NGI TIU DNG Chu PhmNgc Sn, PhmTh nh, Dip Ngc Sng Hi Hahc TP H Ch Minh CngtyDch v KHCN Sc KHi ng HI THO BAO B V AN TON THC PHM- 04/03/2014 Bao b thc phm, thc ung, gi chung l thc phm, c nhimv: bo v thc phm i vi nhng bin i l, hahc, sinhhc ca mi trng bnngoi gi c luthc phm khngb hng, giplu thngphnphi trong nc vgia ccnc thc phm cnnguynvn khi n tayngi tiudng. Mt khc, iu cc k quantrng lchnhbaob phi gi nguyn c cc c trng dinh dng v cmquan ca thc phm, phi bo m thc phm an ton, khngc gyratrongthc phm cha trongbaob nhng bin i dnh, khhay khngpht hin c bng gicquan thngthng, nhng cth nh hng xu n sc khe ngi tiudng. Nhiu loi bao b thc phm hin ang c s dng: * hp carton * ccvt cha bng nha, bng thy tinhhay kimloi, * ccmngbc bng giy trngnha hay bng nha, c nguy c thi nhim ha cht vo thc phm cha, mc thi nhim ty theo: * bn cht ca baob, * bn cht ca thc phm, *hmlng cht thi nhim trongnn baob * iu kin lu tr, * cchthc chun b, ch bin thc phm * cchs dng. Mt s ha cht ny c kh nng tch ly lu di trong c th ngi thng qua dy chuyn thc phm v c nguy c gy ng c mn tnh thng thng rt kh lng trc c Bo co ny s cp n: ccbaob thc phm bng nha hin ang c s dng ph bin trongnc : * polyethylene, polypropylene (cc loi bao b, * polystyrene ( Hp xp polystyrene, hp cha cng, nh loi expanded polystyrene ) * polyvinyl chloride (hp, nha trong bc thc phm, giy tm nha gi ph mai , b), * Polycarbonate (chai sa cho tr con) , * polyethylene terephthalate, (chai l cho thc ung) * nha melamin (chn a hp cha, khay cha) * giy bc trng nha, * cc mng bc nha loi PVC c cht ha do) ng quan tmnhiu nht l: polystyrene, PVC, polycarbonate, melamine, PET nhng hacht cth thi nhim vothc phm, *cch o t, nh gi mc thi nhim cho tng cht hoc tng mc thi nhim theo cc tiu chun quc t v Vit Nam * nhng cch thc s dng sao cho mc thi nhimnu c phi di mc cho php, mbo an ton cho ngi tiu dng. Cc ha cht thi nhim t bao b: -hp xp polystyrene thi ra toluene, ethylbenzene, xylenes, styrene - bao b PVC, cc mng bc PVC c th thi ra DEHP hay DEHA, DINP, nu cc cht ny c s dng lmcht ha do cho nha - bao b polycarbonate c th thi ra monomer Bisphenol A, diphenyl carbonate cha phn ng, mi quan tm ln hin nay l cc bnh sa cho tr con. - nha melamine-formaldehyde c th thi ra melamine hay/v formaldehyde cha kp phn ng v b nht trong nn nha - PET c th thi ra acid terephthalic v phn no acid isophthalic Ngoi ra cn lu n cc kimloi nng c th thi ra t bao b ti ch, bao b c cht n lmc. MI NGUY HIM CA CC HA CHT THI VO THC PHM *Ni chung, cc cht thi vo thc phm thng khng nhiu c th gy ng c cp tnh. *iu ng quan tm l kh nng tich ly lu di ca cc ha cht ny, c th gy ng c mn tnh thng l nguy him, kh lng trc c. Tc nhin ng c mn tnh cn ty thuc c a ca ngi b nhim. *Styrene, Ethylbenzene tich ly c th. gy ung th cho ngi, IARC xp vo loi 2B *DEHA cng nh DEHP, mt s phthalate khc c th gy ri lon h thng ni tit, gy c ch c quan sinh sn nam gii v gy dy th sm n gii. V kh nng gy ung th th IARC xp vo hng 3 tc khng c bng chng gy ung th cho ngi. Phi nhim lin tc c th lm tn