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September 18, 1969
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AROCLOR-WILDLIFE: THE EFFECT OF CHEMICAL CLEAN-UP PROCEDURES ON THE QUANTITATIVE RECOVERY AND ELECTRON CAPTURE RESPONSE OF THE AROCLOR 1200
e* P '*
SERIES
: W. R. Richard General Offices
Keller Farrar Wheeler
Res Res GO
The effects of three chemical clean-up procedures on the Aroclor 1200 series have been investigated. The chemical procedures in question; nitration, saponification, and treatment with sulfuric acid were originally proposed by pesticide analysts for the clean-up and identification of pesticides in residue extracts. Later when polychlorinated biphenyls (PCBs) were identified as environmental contami^nants these procedures were extended to the clean-up and identification of PCBs in residue extracts.
Conclusions
1. The quantitative recovery and EC response of Aroclors
are not effected by saponification or treatment with
sulfuric acid.
'
2. Nitration can have a significant deleterious effect on the quantitative recovery and EC response of Aroclor 1242.
3. The extent of the effect of the nitration treatment is dependent on the temperature and exposure time employed as well as the Aroclor treated.
4. Analysts employing nitration procedures prior to EC ; analysis may or may not, depending on the conditions
used, see an EC response for Aroclor 1242 if present.
. '
We have found that saponification and treatment with sulfuric acid do not effect the quantitative recovery nor the electron capture (EC) response of the Aroclors. However, the nitration procedures have significant deleterious effects on both the quantitative recovery and EC response of the lower chlorinated biphenyls such as Aroclor 1242. The effect of this treatment on the Aroclors are shown graphically in Figures 1 - 7.
The fact that the lower chlorinated biphenyls are nitrated under these conditions has been verified by GC/Mass identifi cation of the products as 'nitrochlorobiphenyls.
The nitration procedure employed was referenced by Risebrough* lErro, F., Bevenue, A., and Beckman, H., Bull. Environ. Cont. Toxicol., 372 (1967)] in his Nature article on PCB residues : in the environment.
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To: W. R. Richard Page 2.......
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Additionally, we have investigated a similar nitration
procedure used by Widmark and co-workers (private communi
cation via R. E. Keller). This treatment differs from
Risebrough's in that a shorter exposure time and a lower rtemperature are employed. The Widmark method greatly
diminishes the effects observed with Risebrough's referenced
method.
.
db Attach. - 7*
E. S. Tucker
*A quote from Risebrough's article [Nature, 220, 1098 (1968)], "The DDT compounds are destroyed by nitration'and p,p'-DDT, DDD, and toxaphene are dehydrochlorinated by saponification with alcoholic KOH. PCB is not degraded by either procedure".
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Solvent ^^^Response
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T 1---------1----------1 ' I----------1----------I T I I i---------1 '? I ' '*
FIGURE 1.
" '
Electron capture gas chromatographic
trace of (A) biphenyl'treated with
1:1 mixture of nitric and sulfuric
acids and extracted into hexane,
(B) biphenyl treated with distilled
with distilled water and extracted
into hexane, and (C) untreated biphenyl
standard in hexane.
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FIGURE 2. Electron capture gas chromatographic
trace of (A) Aroclor 1242 and treated
with 1:1 mixture of nitric and sulfuric
acids and extracted into hexane, (B)
' Aroclor 1242 treated with distilled
water and extracted into hexane, and
(C) untreated Aroclor 1242 standard in
hexane.
.
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FIGURE 4.
Electron capture gas chromatographic trace of (A) Aroclor 1254 treated with 1:1 mixture of nitric and' sulfuric acids and extracted into hexane, (B) Aroclpr 1254 treated with distilled water and extracted into hexane, and (C) untreated Aroclor 1254 standard in hexane.
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AROCLOR 126C
FIGURE 5 .
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1
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A ro c lo r 1260 sta n d a rd in hexane.
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FIGURE 6 .
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. *
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