MC LC

A. B. M U ........................................................................................................... 1 NI DUNG ....................................................................................................... 3 1. THUC BO V THC VT H CARBAMATE V TNH HNH TN D HA CHT BO V THC VT TRONG RAU QU ................... 3 1.1. 1.2. 1.3. Thuc bo v thc vt h carbamate ...................................................... 3 Cc Hot Cht Thuc Tr Su Nhm Carbamate [4] ............................ 4 Tnh hnh tn d ha cht bo v thc vt trong rau qu .................... 10

2. XC NH D LNG THUC BO V THC VT H CARBAMATE C TRONG RAU QU ........................................................... 12 2.1 2.2 2.3 Quy trnh ly mu ................................................................................. 12 Chun B Mu ...................................................................................... 21 Mt S Phng Php Phn Tch D Lng Carbamate ...................... 23

2.4 Dng C , Ha Cht , Thit B V Quy TrnhTin Hnh Xc nh D Lng Thuc Bo V Thc Vt H Carbamate ............................................. 25 C. D. KT LUN ..................................................................................................... 34 TI LIU THAM KHO ............................................................................... 35 A. M U Thi gian gn y tnh trng thc phm nhim d lng thuc bo v thc vt qu mc cho php vn ang din ra ht sc nghim trng. Nhiu v ng c thc phm xy ra hng lot, c xc nh c lin quan n d lng thuc bo v thc vt c trong rau, c, qu. Khng ch dng li mc gy ng c, d lng thuc bo v thc vt cn li trong rau qu cn c nghi ng l c nhng mi nguy ln nh kh nng gy ung th hay t bin gen. Do , vic xc nh d lng thuc tr su cn li trong rau qu l vic lm ht sc cn thit xc nh mc an ton ca rau v ngn chn nh hng trn ngi, ng vt v

mi trng sng. Mt trong nhng nhm thuc bo v thc vt c s dng rt ph bin hin nay l thuc tr su h Carbamate (CBM). Thuc tr su h Carbamate l loi thuc tr su thng mi c hiu qu cao, c dng nhiu trong nng nghip nh l thuc tr su, tr c, tr nm,.... C hn 50 loi CBM c bit ti phn ln l t tng hp, c s dng kh ph bin trong nng nghip t nhng nm 1960 nh tc dng c trn cn trng cao. Tnh trng thc phm nhim d lng thuc bo v thc vt qu mc cho php din ra ht sc nghim trng. Nhiu v ng c thc phm hng lot xy ra, c xc nh c lin quan n d lng thuc bo v thc vt c trong rau, c, qu. Carbamate (CBM) l nhm thuc bo v thc vt rt ph bin. Nhng thuc tr su h Carbamate c s dng thay th cho nhng loi thuc tr su cha Clo nh DDT hay cha phosphor, bi CBM khng bn, d b phn hy di tc ng ca mi trng. Tuy nhin, thuc tr su hc Carbamate c nghi ng l c kh nng gy ung th v t bin gen bi chng cng l nhng cht gy c ch enzyme acetylcholinesterase. CBM a s l nhng cht c i vi con ngi c xp vo nhm c I hoc II l nhng cht c v cc c theo tiu chun Vit Nam. Vic tng s dng thuc tr su h Carbamate t ra vn v nguy c i vi ngh trng rau m mi trng sng ca con ngi. Vi cc mu rau qu c sn, vn l ta i tm cc quy lut xc nh lng thuc bo v thc vt h carbamate cn d gip chng ta c th la chn c nhng mu rau qu t tiu chun ng thi d c hng gii quyt v vn ng c thc phm do h thuc ny gy nn nhiu. Cng mc ch quy m nh, nhm chng em a ra cch xc nh d lng thuc h carbamate cn d trong rau qu gp phn lm gim nhng trng hp ng c cng nh lng thuc d tha cn tch t trong c th con ngi chng ta. V cng chnh l ti ma nhm chng em thc hin XC NH D LNG THUC BO V THC VT H CARBAMATE CN D TRONG RAU QU.

B. NI DUNG 1. THUC BO V THC VT H CARBAMATE V TNH HNH TN D HA CHT BO V THC VT TRONG RAU QU
1.1.

Thuc bo v thc vt h carbamate

gia tng nng xut, con ngi thc hin nhiu bin php ci tin k thut nh s dng ging mi, phn bn, thc hin ng k thut Yu t bo v ma mng trnh s h hi do cn trng gy ra l iu khng th thiu. con ngi nghin cu nhiu bin php tiu dit cn trng. Thuc bo v thc vt c s dng bo v cy trng, l mt gii php d c s dng trong nhiu thp k. nhiu nhm thuc c s dng BVTV bao gm nhm thuc Clo, nhm Phtpho, nhm Ln, nhm Carbamate. Trong , thuc BVTV nhm Carbamate c nh gi l nhm thuc BVTV hiu qu nht.

Trc nhu cu Bo v thc vt bng cng ngh sinh hc v vi sinh cho nhng sn phm t thc vt an ton cho ngi s dng v bo v mi trng, phng php bo v bng sinh hc ngy cng chim u th. Tuy nhin, thuc BVTV nhm Carbamate c s dng mt lng ln bo v thc vt. Nhng u im ca thuc BVTV nhm Carbamate trong qu trnh s dng nh: kh nng gy c cp tnh vi ng vt mu nongsthaaps hn cc loi thuc BVTV khc, t c i vi c, khng tn ti lu trong nng sn v khng bn trong mi trng. Thuc BVTV nhm Carbamate c hiu lc kh n nh, t ph thuc ngoi cnh nh thuc BVTV nhm Ln hu c. S dng thuc BVTV nhm Carbamate khng ng k thut nh s dng qu liu, thi gian thu hoch cy trng khng m bo thi gian phn hy thuc s gy nhim mi trng, nh hng n sc khe con ngi v ng vt. Carbamat l cc dn xut hu c ca acid cacbamic, gm nhng ho cht t bn vng hn trong mi trng t nhin, song cng c c tnh cao i vi ngi v ng vt. Khi s dng, chng tc ng trc tip vo men Cholinestraza ca h thn kinh v c c ch gy c ging nh nhm ln hu c.
1.2.

