gia Hà Nội, Hà Nội 12 Trần Mạnh Trí, Đào Thu Giang, Đặng Văn Đoàn, Đỗ Quang Huy, Nguyễn Đức Huệ (2013), “Phương pháp động lực học trong vi. .. Phạm Hùng Vi t, Trần Thị Thu Hiền (2004), "Nghiên cứu phương pháp phân tích đa dư lương HCBVTV trong nước sử dụng kỹ thuật chiết pha rắn than đen graphit (carbonpack B) kết hợp với sắc ký khí - khối phổ (GC/MS) và sắc ký lỏng cao áp (HPLC)", Tạp chí Phân tích Hóa, Lý và Sinh học, T9(1), tr 30-37 6 Đào Thanh Hùng (2003), Nghiên cứu một số pha tĩnh tinh thể lỏng sử dụng trong sắc kí khí cột mao quản, Luận... kết hợp với sắc kí khí GC/FID và GC/MS xác định các hyđrocacbon thơm nhóm BTEX trong không khí”, Tạp chí phân tích Hoá, Lý và Sinh học, T12(4), tr 8-13 3 Nguyễn Đức Huệ (2005), Các phương pháp phân tích hữu cơ, NXB Đại học Quốc gia Hà Nội, Hà Nội 4 Nguyễn Đức Huệ, Nguyễn Nhị Hà (2003), "Nghiên cứu phương pháp phân tích đa dư lượng HCBVTV trong nước sử dụng cột chiết pha rắn than hoạt tính ôxi hoá kết... sĩ hoá học, Vi n công nghệ Hoá học, Trung tâm Khoa học Tự nhiên và Công nghệ Quốc gia, Hà Nội 136 7 Quy chuẩn Vi t Nam QCVN 01:2009/BYT: Quy chuẩn kỹ thuật quốc gia về chất lượng nước ăn uống 8 Tiêu chuẩn Vi t Nam TCVN 6910-1:2001, Độ chính xác (độ đúng và độ chụm) của phương pháp đo và kết quả đo - Phần 1: Nguyên tắc và định nghĩa chung 9 Tiêu chuẩn Vi t Nam TCVN 6663-6:2008, Chất lượng nước - Lấy... Huế, 50, tr 165-174 14 Nguyễn Anh Tuấn, Nguyễn Đức Huệ, Trần Mạnh Trí (2004), Nghiên cứu chế tạo kim bơm mẫu dùng trong vi chiết pha rắn để phân tích một số hoá chất Pyrethoid”, Tạp chí phòng chống sốt rét và các bệnh ký sinh trùng, 4, tr 59-65 15 Phạm Hùng Vi t (2005), Sắc ký khí - Cơ sở lý thuyết và khả năng ứng dụng, NXB Đại học Quốc gia Hà Nội, Hà Nội 137 2 Tiếng Anh 16 A Kot-Wasik, J Debska,... environmental quality standards in the field of water policy 42 E Adomaviciute, K Jonusaite, J Barkauskas, V Vickackaite (2008), In-groove carbon nanotubes device for SPME of aromatic hydrocarbons, Chromatographia 67, pp 599-605 43 EC (2006), Council Directive 1999/13/EC of 11 March 1999 on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities... Conshohocken, PA, 2013 33 Berg Fohn R (1997), Method and device for solid phase microextraction, United States Patent 6164144 34 Bernhard Rothweiler (2014), Analysis of volatile organic compounds in environmental waters using the agilent 7697A headspace and 7890B/5977A GC/MS, Solution Note, Agilent Technologies 35 Biziuk., Przyjany A (1996), Review: Methods of isolation and determination of valatile... installations 44 Eduardo J Bottani and Juan M.D Tascón (2008), Adsorption by Carbons, Elsevier Publishers 45 EPA 5021A (2003), Volatile organic compounds in various sample matrices using equilibrium headspace analysis 46 EPA (2006), Code of Federal Regulations Title 40: Protection of Environment Chapter I: Environmental Protection Agency Subchapter C: Air Programs Part 51, Subpart F, Section 51.100