Document OEXpDnOQKBK4OwVwJz8Y44bw
)
Absence of cliJ ormatod dibouzca j ovHs end dioci.zofurans from aquatic ,m`.-ra la
By V. Zilko I j.in v i r o nr C' n i C ;\n a *
Fj ./jfl if-.' i if./o>; J C''J SbebioHj At. A',u.r tn , b. B.
%J. %ru/,trh
^ a/ ?. M (<?> )
MONS 205965
liesidues of chlorinated dibonzodioyins and d1benzofurnns were not ueter table at detection limits of 0.0'+, C.02, 0.0?, 0.01 ~nd 0.01 ug/g on tissue wot weight basis, for 2,3,7jS-tctnchlorodibenzodioxm t'fCDD) , a mixture of di-, tri-, and tetracnlorodioenzofuran (CDF), two isomeric hcxachiorodibenzodioxins (riCDD), octacklorodi benzodioxm (uCDD), and octachlorodibenzofuran (OCDf), respectively, in the muscle and liver of white shark ((fl-Cl'l3 rqdon carchnrias), eggs of dounlecrested coiuicnntr. TPhalacrocorax .furit^u^) and herring gulls (ba.rus argentaius), muscle of eel (Anguill.3 x.nstro_ta5-*and clma pickerel (Esox niger), and" ir. conierctaf samples oi herring oil and groundrich-herring fishmeal.
Chlorinated dibonzodioxins are impurities present in chlorinated phenols and herbicides based on chlorinated phenols il,2). TCUD and liCDD arc the most toxic chlorinated riibenzodloxJns (3). According to o preliminary report (4) chlorinated dinenzodioxins do not occur widely in tne environ ment, although they were detected some time ago in certain poultry feeds and found resvonsible for hydropcricardiun in chickens (chick edema factor, ?).
Chlorinated dibensofurans were detected in some commercial polychlorinated biphenyl (FCn) preparations (6). Their presence in environmental samples was not Investigated.
A method for the separation of chlorinated dibenzodioxins from K13 was described (7) and the uptake of chlorinated dibenzodioxins was studied m chickens (ti).
Exp erirnental
White shark, was landed on Deer Island, New Brunswick, Canada, and samples of muscle and liver were provided ov Mr. S. ft. Taboo of tins Station. Eggs of cormorants and herring gulls, collected on
HONS 205966
Faipot Island, Hay of Funuy. Canada, were the same as in our previous study C95 - dels and pickerel were taken from the St. John luver, .,ew brunswi-k.
Samples of herring oil and fishmeal were obtained from a renuction plant in few urunsviCK. Cnlomjted dibensoai^xmj and dibeneofuran stvV>,rus were supplied oy Dr. 'J. Firestone (FDA, ...acm agton, b.C.) anu so were pamrints 12,8).
The extraction and cleonnp were carried out as
described (10). Fractions I and II thus obtained
were furtner chromatographed on alumina (7) under
slightly modified conuitions. Alumina (Fisher
Scientific a-!)Ho, 2 g), activated at 130C overnight,
was placed in a 45 x 0.5 cm column. Cample, dissolved
in 1.5 ml of pesticide-grade hexane (fisher Scientific
H-3O0) containing
methylene chloride (Fisher
Scientific D-37), was applied to the column, washed
into the column by an additional 1.5 ml of solvent and
the column was percolated with the same solvent to
collect 20 ml of effluent. Further elution was
carried out. with 20$ methylene chloride in pcsticide-
'gradc hexane ana 10 ml of effluent was collected.
Fractions I and 11 of the original cleanup thus
yielded fractions I 1, I II, and 11 I, II II,
respectively. The behaviour of PCB in this procedure
was tested by using Aroclors 1221, .1237, 124.2, 12h3,
12 54, 1260, and 1268, and Phennclor Df-o. Cnro.aito-
graohy of a con lercnl preparation of chlorinated
naphthalenes was also earned out. If the 20 #
methylene chloride fraction conlainoc. 4CB, it was
rechronatographed as described.
Conditions of gas chrona togn^hy were as described (11,12). CDF and TODD were determined by chromatography on the h$ G1S-30 column, flic 3$ 0/-210 column was used for iiCDD, OCDD, anu iXDF.
The recovery of chlorinated cl ibenzod toxins and dibenzofurnns was deterniaed in spikee samples of fishmeal.
Refluxing with 3$ methanolic potassium hydroxide for 1 h was used in some cases for furtner cleanup of fractions II JI.