Cc Hot Cht Thuc Tr Su Nhm Carbamate [4]

BENFURACARB: Cng thc ha hc:

Tn ha hc(IUPAC): ethyl N -[2,3-dihydro -2,2-dimethyl -7- benzofuranyl Cng thc phn t: C20H30N2O5S Khi lng phn t: 410.5

Tnh cht vt l: Dng st mu nu im si: 110oC/ 0.023 mmHg p sut ha hi: <1x10-2 mPa(200C) tan: Nc: 7.74 mg/l (pH 6.5, 200C) Benzen, dichloromethane, ethanol, acetone, hexane, xylene, ethyl acetae: >1000g/l (200C) bn: n nh trong mi trng trung tnh v baz yu, khng n nh trong mi trng baz mnh v acid. Phn hy 2270C

CARBARYL: Cng thc ha hc:

Tn ha hc (IUPAC):1-naphtyl methyl carbamate Cng thc phn t: C12H11NO3 Khi lng phn t: 201.2 Tnh cht vt l:

Tinh th khng mu Nhit nng chy: 1420C p sut ha hi : 4.1x10-2mPa(23.50C) tan: Nc: 120 mg/l(200C) Tan ng k trong dung mi hu c phn cc dimethyl formamide, dimethyl sulfoxide: 400-500(g/kg; 250C), acetone: 200-300 (g/kg; 250C), cyclohexanone: 200-250 (g/kg; 250C), isopropanol: 100 (g/kg; 250C), xylene: 100 (g/kg; 250C) bn: n nh diu kin trung tnh v acid yu. Thy phn trong mi trng kim thnh 1-naphthol DT50: 12 ngy(pH 7), 3.2 gi(pH 9) n nh di nh sng v nhit. CARBOSULFAN: Cng thc ha hc:

Tn ha hc (IUPAC): 2,3-dihydro-2,2-dimethylbenzofuran-7-yl(dimethyl amithio) methyl carbamate Cng thc phn t: C20H32N2O3S Khi lng phn t: 380.5 Tnh cht vt l:

dng st mu nu cam im si: 124-1280C p sut ha hi: 0.041 mPa (250C) tan: Nc: 0.3 ppm (250C) Tan trong hu ht dung mi hu c: xylene, hexane, chloroform, dichloromethane, methanol, ethanol, acetone, bn: DT50(250C): trong nc tinh khit: < 1 gi(pH 4), 22 gi(pH 6), 7.6 ngy(pH 7), 14.2 ngy(pH 8), >58.3 ngy(pH 9)

FENOBUCARB: Cng thc ha hc:

Tn ha hc (IUPAC): 2 sec butyl phenyl methyl carbamate Cng thc phn t: C12H17NO2 Khi lng phn t: 207.3 Tnh cht vt l: Tinh th rn khng mu

im nng chy: 31-320C im si: 112-113oC/ 0.02 mmHg p sut ha hi : 13 mPa (200C) tan: Nc: 420 mg/l (200C), 610mg/l (300C) acetone, benzene, chloroform, xylene, toluen >1(kg/kg, nhit d phng) bn: n dnh di iu kin bo qun bnh thng. n nh vi nh sng. Thy phn bi acid v kim. DT50, 200C: > 28 ngy(m pH 2), 16.9 ngy (pH 9), 2.06 ngy (pH 10).

ISOPROCARB: Cng thc ha hc:

Tn ha hc (IUPAC): 2 iso propyl phenyl methyl carbamate Cng thc phn t: C11H15NO2 Khi lng phn t: 193.2 Tnh cht vt l: Tinh th khng mu.

im nng chy: 93-960C im si: 128-129oC/ 20 mmHg p sut ha hi : 2.8 mPa (200C) tan: Nc: 0.265 g/l acetone: 400 g/l methanol: 125 g/l bn: thy phn trong mi trng kim.

METHOMYL: Cng thc ha hc:

Tn ha hc (IUPAC): S-methyl N-(methyl carbamoyloxy)thioacetimidate Cng thc phn t: C5H10N2O2S Khi lng phn t: 162.2 Tnh cht vt l: Tinh th khng mu c mi lu hunh nh. im nng chy: 78-790C

p sut ha hi : 0.72 mPa (250C) tan: Nc: 57.9 g/l MeOH: 100, acetone: 730, ethanol: 420, isopropanol: 220, toluen: 30(g/kg, 250C) bn: n nh trong nc 30 ngy(pH 5& 7) DT50: 30 ngy(pH9) n nh nhit ti 1400C . n nh di nh sng mt tri 120 ngy khi ngoi tri.
1.3.

