農薬中のダイオキシン類のBPX5カラムによる全異性体分析

全文

(1)Congener Specific Analysis of Dioxins in Agrochemicals using BPXS Column Shigeki MASUNAGA, Takumi TAKASUGA and Junko NAKANISHI Synopsis Dioxin impurities in old Japanese agrochemical formulations were analyzed by GCIMS using BPXS column. The three chemicals studied, namely pentachlorophenol (PCP), chlomitrophen (CNP) and nitrophen (NIP), were herbicides used extensively in Japan. All the peaks on the chromatograph were determined. These data provide precious information that can be used for source identification of dioxin pollution in environmental media. They also showed the followings: The major polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in the PCP formulations were those that could be formed from the PCP and its lower chlorinated chlorophenol, mainly 2,3,4,6-tetrachlorophenol. The major PCDDIDFs in CNP formulations were those that could be formed from 2,4,6-trichlorophenol and its further chlorinated phenol, 2,3,4,6tetrachlorophenol. The composition of those PCDDIDFs that could be formed the major constituent of the raw material were relatively constant among the agrochemical samples. However, the compositions of less major PCDDIDFs were different among the samples.. @. 1.. I$CLblC. B % t z + % % k L T % 3 h T b \ 7 z 9 4 &*Y Y%$fi<,&Ifi:aD y.4 & * v Y R ~ ~ % R ~2zf&A 3 i @ ? ? % 5 ~ T b \Z 5 k fi:%@$hTb\6 (&?!kith, 1998, Masunaga e t a l . , 1998), Lfih L, El $-T i $ h h 7 z B % 9 ~ j l . 4&J-L3F->+%%tzHT6 ~lEBi3$F%tz&?2b\,%%btA&%iz93$&7z& b ~ , ! s %-?-D9.4' ~ ~ ~&*YY@D%BE??Bq% , L'fz, $filiS@%a>+Zf&%'n't3II;IJt~BET6 DT (Masunaga et. al. , 2000), Z Z T 6 3B P X 5 35 ?ACrL a Z ~ @ % ? ? $ E P T 5 . l). 2. 2.1. RHk%;% EZZH. &%%%$i3 1998 +tz&k LT%&!%k%,%!% D&%fih b$&&7-, %tfiizi?+ ~'fz%%$i342T& 5'. Y 3 - 1 ~ f s & ~ D ~ 1 . ~ 9 3 $ h - i l L \ f z %2D T & h b D F J , k@wy4%+YYTa%BEfi:8fi1 - > ' f c 4 2 9 9 ~ ~ 7 r l - / I(.P C P ) , ~ U U = b a 7 1 Y ( C N P ) . ;tj'LU, z b U 7 r Y ( N I P ) 0 3 %%a>,!s%tr-b\T Z' Z' T$Ep-+6, %$$t~H?5~l@@b3 Table 1 iL% L'fz,, & b \ B%fi:93$&LTb\7zZ'k i i k + H D ~ 3 2 i ~ t & $ ~ ~. *g?gaeA%Bg$4qR%* 2 9 --BEZEIYrn%Z Department of Environmental Engineering Science, Institute of Environmental Science and Technology, Yokohama National University. 2,. $4Yt3@7%BS%B, &@mzErn%%B$%. Core Research for Evolutional Science and Tecl~nology, Japan Science and Technology Corporation 3' $j&7373 /?-7 Shimadzu Techno-Research Inc. *) * g $ ~ B e A q ~ g $ 4 % 2~9% -Bge&g@qR%Z * Department of Environmental R~skManagement, Institute of Environmental Science and Technology, Yokohama National Unviersity. (1999 % 11 A 1 B g$i).

