I HC QUC GIA H NI TRNG I HC KHOA HC T NHIấN Hong Quc Anh NGHIấN CU PHN TCH V NH GI HM LNG CC POLYBROM DIPHENYL ETE TRONG NHA V BI TI MT S KHU TI CH RC THI IN T LUN VN THC S KHOA HC H Ni - 2014 I HC QUC GIA H NI TRNG I HC KHOA HC T NHIấN Hong Quc Anh NGHIấN CU PHN TCH V NH GI HM LNG CC POLYBROM DIPHENYL ETE TRONG NHA V BI TI MT S KHU TI CH RC THI IN T Chuyờn ngnh: Húa phõn tớch Mó s: 60440118 LUN VN THC S KHOA HC Ngi hng dn khoa hc: Hng dn chớnh: PGS.TS T Bỡnh Minh Hng dn ph: TS V Cụng Sỏu H Ni - 2014 LI CAM OAN Tụi cam oan Lun thc s khoa hc vi ti Nghiờn cu phõn tớch v ỏnh giỏ hm lng cỏc polybrom diphenyl ete nha v bi ti mt s khu tỏi ch rỏc thi in t l cụng trỡnh nghiờn cu ca bn thõn Cỏc thụng tin tham kho dựng lun c ly t cỏc cụng trỡnh nghiờn cu cú liờn quan v c nờu rừ ngun gc danh mc ti liu tham kho Cỏc kt qu nghiờn cu lun l trung thc v cha c cụng b bt kỡ cụng trỡnh khoa hc no khỏc H Ni, ngy 01 thỏng 06 nm 2014 Hc viờn Hong Quc Anh i LI CM N Vi lũng bit n sõu sc, tụi xin chõn thnh cm n PGS.TS T Bỡnh Minh ó tin tng giao ti, nh hng nghiờn cu, tn tỡnh hng dn v to nhng iu kin tt nht cho tụi hon thnh Lun ny! Tụi xin chõn thnh cm n TS V Cụng Sỏu, Vin Khoa hc hỡnh s, B Cụng an, l ngi ng hng dn tụi thc hin Lun ny Tụi xin by t lũng bit n chõn thnh ti cỏc thy, cụ, cỏn b, k thut viờn ca B mụn Húa hc phõn tớch ni tụi thc hin Lun vn; c bit l PGS TS T Th Tho, TS Phm Th Ngc Mai, TS Nguyn Th nh Hng ó giỳp , to iu kin v cho tụi nhiu li khuyờn giỏ tr thi gian tụi thc hin Lun vn! Tụi cng xin gi li cm n ti cỏc thy, cụ, cỏn b, k thut viờn Khoa Húa hc, cỏc anh ch l Nghiờn cu sinh, Hc viờn cao hc v bn bố ng khúa K23 ó giỳp , ng viờn tụi sut quỏ trỡnh hc v nghiờn cu ti Khoa Húa hc, Trng i hc Khoa hc T nhiờn, i hc Quc gia H Ni H Ni, ngy 01 thỏng 06 nm 2014 Hc viờn Hong Quc Anh ii MC LC Trang Danh mc ch vit tt vii Danh mc hỡnh viii Danh mc bng ix M u CHNG TNG QUAN 1.1 Gii thiu v cỏc Polybrom diphenyl ete 1.1.1 Cu trỳc, phõn loi, cỏch gi tờn PBDEs 1.1.2 Tớnh cht vt lớ v tớnh cht húa hc ca PBDEs 1.1.3 c tớnh ca PBDEs 1.1.4 Tỡnh hỡnh sn xut, s dng v thi b PBDEs 10 1.1.4.1 Tỡnh hỡnh sn xut PBDEs thng mi 10 1.1.4.2 Tỡnh hỡnh s dng PBDEs thng mi 12 1.1.4.3 S thi b cỏc sn phm cha PBDEs thng mi 14 1.1.5 S phõn b v chuyn húa ca PBDEs mụi trng 15 1.1.5.1 PBDEs mụi trng nc, trm tớch v sinh vt 15 1.1.5.2 PBDEs mụi trng khụng khớ v bi 16 1.1.6 Cỏc qui nh hin cú v PBDEs 18 1.2 Tng quan v phng phỏp phõn tớch cỏc Polybrom diphenyl ete 1.2.1 Phng phỏp x lớ mu phõn tớch PBDEs 19 19 1.2.1.1 X lớ mu nha 19 1.2.1.2 X lớ mu bi 21 1.2.2 Phng phỏp phõn tớch PBDEs trờn h thng