Tnh hnh tn d ha cht bo v thc vt trong rau qu

Theo bo co ca Cc Bo v thc vt, c 23% s h nng dn vi phm quy nh v s dng thuc bo v thc vt, dn n tn d ha cht bo v thc vt trn nng sn. Mt s loi thuc tr su c hi b cm s dng nhng hin vn c nhiu ngi tm cch a v nng thn. S mu rau, qu ti c d lng ha cht bo v thc vt chim t 30-60%, trong s mu rau, qu c d lng ha cht bo v thc vt vt qu gii hn cho php chim t 4-16%, mt s ha cht bo v thc vt b cm s dng nh Methamidophos vn cn d lng trong rau. u nm 2009, Cc Bo v thc vt ly 25 mu rau v nm mu qu ti cc tnh pha Bc (TP H Ni v tnh Vnh Phc) kim nh. Kt qu c 11 mu rau c d lng thuc bo v thc vt mc khc nhau. cc tnh pha Nam, trn 35 mu rau v 5 mu qu ly TP H Ch Minh, Bnh Dng, Tin Giang, kt qu trn 50% mu c d lng thuc bo v thc vt mc khc nhau. Ti TP H Ch Minh, trong su thng u nm 2009, qua kim nghim hn 2.200 mu rau, qu ti ba ch u mi (Bnh in, Hc Mn, Th c), pht hin 50 mu dng tnh (t l 2,4%), cao hn so vi cng k nm 2008 l 1,3%. Cn ti Bnh Dng, phn tch gn 310 mu rau ly cc ch, vng sn xut, bp n tp th trong tm thng u nm 2009 c gn 80 mu c d lng thuc bo v thc vt.

Trn th gii, ti n , Cuc iu tra c B Nng nghip n tin hnh trong mt nm t thng 11 nm 2007 n thng 10 nm 2008 trn ton t nc n . Kt qu l 18% rau v 12% hoa qu ni a v nhp khu ca n u c d lng thuc tr su, k c nhng loi thuc tr su b cm, trong 4% lng rau v 2% lng hoa qu c d lng thuc tr su cao hn mc cho php. Khong 18% (664 mu) trong tng s 3.648 mu rau nh mp ty, c chua, bp ci v sp l u c d lng thuc tr su. Cc loi rau nh bp ci, sp l v c chua c d lng thuc tr su ln nht. Cc loi thuc tr su tm thy trong cc loi qu ch yu l chlorpyriphos, monocrotophos, profenophos v cypermethrin. Ti Vit Nam, ch tnh ring nm 2008, c nc c 6.807 v nhim c thuc bo v thc vt vi 7.572 trng hp, t vong 137 trng hp. c tnh, Vit Nam c khong 15-29 triu ngi thng xuyn tip xc vi thuc BVTV. Nguy hi hn, 70%trong s ny c triu chng ng c. Lng thuc BVTV s dng trn mt n v din tch t canh tc vt mc khuyn co 2,81 ln ng bng sng Hng v 3,71 ln ng bng sng Cu Long. Bng 1. Mc d lng ti a cho php s dng thuc tr su carbamat mt s quc gia. Carbofur Quc gia i tng an (mg/kg) Nht Bn Vit Nam (Quyt nh 46/2007/Q C chua, c rt 0,1 0,05 Xoi To, nho, l 0,3 Carba yl (mg/k g) 3,0 5,0 Propox ur (mg/kg ) 1,0 3,0 Fenobuca rb (mg/kg) 0,3

-BYT) EU Tri cy 0,1 1 0,05

2. XC NH D LNG THUC BO V THC VT H CARBAMATE C TRONG RAU QU 2.1 Quy trnh ly mu[3] 2.1.1 Yu cu chung vic ly mu phi c tin hnh sao cho mu th thu c mang tnh i din cho l rung sn xut c , l , ha hc hay thnh phn vi sinh vt Phng php ly mu , khi lng mu th nghim ph thuc vo mc ch ca vic ly mu , qui m cch thc sn xut , tng loi rau c th 2.1.2 Thi im ly mu Mu c ly ti thi im thu hoch , trnh thi gian nng gt hay dang ma 2.1.3 Xc nh l rung sn xut cn ly mu Trc khi tin hnh ly mu , cn xc nh : Ch l rung sn xut , a ch , s gii tha v din tch ca l rung , chng loi rau cn ly mu. Trng hp l rung c kch thc ln phi chia thnh cc l rung nh theo quy nh S mu th nghim , mu lu ( nu cn ) , s mu n ti thiu trn mt mu th nghim , s phn b cc im ly mu trn l rung sn xut 2.1.4 Dng c ly mu Dng c ly mu phi sch , kh , sc bn , khng g , khng gy dp nt v khng lm thay i thnh phn ha hc ca sn phm 2.1.5 Vt cha mu

Vt cha mu phi c dung tch v hnh dng ph hp vi kch thc ca cc n v mu . Vt liu ca vt cha tip xc trc tip vi mu phi khng thm nc , khng ha tan , khng hp th v khng gy tn thng c gii cho rau Vt cha mu phi sch , kh , c tc dng bo v c mu , khng lm nh hng n kt qu phn tnh tnh cht vt l v ha hc ca mu Tm lc mu phi c din tch ph hp vi kch thc v khi lng mu chung . tm lc mu phi sch , kh , khng lm thay i tch cht vt l ha hc ca mu 2.1.6 Cch tin hnh ly mu[1] Xc nh s mu th nghim ti thiu v s mu n ti thiu L rung sn xut do mt h hoc mt doanh nghip qun l L rung sn xut c din tch L rung sn xut c din tch din tch 5 Ha : mi l ly ti thiu mt mu th nghim 5 Ha : phi chia ra thnh nhiu l nh c