thng gan. Bisphenol A c th nh hng xu n kh nng sinh sn ca c nam v n, lm thay i chc nng ca h min dch, gy ri lon hnh vi v kh nng nhn thc. V lu di, n c th gy tn thng no b, gy ra cn bnh Alzheimer v mt s bnh ung th *Melamine s gy sn thn nu c s hin din ca acid cyanuric, formaldehyde lu di c th gy ung th , lm tn thng h h hp, *Kim loi nng cng l mt mi nguy him cho sc khe NHNG QUY NH CA VIT NAM V CC NC NGOI LIN QUAN N S THI NHIM HA CHT T BAO B THC PHM Nhn chung nhng quy nh ca Vit Nam v mc thi nhim ca bao b vo thc phm c nhiu im tng ng vi quy nh quc t. *Quy chun k thut quc gia QCVN 12-1:2011/BYTquy nh nhng yu cu k thut v qun l v v sinh an ton i vi bao b, dng c bng nha tng hp tip xc trc tip vi thc phm. *Quy chun k thut quc gia QCVN 12-2:2011/BYTquy nh nhng yu cu k thut v qun l v v sinh an ton i vi bao b, dng c bng cao su tip xuc trc tip vi thc phm. *Quy chun k thut quc gia QCVN 12-3:2011/BYTquy nh nhng yu cu k thut v qun l v v sinh an ton i vi bao b, dng c bng kimloi tip xc trc tip vi thc phm V nguyn tc nh gi mc an ton ca mt bao b thc phm, nn tin hnh 2 bc: *Th trnvt liu: xc nh hm lng cc cht c th thi nhimtrong nn nha * o trn thc phm (hay mt nn mu c c tnh tng ng vi thc phm cha): mc thi nhim ca cht theo quy nh. Th vt liu Th thi nhim Ch tiu kim tra Vit Nam Hn Quc Ch tiu kim tra Vit Nam Hn Quc Tng s cht bay hi (styrene, toluene, ethylbenzene, n-propylbenzene) 5mg/g 5mg/g Cn kh 240 g/mL (heptane) 240 g/mL (heptane) Polystyrene trng n (dng cha nc si) 2 mg/g 2 mg/g 30 g/L (Ethanol 20%, Nc, acid acetic 4%) 30 g/mL Styrene v Ethylbenzene 1 mg/g 1 mg/g Ch 100 g/g - 1mg/L (acid acetic 4%) 1mg/L Lng KMnO4 s dng 10 mg/L 10 mg/L SO SNH TIU CHUN V BAO B POLYSTYRENE CA VIT NAM V HN QUC CCH NH GI MC AN TON CA BAO B THC PHM V MT S KT Qu V phn tch cc bao b plastic , cc labo kimnghimda trn: *quy chun k thut quc gia QCVN 12-1:2011/BYT *mt s ti liu nc ngoi nh FDA M, i Loan, Hn quc chng hn. Phng php phn tch: *Sc k kh/u d FID, Sc k kh ghp khi ph, GC-MS, GC-MS/MS, Sc k lng ghp khi ph LC-MS, LC-MS/MS c s dng nhiu cho cht thi nhimhu c, *Phng php so mu, quang ph hp thu nguyn t, ICP-OES, ICP-MS thng c dng cho kimloi nng ch, Cd. O MC THI NHIM T BAO B THC PHM i vi khu ny, l ra nn o mc thi nhimvo mt thc phm xc nh th mi nh gi ng c v mc thi nhim vo thc phm y. Nh nu trn, mc thi nhimph thuc vo nhiu yu t: nn thc phm, nn nha, hmlng cc cht c th thi nhimnmtrong nn nha, hmlng monomer cn tn ng, nhit , thi gian tip xc ca thc phmvi bao b. Tuy nhin th nh vy th va phc tp, va kh quy nh chung mc thi nhim ti a cho php. Do ngi ta thng dng mt mi trng ph hp c nhng c tnh chung ca thc phm(simulants): *i vi thc phmt bo nhiu nc c th dng nc hay dung dch nc 20% Ethanol trong 30 pht 60 o C. * Vi thc phmnhiu bo c th dng n-heptane 25 o C trong 1 gi. CC DUNG DCH SIMULANT THEO DIRECTIVE 97/48/EC ngy 29/7/1997 Loi thc phm Dung dch Simulant Gi tt Thc phm c nc pH > 4,5 Nc ct Simulant A Thc phm c nc c tnh acid pH 4,5 Acid acetic 3% trong nc Simulant B Thc phm c cn