sc kớ khớ ph 23 1.2.2.1 Tỏch cỏc PBDEs bng sc kớ khớ 23 1.2.2.2 nh tớnh v nh lng PBDEs bng ph 26 CHNG I TNG V PHNG PHP NGHIấN CU 28 2.1 Thit b, dng c, húa cht, cht chun 28 iii Trang 2.1.1 Thit b 28 2.1.2 Dng c 29 2.1.3 Húa cht 29 2.1.4 Cht chun v cỏch pha ch cỏc dung dch chun 31 2.1.4.1 Cỏc dung dch chun gc 31 2.1.4.2 Cỏc dung dch chun lm vic v dung dch chun dng ng chun 31 2.2 Ni dung nghiờn cu 33 2.2.1 Ch tiờu phõn tớch 33 2.2.2 i tng phõn tớch 33 2.2.3 Phng phỏp ly mu, bo qun mu v thụng tin mu phõn tớch 34 2.2.3.1 Phng phỏp ly mu v bo qun mu nha 34 2.2.3.1 Phng phỏp ly mu v bo qun mu bi 34 2.2.3.2 Thụng tin mu phõn tớch 34 2.2.4 Phng phỏp nghiờn cu 36 2.2.4.1 Phng phỏp phõn tớch PBDEs trờn GC-MS v x lớ s liu 36 2.2.4.2 Nghiờn cu qui trỡnh x lớ mu v xỏc nhn giỏ tr s dng ca phng phỏp 36 2.2.4.3 Phõn tớch mu 37 2.2.4.4 ng dng s liu phõn tớch ỏnh giỏ mc phỏt thi v ỏnh giỏ ri ro 37 2.3 Thc nghim 38 2.3.1 Phng phỏp phõn tớch PBDEs trờn thit b GC-MS v x lớ s liu 38 2.3.1.1 iu kin phõn tớch PBDEs trờn thit b GC-MS 38 2.3.1.2 Tớnh toỏn kt qu phõn tớch bng phng phỏp pha loóng ng v v ni chun 39 2.3.1.3 ỏnh giỏ n nh ca tớn hiu phõn tớch 41 2.3.1.4 Xỏc nh gii hn phỏt hin v gii hn nh lng ca thit b 41 2.3.2 Nghiờn cu qui trỡnh x lớ mu v xỏc nhn giỏ tr s dng ca phng phỏp iv 41 Trang 2.3.2.1 Cỏc thớ nghim vi mu trng 41 2.3.2.2 Cỏc thớ nghim ỏnh giỏ thu hi PBDEs cỏc bc qui trỡnh 42 2.3.2.3 Xỏc nhn giỏ tr s dng ca phng phỏp phõn tớch i vi mu nha 44 2.3.2.4 Xỏc nhn giỏ tr s dng ca phng phỏp phõn tớch i vi mu bi 44 2.3.2.5 Xỏc nh gii hn phỏt hin v gii hn nh lng phng phỏp 45 2.3.3 Phõn tớch mu 45 2.3.3.1 Phõn tớch mu nha 45 2.3.3.2 Phõn tớch mu bi 46 2.3.4 ng dng s liu phõn tớch ỏnh giỏ phỏt thi v ỏnh giỏ ri ro 47 2.3.4.1 ỏnh giỏ mc phỏt thi 47 2.3.4.2 ỏnh giỏ ri ro 47 CHNG KT QU V THO LUN 48 3.1 Kt qu nghiờn cu trờn thit b 48 3.1.1 Sc tng ion v thi gian lu ca cỏc ch tiờu PBDEs 48 3.1.2 Tớnh toỏn h s ỏp ng ca cỏc cht chun 49 3.1.3 n nh ca tớn hiu phõn tớch 51 3.1.4 Gii hn phỏt hin v gii hn nh lng ca thit b 52 3.2 Kt qu nghiờn cu qui trỡnh x lớ mu 53 3.2.1 Kt qu cỏc thớ nghim vi mu trng 53 3.2.2 Kt qu cỏc thớ nghim xỏc nh thu hi 53 3.2.2.1 thu hi ca PBDEs cỏc quỏ trỡnh chit 53 3.2.2.2 thu hi ca PBDEs quỏ trỡnh dch chit bng axit & kim 55 3.2.2.3 thu hi ca PBDEs quỏ trỡnh lm sch dch chit mu bng ct a lp 56 3.2.3 Kt qu xỏc nhn giỏ tr s dng ca qui trỡnh x lớ mu nha 57 3.2.4 Kt qu xỏc nhn giỏ tr s dng ca qui trỡnh x lớ mu bi 60 3.2.5 Xỏc nh gii hn phỏt hin v gii hn nh lng ca phng phỏp 64 v Trang 3.3 Kt qu phõn tớch mu 65 3.3.1 Kt qu phõn tớch hm lng PBDEs