5 Ha , mi l nh ly ti thiu mt mu th nghim

S mu n ti thiu trn mt mu th nghim ph thuc vo loi rau v din tch l rung Bng 2 . S mu th nghim ti thiu v s mu n ti thiu loi rau din tich l rung sn xut (ha) Rau qu phn c loi ln ( khi lng trung bnh ln hn 250g/n v) Rau qu phn c 0,1 1 5 5 1 5 s mu th nghim ti thiu s mu n ti thiu trn mt mu th nghim

loi rau

din tich l rung sn xut (ha)

s mu th nghim ti thiu

s mu n ti thiu trn mt mu th nghim

Rau qu phn c loi ln ( khi lng trung bnh ln hn 250g/n v) loi trung bnh v loi nh ( khi lng trung bnh < 250 g/n v ) t 0,1 n 1 t 1 n 5 5 1 1 1 t 5 n 8 t 8 n 12 t 12 n 16 5 1 5

L rung sn xut c nhiu h qun l ( hp tc x , t hp tc ) L rung sn xut c din tch L rung sn xut c din tch din tch 5 Ha : mi l ly ti thiu mt mu th nghim 5 Ha : phi chia ra thnh nhiu l nh c

5 Ha , mi l nh ly ti thiu mt mu th nghim

s mu n ti thiu cho mt mu th nghim ph thuc vo s h tham gia sn xut trong mt l rung (n). S mu n ti thiu t l vi s h ly mu ti thiu v t l vi nhng khng c t hn 5 mu trng hp l rung do nhiu h qun l nhng khng cng iu kin sn xut th phi ly mu ring ca tng h v mu ch i din chho h sn xut d Xc nh c mu phng th nghim ti thiu C mu phng th nghim ti thu ty thuc vo loi rau v c quy nh c th Bng 3 . C mu phng th nghim ti thiu

c mu Nhm rau loi rau b phn c ly mu phng th nghim ti thiu Rau gia v Mi ty, rau hng, th l, ta t, kinh gii i vi cc loi rau phn c loi ln , n v c khi lng trungbnh> 250 g ( ci bp ,) i vi cc loi rau phn c loi trung bnh , n v c khi lng Rau n l trung bnh t t 25 g n 250 g (ngn su su , cn ty, ti ty, ) i vi cc loi rau phn c loi nh , n v c khi lng trung bnh < 25 g ( rau dn , mng ti , rau day , rau ngt , rau mung , ) X lch cun , rau dip , ci xon Phn n c ( nguyn cy ) Phn n c rau n hoa i vi cc loi rau phn c loi ln , n v c khi lng trung Rau n qu bnh > 250 g ( b xanh , bu, b ng , da chut,c tm , u bp , c chua ) i vi cc loi rau phn c loi Nguyn qu 20 qu Nguyn qu 10 qu ( bp ) Suplo ( nguyn cy ) 10 cy 10 cy Phn n c 1kg Phn n c 2 kg Phn n c Phn n dc (nguyn cy ) 0,5 kg

10 cy

c mu Nhm rau loi rau b phn c ly mu phng th nghim ti thiu trung bnh , n v c khi lng trung bnh t t 25 g n 250 g (t , c pho , ) i vi cc loi rau phn c loi nh , n v c khi lng trung bnh < 25 g (u rau cc loi ..) Su ho Nguyn c 10 c 10 cy ( hay 1 kg ) Nguyn qu ( hay 1 kg )

1 kg

Rau n thn

Mng ty

Phn n c ( nguyn cy )

c ci , c rt , khoai ty, khoai s , c hnh ty, c ti . Hnh c , ti c Hnh l , h Rau mm nm thc phm cc loi Rau qu phn c loi rt ln (> 2kg/n v sn phm) ( ti)

Nguyn c

0,5 kg

Rau n c

Nguyn c Phn n c ( nguyn cy ) Phn n c ( nguyn cy ) Phn n c ( nguyn cy ) -

1 kg 1 kg

loi khc

0,5 kg

0,5 kg 5 n v

Xc nh c mu n ti thiu

c mu n ti thiu ca cc loi rau , m, tnh bng kilogam hoc cy , c , qu , bp theo cng thc sau :

Trong : A a k l c mu phng th nghim ti thiu , tnh bng kilogam hoc cy , l s mu n cn ly l s ln gin lc mu (k=0 hay 1 ) i vi cc loi rau c ln ( >250g / n v ) v khng cn lu mu k=0 i vi cc loi rau cn li v cn lu mu k=1 Xc nh v tr ly mu n i vi rau cha thu hoch cn nguyn vn trn cy V tr ly mu n vi rau cha thu hoch ph thuc vo din tch , hnh dng l rung sn xut Rau ti phn c loi ln , n v c khi lng trung bnh > 250g : ly mu n phn phi u theo ng cho hay hnh zigzag

c , qu , bp

Rau phn c loi trung bnh , n v c khi lng trung bnh t 25g n 250g v loi rau phn loi nh, n v c khi lng trung bnh nh hn 25g: L rung sn xut c hnh dng hp chy di : ly mu theo hinh zigzag , s im ly mu n ty thuc vo din tch trng L rung sn xut c hnh dng cn i : ly mu phn phi u theo ng cho , theo tuyn dc hoc theo tuyn ngang , s im ly mu n cng ty thuc vo din tch trng Cch chn im ly mu n di vi rau cha thu hoch