(2) Table 1. Agrochemical samples analyzed in this study !. If&%. BaPa%%. (R.tip-4 -8BF). Fik. 1 %R&. 33. @S% ERfi%+/~rl.No.. (%). ~ Y P P U U ~ S I - I L ~ K J P A25~ PCP-1 967. El. PCP $?#I. 25. s ;iP;BS&rf;;2?f_. I. -*it=@ 5 Dl&. '. 75. 1;. 13.4. I I. 1.2. 4 2 . 1 0 / ~ ~E31. R Y P ~ U U ~ ~ / - D 3~4F ~ Y. PCP-1970. D o A3 ?*ij$J. PCP .MCP l%sjPJ. -*iC% 2-)tT/l/-4-3 u ~ 7 z I q F - @ @ 7 ' 9 / r L r x f IL. ZRE% 45q10a. % @ R H f L 2'. , 85.4 4Y5'3~~7s/-/l/'fI.Y P A ) 1 13.4 3. PCP-1971. -*/C%. )"A'yX2BJ. ZRE%. 2 - $ ~ , p - 4 - ~ u P 7 z / ~ ~ @ @ 7 /. PCP~MCPRSBJ,l/zxy,,. I 1. @@g%fL. 46q10A. 1.2. / 85.4. 2". f. PCP-?. CNP-1978. CNP- 198 3. CNP- 1986. CNP-1987. CNP-1989. NIP-1969. PcP%iijPJ25. ,-. -a. t79.r MO %#J CNP t294 MO TL#J CNP 9294 Mo OL#J CNP TL#J ?>'r4 MO TL#J CNP f L 8 J. =y?$h#j. -. > @. (EPBrlB< *l@;f;%>. F. 1. J. 1. 3 F R E i k 9 53.10/~~8050. 9.0. 1 91.0. I. C N P (2, 4,6-\y ~ D I L ~ ~ Z I LP-~ ~Z Z'I -C ~Z \ -7,L) !I. I. ?w!%?@ff L!kB%. 1. .tfY3-4{k9(&) 86.10-90304F. 80. C N P (2, 4, 6 - \ Y l ~ i b 7 r ~ ) b - 4 ' - ~ \ ~ 7 r z ) b ~ -T,~) 1 20 -. G&&B#J ? L i H J % C N P (2, 4,6- \Y ~ P ) L ~ ~ Z ) L - ~ ' - Z \ P ~ I . Z ) I / I :. 1. 80. 1. 20. 1. 8%?@#J $Lik%I%. 80. 2 , 4 - - 2 3 a l L 7 r z r L - 4 - ~ 1. u 7 7 =IL=--S-IL. 11. 7.0. E f@ . g%. 1. 93.0. Figure 1 K ZL?zo 3387 F7 F \ Y 7 g 9 # $ E g B / n '. I. YY3-4ik9(&) 83.10/607.08 F. 20 80. 1 fLik#j% C N P (2, 4, 6-\)9~)b7r~)I.-4'-~)~71~)1/1: -7,1.) I 20. &&,B#J. & ~ l t i ~ ? ~ f ir : , a,k 5 f~@&a>%Fh L?z@%~> HQ%33V~TAfi:%%$h6 22f i i S Z h 5 ~. 2.2 h\%J%& %%@%?&a>&@% 3 x 3. S2WkFI%. 25. I. 2 , 4 , 6 - b / b 9 U P 7 r I-/L-4'-z ,l/z ,L. 94 0 9 CNP Rs8J. 1j. ~ ~ j r 9 o u 7 r / ) - - 1 ~. YY+I'{~~(&) 87.10/00607F YY3-4{t=Y(?%) 89.10/11202F. RZG%iCYI% (&I 44.10/039193. fiZtirL C~,BIJZL~C~ -B@!.sY7 s + - r k " 7 !,BPX5 (SGE, 60 m x 0.32 mm (h@), @B =0.25 pm) 2 DB-17HT (JkW, 60 m x 0.32 mm (h@), BE= 0.15 p n ) O I 2 ~ ~ 7 s 5 4 ? 2 R b \ T ! $ 2 T a > 2 , 3 , 7 , 8 - i B @ @ % z B L , $ biz, 4?a>#!lD3Wk #to-? h*TZ&L7zo. 0.

