UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
DATE: April 7, 1980
subject: Interim Report - Organic Analyses and TCOD Determination In Extracts of
Samples Collected from the Hempstead Resources Recovery System Incinerator.
prom: James B. Homolya, Research Chemist
RFSO, ESRL, MD-84
to: Or. J. Spatola, Chief
A1r Monitoring Section, 2-SA
At this time, sufficient data have been acquired from analyses of the
Henpstead samples taken during the July experiments to provide an Interim
report of results. Also the Northrop Services report which was reviewed
by Region II personnel has been finalized to Include a discussion of
experiments designed to verify the results which suggested that both
formaldehyde and acetaldehyde were present In the emissions. Those
experiments Indicated that the formate and acetate found 1n the Implnger
were not the result of artifact formation, but could be formed by the
oxidation of formaldehyde and acetaldehyde via hydrogen peroxide 1n the
Implnger solutions. However, we cannot be entirely sure that certain
unknown species were oxidized 1n solution. I must again point out that
all of these experiments were carried out 1n an attempt to verify the
findings from a single source characterization sample. Undoubtedly,
any future characterization measurements at the Hempstead plant should
be deslnged to specifically collect sufficient samples for formaldehyde
determinations. He feel that the 1n-stack formaldehyde levels may be
quite variable, reflecting shifts in the operating modes of the furnace
from complete Incineration to partial pyrolysls. The latter condition
would be expected to result 1n higher formaldehyde levels.
Attached are Interim reports from Wright State University and the Analytical
Chemistry Branch of EPA's Health Effects Research Laboratory which discuss
current results of the collaborative analyses of certain Hempstead extracts
for TCDO. Our decision to look for these compounds was based upon the
Identification of polychlorlnated phenols present 1n samples analyzed by
"cursory" gc/ms techniques (attached Northrop Report, ES-TR-80-04, pp 14-19.
Samples from Runs 1-3 shown 1n Table 4 of the Northrop report have been
assayed for total TCOD by Wright State. At this time the Implnger extracts
for Runs 2 and 3 have been analyzed by HERL. A sunmary of the laboratories'
findings 1s given 1n Table 1.
Table 1
Analyses of Hempstead Extracts for Total TCOD (nanograms)
Run #

Implnger
XAD-2 Cartridge
Total
ws
HERL
US
WS
1
*
*
23.3 ng
23.3 ng
2
10.7
8
28.4
39.1
3
34.3
33.6
35.0
69.3
~Sample discarded.
CPA Fam 1J20-* (Rav. J-74)

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The confirmatory analyses by HERL have not yet been completed because of
delays caused by Instrumentation problems at Wright State. The results
from two samples that have been analyzed are 1n good agreement with the
Wright State data. We hope to have comparable TCOO analyses for all samples
completed within the next two weeks.
From their reports, there appears to be some disagreement between each
laboratory's estimate of specific TCDD Isomers present and quantitation of
the 2,3,7,8-TCDD. This problem Is rooted In the fact that neither laboratory
has analytical standards for all 22 TCDD Isomers, making specific Isomer
Identification and quantitation tenuous. It Is my understanding that only
Dow Chemical Co. and Dr. Rappe, University of Umea, Sweden, have prepared
small quantities of all of the tetra Isomers.
Recently Wright State was sent the particulate fractions from Runs 1-3
which they will extract and analyze for total TCDD. For completion of the
present project, both Wright State and HERL will attempt to determine the
concentrations of higher chlorinated dloxlns 1n the extracts. These results
m*y give us a clue as to the origin of the TCDD In the flue gases. Table 2
Is abstracted from the work of Rappe, et al., 1n which purified chloro-
phenates were sprayed on leaves which were then burned In the laboratory.
The distribution of chlorinated d1benzo-d1ox1ns were remarkably different
for the two chlorophenates studied.
I understand that Midwest Research Institute has Identified 2,4,5- and 2,4,
6-tr1ch1oropheno1 In similar extracts taken from Hempstead samples collected
1n August, 1979. It will be Interesting to examine the similarity 1n the
distribution of dloxlns to those samples from July. As the progress of
our work nears completion, I will prepare a final report to consolidate
the results from both laboratories for your review and comment.

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Table 2
Amounts of PCDOs Found 1n Burning Experiments of Purified Chlorophenates*


(ug PCDDs / g chlorophenate)

2,4,6-Trlchloro-

Phentachloro-

phenate


phenate

original
birch leaves
original
birch leaves

sample
charcoal
sample
charcoal
Tetra-CDDs
< 0.02
2100
< 0.02
5.2
Penta-CDDs
< 0.03
5.0
< 0.03
14
Hexa-CDDs
< 0.03
1.0
< 0.03
56
Hepta-CDDs
< 0.1
3.0
0.3
172
Octa-CDD
< 0.1
6.0
0.9
710
~from: Rappe, et a!., Chemosphere, No. 3, pp 269-281. 1978.
cc: w/o attachments
Dr. A. Ellison
Dr. J. Wagman
Dr. A. Altshuller
Dr. W. Wilson
cc: w/attachments
rfKr.	R.	Ogg, Region II (3 copies)
Nr.	R.	Harless, HERL
Dr.	H.	DeLarco, OTS, HQ
Mr.	A.	Freeman, IERL, Cincinnati
Dr.	B.	Del linger, NSI
Mr. J.	Cheney, ESRL

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