Hnh 1 . ly mu n theo ng cho

Hnh 2 . ly mu n theo hnh zigzag

Hnh 3 . ly mu n theo tuyn dc

Hnh 4 . ly mu n theo tuyn ngang

i vi rau thu hoch nhng cn nm trn rung

Rau thu hoch c xp thnh ng trn rung: s mu n cng c tnh theo din tch trng. Mu n c ly phi phn b u cc dng theo t l tng ng vi khi lng hay kch thc ca ng rau .Cc v tr ly mu phi phn b u trong ng ti 3 lp : lp trn ,lp gia, lp y Rau thu hoch v c xp vo vt cha ( bao, thng , hp, st) th s mu c ly theo ch tiu TCVN 5102:1990 Bng 4 . s mu n , cch ly mu n i vi rau thu hoch c xp vo vt cha S vt cha ( bao , gi ) ging nhau s mu n c ly ( mi bao , mi gi ly 1 mu n) 100 101 n 300 301 n 500 501 n 1000 >1000 5 7 9 10 t 11 n 15

Xc nh v ly nv mu Mi dim ly mt mu n t mt hay nhiu cy sao cho khi lng hoc s lng mu n ti thiu Cy c ly mu phi sinnh trng bnh thng , khng d dng, khng b su bnh gy hi v cch b ti thiu 1m , b hng ngoi cng Thoa tc ly n v mu : s dng gng tay bng nilon hay cht do loi dng 1 ln , ly mu nh nhng bng tay, khng lm dp nt rau . Mi mu n phi ring mt ti ri chuyn v tm lc mu

 i vi rau n qu : qu c ly u phn thn v nhnh nhng khng ly qu ngn , qu gc , ngt cung qu bng tay nu qu nh phi dng dng c ly mu thu ly tng qu i vi rau n l : ct cy loi b phn gc , l gi v l gc. Hoc ct ly phn thn l ngn n c i vi rau n c : nh nh nhng tng c ln khi mt t hoc phi o bi , lt t thu ct ly tng c Trong trng hp rau qu c ly b vy bn bn v t, nn s dng giy mm sch lau chi tht nh nhng n khi sch kh Thit lp mu th nghim hn hp mu , gin lc mu c tin hnh trn tm lc mu i vi rau , c c phn loi c nh : a ton b mu n vo tm lc mu , trn u thnh mu chung. Dn mng , chia lng mu chung thnh 4 phn, ly hai phn dng lm mu th nghim, hai mu cn li dng lm mu lu i vi cc loi rau n l , rau n qu , c phn c loi trung bnh v loi ln , cn lu mu: ln lt tng mu n c trn u, tch thnh 2 ( hay 4) phn , ly 1 phn (hay 2 phn ) dng lm mu th nghim . Phn cn li lm mu lu i vi loi rau c khi lng ln v khng cn lu mu ( k=0) th tm lc mu ch l ni hn hp cc mu n thanh mu th nghim 2.1.7 Bo qun v vn chuyn ti phng th nghim Sau khi ly mu phi ng gi , bo qun v vn chuyn n ngay phng th nghim gim thiu ti a s thay i trng thi , tnh cht ban u ca mu.Thi gian gi mu tt nht l trong vng 24 gi c x l trong phng th nghim

Bao gi mi mu rau bng mt trong nhng loi mng bao nh PE, LDPE,HDPE. Khng xp chng qu nhiu thng hp, khng nn qu cht d gy dp nt mu Bo qun mu nhit 100C n 150C trong khoang xe lnh chuyn dng hoc trong thng cch nhit c cha lnh 2.2 Chun B Mu[2]

Mu th c nghin trong my nghin mu n khi ng nht. 2.2.1 Chun b phn mu th Chit xut mu th Cn khong 20 g mu th c ng nht ,chnh xc ti 0.01 g vo bnh tam gic dung tch 250 ml. Thm vo bnh 100 ml hn hp dung mi 1 (V1), y np kn, lc u 30 pht, a v nhit phng. Thm 10 g Na2SO4 khan, yn 30 pht. Dng pipet dung tch 10 ml ly chnh xc 10 ml (V2) dch lng thu c cho vo bnh cu 50 ml v c cn 40 OC bng h thng c quay chn khng. Dng pipet thm 2 ml hn hp dung mi 3, lc u c dung dch A. Lm sch mu th Ni hai ct SPE Carbo V NH2 li vi nhau, dng ng ong ly 10 ml hn hp dung mi 3 (3.9) hot ha ct. Chuyn ton b dung dch A vo ct. Ra gii bng 15 ml hn hp dung mi 3 .C cn dung dch thu c 40OC bng h thng c quay chn khng. Dng pipet thm 2 ml (VE) hn hp dung mi 2 vo thu c phn mu th. 2.2.2 Chun b phn mu trng

Mu trng l mu khng cha d lng benfuracarb, carbaryl, carbosulfan, fenobucarb, isoprocarb v methomyl, c chun b nh phn chun b mu th .

2.2.3 Chun b phn mu kim tra hiu sut thu hi Cn khong 20 g mu trng c ng nht ,chnh xc ti 0.01 g vo bnh tam gic dung tch 250 ml. Dng micropipet thm 40 l dung dch chun trung gian yn trong nhit phng ti thiu 15 pht. Tip tc thc hin chun b nh phn chun b mu th . 2.2.4 iu kin phn tch Tc dng pha ng: 0,2 ml/pht Nhit bung ct: 40OC Chng trnh dung mi: Thi gian(pht) 0 1 10 25 26 35 % dung mi pha ng 1 50 50 5 5 50 50 % dung mi pha ng 2 50 50 95 95 50 50