mu nha 65 3.3.2 Kt qu phõn tớch hm lng PBDEs mu bi 68 3.4 ng dng s liu phõn tớch c ỏnh giỏ mc phỏt thi v ỏnh giỏ ri ro ca PBDEs 73 3.4.1 ỏnh giỏ mc phỏt thi ca PBDEs t nha bi nh 73 3.4.2 ỏnh giỏ ri ro ca PBDEs i vi sc khe qua hp th bi 75 KT LUN 77 TI LIU THAM KHO 79 PH LC 82 Ph lc 1: V trớ nhúm th v kớ hiu ca 209 ng loi PBDEs 82 Ph lc 2: Ph lc A (Cỏc cht phi loi b) ca Cụng c Stockholm (trớch) 86 Ph lc 3: Gii hn chp nhn c v thu hi v lch chun tng i ca cỏc PBDEs theo Method 1614 ca US EPA 87 Ph lc 4: Mt s sc phõn tớch cỏc PBDEs 88 vi DANH MC CH VIT TT Ch vit tt Ting Anh Ting Vit ABS Acrylonitrile butadiene styrene Nha acrylonitrin butadien styren BFRs Brominated flame retardants Cht chng chỏy h brom Electron ionization Ion húa va p electron Expanded polystyrene Nha polystiren m rng Gas chromatography Mas spectrometry Sc kớ khớ ghộp ni ph MSD Mass spectrometry detector Detector ph NCI Negative chemical ionization Ion húa húa hc õm PBDDs Polybrominated dibenzo dioxins Polybrom dibenzo dioxin PBDEs Polybrominated diphenyl ethers Polybrom diphenyl ete PBDFs Polybrominated dibenzo furans Polybrom dibenzo furan Persistent Organic Pollutants Cỏc cht ụ nhim hu c khú phõn hy ppb Part per billion Nng / hm lng phn t ppm Part per million Nng / hm lng phn triu Restricton of Hazardous Substances Ch th v hn ch cỏc húa cht c hi Selected ion monitoring Ch quan sỏt chn lc ion EI EPS GC-MS POPs RoHS SIM vii DANH MC HèNH Trang Hỡnh 1.1 Cụng thc cu to tng quỏt ca cỏc PBDEs Hỡnh 1.2 C ch hỡnh thnh PBDDs v PBDFs t DecaBDE Hỡnh 1.3 Sc tỏch 40 PBDEs bng sc kớ khớ 24 Hỡnh 3.1 Sc tng ion ca 08 ch tiờu PBDEs v cht ni chun 48 Hỡnh 3.2 So sỏnh thu hi v lch chun tng i ca cỏc PBDEs qui trỡnh phõn tớch mu nha PBDE-N1 v PBDE-N2 58 Hỡnh 3.3 Qui trỡnh PBDE-N1 phõn tớch PBDEs mu nha 59 Hỡnh 3.4 So sỏnh thu hi v lch chun tng i ca cỏc PBDEs qui trỡnh phõn tớch mu bi PBDE-B1, PBDE-B2 v PBDE-B3 61 Hỡnh 3.5 Qui trỡnh PBDE-B1 phõn tớch PBDEs mu bi 63 Hỡnh 3.6 T l phn trm v hm lng ca tng ch tiờu PBDEs so vi hm lng PBDEs tng ca cỏc mu nha 66 Hỡnh 3.7 So sỏnh hm lng PBDEs tng mu nha ca lun vi mt s nghiờn cu tng t ti Nht Bn v Hn Quc 67 Hỡnh 3.8 T l phn trm v hm lng ca tng ch tiờu PBDEs so vi hm lng PBDEs tng ca cỏc mu bi 70 viii DANH MC BNG Trang Bng 1.1 Phõn loi PBDEs theo s nguyờn t brom phõn t Bng 1.2 Cụng thc, tờn gi v kớ hiu ca mt s PBDEs Bng 1.3 Tớnh cht vt lý ca mt s PBDEs Bng 1.4 Tớnh cht vt lý ca mt s PBDEs thng mi Bng 1.5 Mt s liu lng v nng gõy c ca PBDEs Bng 1.6 Thnh phn ca mt s PBDEs thng mi v phng phỏp húa hc tng 10 hp mt s nhúm PBDEs Bng 1.7 Lng PBDEs thng mi