(3) +. +. [. h+f>-. mQPHz h)y>. 1N-KOH. 1N - K O H ~ E ( 2 ~ ). I 1 N-KOHW. 1 N-KOHR. I. <%P 3 I. Figure 1.. 3. %%k%% 3.1 BPX5 A ~ #Eli2. A n a l y t i c a l procedure. L I Z # ~ I $ Q ~ ~ * I ' 3.2 ~ % s~B#>Hr@3t~ ~ P c P 2c N P ~ Z ~ L \ T ~ F J E # + U I E ~ % # a>$Hr;k$@f;r*&,. id; DB-5 (J&W) 2 fl C T h 6 , k 0 - 3 a>m$i3 Ryan e t a l . 1991 i~ k -> Tz, %%& Table 2 iZ?T, BPX5 i Z k 6aqgi3$-a>%RkAlbTa>&f?-> Tza>iZ$+ L T , DB-17HT 75 7 A i ~ % L \ T i 3 m - " f ~ 7 ~ 1 k i z 9 L \ - C ~ ~ & U I $ f 3 -k8A? l k i Z % L \ T % q $ f;rf?9Tco + Z T , r n % ? A i Z % I j - a t o - P a > % L i ~ f 2 2 5 3 9 i ~~ M ~ i t d d; ; , 9 E%%fx%I+ir%k;bj- a@lJ$y.-P fis DB-17~TT@b $ L T L ' 6 %. P c P a > % % m a , j7"4 d - + v ~ @ B a > % R i r &L\RE#T 63 6 H7CDDs, H7CDFs I.Z% I-f 6 Rl'!k#. gt2, ? a > l i & i r E L B 2 f ~ , fZ9-C+ElP6iE.fb5 a> i3&@& $ $L)i BPX5 2 7 A iZ 16 @8k#$ ga>%%kfd?50. Figure 2. 2. ZZTi-h$&i$!?a> BPX5 7 5 7 A i ~ k 6 * t ' - - 3 ~ ~ a > g z f ; r $ g + T 6 , BPX5 a> to-3 a>@y)JIE%. +R. Figure 3 ~L?$L. Film% L7co. X:~r;k)d:49 a > 3 $ $ 2 T i r q ~ \ T 8 R i r - $ L T. L \ 6 , LiJhL, f;&%UT;a>lFlE#i~;fj'L\-CBt% # ~ : ~ F t ; i 3 3 $ $ P ~ ' ~ ~9fii T h fb~9 ~ \ 7 ~ $ ,bi~F$$if iZ& 6 2, H,CDDs T i 3 PCP-1967 2 PCP-1971 @!YI{JJT% 9 , 7 = I -lbf;r&%ik L T P c P 2 gr;k'if6%il.rwn7#k ~~-(r&.fb6aaTa, 2 , 3 , 4 , 6 - T b 7 3 U U 7 1I -lb (T~CP)a> 2 9. 3-d~b!ikC?59'4&+V~Rt!k#T636 1 , 2 , 3 , 6 , 7 , 8 - , 1 , 2 , 3 , 6 , 8 , 9 - , 1,2,4,6,7,9-HJDD.

(4) Table 2. Congener specific determination of dioxins in agrochemicals by BPX5 column (concentration: nglg formulation) Sample-Expiry date PCP-1967 PCP-1 970 PCP-1 971. PCP-? CNP-1978 CNP-1983 CNP-1986 CNP-1987 CNP-1989 NIP-1969.

(5) Table 2. (Continued) Congener specific determination of dioxins in agrochemicals by BPX5 column (concentration: nglg formulation). Sample-Expuy date PCP-1967 PCP-1970 PCP-1971 Active ineredient (%) 25.0% 13.4% 13.4%. PCP-? CNP-1978 CNP-1983 CNP-1986 CNP-1987 CNP-1989 NIP-1 969 25.0% 9.0% 20.0% 20.0% 20.0% 20.0% 7.0%.

(6) Table 2. (Continued) Congener specific determination of dioxins in agrochemicals by BPX5 column (concentration: nglg formulation). Sample-Exphy date PCP-1 967 PCP-1 970 PCP-1971. PCP-? CNP-1978 CNP-1983 CNP-1986 CNP-1987 CNP-1989 NIP-1 969. * For better reliability, italicized values are selected from the results obtained on DB-17HT column under better sample dilution condition.. Q).

(7)

(8) lo;'.