Th tch bm mu: 5 l. 2.2.4 Dng ng chun Xy dng ng chun ( tng quan gia nng v din tch pic ca cht chun) ca cc thuc BVTV ti 5 im c nng tng ng trong cc dung dch chun lm vic trn nn mu trng bng cch dng pipet thm ln lt 2 ml cc

dung dch chun lm vic vo cc nn mu trng c chun b phn chun b mu trng . 2.2.5 Xc nh Bm ln lt dung dch mu trng ,dung dch mu th ,dung dch mu kim tra hiu sut thu hi vo thit b sc k lng hiu nng cao. Xc nh nng ca mu th v mu kim tra hiu sut thu hi bng ni suy ng chun hoc chun b mu li vi lng cn t hn( khng c hiu chnh vi hiu sut thu hi). 2.3 Mt S Phng Php Phn Tch D Lng Carbamate 2.3.1 Phng php sc k kh Phng php sc k kh ra i vo nhng nm 1960, phng php sc k kh (GC) tr thnh phng php ch yu phn tch d lng thuc bo v thc vt v nhiu l do : S ra i ca ct mao qun vi hiu nng tch rt cao , cc u d nhy vi hp cht bt electron nh u d ECD ( electron capture detector), NPD ( nitrogen- phosphorous detector), FPD ( flame photometric detector), v u d MS ( mass detector) Thi gian phn tch nhanh S ra i ca k thut bm mu nh on column in jection, chng trnh ha nhit bung tim ( programmed temperature vaporizer PTV ) . Tng kh nng phn tch d lng ca GC Mt s phng php phn tch bng sc k kh: phng php phn tch trc tip bng GC/MS ph ng ph p GC/ECD c to dn xut

2.3.2 Phng php sc k lng hiu nng cao Ngy nay sc k kh vn l phng php ch o, Ph bin trong phn tch d lng thuc bo v thc vt Tuy nhin sc k lng ( LC ) to ra c nhiu u im hn khi phn tch nhng hp cht phn cc , hp cht t bn nhit nh CBM , nhng hp cht khng bay hi Sc k lng cng c ng dng rng ri khi k thut c sc k , k hut sca81 k pha o pht trin. S ra i ca cc u d nhy nh u d UV , u d DAD , u d qunh quang , u d phi kh S pht trin ca k thut sc k lng phi kh ( LC MS) trong vi nm gn y cho kh nng nh danh cc hp cht vi nhy c th so snh vi CG MS Mt s phng php phn tch bng sc k lng : phng php HPLC / UV Phng php HPLC/FD phng php HPLC/MS 2.3.3 Phng php ELIZA Phng php ELIZA l phng php cn c trn nguyn l ca min dch hc. Hin nay c mt s cng ty nc ngoi sn xut sn nhng b thuc th phn tch nh lng dng ring cho tng loi thuc bo v thc vt. Phng php ny tng i nhanh nhng kh t tin , thch hp cho vic phn tch tng loi thuc bo v thc vt khi bit r mu rau qu phun loi thuc bo v thc vt no 2.3.4 Phng php c ch men ( Enzyme inhibition) Phng php da trn php th ellman , ng dng hin tng c ch men Acetylcholinesterase (ChE ) ca nhm thuc bo v thc vt ln hu c v carbamate.

Phng php ny r tin , phn tch nhanh , hng lot. Vi nhng mu rau qu phun nhiu loi thuc bo v thc vt trn mt mu dng phng php ny c th bn nh lng tng hm lng d lng thuc bo v thc vt ln hu c v carbamate. iu ny c ngha to ln trong vic kim tra mang tnh sng lc , gip ngn chn nhng l hng rau qu c cha d lng thuc bo v thc vt cao trc khi a ra th trng nhm bo v sc khe ngi tiu dng 2.3.5 Phng php sc k in di mao qun Phng php ny da trn nn tng ca phng php do Moye et al. pht hin.Carbamate c tch trn ct mao qun vi pha tnh v h pha ng thch hp , c thy phn sinh ra metylamin, metylamin sinh ra s tip tc phn ng vi dung dch o phthalaldehyd ( OPA) v 2 mecaptoetanol ( MERC) to dn xut hunh quang 1 hydroxyetylthio 2 metylisoindol v c pht hin trn u d hunh quang . u im ca vic tch trn ct mao qun l hiu nng tch rt cao , s a ly thuyt ca ct > 50000 . Thit b c xem l gn nh hn v thay th phn no h thng phn ng sau ct 2.4 Dng C , Ha Cht , Thit B VQuy TrnhTin Hnh Xc nh D Lng Thuc Bo V Thc Vt H Carbamate 2.4.1 Thuc th Ha cht, thuc th dng trong cc php phn tch phi l loi tinh khit phn tch. Axeton, tinh khit phn tch. Diclometan, tinh khit phn tch. Ete du ha, tinh khit phn tch, nhit si 35-600C Metanol, tinh khit phn tch.

 Toluen, tinh khit phn tch. Axetonitril, tinh khit phn tch. Hn hp dung mi 1, axeton, diclomethan, ete du ha vi t l th tch bng 4: 3: 3. Hn hp dung mi 2, metanol v nc vi t l th tch bng 2:1. Hn hp dung mi 3, Axetonitril v toluen vi t l th tch bng 3:1. Nc ct, tinh khit phn tch. Axit axetic, tinh khit phn tch. Dung mi pha ng 1: axit axetic 0,1%(v/v) trong nc. Dung mi pha ng 2: axit axetic 0,1%(v/v) trong metanol. Natri sulfat khan, hot ha 1300C trong 8h, ngui trong bnh ht m, y kn. SPE Carbo 500mg/8ml. SPE NH2 500mg/6ml. Cc cht chun benfuracarb, carbaryl, carbosulfan, fenobucarb, isoprocarb v methomyl bit tinh khit. Dung dch chun gc, nng 1000 g/ml Dng cn phn tch cn khong 0.01 g tng cht chun ,chnh xc n 0.01 mg, cho vo cc bnh nh mc dung tch 10 ml, ho tan v nh mc n vch bng metanol. Dung dch chun trung gian, nng 10 g/ml Dng micropipet ly 200 l tng dung dch chun gc cho vo bnh nh mc dung tch 20 ml, ho tan v nh mc n vch bng hn hp dung mi 2 .