Ethanol 10% trong nc Simulant C Thc phm bo Du oliu hay simulant khc cho thc phm bo Simulant D Thc phm kh Cha c Thi gian d kin bao b tip xc thc phm Thi gian th thi nhim Nhit tip xc khi s dng Nhit th thi nhim t 5 pht 5 pht T 5 o C 5 o C 5 pht < t 0,5 gi 0,5 gi 5 o C < T 20 o C 20 o C 0,5 gi < t 1 gi 1 gi 20oC < T 40oC 40oC 1 gi < t 2 gi 2 gi 40 o C < T 70 o C 70 o C 2 gi < t 4 gi 4 gi 70 o C < T 100 o C 100 o C hay T hon lu 4 gi < t 24 gi 24 gi 100 o C < T 121 o C 121 o C t > 24 gi 10 ngy 121 o C < T 130 o C 130oC 130 o C < T 150 o C 150 o C* T > 150oC 175 o C* THEO DIRECTIVE 97/48/EC *Ch s dng cho simulant D. Vi simulant A, B, C, c th o thi nhim nhit hon lu vi thi gian = 4 ln thi gian 100 o C hay nhit hon lu ca simulant SIMULANT TNG NG VI D CHO THC PHM BO THEO 97/48/EC CC DUNG DCH SIMULANT THEO EU 10/2011 Simulant A : Ethanol 10% (v/v) choccthc phmcnc Simulant B: acid acetic 3% (w/v) choccthc phmctnhacid Simulant C: Ethanol 20% (v/.v) choccthc phmccn Simulant D1: Ethanol 50% (v/v) chothc phm bo Simulant D2: du thc vt choccthc phmbo Simulant E: Tenax PPPO [ poly(2,6-diphenyl-p-phenylene) oxide] , 60-80 mesh, l xp 200 nm cho cc thc phm kh Cc vt dng cha mi loi thc phmth nn th thi nhimvi A, B, Thi gian d kin bao b tip xc thc phm Thi gian th thi nhim Nhit tip xc khi s dng Nhit th thi nhim t 5 pht 5 pht T 5 o C 5 o C 5 pht < t 0,5 gi 0,5 gi 5 o C < T 20 o C 20 o C 0,5 gi < t 2 gi 2 gi 20 o C < T 40 o C 40 o C 2 gi < t 6 gi 6 gi 40 o C < T 70 o C 70 o C 6 gi < t 24 gi 24 gi 70 o C < T 100 o C 100 o C hay T hon lu 1 ngy < t 3 ngy 3 ngy 100 o C < T 121 o C 121 o C * 3 ngy < t 30 ngy 10 ngy 121 o C < T 130 o C 130 o C* Trn 30 ngy iu kin ring 130 o C < T 150 o C 150 o C* 150 o C < T 175 o C 175 o C* T > 175 o C iu chnh T = T tip xc thc vi thc phm THEO EU 10/2011 *Ch s dng cho simulant D2 v E. Trng hp th di p sut cao, c th thc hin nhit ghi. Vi simulant A, B, C, D, c th o thi nhim nhit hon lu vi thi gian = 4 ln thi gian 100oC hay nhit hon lu ca simulant Th thi nhim Ch tiu kimtra iu kin ngmthi Dung dch ngmthi Gii hn ti a Cn kh 25oC, 1 gi Heptane (3) 30g/mL 60oC, 30 pht Ethanol 20 % (4) 30g/mL 60oC, 30 pht (7) Nc (5) Acid acetic 4% (6) TRNG HP BAO B PE V PP (3) pdng chothc phm bo, du n (4) pdng chothc ung ccn (5) pdng chothc phm cnc cpH >5 (6) pdng chothc phm cnc cpH 5 Th vt liu Th thi nhim Ch tiu kim tra Gii hn ti a Ch tiu kim tra iu kin ngm thi Dung dch ngm thi Gii hn ti a Tng s cht bay hi (styrene, toluene, ethylbenzene, n-propylbenzene) 5mg/g Cn kh 25 o C, 1 gi Heptane (3) 240 g/mL Polystyrene trng n (dng cha nc si) 2 mg/g 60 o C, 30 pht Ethanol 20 % (4) 30 g/mL Styrene v Ethylbenzene 1 mg/g 60 o C, 30 pht (7) Nc (5) Acid acetic 4% (6) TRNG HP POLYSTYRENE (3) pdng chothc phmbo, du n (4) pdng chothc ung ccn (5) pdng chothc phm cnc cpH >5 (6) pdng chothc phmcnc cpH 5 (7) pdng chovt cha c s dng nhit >100 o C, iu kin ngmthi l95 o C, 30 pht Th vt liu Th thi nhim Ch tiu kim tra Gii hn ti a Ch tiu kim tra