tiờu th trờn th trng nm 2001 11 Bng 1.8 ng dng ca PBDEs cỏc loi vt liu 12 Bng 1.9 ng dng ca cỏc vt liu cú s dng cht chng chỏy PBDEs 13 Bng 1.10 iu kin x lớ mu nha cho phõn tớch PBDEs 20 Bng 1.11 iu kin x lớ mu bi cho phõn tớch PBDEs 22 Bng 1.12 iu kin tỏch cỏc PBDEs bng sc kớ khớ 25 Bng 1.13 iu kin phõn tớch cỏc PBDEs bng detector ph 27 Bng 2.1 Cỏch chun b nn mu gi, cỏc dung dch v ct lm sch dch chit 30 Bng 2.2 Thụng tin cht chun s dng nghiờn cu phõn tớch PBDEs 31 Bng 2.3 Cỏch chun b v mc ớch s dng ca cỏc dung dch chun PBDEs 32 Bng 2.4 Thụng tin v mu nha v mu bi nghiờn cu lun 35 Bng 2.5 iu kin tỏch v phõn tớch cỏc PBDEs bng GC-MS 38 Bng 3.1 Thi gian lu sc kớ ca cỏc 08 ch tiờu PBDEs v cht ni chun 49 Bng 3.2 H s ỏp ng ca cht chun thng i vi cht chun ỏnh du ng v 49 Bng 3.3 H s ỏp ng ca cht chun ỏnh du ng v i vi cht ni chun 50 Bng 3.4 lch chun tng i ca din tớch pic sc kớ phõn tớch lp li ln dung dch chun CS10 v CS500 51 Bng 3.5 Gii hn phỏt hin v gii hn nh lng ca thit b i vi cỏc PBDEs 52 ix Trang Bng 3.6 thu hi ca PBDEs cỏc quỏ trỡnh chit 54 Bng 3.7 thu hi ca PBDEs quỏ trỡnh dch chit bng axit v kim 55 Bng 3.8 thu hi ca PBDEs quỏ trỡnh lm sch dch chit mu bng ct silicagel a lp 56 Bng 3.9 thu hi v lch chun tng i ca cỏc PBDEs qui trỡnh phõn tớch mu nha PBDE-N1 v PBDE-N2 58 Bng 3.10 thu hi v lch chun tng i ca cỏc PBDEs qui trỡnh phõn tớch mu bi PBDE-B1, PBDE-B2, PBDE-B3 61 Bng 3.11 Gii hn phỏt hin v gii hn nh lng ca phng phỏp i vi cỏc PBDEs cho mu nha v mu bi 64 Bng 3.12 Kt qu phõn tớch hm lng PBDEs mu nha (ng/g) 65 Bng 3.13 Kt qu phõn tớch hm lng PBDEs mu bi (ng/g) 68 Bng 3.14 Hm lng PBDEs mu bi nh ca mt s nghiờn cu khỏc 72 x M U Sc khe ngi ang b e da bi cỏc cht ụ nhim hu c khú phõn hy (POPs) phỏt thi vo mụi trng t cỏc hot ng sn xut cụng nghip, canh tỏc nụng nghip v phỏt sinh khụng ch nh Cỏc hp cht ny rt c hi, bn vng mụi trng, d phỏt tỏn v cú kh nng tớch t sinh hc cao Hng ti mc tiờu qun lớ an ton, gim phỏt thi v loi b hon ton cỏc cht POPs mụi trng, nm 2004 mt cụng c quc t l Cụng c Stockholm v cỏc cht ụ nhim hu c khú phõn hy (sau õy gi tt l Cụng c Stockholm) chớnh thc cú hiu lc nhiu quc gia, ú cú Vit Nam Polybrom diphenyl ete (PBDEs) l mt nhúm cỏc hp cht c brom, bao gm 209 ng loi, c sn xut v s dng rng rói t nhng nm 1970 cỏc ngnh cụng nghip in v in t, xõy dng, giao thụng ti, dt, sn xut gia dng, lm cht chng chỏy cho polyme, m, vi,Cỏc PBDEs cú c im chung l d bay hi nờn chỳng cú th phỏt tỏn t ngun phỏt thi (cỏc sn phm cụng nghip cú cha PBDEs) mụi trng tip nhn (mụi trng khụng khớ, bi, t, nc, trm tớch, sinh vt, ngi) Cỏc cht ny cú th phỏt thi mụi