 Dung dch chun lm vic Dung dch chun lm vic 1, nng 0.01 g/ml. Dng micropipet ly 20 l dung dch chun trung gian cho vo bnh nh mc dung tch 20 ml, ho tan v nh mc n vch bng hn hp dung mi 2 . Dung dch chun lm vic 2, nng 0.03 g/ml Dng micropipet ly 30 l dung dch chun trung gian cho vo bnh nh mc dung tch 10 ml, ho tan v nh mc n vch bng hn hp dung mi 2 . Dung dch chun lm vic 3, nng 0.3 g/ml. Dng micropipet ly 300 l dung dch chun trung gian cho vo bnh nh mc dung tch 10 ml, ho tan v nh mc n vch bng hn hp dung mi 2 . Dung dch chun lm vic 4, nng 1.0 g/ml. Dng pipet ly 1 ml dung dch chun trung gian cho vo bnh nh mc dung tch 10 ml, ho tan v nh mc n vch bng hn hp dung mi 2 . Dung dch chun lm vic 5, nng 1.5 g/ml. Dng pipet ly 1.5 ml dung dch chun trung gian cho vo bnh nh mc dung tch 10 ml, ho tan v nh mc n vch bng hn hp dung mi 2 . Kh nit, c tinh khit khng nh hn 99%. 2.4.2 Thit b, dng c[2] S dng cc thit b, dng c ca phng th nghim thng thng v c th nh sau: Bnh nh mc, dung tch 10 ml v 20ml. Pipet, dung tch 2 v 10 ml, chia vch n 0.1 ml.

 Micropipet, dung tch t 20 l n 100 l, t 50 l n 200 l v t 200 l n 1000 l. Bnh tam gic dung tch 250 ml. Bnh cu dung tch 50 ml. ng nh git. ng ong, dung tch 25 ml v 100ml. Cn phn tch, c th cn chnh xc n 0.01 mg. Cn k thut, c th cn chnh xc n 0.1 g. Xyranh, dung tch 5ml. Mng lc 0.45 m PTFE. My nghin mu. H thng c quay chn khng. Thit b sc k lng , c trang b nh sau: H thng HPLC Shimadzu vi h phn ng sau ct, u d hunh quang (FD), Ct phn tch C18, My lc nc v trao i ion millipore. H thng tim mu t ng SIL 20A Shimadzu, u d hunh quang RF - 10 Axl c to dn xut sau ct. Ct phn tch HRC - ODS AS0678 Kch thc 20 cm x 4.6 mm x 5m Ct bo v GHRC - ODS FU3445

 Injector tim t ng SIL - 20A B iu nhit CRB - 6A Mt s thit b khc 2.4.3 Tin hnh xc nh d lng thuc bo v thc vt h carbamate bng phng php sc k lng hiu nng cao ( HPLC )[3] Phng php sc k lng cao p (HPLC) u d hunh quang (FD) c to dn xut sau ct c coi l mt phng php c tnh u vit, c s dng hin nay xc nh 10 lai carbamate ph bin thng dng lm thuc bo v thc vt: Aldicard Sulfoxide; Aldicarb sulfone; Oxamyl; Methomyl; 3-Hydroxycarbofuran; Aldicarb; Propoxur; Carbofuran; Carbaryl; Methiocarb. Nguyn tc ca phng php HPLC to dn xut sau ct l da vo c tnh khng bn ca nhm CBM trong mi trng kim. Sau khi tng loi CBM tch trn ct sc k pha o, c thy phn trong mi trng baz sinh ra methyl amin, sau methyl amin phn ng vi thuc th O phthalaldehyde (OPA) v 2 mercaptoethanol to ra dn xut hunh quang 1 hydroxytylthio 2 metylisoindol. tin hnh chit tch v lm giu mu bng hai phng php chit pha rn (SPE) v chit lng lng (LLS) nh quy trnh 1 v quy trnh 2. Ct SPE C18 - 500 mg ca Varian. Dung mi dng cho chit lng lng l dichloromethane (CH2Cl2) (b.p 40oC). Tin hnh chit 3 ln lm sch bng silica. ui dung mi bng kh N2 khan tinh khit 99.99% sau lc qua mng lc 0.2 m trc khi phn tch. Thm chun ln lt 100 ppb, 500 ppb, 1500 ppb nh gi ng v tin cy ca phng php. Khi c quay MeOH bay hi, dung dch b c l do mt s cht t phn cc tan tt trong MeOH hn trong nc. Dung dch sau khi c quay i vi mu rau cn

khong 30 ml, m bo t l MeOH: H2O khong 1: 2. ng vi t l MeOH:H2O khong 1 : 2 th hiu sut ca qu trnh chit lng-lng t cao nht Quy trnh chit tch i vi rau :

Cn 20g rau + 50 ml MEOH

Xay nhuyn

Lc (p sut km )
Ra b ta ( 40 ml )

Dung dch thu c

C quay

Dung dch thu c

Trng bnhc quay bng 40 ml CH2Cl2

Chit lng lng bng CH2Cl2 ( 4 ln khong 60 ml)