1
Results and _Di scur.si on
To detect TCDD, IICDD, and CDF, fractions I and II of the clranup-chromatograniiy must cc further chromatographed on alumina. The HCuD standard contained
MONS 205967
lJ )
two isomers with retention U'ios of 0.87 and 1.00 rolative to decachlorobi phenyl, respectively. He former is recovered mainly :n tract: m: I II, the latter In fraction T1 II. TCDD (.retention time of 1.86 relative to p,p'-DDE) is equi11y civided between Jructions 1 II ana i[ II, while CDF' (retention times of 0,b2, 0.39, ana J .yd, relative to p respectively) is eluted In fraction il II. OCuD and OCDF are olulod in fraction I and because of the Jong retention times (3.68 and 2. r>3 relative to doc .c'dorobiphenyl, respectively) may be quantified directly in this fraction. After chromalogranby on alumina, UCDD and DCDF appear in fraction 1 11.
In samples containing a large amount of p,u'-DDT, some of jt may be eluted m fraction J[ and occur finally m fraction II II, where it interferes -nth the quantification of CDF. Tms interference is eliminate^ oy refluxing traction II h with .rolhanolic potassium hydro.:i Jo, CDF' is not affected by tms treatment while p,pl-DDT yields t^p'-DDL.
Analyses of suited samul es of commercial fishnenl are su; ins rised j a Table 1.
TaP.LS 1 Analysis of spiked fishr.e-il samples pn/g, wet weight
Sample
1 2 3
TCDD
Added_ round
1.13
0. 89 0.22
0.96 0.0b
0.33
liCDD
_A Iced Founu
1.03 J . 08 0. 2 ci
i.x`; J.Ot 0.31
0CDD Added _Found
1.30
0.6 6' 0.32
J .29
0. 67 0. 50
CDF
0CDF
Ad_ded Found
Addpq Fqu:id
4
1.21 1. bl
0.91 0.96
5
U.60 0.62
o,b.- 0.36
6
0.30 0.23
0.21 0,1b
Levels of I'CB (as Aroclor l?pb) and chlorinated hydrocarbon pesticides m samples arinlysi-d for chlorinatec dibonsodioxins and dioensofurans are presented in Table 2.
With the exception of the white shark liver extract, i he removal of PC3 fron fraction I in fraction I 1 caused no difficulties. Neither iCo nor any other
MONS 205968
t. J J
peaks were detected in the fraction I II. In the shark liver extract, containing F'CB in very high concentration, sone PC3 v:ere carried over into fraction 1 II and this fraction was rcchroraatopraphed. No peaks were detectable after rcchromitography.
TABLE 2
PCD and chiorinated hydrocarbon pesticides m analysed samoles
Sample
Tissue
4g/g wet weight PC3 p, p 1 -DDE p,p(-DDD p , p'-our
Herring oil Fishmeal
3.55 0.54
Chain
pickerel Eel
muscle 3? muscle 0.46
Doubie-c rested
cormorant eggs 45.6
Herring gull O 00^ c 7.45
white shark muscle 0.7? M * liver 218
2.27 0.19
0.15 0.48
32.1 ' 2.70 0.44 335
0.11
0.03 0.13
_ _ 43
o.37 0.10
0.08 0.15
0.10 0.10 0.12
63
No peaks corresponding to the available CDF standards, 5CDD, and HO DO were detected in fractions II II after reflux with methanol ic potassium hydroxide. Fraction II II of the shark liver extract had to be rcchroma tegraphed.
An unidentified peak with a retention tine of 0.89 relative to pjp'-DDC, yielding a peak with retention time of 0.5^ relative to p,n'-DDE, after the potassium hydroxide treatment, was present in most II II fractions. Another small peak with a retention time of 0.76 relative to p,p'-DDE, unchanged by the potassium hydroxide treatment was present in several II II fractions.
The chromatography on alumina (7) as modified in this work is very efficient in removing PCB in the 2% methylene chloride fraction. In inoael exeeriments 700 ng of Aroclors 1242, 1254, 1260, and 1268, Phenoclor DP-6, and chiorinated naohthalenes was completely eluted in this fraction. One rechromato graphy of the 20; methylene chloride fraction was necessary to remove 500 eg of Aroclor 1254, 1260, anu Phenoclor DP-6 and no peax.s were detected in the chromatograms cf the purified fractions. Peaks with
MONS 205969
() )
retention times of 0.2j, 0,53) and 1.07 relative
to Ujp'-DDK, respectively, were found in the
rechromatographed 20JS methylene chloride fractions
of Aroclors 1248 and 1242, when 800 pg was
originally applied to the column. Aroclors 1232
and 1221 yielded under the same conditions one
,
additional peak with a retention time of 0.09
relative to p,p'-DDE, 'The peak with retention
time of 1.07 was absent from Aroclor 1221. Accord
ing to a preliminary investigation by mass
spectrometry, the rechromatographed 20# methylene
chloride fractions of Aroclors 1248, 1242, 1232,
and 1221 contain mono-, di-, and trichlorobiphenyls,
mono-, and djchloroterphcnyls, and some other
unidentified compounds (0. Hutzinger, personal
c omraunica tion).