(9) a> 3 9 a > $ H y j f i k f i ~ % i @ L T ~ \L\ /, h t z H L , PCP-1970 PCP-?Ttdr?/h?/h 1,2,3,4,6,82 1,2,3,4,7,8-H6CDD a)$H&SlI&fi$8< t/hbCa. .. R#ThbPCPk b Y 3 ~ a 7 r l - I L (TrCP) 2 a > E 6 t r L ! I & L 7 ~ 2 % k b / h 6 a > T , r /h b a>&%R#P iz idrk@m TrCP +@@fix& ijh->7za>TCdrf2L\il~2Rb/h6.M&Ic H6CDFs T % ,PCP-1967 2 PCP-1971 fi;{GTb\6a>tZx4fL T , PCP-1970 2 PCP- ? T C2 1,2,3,4,6,7-, 1,2,3,4,7,8-,1,2,3,4,7,9-H6CDFf2k"a) 1,2,3,4. *. *. a>fCEi~%SfiXA-7~Et%#fi$B Q7TL\60 f$2 LTCdr PCP-? a>F.4A-+VY$H&fi$f&a,% a > m ~ z g ~ \ f i ; r k5$itrga5, ~\~ rj-~idrgig~ =-kxa>@Sizb; 5 q % t % 2 ~ h 6 0 C N P TCdr P C P 2 Cdr~CZ!&%%RE@,?/h % - Y ~ Y ~ - ~ - ~ ~ (PCDDS) & + Va>@@fis8 Y < , ?ZTa>E~%#$H&fi$%%$?a7TLL\-Bfi~E b dZT L \ 6 , !$!i~j T,CDDs T idr 1,3,6,8-2 1,3,7,9-T4CDD 90%Uk2&&. ?/hbDFa7a>k $%k@b'!l-%LL-crL\6, ZbbCdrCNPa>R$$ T h 6 2,4,6-TrCP a> 2 *3fizlk& L T T 3 6 j7" / r ' % + V Y T h 6 , P5CDD TCdr&gf2 3 9 a ) k 0 3fi;5T&b/h7z0 :a> 3 to-3&@&'S6 4 9 0 B##, ? f 2 b % , 1,2,3,6,8-,1,2,3,7,9-, 1,2,4,7,9-,% k U , 1,2,4,6,8-P5CDDCdr, e T R$$a> 2,4,6-TrCP 2 ?h2$EbZ%%lk $ h7z 2,3,4,7-TeCP 2 a > l k e ib; ~ -> T & @j36 F.4 A+ + e w # T b i , a 0 $ ~ & k t : d r &2~q\ a > % ~ (CNP-1978 2 CNP-1983) 2 % L L \ 3 9 a>%$$ (CNP-1986, CNP-1987, CNP-1989) a>?/h?/ha> pa7T%i@LTL\6, $ b i z , H,CDDs 9 T4CDFs, P,CDFs, H,CDFs a>$$R&#h Ta>#H&T6 ,m@. SIH*M #&%M, @#@I$,. P E @ 3 , 1998. R S % 2 E 9 g ? % @ t z % i 3 6 F ' 4 % * V Y % ~ @ 3@, ?%BQA?E%$+y@%-IZ YP+$Zg 24: 1-. 10. Masunaga, S., Sakurai, T., Ogura, I., Nakanishi, J., 1998. Mass balance of dioxins in Tokyo Bay and Kasumigaura Lake basin in Japan. Organohalogen Compounds 39: 81-84. Masunaga, S., Takasuga, T., Nakanishi, J., 2000. Dioxin and co-PCB impurities in some Japanese agrochemical formulations, t r & b \ 2 ~ 2 % ~ ~ ~ 3 ~ C z 3 " 1 ~ - - 7 " / n \ i 3 $ / h 7Chemosphere ~ (Submitted). fi', H6CDDs +H7CDFs TCdr%Ti3%bf6a'->7z0 % Ryan, J. J., Conacher, H. B. S., Panopio, L. 7z, P5CDFs, H6CDFs, $3 b; U, H7CDFs Ti3% L L \ G., Lau, B. P. Y., Hardy, J. A., 1991. Gas 3 9 a > % $ $ a > ~ a 7 T % & L \ d f E b & T L \ ~Z, h b chromatographic separations of all 136 idrR?$+~a>@@$Ea>S~\%Cr@~ LTW 6 tetra- to octa- polychlorinated dibenzo%D2Eb/h6. p-dioxins and polychlorinated dibenzofurans on nine different stationary phases, J o f Chromatography 541 : 134-183..

(10)