trng c cỏc sn phm cha chỳng ang c s dng v c bit l cỏc hot ng thi b, tỏi ch, tiờu hy cỏc sn phm ó ht thi gian s dng Cỏc PBDEs ó c chng minh l cú nh hng xu n cỏc chc nng ni tit c th ngi v cỏc vt nuụi nh, liờn quan ti mt lot cỏc v sc khe nh suy gim trớ nh, kh nng nhn thc v sc dch, ng thi gõy d tt h sinh sn, bnh ung th Do tỏc ng c hi ca PBDEs i vi h sinh thỏi l rt nghiờm trng cỏc cht ny li c s dng rt ph bin, nm 2009 Cụng c Stockholm ó a mt s nhúm PBDEs cú s nguyờn t brom cao (bao gm cỏc nhúm TetraBDEs, PentaBDEs, HexaBDEs, HeptaBDEs vi s nguyờn t brom t n 7) vo danh sỏch cỏc cht POPs b cm s dng Vit Nam l mt nhng quc gia u tiờn tham gia Cụng c Stockholm v ang n lc thc hin cỏc k hoch quc gia bo v mụi trng cng nh sc khe ngi trc s e da nghiờm trng ca cỏc cht POPs núi chung v cỏc PBDEs núi riờng Tuy nhiờn, vic gii bi toỏn kim soỏt, gim thiu, loi b PBDEs Vit Nam cũn rt nhiu khú khn, nh cụng c phỏp lớ cha hon chnh, s thiu thn c s d liu thc t, cỏc hot ng tiờu hy, tỏi ch din t phỏt, ý thc ca ngi dõn v mc 11 nguy him ca cỏc PBDEs cha c thc tnh,v nht l nng lc phõn tớch cỏc PBDEs ti cỏc phũng th nghim cũn hn ch Chỳng tụi hng n vic nghiờn cu qui trỡnh phõn tớch cỏc PBDEs cỏc i tng l nha cỏc thit b in, in t v bi nh, õy l cỏc i tng phõn tớch tng i mi v cha c quan tõm nhiu cỏc nghiờn cu trc õy ti Vit Nam Phng phỏp phõn tớch c chỳng tụi s dng l phng phỏp sc kớ khớ ph phõn gii thp, nh lng bng phng phỏp pha loóng ng v v ni chun, õy l phng phỏp cú nhy, chớnh xỏc cao dựng cho phõn tớch lng vt v siờu vt cỏc cht hu c nn mu phc tp, c dựng lm phng phỏp tiờu chun ca cỏc c quan mụi trng hng u trờn th gii nh USEPA S liu phõn tớch hm lng PBDEs i tng i din cho ngun phỏt thi v mụi trng tip nhn c dựng tớnh toỏn h s phỏt thi, qua ú khụng ch ỏnh giỏ c mc ụ nhim mụi trng m cũn gúp phn kim soỏt cỏc hot ng sn xut, tỏi ch nha ang phỏt trin mt cỏch t phỏt hin ti mt s lng ngh th cụng nghip bc Vit Nam nh Hi Phũng, Hng Yờn, H Ni, Lun thc s khoa hc vi ti Nghiờn cu phõn tớch v ỏnh giỏ hm lng cỏc polybrom diphenyl ete nha v bi ti mt s khu tỏi ch rỏc thi in t c thc hin nhm mc ớch úng gúp mt phn vo cụng tỏc bo v mụi trng, mt xu hng mang tớnh thi i ca khoa hc núi chung v ngnh húa hc phõn tớch núi 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Sakai (2006) Leaching characteristics of polybrominated diphenyl ethers (PBDEs) from flame-retardant plastics Chemosphere, 65, 506-513 [19] Anthony F Lagalante, Courtney S Shedden, Peter W Greenbacker (2011) Levels of polybrominated diphenyl ethers (PBDEs) in dust from personal automobiles in conjunction with studies on the photochemical