iu kin ngm thi Dung dch ngm thi Gii hn ti a Vinyl chloride 1g/g Cn kh 25 o C, 1 gi Heptane (3) 150 g/mL Cresyl phophate 1g/g 60 o C, 30 pht Ethanol 20% (4) 30 g/mL Hp cht dibutyl thic 50 g/g 60 o C, 30 pht Nc (5) Acid acetic 4% (6) (3) pdng chothc phmbo, du n (4) pdng chothc ung ccn (5) pdng chothc phm cnc cpH >5 (6) pdng chothc phm cnc cpH 5 TRNG HP BAO B PVC Th thi nhim Ch tiu kimtra iu kin ngm thi Dung dch ngm thi Gii hn ti a Caprolactam 60 o C, 30 pht Ethanol 20% (4) 15 g/mL Cn kh 25 o C, 1 gi Heptane (3) 30 g/mL 60 o C, 30 pht Ethanol 20% 60 o C, 30 pht Nc (5) Acid acetic 4% (6) (3) pdng chothc phmbo, du n (4) pdng chothc ung ccn (5) pdng chothc phm cnc cpH >5 (6) pdng chothc phm cnc cpH 5 TRNG HP BAO B NYLON TRNG HP POLYCARBONATE Th thi nhim Ch tiu kimtra iu kin ngm thi Dung dch ngm thi Gii hn ti a Antimony 60 o C, 30 pht (7) Acid acetic 4 % 0,05 g/mL Germanium 0,1 g/mL Cn kh 25 o C, 1 gi Heptan (3) 30 g/mL 60 o C, 30 pht Ethanol 20 % (4) 60 o C, 30 pht (7) Nc (5) Acid acetic 4 % (6) TRNG HP NHA PET (3) pdng chothc phmbo, du n (4) pdng chothc ung ccn (5) pdng chothc phm cnc cpH >5 (6) pdng chothc phmcnc cpH 5 (7) pdng chovt cha c s dng nhit >100 o C, iu kin ngmthi l95 o C, 30 pht TRNG HP NHA MELAMINE FORMALDEHYDE, PHENOL-FORMALDEHYDE Th thi nhim Ch tiu kimtra iu kin ngmthi Dung dch ngmthi Gii hn ti a Phenol 60 o C, 30 pht Nc 5 g/mL Formaldehyde m tnh Cn kh 25 o C, 1 gi Heptane 30 g/mL 60 o C, 30 pht Ethanol 20 % 60 o C, 30 pht Nc Acid acetic 4% i vi mng bc PVC c cha DEHA, DEHP th nn lm3 php o: * Th vt liu: o DEHA, DEHP trongmngbc, * o thi nhim 2 trng hp: - thi nhim trongethanol 20% 60 o C trong30 pht theo t l 1cm 2 mu mng bc/2ml dung dch (o mt mt thi nhim) i vi thc phm nhiu nc - thi nhim trongn-heptan 25 o C trong1 gi theo t l 1cm 2 mu mng bc/2ml dung dch (o mt mt thi nhim) i vi thc phm bo, du n *Lu l mt s nc nh Chu u, Hn quc DEHP v DEHA b cms dng trong bao b thc phm ngoi tr trng hp chc chn l khng c thi nhim vo thc phm . Di-n-butyl phthalate, benzyl-n-butyl phthalate, bisphenol A khng c s dng sn xut bnh sa , k c nm ngm theo FDA Hn Quc. *Theo Commision Regulation (EU) No 10/2011 ngy 14/1/2011: SML(DEHP): 1,5 mg/kg thc phm hay simulant SML(DEHA): 18 mg/kg thc phm hay simulant SML(DBP): 0,3 mg/kg thc phm hay simulant SML(BBP): 30 mg/kg thc phm hay simulant THI NHIM DEHP, DEHA T MNG BC PVC THI NHIM KIM LOI NNG T BAO B NHA VO THC PHM Trong tt c trng hp: Th vt liu Th thi nhim Ch tiu kim tra Gii hn ti a Ch tiu kim tra iu kin ngm thi Dung dch ngm thi Gii hn ti a Ch 100g/g Kim loi nng 60 o C, 30 pht (7) Acid acetic 4% 1g/mL Cadmium 100g/g Lng KMnO 4 s dng Nc 10 g/mL MT S KT QU PHN TCH BAO B NHA TI CNG TY SC K HI NG Cht thi nhim Bao b Th vt liu Gii hn ti a Th thi nhim Gii hn ti a Styrene, ethylbenzene, xylenes, toluene Hp xp polystyrene 83-215 mg/kg 5000 mg/kg Bisphenol A Bnh sa 0,5-1,5 g/L 2500 g/L DEHP Giy trng nha gi b, ph mai 15-218 g/kg 2500 g/kg KT QU PHN TCH MT S BAO B THC PHM Cc bao