The species analysed in this work arc in high trophic levels of the aquatic food web and may serve as good indicators of environmental contamination by cumulative compounds. The results indicate no detecta ole contamination of the food chains by chlorinated dibenzodioxms and dibenzofurans.
The leaka ;e of TCDD into the environment may
occur mainly from the applications of 2,4,5-T. Ihis may be insignificant, since, in the past, the levels of TCDD in 2,4,5-T were 20 pg/g or less 1,4) anc preliminary reports indicate that TCDD is not very mobile in the environment t13)* however, the extreme toxicity of TCD) warrants a thorough investigation of the problem.
Tetra-- ani pentachlorophenol are probably the main source of dCDD and UCDD. containing these compounds in the ;ig/g range (2). Similarly to TCDD,
HCDD, and OCD'D originate -in the producuion of these phenols and are not generated in the enviroment, where other types of condensation reactions take place (14,15). The amount of hCirD mu OCOD released into the environment may no very small.
, Commercial PCB preparations are a potential source of chlorinated dibcnv.ofarms. ho detailed data on the levels of chlorinated dibenzofurjns in PCB preparations are available. It is possible that
the leakage of ihiorinated dibenzofurans into the environment is legligible.
Additional spotchecks in different geogrmhjc areas are required to assess the contamination ol the environment by chlorinated dibenzodioxins and dibenzofurans.
MONS 205970
()
References
,
1.
2.
3.
4. [7.
6.
7. 8.
9. 10. 11. 12.
13.
14. 15*.
WOOLS.OK, E. A. and THOKAS, H. ]'. , ACS, I6lst
rational ,'iecting.. Div. Pesticide Che'.
(1`71).
'
FINESTOLE, D. , HESS, .T., LR0..V, n. L., Mia.OL, n. P., end DmjiICO, A., J. Assoc, OH^c.
Anal. Coexists, jii press (l'//l). JiOAE, V. a., J cm HIS, J. H., > j-,i H.kC iU, G. L. ,
SCnWErZ, !. A., end GxHlrilkG, i . J., ACC,
J'S.lnd Notional Meeting, Div. Pesticide Chera.
(1971). WOULCoh, E. A., ACS, l6ind National jeeting,
i;iv. pesticide Chem, (1971).
HESS, . , HiCGIABOTi'iAi-i, G. H, , and FIRoSTOpE, D. , J. Assoc. Uffic. Anal. Chemists _23, 6 Pc?
(1970). VOS, J. G., kOEilAA, a. K., \(Ah bin r:AAS, h. L.,
1 Eh mOlWEm DE nh.UJW, E, C., and DK VOS, h. H. ,
Fd. Cosmetics Toxicol. 8, o?1; (1970).
PORTErt, 1!. L. and BHHaE, J. A., J. Assoc. Ofl`ic.
.nal. Chemists, in press (197)). FihEB.`G,.Z, 0., rLlCA, 0. r'. , REDS, J., and
HlGGlJ.bOTiiAh, U. . ,i. Assoc. Cific. Anal ,
Cnemists, in nrscs (1971).
ZITKO, V., and CHul, p.
A., hull. Environ,
Ccntam. Toxicol. 2(J),(1972). ZITaO, 9., Bull. Environ. Contois. 'loxicol,, 6,
NCh (1971).
ZITkO, V., d. ChronnWr. 12, Mfi 0 971). ZITx'A), V., HuTAihGEh, 0., .<.,JECOd, \i. D., and
'
CHOI, i. M. A.. Bull, environ. Contam. Toxicol.,
in press (1972).
KEAHKi'.Y,- P. C., i>S,.3.fiE, A., NELLI AG , C. G., __
-tOOLoUh , o. A*, a nd f D1. jj'csii, 0 R., ACS, lo2nd
National heeling, Div. Pest.iclue Chem. (197-1). hUhAixATA, a, and XlMARAUA, M., mrsidue Reviews 29,
13 (190). ST&ilL, H. I., PAPEHF'USS, h. U., iWEDBT'JEG , h. A.,
and P.OsEhTS, R, A., ACS, loHno Potions 1 nee ting,
Div. Pesticide Chem. (1971).
HONS 205971