degradation of decabromodiphenyl ether (BDE-209) Environment International,... qu phõn tớch hm lng PBDEs trong mu nha (ng/g) 65 Bng 3.13 Kt qu phõn tớch hm lng PBDEs trong mu bi (ng/g) 68 Bng 3.14 Hm lng PBDEs trong mu bi trong nh ca mt s nghiờn cu khỏc 72 x M U Sc khe con ngi ang b e da bi cỏc cht ụ nhim hu c khú phõn hy (POPs) phỏt thi vo mụi trng t cỏc hot ng sn xut cụng nghip, canh tỏc nụng nghip v phỏt sinh khụng ch nh Cỏc hp cht ny rt c hi, bn vng trong mụi trng, d phỏt tỏn... cụng c quc t l Cụng c Stockholm v cỏc cht ụ nhim hu c khú phõn hy (sau õy gi tt l Cụng c Stockholm) chớnh thc cú hiu lc nhiu quc gia, trong ú cú Vit Nam Polybrom diphenyl ete (PBDEs) l mt nhúm cỏc hp cht c brom, bao gm 209 ng loi, c sn xut v s dng rng rói t nhng nm 1970 trong cỏc ngnh cụng nghip in v in t, xõy dng, giao thụng vn ti, dt, sn xut gia dng, lm cht chng chỏy cho polyme, m, vi,Cỏc PBDEs cú... tớch cỏc PBDEs trong cỏc i tng l nha trong cỏc thit b in, in t v bi trong nh, õy l cỏc i tng phõn tớch tng i mi v cha c quan tõm nhiu trong cỏc nghiờn cu trc õy ti Vit Nam Phng phỏp phõn tớch c chỳng tụi s dng l phng phỏp sc kớ khớ khi ph phõn gii thp, nh lng bng phng phỏp pha loóng ng v v ni chun, õy l phng phỏp cú nhy, chớnh xỏc cao dựng cho phõn tớch lng vt v siờu vt cỏc cht hu c trong nn mu phc... PBDEs trong 2 i tng i din cho ngun phỏt thi v mụi trng tip nhn c dựng tớnh toỏn h s phỏt thi, qua ú khụng ch ỏnh giỏ c mc ụ nhim mụi trng m cũn gúp phn kim soỏt cỏc hot ng sn xut, tỏi ch nha ang phỏt trin mt cỏch t phỏt hin nay ti mt s lng ngh th cụng nghip min bc Vit Nam nh Hi Phũng, Hng Yờn, H Ni, Lun vn thc s khoa hc vi ti Nghiờn cu phõn tớch v ỏnh giỏ hm lng cỏc polybrom diphenyl ete trong. .. ix Trang Bng 3.6 thu hi ca PBDEs trong cỏc quỏ trỡnh chit 54 Bng 3.7 thu hi ca PBDEs trong quỏ trỡnh ra dch chit bng axit v kim 55 Bng 3.8 thu hi ca PBDEs trong quỏ trỡnh lm sch dch chit mu bng ct silicagel a lp 56 Bng 3.9 thu hi v lch chun tng i ca cỏc PBDEs trong 2 qui trỡnh phõn tớch mu nha PBDE-N1 v PBDE-N2 58 Bng 3.10 thu hi v lch chun tng i ca cỏc PBDEs trong 3 qui trỡnh phõn tớch mu bi... 20-31 [2] Athanasios Besis, Constantini Samara (2012) Polybrominated diphenyl ethers (PBDEs) in the indoor and outdoor environments A review on occurrence and human exposure (Review) Environmental Pollution, 169, 217-229 [3] Bieniek D., Bahadir M., Korte F (1989) Formation of heterocyclic harzadous compounds by thermal degradation of organic compounds Heterocycles, 28, 719-722 [4] Burcu Binici, Mine Bilsel,... 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