b phn tch u t cht lng, mc thi nhim u di mc cho php. Lu l hmlng bisphenol A thi nhim cc k xa di mc cho php. M Canada cho rng hmlng ny rt nh v do khng c kh nng gy hi cho sc khe emb. Tuy nhin Chu u cms dng bis phenol A trong sn xut bnh sa cho emb (Commission Regulation (EU) 321/2011 ngy 1/4/2011). Kt qu phn tch caprolactamtrong 50 mu thc phm c bo cha trong bao b polyamide (Nylon 6) bng LC-MS Vin Quc gia v Sc khe ca M cho thy 9/50 mu c nhimcaprolactam mc 2,8- 13 mg/kg, di gii hn ti a cho php l 15 mg/kg. Chn mu thc phm c pht hin caprolactam u cha trong bao b nylon c hp nng. (Bradley E.L. et al, Food Addit Contam, 2004, 21(12), 1179-1185). Mt th nghimkhc phn tch s thi nhimvo ethanol 95% (simulant c php dng thay th cho du oliu hay n-heptane theo European Directive 97/48/EC ngy 29/7/1997) 60 o C trong 310 pht ca 40 mu bao b nylon dng cha thc phmbo nh xc xch, c g, pate) cho thy i a s u thi nhimcaprolactam, trong c 15 mu vt qu mc cho php 15 mg/L (17-29,7 mg/L) DEHA TRONG MNG BC THC PHM PVC Ngy 29/7/2013, Bo mng Tn Hoa X, Nhn dn ca Trung Quc a tin Knh truyn hnh CCTV cho bit mng bc bo qun thc phm PVC ti Trung Quc c cha cht do cm s dng l diethyl hexyl adipate (DEHA). Theo CCTV, Trung tm t vn k thut bo v mi trng Bc Kinh ly 16 mu mng bo qun PVC t cc siu th ca Bc Kinh, Thng Hi, Qun Chu kim nghim. Kt qu kim trachothy co 15/16 loi ccha cht do cm s dng lDEHA. Trong o, mc thp nht vt ngng chophp0,05% 98 ln, caonht vt ngng 472 ln (tnhra236 gram/kg mngPVC), bnhqunvt ngng gp 200%. S mu phn tch S mu pht hin Th vt liu Gii hn ti a Th thi nhim Gii hn ti a 6 5 7,2 - 28,1 % 0,05 % 12 10 0,12 1,52 mg/L (EtOH 20%, 60oC, 30 pht) 18 mg/L 12 10 33 117 mg/L (heptane, 25oC, 1 gi) 18 mg/L KT QU PHN TCH DEHA TRONG MT S MNG BC THC PHM Kt qu trn ch c tnh thamkho, khng c tnh i din (s mu o qu t), tuy nhin cng cho thy c th s dng cc mng bc ny cho cc thc phm nhiu nc, nhng phi tht d dt khi s dng cho cc thc phm nhiu bo, nht l thc phmnng VI NGH *Nhin chung nn hn ch dng bao b nha do cha hay gi thc phm nng, nht l thc phmnhiu bo. *Hn ch bc thc phmnhiu bo bng mng mng PVC, nht l khi hm nng hay ch bin trong l vi sng. *Hn ch cha thc phm trong cc chn bt bng nha melamine-formaldehyde, chai l bng polycarbonate hm nng trong l vi sng. *Tuy mt s bnh sa polycarbonate bn trn th trng c phn tch c mc thi nhim di xa mc cho php , m bo tht an ton cho em b, dng bnh thy tinh hoc bnh polypropylene th tt hn. Nhiu nghin cu cho thy hm lng thi nhim tng vi thi gian s dng bnh do s lo ha (SML theo EU 10/2011 l 0,6 mg/kg ) *Cng nn d dt khi dng bao b PET hay polycarbonate cha thc n chua (c tnh acid) hmnng v polymer c th b thy phn acid di tc dng nhit lm tng mc thi nhim bis phenol A hay acid terephthalic vo thc phm. *i vi nh sn xut, khng dng nha ti ch sn xut bao b thc phm do nguy c c tp cht c th nh hng xu n sc khe. Vi nha ti ch, qu trnh ch bin to ra nha c cht lng km, c th cha nhiu monomer d thi nhimvo thc phm. *Ngi tiu dng ch nn s dng mt ln bao b thc phm. THNH THT CM N