Dung dch hu c thu c

Cho qua SPE ( silica) ( nhi ct 1.5g )

ra gii bng CH2Cl2( khong 15 ml )

Dung dch thu c

bay bt dung mi ( gi nhit khong 50 0C )

ui dung mi bng kh N2
nh mc 1 ml (CH2Cl2 )

lc qua mng lc 0.2 m

Phn tch bng HPLC

Silica hot ha bng CH2Cl2 : C6H6 = 7:3

2.4.4 Tnh kt qu[1] D lng tng thuc tr su (X), biu th bng miligam trn kilogam (mg/kg), c tnh theo cng thc:
X X0 VE V1 P V2 m 100

trong : X0 : l nng cc d lng thuc tr su trong dung dch mu th c xc nh theo7.8, tnh bng microgam trn mililit (g/ml); VE : l th tch phn mu th thu c , tnh bng mililt (ml); V1 :l th tch dch chit thu c , tnh bng mililt (ml); V2 :l th tch dch chit c ly ra c cn , tnh bng mililt (ml); m :l khi lng mu th, tnh bng gam (g); P:l tinh khit ca cht chun, tnh bng phn trm (%). 2.4.5 kt qu[3] Hiu sut thu hi ca phng php: t 70 % n 110 %.
Bng 5: Hiu sut thu hi mu rau thm chun 100 ppb Hiu sut thu hi TB (%) RSD Cht phn tch ( n = 3)

Mu rau RSD

Mu gng RSD

Aldicard Sulfoxide Aldicarb sulfone Oxamyl Methomyl 3-Hydroxycarbofuran Aldicarb Propoxur Carbofuran Sevin (carbaryl) Methiocarb Aldicard Sulfoxide Aldicarb sulfone Oxamyl Methomyl 3-Hydroxycarbofuran Aldicarb Propoxur Carbofuran Sevin (carbaryl) Methiocarb

72.8 1.7 91.5 1.0 92.1 0.6 108.6 1.7 93.2 0.8 91.8 1.1 89.6 1.2 92.7 1.3 93.7 1.2 96.6 1.9 72.8 1.7 91.5 1.0 92.1 0.6 108.6 1.7 93.2 0.8 91.8 1.1 89.6 1.2 92.7 1.3 93.7 1.2 96.6 1.9

77.7 3.1 91.7 1.2 93.4 1.8 93.5 1.1 89.9 2.4 93.4 2.2 92.4 1.1 94.5 1.1 110.7 1.5 95.9 3.1 77.7 3.1 91.7 1.2 93.4 1.8 93.5 1.1 89.9 2.4 93.4 2.2 92.4 1.1 94.5 1.1 110.7 1.5 95.9 3.1

Gii hn xc nh ca phng php (LOQ): 0,02 mg/kg ( cho tng hot cht). bng 6 . Gii hn pht hin ca phng php

lp li ca phng php: 15%

C. KT LUN Phng php HPLC u d hunh quang phn tch d lng CBM c ng dng tt i vi mt s mu trn thc t. Gii hn pht hin vi mi cht khc nhau khong vi chc ppb trn mu tht . Chnh v chn lc vi CBM nn phng php sc k lng hiu nng cao u d hunh quang (FD ) c cc t chc trn th gii cng nhn l phng php tiu chun phn tch d lng CBM trong t, nc, thc phm. Ha cht bo v thc vt l nhng hp cht c ngun gc t nhin hoc tng hp ha hc c dng phng v tr sinh vt gy hi cy trng v nng sn. Ha cht bo v thc vt gm nhiu nhm khc nhau, gi theo tn nhm sinh vt gy hi, nh thuc tr su dng tr su hi, thuc tr bnh dng tr bnh cy Thuc tr su l mt loi cht c s dng chng cn trng. Chng bao gm cc thuc dit trng v thuc dit u trng dit trng v u trng ca cn trng. Cc loi thuc tr su c s dng trong nng nghip, y t, cng nghip v gia nh. Vic s dng thuc tr su c cho l mt trong cc yu t chnh dn ti s gia tng sn lng nng nghip trong th k 21. Gn nh tt c cc loi thuc tr su u c nguy c lm tham i ln cc h sinh thi; nhiu loi thuc tr su c hi vi con ngi; v cc loi khc tch t li trong chui thc n. Ngy nay vi cc dng c v cc phng php hin i, ngi ta c th kim tra xc nh c kh chnh xc lng thuc tn d trn cc nng sn c th ti hng phn nghn mg. Thi Lan v nc ta hin nay c b dng c c th xc nh d lng ti a cho php ca cc thuc tr su gc Ln hu c v Carbamate trn cc loi rau, qu v thc phm rt nhanh chng, cho kt qu ch sau 1 ting ng h, thao tc n gin v chi ph thp. Cc c s sn xut v tiu dng c th dng b dng c ny t kim tra mc an ton ca thuc BVTV trn nng sn, thc phm trc khi cung ng v s dng

D. TI LIU THAM KHO [1] Phng php xc nh Carbamate trong rau,Tp ch pht trin khoa hc cng ngh, Tp 12 ,S 9 , 2009 [2] Quyt nh ban hnh s 219/Q/BVTV , Cc Trng Cc bo v thc vt , 17/2/2011 [3] Science & Technology Development, Vol 12, No.09 , 2009 [4] TCVN 9016-2011 Rau ti - phng php ly mu trn rung sn xut,H Ni , 2011 [5] tailieu.vn/xem-tai-lieu/nhom-thuoc-tru-sau-carbamate.542925.html